The dynamics of electrically charged soot particles in a premixed ethylene flame

A tandem differential mobility analyzer (DMA) is used to measure selectively the size distributions of soot particles carrying 0, ±1, ±2, ±3, and ±4 units of electrical charge. Near soot inception the size distribution is unimodal, with a mean diameter , and the particles are electrically neutral. With increasing height above the burner a bimodal size distribution evolves. The lower size mode remains electrically neutral with increasing height in the flame and retains its shape and intensity. In contrast, the upper mode includes progressively higher fractions of charged particles that reach levels of 33% positively and 33% negatively charged. At a fixed height, the size distribution narrows and shifts to a larger diameter as the number of charges per particle increases. At a fixed particle size, the number of charges obeys a Boltzmann distribution which is independent of height in the flame. These dynamics are examined in the context of a coagulation model that includes Coulomb forces and assumes small fractions of +1 and −1 particles are rapidly formed shortly after soot inception. The predictions closely mimic the observed evolution in charged particle size distributions and reproduce the experimentally observed Boltzmann charge distributions.     

A comparison of soot size and charge distributions from ethane, ethylene, acetylene, and benzene/ethylene premixed flames

The size and electrical charge distributions of soot particles generated in rich premixed flames are examined using a nano-differential mobility analyzer (nDMA). The aim is to investigate how these distributions vary with the choice of fuel, diluent, and flame gas velocity. The measured soot size distributions are typically bimodal. The dynamics of the upper size mode is qualitatively independent of the fuel. At increasing heights above the burner this mode increases in diameter and volume fraction, but decreases in number concentration, as expected from surface growth and coagulation. At about 6 mm above the burner a small fraction of the particles, <10%, acquire a bipolar charge. The charge is associated with the upper mode, where the fractions of positive and negative particles evolve to a Boltzmann distribution, whereas the lower mode remains electrically neutral. The existence of the lower mode depends sensitively on the choice of fuel, the flame gas velocity, and the diluent. Comparison to model calculations of flame structure reveals that as each of these are varied, the lower mode exhibits an inverse correlation with temperature, hydrogen atom, and pyrene concentrations.     

Size and charge of soot particles in rich premixed ethylene flames

A nano differential mobility analyzer (DMA) is used to measure both the size and electrical charge distributions of soot particles generated during rich premixed combustion. The size distributions are bimodal. One mode peaks at diameters below the 3 nm lower limit of the nano DMA and falls off nearly exponentially with increasing particle diameter. The intensity of this mode persists with increasing height above the burner suggesting that it represents the continued formation of new particles. The second mode is lognormal in shape. Its intensity decreases and the mean diameter increases with increasing height above the burner due to coagulation and surface growth as the particles rise in the flame. The DMA measurements show that a substantial fraction of the soot particles are electrically charged in the flame, predominantly with a single charge per particle and with essentially equal numbers of positive and negative particles. These charged particles belong solely to the upper mode, whereas the lower mode remains charge neutral, suggesting that ions do not act as soot nuclei. Following soot inception, the fraction of charged particles quickly increases with height above the burner and stabilizes at ∼30% of the upper mode for each polarity.     

Evolution of soot size distribution in premixed ethylene/air and ethylene/benzene/air flames: Experimental and modeling study

The effect of benzene concentration in the initial fuel on the evolution of soot size distribution in ethylene/air and ethylene/benzene/air flat flames was characterized by experimental measurements and model predictions of size and number concentration within the flames. Experimentally, a scanning mobility particle sizer was used to allow spatially resolved and online measurements of particle concentration and sizes in the nanometer-size range. The model couples a detailed kinetic scheme with a discrete-sectional approach to follow the transition from gas-phase to nascent particles and their coagulation to larger soot particles. The evolution of soot size distribution (experimental and modeled) in pure ethylene and ethylene flames doped with benzene showed a typical nucleation-sized (since particles do not actually nucleate in the classical sense particle inception is often used in place of nucleation) mode close to the burner surface, and a bimodal behavior at greater height above burner (HAB). However, major features were distinguished between the data sets. The growth of nucleation and agglomeration-sized particles was faster for ethylene/benzene/air flames, evidenced by the earlier presence of bimodality in these flames. The most significant changes in size distribution were attributed to an increase in benzene concentration in the initial fuel. However, these changes were more evident for high temperature flames. In agreement with the experimental data, the model also predicted the decrease of nucleation-sized particles in the postflame region for ethylene flames doped with benzene. This behavior was associated with the decrease of soot precursors after the main oxidation zone of the flames.     

