Nitric oxide concentration measurements in atmospheric pressure flames using electronic-resonance-enhanced coherent anti-Stokes Raman scattering

We report the application of electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) for measurements of nitric oxide concentration ([NO]) in three different atmospheric pressure flames. Visible pump (532 nm) and Stokes (591 nm) beams are used to probe the Q-branch of the Raman transition. A significant resonance enhancement is obtained by tuning an ultraviolet probe beam (236 nm) into resonance with specific rotational transitions in the (v’=0, v”=1) vibrational band of the A²Σ⁺–X²Π electronic system of NO. ERE-CARS spectra are recorded at various heights within a hydrogen-air flame producing relatively low concentrations of NO over a Hencken burner. Good agreement is obtained between NO ERE-CARS measurements and the results of flame computations using UNICORN, a two-dimensional flame code. Excellent agreement between measured and calculated NO spectra is also obtained when using a modified version of the Sandia CARSFT code for heavily sooting acetylene-air flames (φ=0.8 to φ=1.6) on the same Hencken burner. Finally, NO concentration profiles are measured using ERE-CARS in a laminar, counter-flow, non-premixed hydrogen-air flame. Spectral scans are recorded by probing the Q₁ (9.5), Q₁ (13.5) and Q₁ (17.5) Raman transitions. The measured shape of the [NO] profile is in good agreement with that predicted using the OPPDIF code, even without correcting for collisional effects. These comparisons between [NO] measurements and predictions establish the utility of ERE-CARS for detection of NO in flames with large temperature and concentration gradients as well as in sooting environments. PACS 07.88.+y; 42.62.Fi; 42.65.Dr     

单脉冲喇曼散射技术测量高压燃烧场组分浓度

介绍了自发喇曼散射技术的基本原理、实验方法及对高压燃烧场的测量结果。利用Nd:YAG激光的三倍频输出激发振动喇曼散射,在单脉冲条件下测量了高压模拟燃烧室内不同化学配比条件下以氢气-空气预混燃烧场为主要组分(N2,O2,H2O,H2等)的喇曼光谱,获得了主要组分浓度随燃烧时间、燃烧场压力的变化规律。实验中利用偏振技术有效地提高了信噪比。通过优化激光光束形状及光路设计避免了等离子体光谱对喇曼信号的干扰。     

Cavity ring-down measurements of seeded NO in premixed atmospheric-pressure H2/air and CH4/air flames

Quantitative aspects of using cavity ring-down absorption spectroscopy near 226 nm for measurements of NO mole fractions in premixed atmospheric-pressure flames are discussed. Measurements in methane–air flames showed strong broadband absorption near 226 nm by hot CO₂ molecules, precluding using the cavity ring-down method in these flames at atmospheric pressure. In hydrogen–air flames, the broadband absorption at this wavelength was substantially lower. Absorption cross sections derived from non-seeded cavity ring-down spectra suggest that absorption by water is the major contribution to the background in these flames. The detectability limit for NO by cavity ring-down measurements in hydrogen–air flames using the current setup is estimated to be 10 ppm. Effects of the cold boundary layer on the measured NO mole fraction were accounted for by measuring the radial distributions of temperature and NO mole fraction using coherent anti-Stokes Raman scattering and laser-induced fluorescence (LIF), respectively. Measurements performed in seeded stoichiometric and lean hydrogen–air flames showed no reburning at temperatures above 1750 K, demonstrating the adequacy of using these flames for calibration of LIF measurements. At lower temperatures, the mole fraction of NO in the hot gases was up to 30% lower than that expected from the degree of seeding in the cold gases. PACS 42.62.Fi; 42.68.Ca; 82.33.Vx     

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.     

