High-sensitivity detection of polycyclic aromatic hydrocarbons adsorbed onto soot particles using laser desorption/laser ionization/time-of-flight mass spectrometry: An approach to studying the soot inception process in low-pressure flames

Species adsorbed at the surfaces of soot particles sampled at different locations in a low-pressure methane flame have been analyzed. The analysis method is laser desorption/laser ionization/time-of-flight mass spectrometry (LD/LI/TOF-MS) applied to soot particles deposited on a filter after probe extraction in the flame. In order to fully characterize the experimental apparatus, a strategy of systematic investigations has been adopted, beginning with the study of less complex systems constituted by model soot (standard polycyclic aromatic hydrocarbons, PAHs, adsorbed on black carbon), and then natural soot sampled from a literature reference ethylene flame. This characterization allowed a good understanding of the analytical response of PAHs to the desorption and ionization processes and the definition of the optimal experimental conditions. The soot PAH content was then investigated on a low-pressure methane/oxygen/nitrogen premixed flat flame (? = 2.32) as a function of the sampling height above the burner (HAB). The obtained mass spectra are reproducible, fragment-free, well resolved in the analyzed m/z range and they are characterized by an excellent signal-to-noise ratio. They all feature regular peak sequences, where each signal peak has been assigned to the most stable high-temperature-formed PAHs. The structure of the mass spectra depends on the sampling HAB into the flame, i.e., on the reaction time. An original contribution to the data interpretation comes from the development of a new sampling method that makes it possible to infer hypotheses about the PAH partition between the gas phase and the soot particles. This method highlights the presence of high-mass PAHs in the soot nucleation zone, and it suggests the importance of heterogeneous reactions occurring between flame PAHs and soot particles.     

A statistical approach to develop a detailed soot growth model using PAH characteristics

A detailed PAH growth model is developed, which is solved using a kinetic Monte Carlo algorithm. The model describes the structure and growth of planar PAH molecules, and is referred to as the kinetic Monte Carlo-aromatic site (KMC-ARS) model. A detailed PAH growth mechanism based on reactions at radical sites available in the literature, and additional reactions obtained from quantum chemistry calculations are used to model the PAH growth processes. New rates for the reactions involved in the cyclodehydrogenation process for the formation of 6-member rings on PAHs are calculated in this work based on density functional theory simulations. The KMC-ARS model is validated by comparing experimentally observed ensembles on PAHs with the computed ensembles for a C₂H₂ and a C₆H₆ flame at different heights above the burner. The motivation for this model is the development of a detailed soot particle population balance model which describes the evolution of an ensemble of soot particles based on their PAH structure. However, at present incorporating such a detailed model into a population balance is computationally unfeasible. Therefore, a simpler model referred to as the site-counting model has been developed, which replaces the structural information of the PAH molecules by their functional groups augmented with statistical closure expressions. This closure is obtained from the KMC-ARS model, which is used to develop correlations and statistics in different flame environments which describe such PAH structural information. These correlations and statistics are implemented in the site-counting model, and results from the site-counting model and the KMC-ARS model are in good agreement. Additionally the effect of steric hindrance in large PAH structures is investigated and correlations for sites unavailable for reaction are presented.     

Effect of oxygen-rich combustion on soot formation in laminar co-flow propane diffusion flames

Oxygen-rich combustion is a new type of clean combustion technology with important application prospects. In this work, the effects of oxygen-rich combustion on soot formation in the propane/(O₂+N₂) laminar flow coaxial jets diffusion flame were numerically investigated by using the detailed gas-phase chemical reaction model with the mechanism of tetracyclic aromatic hydrocarbons and the complex thermodynamic properties and transport characteristics parameters. Soot surface growth follows the hydrogen-abstraction-carbon-addition (HACA) model. A hybrid gas-phase mechanism was adopted, which contains a DLR-based polycyclic aromatic hydrocarbons (PAHs) formation, growth model and a gas-phase model. Results show that the oxygen-rich combustion has a great influence on the flame temperature, especially the high temperature region. With the increase of oxygen concentration, the soot formation region of flame broadens and the maximum of soot volume fraction increase from 3.95 ppm to 10.87 ppm. The extra oxygen makes PAHs increased around the nozzle, leading to larger rate in early soot nucleation and surface growth, eventually more soot yield.     

