Dynamics of flow–soot interaction in wrinkled non-premixed ethylene–air flames

A two-dimensional simulation of a non-premixed ethylene–air flame was conducted by employing a detailed gas-phase reaction mechanism considering polycyclic aromatic hydrocarbons, an aerosol-dynamics-based soot model using a method of moments with interpolative closure, and a grey gas and soot radiation model using the discrete transfer method. Interaction of the sooting flame with a prescribed decaying random velocity field was investigated, with a primary interest in the effects of velocity fluctuations on the flame structure and the associated soot formation process for a fuel-strip configuration and a composition with mature soot growth. The temporally evolving simulation revealed a multi-layered soot formation process within the flame, at a level of detail not properly described by previous studies based on simplified soot models utilizing acetylene or naphthalene precursors for initial soot inception. The overall effect of the flame topology on the soot formation was found to be consistent with previous experimental studies, while a unique behaviour of localised strong oxidation was also noted. The imposed velocity fluctuations led to an increase of the scalar dissipation rate in the sooting zone, causing a net suppression in the soot production rate. Considering the complex structure of the soot formation layer, the effects of the imposed fluctuations vary depending on the individual soot reactions. For the conditions under study, the soot oxidation reaction was identified as the most sensitive to the fluctuations and was mainly responsible for the local suppression of the net soot production.     

Formation of soot particles in pyrolysis and oxidation of aliphatic and aromatic hydrocarbons: Experiments and detailed kinetic modeling

Experiments on pyrolysis and oxidation of rich mixtures of various aliphatic and simple aromatic hydrocarbons in reflected shock waves have been performed. The mixtures C₂H₂/Ar, C₂H₆/Ar, C₂H₄/Ar, C₂H₄/O₂/Ar, CH₄/Ar, CH₄/O₂/Ar, C₃H₈/Ar, C₃H₆/Ar, toluene/Ar, and benzene/Ar were studied. The yield of soot and the temperature of soot particles were determined experimentally by the double-beam absorption emission method. The kinetic model of soot formation during the pyrolysis and oxidation of rich mixtures of aliphatic and aromatic hydrocarbons complemented with a set of nucleations of soot particles from both polyaromatic fragments and unsaturated aliphatic hydrocarbons was suggested. This kinetic model of soot formation was successfully tested. It describes the experimental literature data on the yield of the products of pyrolysis and oxidation of acetylene and diacetylene in a shock tube. The results of our experiments and kinetic calculations of the time, temperature, and concentration dependences are in good agreement for all hydrocarbons under study. All the kinetic parameters of the model remained strictly constant.     

Single-walled carbon nanotube formation on iron oxide catalysts in diffusion flames

Single-walled carbon nanotubes (SWCNTs) are shown to grow rapidly on iron oxide catalysts on the fuel side of an inverse ethylene diffusion flame. The pathway of carbon in the flame is controlled by the flame structure, leading to formation of SWCNTs free of polycyclic aromatic hydrocarbons (PAH) or soot. By using a combination of oxygen-enrichment and fuel dilution, fuel oxidation is favored over pyrolysis, PAH growth, and subsequent soot formation. The inverse configuration of the flame prevents burnout of the SWCNTs while providing a long carbon-rich region for nanotube formation. Furthermore, flame structure is used to control oxidation of the catalyst particles. Iron sub-oxide catalysts are highly active toward SWCNT formation while Fe and Fe₂O₃ catalysts are less active. This can be understood by considering the effects of particle oxidation on the dissociative adsorption of gas-phase hydrocarbons. The optimum catalyst particle composition and flame conditions were determined in near real-time using a scanning mobility particle sizer (SMPS) to measure the catalyst and SWCNT size distributions. In addition, SMPS results were combined with flame velocity measurement to measure SWCNT growth rates. SWCNTs were found to grow at rates of over 100 μm/s.     

Modelling soot formation in a premixed flame using an aromatic-site soot model and an improved oxidation rate

An updated rate of O₂ oxidation of one to four ring polyaromatic hydrocarbons in premixed flames is presented based on density function theory simulations of oxygen attack at different radical sites on various PAHs. The rate is in agreement with other rates found in the literature; however, it is several orders of magnitude lower than the currently accepted oxidation rate of multi-ring aromatic species, including soot. Simulations are presented of a premixed flame using this improved rate and a new advanced soot particle model, which is developed in this paper. This model includes unprecedented detail of the particles in the ensemble, including the aromatic content, C/H composition and primary-particle aggregate structure. The O₂ oxidation rate calculated in this paper is shown to give a better prediction of particle number density and soot volume fraction for a premixed flame. The predicted particle size distributions are shown also to describe better the experimental data. Predicted C/H ratio and PAH size distributions are shown for the flame. Computed TEM-style images are compared to experimental TEM images, which show that the aggregate structure of the particles is well predicted.     