Measurements of burning velocities of dimethyl ether and air premixed flames at elevated pressures

Laminar burning velocities of dimethyl ether (DME) and air premixed flames at elevated pressures up to 10 atm were measured by using a newly developed pressure-release type spherical bomb. The measurement system was validated using laminar burning velocities of methane–air flames. A comparison with the previous experimental data shows an excellent agreement and demonstrates the accuracy and reliability of the present experimental system. The measured flame speeds of DME–air flames were compared with the previous experimental data and the predictions using the full and reduced mechanisms. At atmospheric pressure, the measured laminar burning velocities of DME–air flames are in reasonable agreement with the previous data from spherical bomb method, but are much lower than both predictions and the experimental data of the PIV based counterflow flame measurements. The laminar burning velocities of DME–air flames at 2, 6, and 10 atm were also measured. It was found that flame speed decreases considerably with the increase of pressure. Moreover, the measured flame speeds are also lower than the predictions at high pressures. In addition, experiments showed that at high pressures the rich DME–air flames are strongly affected by the hydrodynamic and thermal-diffusive instabilities. Markstein lengths and the overall reaction order at different equivalence ratios were extracted from the flame speed data at elevated pressures. Sensitivity analysis showed that reactions involving methyl and formyl radicals play an important role in DME–air flame propagation and suggested that systematic modification of the reactions rates associated with methyl and formyl formations are necessary to reduce the discrepancies between predictions and measurements.     

Laser-induced fluorescence thermometry and concentration measurements on NOA–X (0-0) transitions in the exhaust gas of high pressure CH4/air flames

Laser-Induced Fluorescence (LIF) excitation spectra in the NOA–X (0-0) band were used for temperature measurements in the postflame region of high-pressure CH₄/air flames. To improve the quality of the measured spectra and to perform reliable line-shape measurements, the initial mixture was doped with approximately 400 ppm NO. At pressures up to 18 bar, excellent agreement was obtained between NO LIF temperatures and NARS/rotational Raman temperatures. Effective broadening coefficients were also determined in these flames. Problems with quantitative concentration measurements of NO and single-pulse temperature measurements at high pressures are discussed.     

利用拉曼散射测量燃烧场的组分浓度及温度

介绍了利用拉曼散射测量燃烧流场温度及组分浓度的物理方法和实验测量结果。利用可调谐KrF准分子激光激发振动拉曼散射（VRS）测量了甲烷－空气燃烧火焰内不同空间的主要组分分子（CH4、N2、O2、H2O等）浓度及温度,测量误差小于10％;另外用N2的拉曼谱拟合测量了火焰的温度,测量精度高于5％。在实验中采用了偏振技术及波长调谐提高了信噪比和测量精度。     

自发喇曼散射技术对燃烧场的诊断

 介绍了利用Nd:YAG激光的三倍频激发自发振动喇曼散射技术对燃烧场的诊断及相关的实验原理，测量了不同配比条件下的CH₄-air预混火焰内的主要组分(N₂，O₂，H₂O，CH₄)及其相对浓度；并分别用分子浓度测温法和斯托克斯谱与反斯托克斯谱强度比法测量了火焰的温度；还对该技术测温、测浓度的不确定度进行了分析。将该技术应用到对复杂的固体燃剂燃烧场的诊断，取得了燃烧场中几种主要燃烧组分（N₂，H₂CO，CH₄，H₂O）的喇曼光谱，以及这些组分在燃烧过程中的变化信息。     

Absolute OH concentration profiles measurements in high pressure counterflow flames by coupling LIF, PLIF, and absorption techniques

A high-pressure combustion chamber enclosing counterflow burners was set-up at ICARE-CNRS laboratory. It allows the stabilization of flat twin premixed flames at atmospheric and high pressure. In this study, lean and stoichiometric methane/air counterflow premixed flames were studied at various pressures (0.1?MPa to 0.7?MPa). Relative OH concentration profiles were measured by Laser Induced Fluorescence. Great care was attached to the determination of the fluorescence signal by taking into account the line broadening and deexcitation by quenching which both arise at high pressure. Subsequently, OH profiles were calibrated in concentration by laser absorption technique associated with planar laser induced fluorescence. Results are successfully compared with literature. The good quality of the results attests of the experimental set-up ability to allow the study of flame structure at high pressure.     

Raman response function of atmospheric air

A model of the full Raman response function of a gas mixture including rotational and vibrational motions of molecules is presented and is applied to examine the properties of the retarded optical nonlinearity of atmospheric air. For few-cycle laser pulses, broadband field waveforms, and/or high gas temperatures, both rotational and vibrational motions can significantly contribute to the Raman response of atmospheric air, with the ratio of the rotational and vibrational parts of the Raman response function controlled by the gas temperature and the temporal shape of the laser field.     