Detailed numerical modeling of PAH formation and growth in non-premixed ethylene and ethane flames

A chemical kinetic mechanism for C₁ and C₂ fuel combustion and PAH growth, previously validated for laminar premixed combustion, has now been modified and applied to opposed flow diffusion flames. Some modifications and extensions have been made to the reaction scheme to take into account recent kinetic investigations, and to reduce the stiffness of the reaction model. Updates have been made to the cyclopentadienyl reactions, indene formation reactions, and aromatic oxidation and decomposition reactions. Reverse reaction rate parameters have been revised to account for numerical stiffness. Opposed flow diffusion flame simulation data for ethylene and ethane flames with the present mechanism are compared to data computed using two other mechanisms from the literature and to experimental data. Whereas the fuel oxidation chemistry in all three mechanisms are essentially the same, the PAH growth pathways vary considerably. The current mechanism considers a detailed set of PAH growth routes, and includes hydrogen atom migration, possible free radical addition schemes, methyl substitution/acetylene addition pathways, cyclopentadienyl moiety in aromatic ring formation, and numerous reactions between aromatic radicals and molecules. It is shown that while bulk flame properties and major species profiles are the same for the three mechanisms, the enhanced PAH growth routes in the present mechanism are necessary to numerically predict the correct order of magnitude of PAHs that were measured in the experimental studies. In particular, predicting concentrations of naphthalene, phenanthrene, and pyrene, to within the correct order of magnitude with the present mechanism show a significant improvement over predictions obtained using mechanisms in the literature. Sensitivity and production rate analyses show that this improvement is attributable to the enhanced PAH growth pathways and updated reaction rates in the present mechanism. The overreaching goal of this research is to generate and fully validate a detailed chemical kinetic mechanism, with as few fitted rates as possible, that can be applied to premixed or diffusion systems, and used with any type of soot model. To that end, in recently published works, the present mechanism has been used to simulate premixed flames, while coupled to a method of moments to determine soot formation, and to simulate diffusion flames, while coupled to a sectional representation for soot formation. The present work extends the validation of the mechanism by applying it to counterflow diffusion flames, for which measurements of large PAH molecules are uniquely available. The validation of PAH growth predictions are of key interest to soot modeling studies as soot inception from PAH combination and PAH condensation are often major constituents of soot production.     

A reaction mechanism for gasoline surrogate fuels for large polycyclic aromatic hydrocarbons

This work aims to develop a reaction mechanism for gasoline surrogate fuels (n-heptane, iso-octane and toluene) with an emphasis on the formation of large polycyclic aromatic hydrocarbons (PAHs). Starting from an existing base mechanism for gasoline surrogate fuels with the largest chemical species being pyrene (C₁₆H₁₀), this new mechanism is generated by adding PAH sub-mechanisms to account for the formation and growth of PAHs up to coronene (C₂₄H₁₂). The density functional theory (DFT) and the transition state theory (TST) have been adopted to evaluate the rate constants for several PAH reactions. The mechanism is validated in the premixed laminar flames of n-heptane, iso-octane, benzene and ethylene. The characteristics of PAH formation in the counterflow diffusion flames of iso-octane/toluene and n-heptane/toluene mixtures have also been tested for both the soot formation and soot formation/oxidation flame conditions. The predictions of the concentrations of large PAHs in the premixed flames having available experimental data are significantly improved with the new mechanism as compared to the base mechanism. The major pathways for the formation of large PAHs are identified. The test of the counterflow diffusion flames successfully predicts the PAH behavior exhibiting a synergistic effect observed experimentally for the mixture fuels, irrespective of the type of flame (soot formation flame or soot formation/oxidation flame). The reactions that lead to this synergistic effect in PAH formation are identified through the rate-of-production analysis.     