Mass spectrometric analysis of large PAH in a fuel-rich ethylene flame

Mass spectrometric analysis by laser desorption-time of flight-mass spectrometry (LDI-TOF-MS) was exploited to extend the detection of flame-formed polycyclic aromatic hydrocarbons (PAH) up to the mass limit of the first soot particles (>2000 Da) in the soot formation region of a premixed fuel-rich (C/O = 1) ethylene flame. The typical decreasing intensity of PAH ion peaks with increasing mass was found in the mass range m/z 500-1700 although a slight enrichment in the heavier part of PAH could be observed to occur along the flame axis. The separation by means of size exclusion chromatography (SEC) into two different classes of PAH followed by UV-visible spectroscopy corroborated the mass spectral identification of large mass PAH. Critical examination of mass spectral features and SEC separation was the starting point for speculation about the changes occurring in PAH growth from planar to concave structures which could be important for soot inception mechanisms.     

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.     

基于光谱诊断的烃类火焰碳烟形成机理研究综述

碳烟主要是烃类燃料不完全燃烧生成的产物,其对人类健康、空气质量以及燃烧装置的使用寿命都会产生有害影响。碳烟生成是一个复杂的物理化学过程,控制碳烟排放,需要克服碳烟生成和燃烧过程中物理和化学演化的巨大差异,这些差异表现为对碳烟纳观结构和表面官能团随碳烟氧化活性反应变化的深入探索研究。近些年,研究人员对碳烟的生成机理开展了系列研究,对碳烟生成各个物理化学反应阶段有了一定认识。结合光谱诊断技术可深入了解燃烧系统碳烟形成过程,确定碳烟颗粒分子组成、精细结构、浓度分布等特征,也可从碳烟结构变化、黑体辐射强度等方面详细了解碳烟形成过程。该文旨在阐述光谱诊断技术对烃类火焰碳烟表征的研究进展和发展趋势,探讨LIBS, LII和LIF等作为诊断工具在包含背景辐射的火焰中检测碳烟生成过程产生辐射强度准确性等问题。主要介绍了烃类火焰碳烟的形成机理(从前驱体产生、生长到颗粒生成、凝聚,最后进行颗粒氧化)。总结了探测碳烟性质光谱诊断方法的应用以及光谱诊断技术对燃烧过程中碳烟表征的研究现状,包括对碳烟体积分数、温度和基于图像处理的碳烟结构表征,反应碳烟前驱体(多环芳烃)、反应气氛、温度等对碳烟颗粒物生成的影响。最...     

Particle formation in opposed-flow diffusion flames of ethylene: An experimental and numerical study

An experimental and numerical study on particles inception and growth is performed in opposed-flow diffusion flames of ethylene and air characterized by different sooting tendencies. Spectrally resolved UV-visible laser induced fluorescence, laser induced incandescence and laser light scattering measurements are used to characterize different classes of combustion-generated compounds. A detailed kinetic model accounting for both gas-phase and particle formation is used. Comparison between experimental results and numerical predictions gives a qualitative view of the mechanism of particle formation in opposed-flow flames.Particle inception is the result of both chemical growth and coagulation of aromatic compounds. In the region close to the flame front where the temperature is relatively high and radicals are abundant, the particle inception is due to a chemical growth mechanism by which aromatic molecules add aromatic radicals leading to the formation of biphenyl-like structures. The growth process continues as high-molecular mass aromatics are moved away from the flame zone towards the stagnation plane by the addition of acetylene and other aromatics forming particles of increasing sizes. Graphitization of these particles and thermal annealing lead to the formation of soot particles. At relatively lower temperatures, found across the stagnation plane, particles growth still occurs and it is mainly due to a process of physical coagulation of PAHs.The experimental and numerical results obtained in this work demonstrate and explain the sensibility of inception and growth of particles to radical concentration and temperature in opposed-flow flame configurations.     

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.     

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.     

基于Raman与FTIR对掺甲烷乙烯/氢气扩散火焰碳烟有序度和官能团的研究

以甲烷、乙烯、氢气混合扩散火焰碳烟为研究对象,采用激光共聚焦拉曼光谱（Raman）和傅里叶红外光谱（FTIR）研究了不同掺甲烷比例下乙烯、氢气混合火焰碳烟有序度及官能团的分布特性,分析了碳烟石墨化和官能团分布,揭示了掺甲烷对乙烯/氢气（氢气比例30%）层流扩散火焰的碳烟生成影响规律。Raman研究表明在甲烷掺混比为3%和7%时,在火焰高度低于4cm位置生成的碳烟有序程度显著降低,表明在此区域存在明显的碳烟生成协同效应;甲烷掺混比增大超过10%时,协同效应基本消失,碳烟有序度上升。FTIR研究表明掺混甲烷对碳烟官能团组成影响明显。掺混甲烷后脂肪族官能团相对含量整体提高。随着甲烷掺杂比的增大,CH₂相对含量增大到一峰值后减小。碳烟中芳香族官能团含量随着火焰高度的上升含量下降明显。掺混3%和7%甲烷,芳香族官能团在2和3 cm火焰高度时,芳香族官能团的含量明显上升。掺混甲烷比高于10%时,芳香族官能团的含量则有所降低。表明少量甲烷掺混使得CH₃和C₃H₃生成有了新的途径,CH₃和C₃H₃增加,而C₂H₄和C₂H₂减少不明显,从而促进了多环芳香烃(PAHs)的生成。继续增加甲烷因为稀释作用会抑制C₂H₂生成从而减少PAHs的生成,芳香族相对含量降低,因而降低了碳烟的生成。研究揭示了甲烷对乙烯/氢气层流扩散火焰中碳烟形成的相互作用：在低甲烷掺混比时存在协同效应促进碳烟生成,而在高甲烷掺混比时协同效应消失。     

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.     

