Experimental and kinetic modeling study of sooting atmospheric-pressure cyclohexane flame

Experimental data and modelling results of the main products and intermediates from a fuel-rich sooting premixed cyclohexane flame were presented in this work. Model predictions well agree with experimental data both in sooting and non-sooting flames. Major and minor species are properly predicted, together with the soot yield. The initial benzene peak was demonstrated to be due to the fast dehydrogenation reactions of the cycloalkane, which gives rise to cyclohexene and cyclohexadiene both via molecular and radical pathways. Once formed cyclohexadiene quickly forms benzene whereas in the postflame zone, benzene comes from the recombination and addition reactions of small radicals, with C₃H₃ + C₃H₃ playing the most important role in these conditions. An earlier soot inception was detected in the cyclohexane flame with respect to a n-hexane flame and this feature is not reproduced by the model that foresees soot formation significant only in the second part of the flame. The model insensitivity of soot to the reactant hydrocarbon was also observed comparing the predictions of three flames of cyclohexane, 1-hexene and n-hexane with the same temperature profile. A sensitivity analysis revealed that soot primarily comes from the HACA mechanism for the three flames, acetylene being the key species in the nucleation. Experimental data on soot inception seem to indicate the importance of the early formation of benzene, that depends on the fuel structure. It is thus important to further investigate the role of benzene and aromatics in order to explain this discrepancy.     

Soot studies of laminar diffusion flames with recirculation zones

This paper describes the unusual sooting structure of three flames established by the laminar recirculation zones of a centerbody burner. The vertically mounted burner consists of an annular air jet and a central fuel jet separated by a bluff-body. The three ethylene fueled flames are identified as: fully sooting, donut-shape, and ring-shape sooting flames. Different shapes of the soot structures are obtained by varying the N₂ dilution in the fuel and air jets while maintaining a constant air and fuel velocity of 1.2 m/s. All three flames have the unusual characteristic that the soot, entrained into the recirculation zone, follows discrete spiral trajectories that terminate at the center of the vortex. The questions are what cause: (1) the unusual sooting structures and (2) the spiral trajectories of the soot? Flame photographs, laser sheet visualizations, and calculations with a 2D CFD-based code (UNICORN) are used to answer these questions. The different sooting structures are related to the spiral transport of the soot, the spatial location of the stoichiometric flame surface with respect to the vortex center, and the burnout of the soot particles. Computations indicate that the spiral trajectories of the soot particles are due to thermophoresis.     

Temperature measurements in sooting counterflow diffusion flames using laser-induced fluorescence of flame-produced nitric oxide

Laser-based diagnostic methods are often used for non-intrusive studies of delicate processes of soot formation. When soot particles are heated by the laser pulse, their size distribution can be estimated from the cooling rate, provided that the local gas temperature is known. However, strong light absorption, scattering and fluorescence in sooting environment hinder non-intrusive laser-based temperature measurements. Methods based on fitting of laser-induced fluorescence spectra work well in stationary flames but usually require temperature tracer seeded into the flame. We have shown that in counterflow diffusion flames, often used for soot-formation studies, enough nitric oxide is produced for two-dimensional temperature imaging. Measured temperature profiles agree very well with chemical kinetic calculations for a variety of fuels if laser intensity is reduced to keep NO excitation in the linear regime. Gas composition affects line shapes at temperatures below 600 K and should be taken into account for accurate measurements.     

Soot formation and temperature field structure in co-flow laminar methane-air diffusion flames at pressures from 10 to 60 atm

The effects of pressure on soot formation and the structure of the temperature field were studied in co-flow methane-air laminar diffusion flames over a wide pressure range, from 10 to 60 atm in a high-pressure combustion chamber. The selected fuel mass flow rate provided diffusion flames in which the soot was completely oxidized within the visible flame envelope and the flame was stable at all pressures considered. The spatially resolved soot volume fraction and soot temperature were measured by spectral soot emission as a function of pressure. The visible (luminous) flame height remained almost unchanged from 10 to 100 atm. Peak soot concentrations showed a strong dependence on pressure at relatively lower pressures; but this dependence got weaker as the pressure is increased. The maximum conversion of the fuel’s carbon to soot, 12.6%, was observed at 60 atm at approximately the mid-height of the flame. Radial temperature gradients within the flame increased with pressure and decreased with flame height above the burner rim. Higher radial temperature gradients near the burner exit at higher pressures mean that the thermal diffusion from the hot regions of the flame towards the flame centerline is enhanced. This leads to higher fuel pyrolysis rates causing accelerated soot nucleation and growth as the pressure increases.     