Toxicology of soot

In this article the toxicological effect of soot exposure on man is explored with emphasis on the role that soot may play in the induction of cancer and respiratory diseases. Soot may be defined as the product of the incomplete combustion of fossil fuels and other organic matter; the resultant soot particulate consists of finely divided carbon particles, hydrocarbons, and tars. Animal studies will also be cited in which the data is suggestive of a potential risk to man. General sources of soot will be identified and their polycyclic aromatic hydrocarbon (PAH) content given, since it is believed that the PAH and PAH derivatives of soot are responsible for most of its carcinogenic and mutagenic effects. However, the reader should not consider this article to be an exhaustive review of the biology of PAH. The relatively new area of genetic toxicology and recent data derived from the mutagenicity testing of various organic extracts of soot and particulate matter will also be reviewed including a discussion of how these studies may indicate a genetic risk to man.This review of the toxicological effects of soot is broken down into six main sections. Each section deals with a particular topic concerning the health, genetic effects or composition and sources of various soots. Section 1 provides an overview of the early studies on the chemistry and biology of soot. It is intended to lay the ground work for the following sections and indicate that much of today's current interest in the study of environmentally important complex mixtures stems from the pioneering research into the medical and compositional aspects of soot.Section 2 provides a general discussion of the sources of soot based on data collected in the United States. This section also deals with the composition of organically extractable material from soots produced by different sources such as general air pollution, coal, coke and automotive exhaust. Emphasis is placed upon the polycyclic aromatic hydrocarbon (PAH) fractions and their derivatives, due to their well documented biological activity. An introduction to the various analytical methods employed to determine the PAH composition of organic soot extracts is also provided which allows the reader an access to the technical methodological literature. In addition, this section lays the ground work for the discussion of determining what chemical fractions and/or individual components of organically extractable soot material is responsible for the mutagenic/carcinogenic activity of soot.Section 3 applies some of the knowledge gained in Section 2 to determine what chemical fractions and individual components of organic soot extracts are responsible for the carcinogenic nature of soot based on animal biossays. In addition, this section deals with the development of the various animal models used in evaluating the carcinogenic potential of organic soot extracts and individual PAH components. Section 3 also discusses the carcinogenic potency of different soot extracts in animal bioassays which is useful in developing human health risk assessments. This section presents data which suggest that organic extracts and various individual components of soot induce tumors in experimental animal models and in turn leads to the discussion presented in the next section (Section 4) which explores the possibility that exposure to soot increases the incidence of cancer in man.The role of human epidemiology and its use to determine whether exposure to soot results in an increased cancer incidence in man is discussed in Section 4. Urban vs rural differences are cited which suggest that living in areas with a higher burden of air pollution may be involved with a higher incidence of lung cancer. The effect of smoking upon the perceived urban vs rural differences is also discussed. Studies are also cited in which the actual amount of particulate air pollution is known. Such studies suggest that the level of soot is positively correlated with lung cancer incidence.Occupational exposure to soot and cancer incidence is also explored because the exposure conditions are more controlled and consistent. In additions, measurement of exposure is made more practical and relevant to the epidemiological data gathered. Therefore, the strongest case for soot exposure resulting in an increased incidence of cancer in man can be made based on these occupational studies.Finally, Section 4 deals with epidemiological studies correlating soot exposure, nonrespiratory cancer and nonmalignant diseases. Such studies are cited to indicate that soot exposure is a health risk to man independent from its perceived ability to increase the risk of lung cancer.Section 4 is presented to make the reader aware that a health risk is apparently associated with exposure to soot. This leads to the discussion of the development and utilization of various short-term in vitro genotoxicity bioassays in the screening of soot extracts and derived fractions for their mutagenic/carcinogenic potential in Section 5.Section 5 presents a summary of the various short-term genotoxicity assays that have been employed to study the genetic effects of various organic soot extracts and fractions. The use of short-term genotoxicity assays allows for the rapid screening of many samples and the requirement of only small sample amounts. Therefore, a complex chemical fractionation of organic soot extracts can be performed with the resulting fractions being tested for their genotoxicity in these short-term bioassays. With the identification of the genotoxic fractions, these fractions can then be further chemically analyzed for their individual component composition. Individual compounds can then be selected for further genotoxicity testing. Following this scheme of chemical/biological analysis it may be possible to identify the individual compounds or groups of compounds that are responsible for the genotoxicity of the whole organic extract of the particular soot under study. With such knowledge at hand it may be possible to design control techniques to reduce the level of these genotoxic components produced during the combustion process. However, it is necessary to realize that these genotoxicity assays may not represent the true genetic or metabolic functions of man. Therefore, soot fractions and individual component compounds that are highly mutagenic in bacterial assay systems, may not be as genotoxic in more advanced mammalian cell bioassay tests.The final section of this review (Section 6) provides a brief discussion of the metabolism of PAH, the DNA binding properties of the reactive metabolites, mechanisms of PAH induced mutagenesis and DNA repair. Such processes are ultimately connected with the mutagenic/carcinogenic potential of the PAHs which play a significant role in the mutagenic/carcinogenic nature of soot particles.     