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.     

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.     

Effects of benzene and naphthalene addition on soot inception in a well-stirred reactor/plug flow reactor

A well-stirred reactor (WSR) followed by a plug flow reactor (PFR) is being used to study soot inception. Soot size distributions were measured using two different dilution probes followed by a nano-differential mobility analyzer (nano-DMA). One of the dilution probes was developed for the PFR section, while the second probe was specifically developed for use in the WSR section. Results are presented on the effect of residence time on the soot size distributions obtained for fixed dilution ratio and equivalence ratio. In addition, a technique to inject aromatics and PAH species in the transition region between the WSR and PFR was developed. Results are presented on the effect of benzene and naphthalene on the soot size distributions obtained for differing seeding concentrations and residence times. The results demonstrate for the first time the sensitivity of the soot particle size distribution to the seeding of aromatic species in a WSR/PFR.     

Modeling and measurements of size distributions in premixed ethylene and benzene flames

This study demonstrates the major differences in the evolution of the particle size distributions (PSDs), both measured and modeled, of soot in premixed benzene and ethylene flat flames. In the experiments, soot concentration and PSDs were measured by using a scanning mobility particle sizer (SMPS, over the size range of 3-80 nm). The model employed calculations of gas phase species coupled with a discrete sectional approach for the gas-to-particle conversion. The model includes reaction pathways leading to the formation of nano-sized particles and their coagulation to larger soot particles. The particle size distribution, both experimental and modeled, evolved from a single particle mode (the nucleation mode) to a bimodal size distribution. An important distinction between the results for the ethylene and benzene flames is the behavior of the nucleation mode which persists at all heights above the burner (HAB) for ethylene whereas it was greatly suppressed at greater HAB for the benzene flames. The explanation for the decreased nucleation mode at higher elevations in the benzene flame is that the aromatics are consumed in the oxidation zone of the flame. Fair predictions of particle-phase concentrations and particle sizes in the two flames were obtained with no adjustments to the kinetic scheme. In agreement with experimental data, the model predicts a higher formation of particulate in the benzene flame as compared with the ethylene flame.     

The Formation of Carbon in Combustion and how to Quantify the Impact on Human Health

We summarize our current research on combustion aerosols. First, sampling devices for the analyses of flame gases are described. The flame gas samples are investigated by mass spectroscopy and by standard aerosol techniques. Time-of-flight mass spectroscopy is well suited to study formation and growth of soot precursor molecules. Fullerenes can also be seen in some mass spectra of flame gases. Presumably, the fullerenes are evaporated from small soot particles in the mass spectrometer by the ionizing laser. Size spectra of soot particles from the flame are presented. The flame is optionally seeded with palladium aerosol to demonstrate that the particle size distribution is not altered during the sampling procedure. It is found that soot particles are already present low in the flame where large molecules are absent.Photoemission is applied to study surface properties of soot particles from the flame. It is shown that the surface of the particles is covered with polycyclic aromatic hydrocarbons (PAH). The PAH can be removed by heating and the properties of the carbon core are revealed. One can thereby distinguish a soot growth from a soot burnout region in the flame. Time-resolved desorption experiments of perylene (a PAH) from model aerosol particles are presented. It is shown that they follow a first order rate law. The photoelectric PAH sensor is introduced as a personal air quality monitor. The danger from inhaling combustion aerosol can be expressed in units of standard cigarettes.     

3-D simulation of soot formation in a direct-injection diesel engine based on a comprehensive chemical mechanism and method of moments

Here, we propose both a comprehensive chemical mechanism and a reduced mechanism for a three-dimensional combustion simulation, describing the formation of polycyclic aromatic hydrocarbons (PAHs), in a direct-injection diesel engine. A soot model based on the reduced mechanism and a method of moments is also presented. The turbulent diffusion flame and PAH formation in the diesel engine were modelled using the reduced mechanism based on the detailed mechanism using a fixed wall temperature as a boundary condition. The spatial distribution of PAH concentrations and the characteristic parameters for soot formation in the engine cylinder were obtained by coupling a detailed chemical kinetic model with the three-dimensional computational fluid dynamic (CFD) model. Comparison of the simulated results with limited experimental data shows that the chemical mechanisms and soot model are realistic and correctly describe the basic physics of diesel combustion but require further development to improve their accuracy.