Molecular species adsorbed on soot particles issued from low sooting methane and acetylene laminar flames: A laser-based experiment

Recent advances in the field of laser desorption/laser ionization mass spectrometry (LD/LI/MS) have renewed interest in these separation methods for fast analysis of chemical species adsorbed on soot particles. These techniques provide mass-separation of the desorbed phase with high selectivity and sensitivity and require very small soot samples. Combining LD/LI/MS with in situ measurements of soot and gaseous species is very promising for a better understanding of the early stage of soot growth in flames. In this work, three lightly sooting laminar jet flames (a methane diffusion flame and two premixed acetylene flames of equivalence ratio (?) = 2.9 and 3.5) were investigated by combining prompt and 50 ns-delayed laser-induced incandescence (LII) for spatially resolved measurements of soot volume fraction (f_v) and laser-induced fluorescence (LIF) of polycyclic aromatic hydrocarbons (PAH). Soot and PAH calibration is performed by two-colour cavity ring-down spectroscopy (CRDS) at 1064 and 532 nm. Soot particles were sampled in the flames and analysed by LD/LI/Time-of-flight- MS. Soot samples are cooled to −170 °C to avoid adsorbed phase sublimation (under high vacuum in the TOF-MS). Our set-up is novel because of its ability to measure very low concentration of soot and PAH together with the ability to identify a large mass range of PAHs adsorbed on soot, especially volatile two-rings and three-rings PAHs. Studied flames exhibited a peak f_v ranging from 15 ppb (acetylene, ? = 2.9) to 470 ppb (acetylene, ? = 3.5). Different mass spectra were found in the three flames, each exhibiting one predominant PAH mass; 202 amu (4-rings) in methane, 178 amu (3-rings) in acetylene,? = 2.9 and 128 amu (2-rings) in acetylene, ? = 3.5. These variations with flame condition contrasts with other recent studies and is discussed. The other PAH masses ranged from 102 (C₈H₆) to 424 amu (C₃₄H₁₆) and are well predicted by the stabilomer grid of Stein and Farr.     

Effect of fuel/air ratio and aromaticity on the molecular weight distribution of soot in premixed n-heptane flames

Soot growth from inception to mass-loading is studied in a wide range of molecular weights (MW) from 10⁵ to 10¹⁰u by means of size exclusion chromatography (SEC) coupled with on-line UV-visible spectroscopy. The evolution of MW distributions of soot is also numerically predicted by using a detailed kinetic model coupled with a discrete-sectional approach for the modeling of the gas-to-particle process. Two premixed flames burning n-heptane in slightly sooting and heavily sooting conditions are studied. The effect of aromatic addition to the fuel is studied by adding n-propylbenzene (10% by volume) to n-heptane in the heavily sooting condition. A progressive reduction of the MW distribution from multimodal to unimodal is observed along the flames testifying the occurrence of particle growth and agglomeration. These processes occur earlier in the aromatic-doped n-heptane flame due to the overriding role of benzene on soot formation which results in bigger young soot particles. Modeled MW distributions are in reasonable agreement with experimental data although the model predicts a slower coagulation process particularly in the slightly sooting n-heptane flame. Given the good agreement between model predictions and experiments, the model is used to explore the role of fuel chemistry on MW distributions. Two flames of n-heptane and n-heptane/n-propylbenzene in heavily sooting conditions with the same temperature profile and inert dilution are modeled. The formation of larger soot particles is still evident in the n-heptane/n-propylbenzene flame with respect to the n-heptane flame in the same operating conditions of temperature and dilution. In addition the model predicts a larger formation of molecular particles in the flame containing n-propylbenzene and shows that soot inception occurs in correspondence of their maximum formation thus indicating the importance of molecular growth in soot inception.     