Application of an enhanced PAH growth model to soot formation in a laminar coflow ethylene/air diffusion flame

A recently developed chemical kinetic scheme for C₂ fuel combustion with PAH growth has been implemented in a parallelized coflow flame solver. The reaction mechanism has been developed to include almost all reasonably well-established reaction classes for aromatic ring formation and soot particle precursor molecular weight growth. The model has recently been validated for zero- and one-dimensional premixed flame systems [N.A. Slavinskaya, P. Frank, Combust. Flame 156 (2009) 1705–1722] and has now been updated and extended to a sooting ethylene/air diffusion flame in the coflow geometry. Updates to the mechanism reflect the latest advances in the literature and address numerical stiffness that was present in diffusion flame systems. The chemical kinetic mechanism has been coupled to a sectional aerosol dynamics model for soot growth, considering PAH-based inception and surface condensation, surface chemistry (growth and oxidation), coagulation, and fragmentation. The sectional model predicts the soot aggregate number density and the number of primary particles per aggregate in each section, so as to yield information on particle size distribution and structure. Flame simulation data for the present mechanism is compared to data computed using two other reaction schemes [J. Appel, H. Bockhorn, M. Frenklach, Combust. Flame 121 (2000) 122–136; N.M. Marinov, W.J. Pitz, C.K. Westbrook, A.M. Vincitore, M.J. Castaldi, S.M. Senkan, Combust. Flame 114 (1998) 192–213]. The computed data are also compared to numerous experimental data sets. Whereas the fuel oxidation chemistry in all three mechanisms are essentially the same, the PAH growth pathways vary considerably. It is shown that soot concentrations on the wings of the flame (where soot formation is dominated by surface chemistry) can be predicted with two of the three mechanisms. However, only the present mechanism with its enhanced PAH growth routes can also predict the correct order of magnitude of soot volume fraction in the low-sooting, inception-dominated, central region of the flame. In applying this chemical mechanism, the parameter α, which describes the portion of soot surface sites that are available for chemical reaction, has been reduced to a theoretically acceptable range, thus improving the quality of the model.     

A numerical study of soot aggregate formation in a laminar coflow diffusion flame

Soot aggregate formation in a two-dimensional laminar coflow ethylene/air diffusion flame is studied with a pyrene-based soot model, a detailed sectional aerosol dynamics model, and a detailed radiation model. The chemical kinetic mechanism describes polycyclic aromatic hydrocarbon formation up to pyrene, the dimerization of which is assumed to lead to soot nucleation. The growth and oxidation of soot particles are characterized by the HACA surface mechanism and pyrene-soot surface condensation. The mass range of the solid soot phase is divided into thirty-five discrete sections and two equations are solved in each section to model the formation of the fractal-like soot aggregates. The coagulation model is improved by implementing the aggregate coagulation efficiency. Several physical processes that may cause sub-unitary aggregate coagulation efficiency are discussed. Their effects on aggregate structure are numerically investigated. The average number of primary soot particles per soot aggregate np is found to be a strong function of the aggregate coagulation efficiency. Compared to the available experimental data, np is well reproduced with a constant 20% aggregate coagulation efficiency. The predicted axial velocity, OH mole fraction, and C₂H₂ mole fraction are validated against experimental data in the literature. Reasonable agreements are obtained. Finally, a sensitivity study of the effects of particle coalescence on soot volume fraction and soot aggregate nanostructure is conducted using a coalescence cutoff diameter method.     

Towards a detailed soot model for internal combustion engines

In this work, we present a detailed model for the formation of soot in internal combustion engines describing not only bulk quantities such as soot mass, number density, volume fraction, and surface area but also the morphology and chemical composition of soot aggregates. The new model is based on the Stochastic Reactor Model (SRM) engine code, which uses detailed chemistry and takes into account convective heat transfer and turbulent mixing, and the soot formation is accounted for by SWEEP, a population balance solver based on a Monte Carlo method. In order to couple the gas-phase to the particulate phase, a detailed chemical kinetic mechanism describing the combustion of Primary Reference Fuels (PRFs) is extended to include small Polycyclic Aromatic Hydrocarbons (PAHs) such as pyrene, which function as soot precursor species for particle inception in the soot model. Apart from providing averaged quantities as functions of crank angle like soot mass, volume fraction, aggregate diameter, and the number of primary particles per aggregate for example, the integrated model also gives detailed information such as aggregate and primary particle size distribution functions. In addition, specifics about aggregate structure and composition, including C/H ratio and PAH ring count distributions, and images similar to those produced with Transmission Electron Microscopes (TEMs), can be obtained. The new model is applied to simulate an n-heptane fuelled Homogeneous Charge Compression Ignition (HCCI) engine which is operated at an equivalence ratio of 1.93. In-cylinder pressure and heat release predictions show satisfactory agreement with measurements. Furthermore, simulated aggregate size distributions as well as their time evolution are found to qualitatively agree with those obtained experimentally through snatch sampling. It is also observed both in the experiment as well as in the simulation that aggregates in the trapped residual gases play a vital role in the soot formation process.     