Soot inception limits in laminar diffusion flames with application to oxy-fuel combustion

For diffusion flames, the combination of oxygen enrichment and fuel dilution results in an increase in the stoichiometric mixture fraction, Zst, and alters the flame structure, i.e., the relationship between the local temperature and the local gas composition. Increasing Zst has been shown to result in the reduction or even elimination of soot. In the present work, the effects of variable Zst on soot inception are investigated in normal and inverse coflow flames, using ethylene as the fuel. Use of the inverse coflow flame underscores the validity of these concepts, since the convective field in the inverse flame directs particles into the fuel-rich region. Sooting limits based on particle luminosity are measured as a function of Zst. The sooting limit is obtained by varying the amount of inert gas until soot appears above a predefined height. For each limit flame, the adiabatic flame temperature is calculated and the flame temperature at the half-height is measured. The flame temperature at the sooting limit is found to increase with Zst for both normal and inverse flames. The effects of residence time are also investigated, and the sooting limit inception temperature is found to be dependent on fuel stream velocity for both the normal and inverse configurations. A simple model applicable to oxy-fuel combustion is presented which describes how increasing Zst results in the reduction and ultimately elimination of soot. This model assumes that soot inception can only occur in a region where critical values for species, temperature, and residence time are met. The soot inception region is shown to be bounded by two isotherms: a low-temperature boundary that is a function of residence time, and a high-temperature boundary that corresponds to the location of a critical local carbon-to-oxygen ratio. The effect of increasing Zst is to move the boundaries of the soot inception zone towards each other, until the zone is infinitely thin and thus the sooting limit is reached. By comparing the model to experimental data, a critical local C/O ratio of 0.53 and a sooting limit inception temperature of 1640 K (for a characteristic residence time of 22 ms) were determined for ethylene.     

Effect of a uniform electric field on soot in laminar premixed ethylene/air flames

The effect of a nominally uniform electric field on the initially uniform distribution of soot has been assessed for laminar premixed ethylene/air flames from a McKenna burner. An electrophoretic influence on charged soot particles was measured through changes to the deposition rate of soot on the McKenna plug, using laser extinction (LE). Soot volume fraction was measured in situ using laser-induced incandescence (LII). Particle size and morphologies were assessed through ex situ transmission electron microscopy (TEM) using thermophoretic sampling particle diagnostics (TSPD). The results show that the majority of these soot particles are positively charged. The presence of a negatively charged plug was found to decrease the particle residence times in the flame and to influence the formation and oxidation progress. A positively charged plug has the opposite effect. The effect on soot volume fraction, particles size and morphology with electric field strength is also reported. Flame stability was also found to be affected by the presence of the electric field, with the balance of the electrophoretic force and drag force controlling the transition to unstable flame flicker. The presence of charged species generated by the flame was found to reduce the dielectric field strength to one seventh that of air.     

A model of particulate and species formation applied to laminar, nonpremixed flames for three aliphatic-hydrocarbon fuels

A detailed kinetic mechanism is developed that includes aromatic growth and particulate formation. The model includes reaction pathways leading to the formation of nanosized particles and their coagulation and growth to larger soot particles using a sectional approach for the particle phase. It is tested against literature data of species concentrations and particulate measurements in nonpremixed laminar flames of methane, ethylene, and butene. Reasonably good predictions of gas and particle-phase concentrations and particle sizes are obtained without any change to the kinetic scheme for the different fuels. The model predicts the low concentration of particulates in the methane flame (about 0.5 ppm) and the higher concentration of soot in the ethylene and butene flames (near 10 ppm). Model predictions show that in the methane flame small precursor particles dominate the particulate loading, whereas soot is the major component in ethylene and butene flames, in accordance with the experimental data. The driving factors in the model responsible for the quite different soot predictions in the ethylene and butene flames compared with the methane flame are benzene and acetylene concentrations, which are higher in the ethylene and butene flames. Soot loadings in the ethylene flame are sensitive to the acetylene soot growth reaction, whereas particle inception rates are linked to benzene in the model. A coagulation model is used to obtain collision efficiencies for some of the particle reactions, and tests show that the modeled results are not particularly sensitive to coagulation at the rates used in our model. Soot oxidation rates are not high enough to correctly predict burnout, and this aspect of the model needs further attention.     