Addition of NO2 to a laminar premixed ethylene-air flame: Effect on soot formation

Experiments were conducted on a laminar premixed ethylene-air flame at equivalence ratios of 2.34 and 2.64. Comparisons were made between flames with 5% NO₂ added by volume. Soot volume fraction was measured using light extinction and light scattering and fluorescence measurements were also obtained to provide added insight into the soot formation process. The flame temperature profiles in these flames were measured using a spectral line reversal technique in the non-sooting region, while two-color pyrometry was used in the sooting region. Chemical kinetics modeling using the PREMIX 1-D laminar flame code was used to understand the chemical role of the NO₂ in the soot formation process. The modeling used kinetic mechanisms available in the literature. Experimental results indicated a reduction in the soot volume fraction in the flame with NO₂ added and a delay in the onset of soot as a function of height above the burner. In addition, fluorescence signals—often argued to be an indicator of PAH—were observed to be lower near the burner surface for the flames with NO₂ added as compared to the baseline flames. These trends were captured using a chemical kinetics model that was used to simulate the flame prior to soot inception. The reduction in soot is attributed to a decrease in the H-atom concentration induced by the reaction with NO₂ and a subsequent reduction in acetylene in the pre-soot inception region.     

发射CT法测量层流乙烯扩散火焰中温度与烟黑浓度分布的实验研究

对于非均匀吸收、发射、无散射的轴对称含烟黑火焰对象,常规双色法不再适用。本文基于烟黑辐射特性,利用烟黑单色辐射强度图像信息采用CT算法同时重建含烟黑火焰温度与烟黑浓度分布,对层流乙烯扩散火焰的温度与烟黑容积份额进行测量,得到了较好的结果。     

Highly radiating hydrogen flames: Effect of toluene concentration and phase

Adapting hydrogen as a carbon-free fuel for industrial applications requires new, innovative approaches, especially when radiant heat transfer is required. One possible option is to dope hydrogen with bio-oils, containing aromatics that help produce highly sooting flames. This study investigates the potential doping effects of toluene on a hydrogen-nitrogen (1:1 vol) flames. Flames with 1–5% toluene, based on the mole concentration of hydrogen, are measured using a combination of techniques including: still photographs and laser-based techniques. Toluene was mixed with hydrogen-nitrogen fuel mixture as either a vapour carried by nitrogen, or as a dilute spray. Spray flames are found to produce substantially more polycylic aromatic hydrocarbons, with significantly more soot near the nozzle exit plane, than the prevaporised flames. Increasing the dopant concentration from 1 to 3% of the hydrogen has a marked effect on soot loading in the flame, although the further increasing the dopant concentration to 5% has a far smaller effect on the soot produced in the flame. Simulations of laminar flames using detailed chemical kinetics support the above findings and reveal details of the competition between soot precursor formation and hydrocarbon oxidation. Correlations of formation rates are non-linear with toluene concentration in cases where toluene represents less than 10% of the fuel, although expected linear relationships are noted beyond this regime up to 1:1 toluene/hydrogen blends. The study provides insight and explanation into effects of toluene as a dopant, comparison between flame doping in gaseous or liquid phases and suggests that flame doping and blending should be treated as different regimes for their global effect on flame sooting characteristics.     

On the sudden reversal of soot formation by oxygen addition in DME flames

Dimethyl ether (DME) is a non-toxic and renewable fuel known for its soot emissions reduction tendencies. In laminar co-flow DME diffusion flames, adding oxygen to the fuel stream increases the sooting tendency until a critical point is reached, at which point the trend suddenly reverses. This work unravels the mechanisms behind this reversal process, and characterizes their contribution to controlling soot production. A series of experimental measurements using diffuse-light line-of-sight attenuation and two-colour pyrometry were performed to measure soot volume fraction and soot temperature considering a fixed mass flow rate of DME and variable addition of oxygen. Soot volume fraction increases from 0.095 ppm in the pure DME flame to 0.32 ppm when the added oxygen concentration reaches 33%. When the oxygen concentration is slightly increased to 35%, soot volume fraction is reduced by 60%. To explain the reasons behind the reversal, a series of numerical simulations were performed, which successfully demonstrated the same trend. Results show that the chemical effects of adding oxygen to the fuel stream are exceedingly more important than the thermal and dilution effects. It was found that the reversal occurred when nearly all DME disassociated before exiting the fuel tube, indicating a sudden transition from a partially premixed DME flame, to one which primarily burns C1 fuel fragments. An analysis of soot formation and oxidation rates showed that near the reversal, soot inception is the least affected process; furthermore, soot precursor availability is not significantly affected in magnitude, rather they appear further upstream. It is concluded that the favourable conditions for rapid DME decomposition into soot precursors enhances soot inception while depleting the necessary species for further soot mass growth, dramatically reducing soot concentration.     