Detailed modeling of size distribution functions and hydrogen content in combustion-formed particles

A kinetic modeling approach is proposed to delve into the nature and chemistry of combustion-produced particles. A sectional method is used for the first time on this purpose. It is based on modeling of gas-to-particle transitions by sections containing 125 lumped species with C numbers ranging from 24 to 4 × 10⁸ and H/C ratio ranging from 0 to 1. This allows not only the mass evolution of particles, but also their hydrogen content to be followed. The model is tested in an atmospheric pressure premixed flat flame of ethylene/oxygen with C/O = 0.8 and cold gas flow velocity of 4 cm/s. Comparison of modeled results with experimental data is satisfying in terms of species concentrations and H/C ratio of the particles. Analysis of model results in comparison with the experimental data has shown that it is possible to distinguish different precursors of particles moving from the exit of the burner into the post-oxidation region of the flame. At particle inception, i.e. just downstream from the flame front, gas-phase PAHs are responsible for particle nucleation and oligomers of aromatic hydrocarbons and small pericondensed hydrocarbons are predominantly present. Then the dehydrogenation process takes place and soot formation starts; in this zone large pericondensed and stacked structures are produced. Further up soot maturation generally linked with dehydrogenation is present, but still a few particles with higher H/C and with low coagulation efficiency are produced and remain present along the flame. The model, in accordance with experimental structural soot analysis, shows that in soot particles condensed structures typical of clusters of large pericondensed hydrocarbons are present whereas high-molecular mass condensed species mainly comprise oligomers of small aromatic compounds of clusters of small pericondensed hydrocarbons.     

Numerical Study of the Swirl Effect on a Coaxial Jet Combustor Flame Including Radiative Heat Transfer

A numerical study of the swirl effect on a coaxial jet combustor flame including radiative heat transfer is presented. In this work, the standard k-ε model is applied to investigate the turbulence effect, and the eddy dissipation model (EDM) is used to model combustion. The radiative heat transfer and the properties of gases and soot are considered using a coupled of the finite-volume method (FVM), and the narrow-band based weighted-sum-of-gray gases (WSGG-SNB) model. The results of this work are validated by experiment data. The results clearly show that radiation must be taken into account to obtain good accuracy for turbulent diffusion flame in combustor chamber. Flame is very influenced by the radiation of gases, soot, and combustor wall. However, swirl is an important controlling variable on the combustion characteristics and pollutant formation.     

柴油机燃用正庚烷及柴油时多环芳香烃与碳烟的演化规律

基于电控燃油喷射柴油机的全气缸取样系统,使用气相色谱-质谱联用仪及程序升温大体积进样方法,对柴油机燃用正庚烷和柴油过程中缸内多环芳香烃(Polycyclic aromatic hydrocarbons,PAHs)和碳烟的演化规律进行了试验研究.结果表明:在燃烧过程中,芘、苯并[a]芘质量随曲轴转角呈单峰变化,萘、芴质量随曲轴转角呈"S"型变化趋势(先降低后升高再降低);碳烟的生成趋势与缸内温度呈较好的一致性,且碳烟与芘随曲轴转角具有相似的单峰状质量变化趋势,只是碳烟峰值出现的时刻稍有滞后.此外,正庚烷与柴油在柴油机中燃烧时生成的PAHs与碳烟具有相似的演化规律.     

Conditional moment closure prediction of soot formation in turbulent, nonpremixed ethylene flames

Results obtained from incorporating a semiempirical soot model into a first-order conditional moment closure (CMC) approach to modeling turbulent nonpremixed flames of ethylene and air are presented. Soot formation is determined via the solution of two transport equations for soot mass fraction and particle number density, with acetylene and benzene employed as the incipient species responsible for soot nucleation, and the concentrations of these species calculated using a detailed gas-phase kinetic scheme involving 463 reactions and 70 species. The study focuses on the influence of differential diffusion of soot particles on soot volume fraction predictions. The results of calculations are compared with experimental data for three sooting ethylene flames and, in general, predictions of mixing and temperature fields within the three flames show good agreement with data. Soot volume fraction predictions are found to be in significantly better accord with data when differential diffusion is accounted for in the CMC-based soot model, supporting the importance of such effects in sooting flames, as previously noted by Kronenburg et al. in relation to methane combustion. Overall, the study demonstrates that the CMC-based soot model, when used in conjunction with a model of differential diffusion effects, is capable of accurately predicting soot formation in turbulent nonpremixed ethylene-air flames.     