Probe measurements and numerical model predictions of evolving size distributions in premixed flames

Particle size distributions (PSDs), measured with a dilution probe and a Differential Mobility Analyzer (DMA), and numerical predictions of these PSDs, based on a model that includes only coagulation or alternatively inception and coagulation, are compared to investigate particle growth processes and possible sampling artifacts in the post-flame region of a C/O = 0.65 premixed laminar ethylene-air flame. Inputs to the numerical model are the PSD measured early in the flame (the initial condition for the aerosol population) and the temperature profile measured along the flame’s axial centerline. The measured PSDs are initially unimodal, with a modal mobility diameter of 2.2 nm, and become bimodal later in the post-flame region. The smaller mode is best predicted with a size-dependent coagulation model, which allows some fraction of the smallest particles to escape collisions without resulting in coalescence or coagulation through the size-dependent coagulation efficiency (γ_SD). Instead, when γ = 1 and the coagulation rate is equal to the collision rate for all particles regardless of their size, the coagulation model significantly under predicts the number concentration of both modes and over predicts the size of the largest particles in the distribution compared to the measured size distributions at various heights above the burner. The coagulation (γ_SD) model alone is unable to reproduce well the larger particle mode (mode II). Combining persistent nucleation with size-dependent coagulation brings the predicted PSDs to within experimental error of the measurements, which seems to suggest that surface growth processes are relatively insignificant in these flames. Shifting measured PSDs a few mm closer to the burner surface, generally adopted to correct for probe perturbations, does not produce a better matching between the experimental and the numerical results.     

Measurement and analysis of soot inception limits of oxygen-enriched coflow flames

This study explores the criteria for soot inception in oxygen-enriched laminar coflow flames. In these experiments we select an axial height in the coflow flame at which to identify the sooting limit. The sooting limit is obtained by varying the amount of inert until luminous soot first appears at this predefined height. The sooting limit flame temperature is found to increase linearly with stoichiometric mixture fraction, regardless of fuel type. To understand these results, the relationships between flame structure, temperature, and local C/O ratio is explored through the use of conserved scalar relationships. Comparison of these relationships with the experimental data indicates that the local C/O ratio is a controlling parameter for soot inception in diffusion flames (analogous to the global C/O ratio in premixed flames). Analysis of experimental results suggests that soot inception occurs when the local C/O ratio is above a critical value. The values for critical C/O ratios obtained from the analysis of experiments using several fuels are similar in magnitude to the corresponding C/O ratios for premixed flames. In addition, temperatures and PAH fluorescence were measured to identify regions in these flames most conducive to particle inception. Results indicate that the peak PAH concentration lies along a critical iso-C/O contour, which supports a theory that soot particles first appear along this critical contour, given sufficient temperature.     

Modeling of particulate carbon and species formation in coflowing diffusion flames of ethylene

A model of species and particulate formation in laminar diffusion flames is presented. The kinetic model is based on the chemistry of fuel oxidation and pyrolysis, the formation of aromatics and their growth into particle nuclei, particle growth by surface reactions, coagulation, and finally particle oxidation. A sectional model is used for the particle phase. The sectional method divides the particle mass range into classes of species each with a rate equation for surface growth, coagulation, and oxidation. An inception model links the gas-phase mechanism with the smallest particle section. Predictions are compared with experimental data in two laminar coflowing diffusion flames of ethylene for which experimental profiles of stable species, aromatic compounds, high-molecular-mass precursor species, and soot are available. The predictions show good agreement with data for total particulates, defined as the sum of soot plus nano-organic carbon particles. The model has a continuous size distribution and is able to address nanoparticles which comprise a significant part of the total particle loading. A conclusion from the sensitivity analysis is that the inception process, the molecular growth process by aromatic addition on particle nuclei, and surface addition of C₂H₂ all play important roles which need to be studied in greater detail to predict the right size distribution and volume fraction of particulates formed in flames.     

Soot size distribution in lightly sooting premixed flames of benzene and toluene

The evolution of particle size distribution function (PSDF) of soot in premixed flames of benzene and toluene was studied on a burner stabilized stagnation (BSS) flame platform. The cold gas velocities were changed to hold the maximum flame temperatures of different flames approximately constant. The PSDFs of all the test flames exhibited a bimodal distribution, i.e., a small-size nucleation mode and a large-size accumulation mode. It was observed that soot nucleation and particle growth in the benzene flame were stronger than those in the toluene flame at short residence times. At longer residence times, the PSDFs of the two flames were similar, and the toluene flame showed a larger particle size distribution range and a higher particle volume fraction than the benzene flame.     