Experimental and numerical study of product gas characteristics of ammonia/air premixed laminar flames stabilized in a stagnation flow

Ammonia has widely attracted interest as a potential candidate not only as a hydrogen energy carrier but also as a carbon free fuel for internal combustion engines, such as gas turbines. Because ammonia contains a nitrogen atom in its molecule, nitrogen oxides (NO_x) and other pollutants may be formed when it burns. Therefore, understanding the fundamental product gas characteristics of ammonia/air laminar flames is important for the design of ammonia-fueled combustors to meet stringent emission regulations. In this study, the product gas characteristics of ammonia/air premixed laminar flames for various equivalence ratios were experimentally and numerically investigated up to elevated pressure conditions. In the experiments, a stagnation flame configuration was employed because an ammonia flame can be stabilized by using such a configuration without a pilot flame. The experimental results showed that the maximum NO mole fraction was about 3,500 ppmv, at an equivalence ratio of 0.9 at 0.1 MPa. The NO mole fraction decreased as the equivalence ratio increased. In addition, the maximum value of the NO mole fraction decreased with an increase in mixture pressure. Furthermore, it was experimentally clarified that the simultaneous reduction of NO and unburnt ammonia can be achieved at an equivalence ratio of about 1.06, which is the target equivalence ratio for emission control in rich-lean two-stage ammonia combustors. Comparison of experimental and numerical results showed that even though the reaction mechanisms employed have been optimized for predicting the laminar burning velocity of ammonia/air flames, they failed to satisfactorily predict the measured species in this study. Sensitivity analysis was used to identify elementary reactions that control the species profiles but have negligible effects on the burning velocity. It is considered that these reaction models need to be updated for accurate prediction of product gas characteristics of ammonia/air flames.     

Computational and experimental investigation of the interaction of soot and NO in coflow diffusion flames

A combined computational and experimental investigation that examines the relationship of soot formation and NO in coflow ethylene air diffusion flames is presented. While both NO and soot formation are often studied independently, there is a need to understand their coupled relationship as a function of system parameters such as fuel type, temperature and pressure. The temperature decrease due to radiative losses in systems in which significant soot is produced can affect flame length and other temperature-dependent processes such as the formation of NO. The results of a computational model that includes a sectional representation for soot formation with a radiation model are compared against laser-induced fluorescence measurements of NO. The sooting characteristics of these flames have been studied previously. Experimentally, a laser near 225.8 nm is used to excite the γ(0, 0) band in NO. Spectrally resolved fluorescence emission is imaged radially, for the (0, 0), (0, 1), (0, 2), (0, 3), and (0, 4) vibrational bands, at varying axial heights to create a two-dimensional image of NO fluorescence. A reverse quenching correction is applied to the computational results to determine an expected fluorescence signal for comparison with experimental results. Modeling results confirm that Fenimore NO is the dominant mechanism for NO production and suggest that for lightly sooting flames (peak soot volume fraction < 0.5 ppm), soot reduces only the Zeldovich NO formation (by a factor of two). For flames with increased soot levels (peak soot volume fraction ∼ 4 ppm), the model indicates not only that Zeldovich NO decreases by a factor of 2.5 through radiation loss, but that non-Zeldovich NO is reduced in the top center of the flame by about 30% through the oxidation of soot.     

Effects of OH concentration and temperature on NO emission characteristics of turbulent non-premixed CH4/NH3/air flames in a two-stage gas turbine like combustor at high pressure