On existence of nanoparticles below the sooting threshold

Nanometer-sized particles were studied by photoionisation mass spectrometry and scanning mobility particle sizer in laminar premixed ethylene flames above and below the critical sooting threshold. For sooting flames, both techniques detected a large number of particles with masses between 1 and 50 ku or diameter around a few nanometers. Neither method detected an appreciable number of particles below the sooting threshold in flames similar to those studied earlier for UV absorption and scattering of transparent soot. The absence of particle signals in both experimental techniques raises the question about the origin of UV absorption under nonsooting conditions.     

A computational study of soot formation and flame structure of coflow laminar methane/air diffusion flames under microgravity and normal gravity

A numerical study is conducted of methane–air coflow diffusion flames at microgravity (μg) and normal gravity (1g), and comparisons are made with experimental data in the literature. The model employed uses a detailed gas phase chemical kinetic mechanism that includes PAH formation and growth, and is coupled to a sectional soot particle dynamics model. The model is able to accurately predict the trends observed experimentally with reduction of gravity without any tuning of the model for different flames. The microgravity sooting flames were found to have lower temperatures and higher volume fraction than their normal gravity counterparts. In the absence of gravity, the flame radii increase due to elimination of buoyance forces and reduction of flow velocity, which is consistent with experimental observations. Soot formation along the wings is seen to be surface growth dominated, while PAH condensation plays a more major role on centreline soot formation. Surface growth and PAH growth increase in microgravity primarily due to increases in the residence time inside the flame. The rate of increase of surface growth is more significant compared to PAH growth, which causes soot distribution to shift from the centreline of the flame to the wings in microgravity.     

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.     

Influence of oxygen concentration on the sooting behavior of ethanol droplet flames in microgravity conditions

The influence of oxygen (O₂) concentration and inert on the sooting and burning behavior of large ethanol droplets under microgravity conditions was investigated through measurements of burning rate, flame temperature, sootshell diameter, and soot volume fraction. The experiments were performed at the NASA Glenn Research Center (GRC) 2.2 s drop tower in Cleveland, OH. Argon (Ar), helium (He), and nitrogen (N₂) were used as the inerts and the O₂ concentration was varied between 21% and 50% mole fraction at 2.4 atm. The unique configuration of spherically symmetric droplet flames enables effective control of sooting over a wide range of residence time of fuel vapor transport, flame temperature, and regimes of sooting to investigate attendant influences on burning behavior of droplets. For all inert cases, soot volume fraction initially increased as a function of the O₂ concentration. The highest soot volume fractions were measured for experiments in Ar environments and the lowest soot volume fractions were measured for the He environments. These differences were attributed to the changes in the residence time for fuel vapor transport and the flame temperature. For the He inert and N₂ inert cases, the soot volume fraction began to decrease after reaching a maximum value. The competition between the influence of residence time, rate of pyrolysis reactions, and soot oxidation can lead to this interesting behavior in which the soot volume fraction varies non-monotonically with increase in O₂ concentration. These experiments have developed new understanding of the burning and sooting behaviors of ethanol droplets under various O₂ concentrations and inert substitutions.     

轴对称含烟黑火焰非均匀温度与烟黑浓度分布同时重建模拟研究

对于非均匀吸收、发射、无散射的轴对称含烟黑火焰对象,常规双色法不再适用。本文基于烟黑辐射特性,提出并模拟研究了同时重建火焰温度与烟黑容积份额的新的辐射测量方法。从重建结果看,重建误差主要集中在火焰中心区域,这是观测路径上测量误差累积的结果。温度重建主要受火焰断面参数分布类型影响,而烟黑容积份额重建主要受测量误差的影响,这由它们与单色辐射强度的内在关系所决定。     