Inhibition of electric field on inception soot formation: A ReaxFF MD and DFT study

The attenuation of soot formation from polycyclic aromatic hydrocarbons during the fuel combustion process is important to human health and environmental pollution. This work studies the mechanism of inhibition soot formation process under electric field. The process of soot formation with the chemical bonding and physical stacking of PAHs nucleation was investigated under the influence of electric field by using ReaxFF molecular dynamics and density functional theory. MD simulation reveals that the electric field in 1 × 10⁻⁵–1 × 10⁻⁴ V/Å induces an alternation in dispersion and stacking of PAH cluster to inhibit the PAH nucleation. The electric field inhibits the dehydrogenation and C–C bond cracking of the initial PAH during chemical growth of PAHs. Due to instability of the 5–7 membered rings, there are fewer bonding sites for large graphite lamella growth. The elucidation of reaction enthalpy of dehydrogenation, dimer growth, and the binding energy of π-π stacking with different direction field, are explored using DFT. The computational work discloses the inhibition mechanism of electric field on PAH development. The characterization results obtained by scanning electron microscopy and the temperature-programmed oxidation shows the coke content and particle size can be reduced under the influence of electric field which validates the computational result. The scientific insights gained here is useful for understanding soot inhabitation phenomenon.     

Soot precursor measurements in benzene and hexane diffusion flames

To clarify the mechanism of soot formation in diffusion flames of liquid fuels, measurements of soot and its precursors were carried out. Sooting diffusion flames formed by a small pool combustion equipment system were used for this purpose. Benzene and hexane were used as typical aromatic and paraffin fuels. A laser-induced fluorescence (LIF) method was used to obtain spatial distributions of polycyclic aromatic hydrocarbons (PAHs), which are considered as soot particles. Spatial distributions of soot in test flames were measured by a laser-induced incandescence (LII) method. Soot diameter was estimated from the temporal change of LII intensity. A region of transition from PAHs to soot was defined from the results of LIF and LII. Flame temperatures, PAH species, and soot diameters in this transition region were investigated for both benzene and hexane flames. The results show that though the flame structures of benzene and hexane were different, the temperature in the PAHs-soot transition region of the benzene flame was similar to that of the hexane flame. Furthermore, the relationship between the PAH concentrations measured by gas chromatography in both flames and the PAH distributions obtained from LIF are discussed. It was found that PAHs with smaller molecular mass, such as benzene and toluene, remained in both the PAHs-soot transition and sooting regions, and it is thought that molecules heavier than pyrene are the leading candidates for soot precursor formation.     

适用于柴油HCCI燃烧的碳烟半经验模型研究

将改进的碳烟半经验模型和简化正庚烷的化学反应机理纳入KIVA-3V程序中,以描述柴油燃烧过程中碳烟的生成和氧化历程。通过以正庚烷为燃料的激波管试验验证发现,在较宽的温度和压力范围内,该碳烟半经验模型可以相对准确地预测碳烟的生成率、颗粒直径和数密度。在定容燃烧器中典型的传统柴油机的扩散燃烧和接近于均质压燃(HCCI)发动机的预混燃烧状况下,应用此碳烟模型进一步研究了喷孔直径和喷射压力对碳烟排放的影响。结果发现模型预测得到的碳烟体积分数分布与试验吻合得较好,同时显示当控制局部当量比小于2.0时可以避免碳烟的生成。     

The effects of hydrogen addition on soot formation in counterflow diffusion n-heptane flames

The effects of H₂ addition on soot formation are investigated in counterflow diffusion n-heptane flames. Three effects including chemical, thermal, and dilution are fully isolated and characterized by additions of H₂, He, and Ar. Soot volume fractions are measured using LE-calibrated LII technique, and flame temperatures are measured using OH-TLAF method along with a thermocouple. Numerical simulations are conducted with a detailed mechanism with soot model. The simulated soot volume fractions and flame temperatures are in good agreement with experimental data. The experimental results show that H₂ addition can greatly reduce the soot formation. It is also found that the chemical and dilution effects suppress soot formation, while the thermal effect with increasing flame temperature promotes soot formation. Kinetic analysis suggests that HACA growth rate could be the dominant factor that controls the final soot formation through the three effects due to H₂ addition.