This study examined the effects of OH concentration and temperature on the NO emission characteristics of turbulent, non-premixed methane (CH₄)/ammonia (NH₃)/air swirl flames in two-stage combustors at high pressure. Emission data were obtained using large-eddy simulations with a finite-rate chemistry method from model flames based on the energy fraction of NH₃ (E_NH3) in CH₄/NH₃ mixtures. Although NO emissions at the combustor exit were found to be significantly higher than those generated by CH₄/air and NH₃/air flames under both lean and stoichiometric primary zone conditions, these emissions could be lowered to approximately 300 ppm by employing far-rich equivalence ratios (?) of 1.3 to 1.4 in the primary zone. This effect was possibly due to the lower OH concentrations under far-rich conditions. An analysis of local flame characteristics using a newly developed mixture fraction equation for CH₄/NH₃/air flames indicated that the local temperature and NO and OH concentration distributions with local ? were qualitatively similar to those in NH₃/air flames. That is, the maximum local NO and OH concentrations appeared at local ? of 0.9, although the maximum temperature was observed at local ? of 1.0. Both the temperature and OH concentration were found to gradually decrease with the partial replacement of CH₄ with NH₃. Consequently, NO emissions from CH₄/NH₃ flames were maximized at E_NH3 in the range of 20% to 30%, after which the emissions decreased. Above 2100 K, the NO emissions from CH₄/NH₃ flames increased exponentially with temperature, which was not observed in NH₃/air flames because of the lower flame temperatures in the latter. But, the maximum NO concentration in CH₄/NH₃ flames was occurred at a temperature slightly below the maximum temperature, just as in NH₃/air flames. The apparent exponential increase in NO emissions from CH₄/NH₃ flames is attributed to a similar trend in the OH concentration at high temperatures.     

高温高压下草酸脱羧反应中的拉曼光谱研究

应用水热金刚石压腔结合拉曼光谱技术研究了高温高压下草酸溶液的热稳定,使用拉曼光谱对其脱羧反应及产物进行监测。结果表明低温升温过程中,草酸的拉曼谱图中各个特征振动峰没有发生变化,随着温度的继续升高,其特征振动峰逐渐变弱。达到一定温度后,羧基的拉曼特征峰消失,草酸发生脱羧反应:C2H2O4—2CO2+H2生成CO2和H2。高温高压下草酸发生热分解的温度压力之间呈线性关系,其线性回归方程为P(MPa)=12.839 T(K)-5 953.7,R2=0.99。草酸脱羧反应的摩尔体积变化与温度压力的关系为ΔV(cm-3.mol-1)=16.69-0.002P(MPa)+0.005 2T(K),R2=0.99。     

高压下1,1’-二羟基-5,5’-联四唑二羟胺盐的振动光谱及同位素效应

用密度泛函理论方法研究1,1’-二羟基-5,5’-联四唑二羟胺盐(HATO)晶体在高压(<40 GPa)下性质。在GGA-PW91计算水平并结合超软势基组对HATO晶体结构进优化,其优化结构能再现实验结果。分子间O…H间距随压力的增加而显著减小;但O—H和N—H键长呈现非单调变化。基于不同压力下的优化晶体结构,利用非周期性计算并经校正因子0.967 9校正,求得相应压力下的红外和拉曼谱。预测最强拉曼峰对应于C—C伸缩和NH₂对称变形,位于1 580 cm-1,与实验结果一致。虽然阴离子不含氢原子,但阳离子的氘代仍对阴离子的振动光谱产生影响。高压导致分子间氢键增强,导致参与氢键的O—H和O—D振动的拉曼波数减小。氘代后,ND₂的拉曼位移的最明显变化是ν₂伸缩振动波数在高压下急剧增加,导致ND₂ ν₂/ν₃在高压下发生偶合。计算出的ν₁至ν₃振动的同位素效应比ν(NH₂)/ν(ND₂)均为1.36～1.38,与由折合质量所求得的值相一致。氘代和压力的变化可引起不同振动模式的偶合。     

Influence of pressure on near nozzle flow field and soot formation in laminar co-flow diffusion flames

Soot formation from combustion devices, which tend to operate at high pressure, is a health and environmental concern, thus investigating the effect of pressure on soot formation is important. While most fundamental studies have utilised the co-flow laminar diffusion flame configuration to study the effect of pressure on soot, there is a lack of investigations into the effect of pressure on the flow field of diffusion flames and the resultant influence on soot formation. A recent work has displayed that recirculation zones can form along the centreline of atmospheric pressure diffusion flames. This present work seeks to investigate whether these zones can form due to higher pressure as well, which has never been explored experimentally or numerically. The CoFlame code, which models co-flow laminar, sooting, diffusion flames, is validated for the prediction of recirculation zones using experimental flow field data for a set of atmospheric pressure flames. The code is subsequently utilised to model ethane-air diffusion flames from 2 to 33 atm. Above 10 atm, recirculation zones are predicted to form. The reason for the formation of the zones is determined to be due to increasing shear between the air and fuel steams, with the air stream having higher velocities in the vicinity of the fuel tube tip than the fuel stream. This increase in shear is shown to be the cause of the recirculation zones formed in previously investigated atmospheric flames as well. Finally, the recirculation zone is determined as a probable cause of the experimentally observed formation of a large mass of soot covering the entire fuel tube exit for an ethane diffusion flame at 36.5 atm. Previously, no adequate explanation for the formation of the large mass of soot existed.     