Soot-visualization strategies using laser techniques

Strategies for spatially resolved soot volume-fraction measurements have been investigated in sooting laboratory flames with known soot characteristics. Two techniques were compared: Laser-Induced Fluorescence in C₂ from Laser-Vaporized Soot (LIF(C₂)LVS), and Laser-Induced Incandescence of soot (LII). The LII signal is the increased temperature radiation from soot particles which have been heated to temperatures of several thousand degrees as a consequence of absorption of laser radiation. The LIF(C₂)LVS technique is based on the production of C₂ radicals from laser-vaporized soot which occurs for laser intensities ≥10⁷ W/cm². A laser wavelength is chosen such that besides vaporizizng the soot, it also excites the C₂ radicals, and the subsequent C₂ fluorescence signal is detected. The signals from both techniques showed good correlation with soot volume fractions in the studied flame. The dependence of the signals on experimental parameters was studied, and the influence of interfering radiation, such as background flame luminosity and fluorescence from polyaromatic hydrocarbons, on studied signals was established. The potential of the two techniques for imaging of soot volume fractions in laboratory flames was demonstrated. Advantages and disadvantages of the studied techniques are discussed.     

The effects of burner stabilization on Fenimore NO formation in low-pressure, fuel-rich premixed CH4/O2/N2 flames

We investigate the effects of varying the degree of burner stabilization on Fenimore NO formation in fuel-rich low-pressure flat CH₄/O₂/N₂ flames. Towards this end, axial profiles of flame temperature and OH, NO and CH mole fractions are measured using laser-induced fluorescence (LIF). The experiments are performed at equivalence ratios between 1.3 and 1.5. The flame temperature is seen to decrease by 200-300 K, with a concomitant decrease in OH mole fraction, upon reducing the total flow rate from 5 to 3 L/min, thus increasing stabilization. At equivalence ratios between 1.3 and 1.5, this decrease in flow rate lowers the maximum CH mole fraction by a factor of 2, and the NO mole fraction by ∼40% in all flames studied. Integrating the reaction rate for CH + N₂ to estimate Fenimore NO formation, using the rate coefficient in GRI-Mech 3.0, and the measured temperatures and CH profiles show very good agreement with the measured NO mole fraction for ? = 1.3 and 1.4, supporting the current choice for this rate. This agreement also shows that the increase in residence time caused by increased stabilization is an important factor in the ultimate impact of the changes in CH mole fraction on NO formation. The results at ? = 1.5 suggest that substantial quantities of fixed nitrogen species, e.g., HCN, are only slowly oxidized in the post-flame zone under these conditions, leading to a significant discrepancy between the measured NO mole fraction and that obtained by integrating over the CH profile. Detailed calculations using GRI-Mech 3.0 predict the experimental results at ? = 1.3 nearly quantitatively, but show increasing differences with the measurements for both CH and NO profiles with increasing equivalence ratio.     

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     

Size distribution and morphology of nascent soot in premixed ethylene flames with and without benzene doping

Particle size distribution functions of nascent soot formed in four burner-stabilized, premixed ethylene-oxygen-argon flames were studied in a spatially resolved manner by online sampling/scanning mobility particle sizer. Particle morphology was analyzed by atomic force microscopy (AFM) of substrate-deposited samples. Two of the four flames were doped with benzene. An aerosol electrometer is introduced to extend the lower detection limit to around 1.5 nm in diameter. The results show that the bimodal behavior of particle size is applicable to all premixed ethylene flames studied. The variation of the size distribution from flame to flame is conclusively attributed to flame temperature variation. Under the condition of an equal carbon concentration, benzene doping leads to negligible changes in the characteristics of the size distribution. For all flames studied, AFM observations show that nascent soot is liquid-like and spreads extensively upon impact on a substrate surface.     

Modelling of aromatics and soot formation from large fuel molecules

There is a need for prediction models of soot particles and polycyclic aromatic hydrocarbons (PAHs) formation in parametric conditions prevailing in automotive engines: large fuel molecules and high pressure. A detailed kinetic mechanism able to predict the formation of benzene and PAHs up to four rings from C₂ fuels, recently complemented by consumption reactions of decane, was extended in this work to heptane and iso-octane oxidation. Species concentrations measured in rich, premixed flat flames and in a jet stirred reactor (JSR) were used to check the ability of the mechanism to accurately predict the formation of C₂ and C₃ intermediates and benzene at pressures ranging from 0.1 to 2.0 MPa. Pathways analyses show that propargyl recombination is the only significant route to benzene in rich heptane and iso-octane flames. When included as the first step of a soot particle formation model, the gas-phase kinetic mechanism predicts very accurately the final soot volume fraction measured in a rich decane flame at 0.1 MPa and in rich ethylene flames at 1.0 and 2.0 MPa.