Mathematical modeling of premixed counterflow combustion of organic dust cloud

In the present study, a mathematical approach is utilized so as to modeling the flame structure of organic dust particle and air through a two-phase mixture consisting in a counterflow configuration where heat loss is taken into account. Lycopodium is considered as the organic fuel in our research. In order to simulate combustion of organic dust particles, a three-zone flame structure has been considered; preheat-vaporization zone, reaction and post flame zones. The variations of the gaseous phase mass fraction and fuel particle mass fraction as a function of the distance from the stagnation plate are obtained. Subsequently, flame temperature and flame velocity in terms of strain rate are studied. Finally, the effect of heat loss on the non-dimensionalized temperature at different heat loss coefficients is investigated.     

甲醇抑制层流预混火焰中碳烟生成的机理

利用矩方法研究了层流甲醇/乙烯预混火焰中碳烟颗粒形成的化学反应动力学机理.模型考虑了颗粒的成核、颗粒间的凝结与聚合、气态组分在颗粒表面的生长与氧化过程.整个机理涉及101种组分和543个基元反应.计算了不同甲醇摩尔分数时碳烟粒子体积分数、粒子直径及重要中间组分的摩尔分数,对乙炔和苯的生成/消耗进行了敏感性分析,揭示了甲醇燃烧过程中氧原子的迁移路径.计算结果表明,甲醇能有效地减少碳烟及其前驱体多环芳香烃、多环芳香烃前驱体物质(如乙炔、炔丙基等)的生成量.燃烧过程甲醇中氧原子在甲醇基、甲醛、羟基、甲醛基、一氧化碳和二氧化碳等物质中迁移.     

Detection of electrically charged soot particles in laminar premixed flames

A particle mass spectrometer has been used to investigate the formation of electrically charged species and soot particles in laminar premixed flames. The mass range was from 600–6 × 10⁵ amu and extends from high molecular hydrocarbons to soot particles of 10 nm diameter. The flames were stabilized on cooled porous plate burners. Acetylene/oxygen flames were investigated at low pressure (30 mbar), and ethylene/air flames were investigated at atmospheric pressure. Soot particles could only be detected in flames showing yellow luminosity, i.e. above the critical C/O-ratio for soot formation. Both positively and negatively charged particles were found, the positive charge dominating in the low pressure acetylene/oxygen flames, the negative charge dominating in the atmospheric ethylene/air flames. With the assumption of spherical shape and constant density, the mass spectra were converted to size spectra. Usually, they show a multiple peak structure which is somewhat difficult to interpret. There are indications that particles may carry multiple (1–2) charges, and also that particles of different types may coexist beside polyaromatic and polyhedral species in the early stage of particle inception.     

Experimental investigation and detailed modeling of soot aggregate formation and size distribution in laminar coflow diffusion flames of Jet A-1, a synthetic kerosene,and n-decane

A fully-coupled soot formation model is developed to predict the concentration, size, and aggregate structure of soot particles in the atmospheric pressure laminar coflow diffusion flames of a three-component surrogate for Jet A-1, a three-component surrogate for a Fischer–Tropsch Synthetic Paraffinic Kerosene (SPK), and n-decane. To model the chemical structure of the flames and soot precursor formation, a detailed chemical kinetic mechanism for fuel oxidation, with 2185 species and 8217 reactions, is reduced and combined with a Polycyclic Aromatic Hydrocarbon (PAH) formation and growth scheme. The mechanism is coupled to a highly detailed sectional particle dynamics model that predicts the volume fraction, structure, and size of soot particles by considering PAH-based nucleation, surface growth, PAH surface condensation, aggregation, surface oxidation, fragmentation, thermophoresis, and radiation. The simulation results are validated by comparing against experimental data measured for the flames of pre-vaporized fuels. The objectives of the present effort are to more accurately simulate the physical soot formation processes and to improve the predictions of our previously published jet fuel soot formation models, particularly for the size and aggregate structure of soot particles. To this end, the following improvements are considered: (1) addition of particle coalescence submodels to account for the loss of surface area, reduction of the number of primary particles, and increase of primary particle diameters upon collision, (2) consideration of a larger PAH molecule (benzopyrene instead of pyrene) for nucleation and surface growth to enhance the agreement between the soot model and the measured chemical composition of soot particles, and (3) implementation of a dimerization efficiency in the soot inception submodel to account for the collisions between PAH molecules that do not lead to dimerization. The results of two different particle coalescence submodels show that this process is too slow to account for the growth of primary particles, mainly because of the limited rate of particle collisions. Soot volume fraction predictions on the wings and at lower flame heights are considerably improved by using benzopyrene, due to the different distribution of the soot forming PAH molecule in the flame. The computed number of primary particles per aggregate and the diameters of primary particles agree very well with the experimentally measured values after implementing the dimerization efficiency for PAH collisions, because of the reduced rate of soot inception compared to growth by PAH condensation. Concentrations of major gaseous species and flame temperatures are also well predicted by the model. The underprediction of soot concentration on the flame centerline, observed in previous studies, still exists despite minor improvements.     