An experimental and kinetic modeling study on nitric oxide formation in premixed C3 alcohols flames

This study provides new quantitative NO concentrations measurements in n-propanol + air and i-propanol + air flames together with a new combustion kinetic model. The heat flux method was employed to stabilize propyl alcohols flames and the initial gas conditions were set to 323 K, 1 atm, and Φ=0.7–1.4. Saturated laser-induced fluorescence was employed to measure NO concentration in the post-combustion region. The presented and literature models, namely the POLIMI and Bohon et al. (2018) kinetic mechanisms, were assessed against new experimental data. Experimental results showed a higher NO formation in the thermal zone for n-propanol flames, whereas i-propanol flames indicate a higher amount of NO formed at fuel-rich conditions. Overall among the tested models, the present mechanism exhibited the best agreement in emulating NO experimental profiles; conversely, numerical simulations from the POLIMI model showed significant inconsistencies at fuel-rich conditions and the Bohon et al. (2018) model was unable to reproduce the measured data, notably underpredicting experimental values at all investigated conditions. However, the present model manifested some uncertainties in reproducing NO formation in the prompt region; therefore, in connection with this important aspect, the new experimental data obtained in this work will provide a valid support to further develop more reliable kinetic models.     

Simultaneous Raman/LIF measurements of major species and NO in turbulent H2/air diffusion flames

A single-pulse spontaneous Raman scattering apparatus, based on a flashlamp-pumped dye laser, was used to determine the concentrations of the major species and the temperature in turbulent H₂/N₂/air jet diffusion flames. The concentrations of nitric oxide were simultaneously measured by Laser-Induced Fluorescence (LIF) after excitation of theA ^{2 +}–X ² transition with a Nd: YAG-pumped dye laser. Some fundamentals of the employed methods, including the calibration procedure, quenching corrections, and accuracy are discussed. Besides a detailed study of the experimental technique, a main goal of the presented investigations was the generation of comprehensive data sets of high accuracy from well-defined turbulent flames which allow for a quantitative comparison with model calculations. Two flames with different fuel dilution and Reynolds numbers were investigated in a pattern of typically 100 measuring locations each comprising 300 single shots. In addition, four flames with different flow velocities but same fuel composition were compared with respect to their temperature and NO concentration profiles. The results show that differential diffusion plays an important role in these flames, especially near the flame base, where the temperature is increased above the adiabatic flame temperature and deviations from adiabatic equilibrium are large. The correlations between NO and mixture fraction and NO and temperature reveal characteristic features of the different flames.     

大气压氩气/空气介质阻挡放电中分子振动温度

使用水电极介质阻挡放电装置,在氩气和空气混合气体放电中,利用光谱方法测量了氮分子(C3Π_u)的振动温度及其随空气含量的变化关系。计算中采用的是氮分子第二正带系(C3Π_u→B3Π_g)的发射谱线,顺序带组有：Δｖ＝-1,Δｖ＝-2和Δｖ＝-3。结果表明：大气压介质阻挡放电中氮分子振动温度范围为1 938～2 720 K,振动温度随空气含量的增加几乎是线性增加的。该工作对研究介质阻挡放电中等离子体的动力学过程具有重要意义。     

苯甲酸分子表面增强拉曼光谱的密度泛函理论研究

基于密度泛函理论,利用量子化学软件,在B3LYP/6-311G**(C,H,S)/Lanl2dz(Ag)水平上对苯甲酸(Benzoic Acid,C7H6O2,BA)进行几何优化,得到BA与Ag原子和Ag离子结合,即C7H5O2-Ag和C7H5O2Ag的平衡构型,在此基础上得到了两种形态的计算拉曼谱图,并和其他文献值进行比较,其中C7H5O2Ag的计算结果与文献中的BA表面增强拉曼光谱的实验值符合得较好。同时采用简正振动分析方法得到其势能分布,从而对其简正振动模式进行了全面归属。