Soot size distributions in rich premixed ethylene flames

Electrical mobility measurements of the soot particles generated in rich premixed ethylene/air flat flames reveal a characteristic lognormal size distribution that is distinct from the self preserving distribution expected from coagulation dominated aerosol dynamics. The distribution changes to a bimodal form as the equivalence ratio and the height above the burner increase. The soot particles are sampled using a three-stage ejector pump, with an overall dilution of the soot mole fraction by 3000, that quenches the flame chemistry and dilutes the sample for analysis by a nano-differential mobility analyzer. The measured soot volume fraction is in good agreement with optical extinction data, quantitatively reproducing the increases previously noted with respect to increasing equivalence ratio and height above the burner. The trends for mean particle diameter are also reproduced, but the mobility diameters are roughly threefold smaller than their light scattering counterparts. Particle number density is found to increase with height, whereas the optical data exhibit the opposite trend. Residence chamber experiments show that with sufficient time the quenched soot sample evolves from the lognormal shape found in the flame to the expected self preserving distribution.     

Soot formation in ethanol/gasoline fuel blend diffusion flames

The aim of this paper is to examine how adding ethanol to gasoline affects soot formation. This is currently an important question with respect to particulate emissions from gasoline powered motor vehicles, but in this paper the ethanol impact is examined in co-flow diffusion flames to decouple combustion chemistry from the effects of engine operating parameters. Soot size distributions are measured as a function of height above the burner for E0, E20, E50, and E85 blends. For all fuels, the size distributions evolve from a single nucleation mode low in the flame through a bimodal distribution at mid heights and finally a single accumulation mode. The soot agglomerates in the accumulation mode, exhibit a bipolar charge. The nucleation mode initially includes charged particles, but becomes electrically neutral with increasing height in the flame. Thermodesorber measurements reveal significant hydrocarbon condensation on nucleation mode particles. This is more extensive for E0, E20, and E50 fuels as compared to E85. In other respects as well, the flames fall into two classes: (1) E85 versus (2) E0, E20, and E50. These groups of flames are visibly distinct and exhibit quantitatively different trends in terms of the size and quantity of particulate matter. The E85 flame appears similar to an ethylene diffusion flame, whereas those in the second group are more akin to a benzene flame. The results are discussed with respect to their implications regarding the effects of ethanol blends on PM emissions from gasoline engines.     

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.     

Hydrogen addition to acetylene-air laminar diffusion flames: Studies on soot formation under different flow arrangements

Axisymmetric co-flowing acetylene/air laminar diffusion flames have been experimentally investigated to study the effect of hydrogen addition on soot formation and soot morphology. An acetylene-hydrogen jet burning in co-flowing air at atmospheric pressure has been studied under different flow arrangements, i.e., premixed and with separate addition of acetylene and hydrogen. Thermophoretic sampling and analysis by transmission electron microscopy are employed for soot diagnostics. Soot microstructure, primary particle size, soot volume fraction, and fractal geometry results are reported. The effect of hydrogen addition on the temperature field is moderate (maximum increase ∼100 K), the effect being greater when hydrogen is premixed with acetylene. Soot volume fraction decreases with hydrogen addition. A shift was noted in the soot volume fraction peak with change in the Reynolds and Froude numbers at the burner exit. The primary soot particle diameter is in the range of 20-35 nm. Soot particles are larger in size close to the burner for the pure acetylene flame. A reverse trend is observed with hydrogen addition. The fractal dimension of the soot aggregates is about 1.7-1.8. It is unaffected by hydrogen addition and location in the flame. Soot aggregate size tends to decrease with hydrogen addition. The results of the present study on the effect of hydrogen addition on soot volume fraction and mean primary particle size are in good correlation with the results of other investigators for ethylene-, propane-, and butane-air flames, which have been described with regard to the HACA mechanism of soot nucleation and growth and enhanced soot oxidation in fuel-rich flames by increased OH radical concentration.