On evolution of particle size distribution functions of incipient soot in premixed ethylene-oxygen-argon flames

The evolution of the soot particle size distribution function (PSDF) and particle morphology are studied for premixed ethylene-oxygen-argon flat flames at equivalence ratio ?=2.07 over the maximum flame temperature range of 1600-1900 K. Experiments were carried out using an in-situ probe sampling method in tandem with a scanning mobility particle sizer (SMPS), yielding the PSDF for various distances from the burner surface. The morphology of the particles was examined by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Within the particle size range that can be detected, the PSDF transitions from an apparent unimodal PSDF for high temperature flames (Tf>∼1800 K) to a bimodal PSDF at lower temperatures (Tf<∼1800 K). The bimodal PSDF has a noticeable trough that separates the nucleation tail and log-normal mode. This mode-transition trough had been previously thought to occur at a fixed particle size, but these results show a continuous shift of the trough location towards smaller sizes with increasing flame temperature. TEM images show that the particles are spherical, even when the PSDF is bimodal, suggesting that the bimodality occurs as the primary particles undergoes mass and size growth, and is not a result of particle aggregation. Atomic force microscopy of substrate deposited particles shows that particles spread and form hill like structures upon impact with the substrate surface, indicating that the particles are liquid-like at the time of impact.     

A stochastic approach to calculate the particle size distribution function of soot particles in laminar premixed flames

We introduce an efficient stochastic approach to solve the population balance equation that describes the formation and oxidation of soot particles in a laminar premixed flame. The approach is based on a stochastic particle system representing the ensemble of soot particles. The processes contributing to the formation and oxidation of soot particles are treated in a probabilistic manner. The stochastic algorithm, which makes use of an efficient majorant kernel and the method of fictitious jumps, resolves the entire soot particle distribution (PSDF) without introducing additional closure assumptions. A fuel-rich laminar premixed acetylene flame is computed using a detailed kinetic soot model. Solutions are obtained for both, the stochastic approach and the method of moments combined with a modified version of the Premix, CHEMKIN code. In this manner, the accuracy of the method of moments in a laminar premixed flame simulation is investigated. It is found that the accuracy for the first moment is excellent (5% error), and mean error for rest of the moments is within 25%. Also the effect of the oxidation of the smallest particles (burnout) has been quantified but was found not to be important in the flame investigated. The time evolution of computed size distributions and their integral properties are compared to experimental measurements and the agreement was found to be satisfactory. Finally, the efficiency of the stochastic method is studied.     

Field measurements of soot volume fractions in laminar partially premixed coflow ethylene/air flames

The conditions under which soot is formed vary widely and depend upon several factors, including pressure, temperature, fuel type, combustor geometry, and extent of premixing. Although it is known that partially premixed flames (PPFs) can become either more or less sooting than their nonpremixed or premixed counterparts, the impact of partial premixing on soot formation across a large equivalence ratio and flow range is still inadequately understood. Comprehensive experimental data are relatively sparse for this important configuration. Herein, we report on soot formation in various ethylene/air PPFs utilizing full-field light extinction. The dimensionless extinction coefficient Kext is an important calibrated constant for the determination of the soot volume fraction for this measurement technique. We find that a value of Kext=7.1 provides results that are in good agreement with benchmark literature data for a nonpremixed flame. We examined the soot microstructures for two flames established at ?=∞ (i.e., nonpremixed) and 5. In both cases, the primary particles were found to be nearly spherical. In case of the nonpremixed flame the average primary soot particle diameter was ∼35 nm, but for the ?=5 flame it was ∼20 nm. However, the parameter responsible for the value of Kext is the average aggregate size and not that of the primary particles. The aggregate sizes are similar for the two flames. We consider this as verification of a constant Kext value over the entire equivalence ratio range. The addition of air to the fuel stream produces an initial increase in the flame height. Further air addition gradually decreases the flame height, which is followed by a more rapid decrease with larger premixing. Likewise, the peak soot concentration first increases with small amounts of air addition (or partial premixing of the fuel stream) and reaches a maximum value at ?∼24. With further air addition, as ? decreases below a value of 20, the soot volume fraction considerably decreases.     

Quantitative measurement of soot particle size distribution in premixed flames - The burner-stabilized stagnation flame approach

A burner-stabilized, stagnation flame technique is introduced. In this technique, a previously developed sampling probe is combined with a water-cooled circular plate such that the combination simultaneously acts as a flow stagnation surface and soot sample probe for mobility particle sizing. The technique allows for a rigorous definition of the boundary conditions of the flame with probe intrusion and enables less ambiguous comparison between experiment and model. Tests on a 16.3% ethylene-23.7% oxygen-argon flame at atmospheric pressure show that with the boundary temperatures of the burner and stagnation surfaces accurately determined, the entire temperature field may be reproduced by pseudo one-dimensional stagnation reacting flow simulation using these temperature values as the input boundary conditions. Soot particle size distribution functions were determined for the burner-stabilized, stagnation flame at several burner-to-stagnation surface separations. It was found that the tubular probe developed earlier perturbs the flow and flame temperature in a way which is better described by a one-dimensional stagnation reacting flow than by a burner-stabilized flame free of probe intrusion.     

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.     

Experimental and computational studies of oxidizer and fuel side addition of ethanol to opposed flow air/ethylene flames

Results of computations based on a detailed chemical kinetic combustion mechanism and results of experiments are compared to understand the influence of ethanol vapor addition upon soot formation and OH radical concentration in opposed flow ethylene/air diffusion flames. For this work, ethanol vapor was added to either the fuel or the oxidizer gases. Experiment and calculations are in qualitative agreement, and both show differing concentrations of soot, soot precursors, and OH depending on whether the ethanol is added to the fuel or oxidizer gases. An explanation for the observed differences for oxidizer or fuel side ethanol addition to opposed flow ethylene/air diffusion flames is proposed, based on an analysis of the chemical kinetic mechanism used in the computations.     

Experimental and computational study on partially premixed flames in a centerbody burner

The centerbody burner was designed with the objective of understanding the coupled processes of soot formation, growth, and burnout. Fuel that issues from the center of the burner establishes two flame zones – one associated with the recirculation zone (RZ) and the other, with the trailing jet. The sooting characteristics in these two flame zones can be quite different because of variations in residence time and transport of reactants and products. Calculations performed for this burner operating under a partially premixed fuel jet suggested that soot in the RZ decreases and that soot in the trailing jet flame increases with the amount of premixing. An experimental and numerical study is performed to aid the understanding of these differences. A time-dependent, axisymmetric, detailed-chemistry computational-fluid-dynamics (CFD) model known as Unsteady Ignition and Combustion using ReactioNs (UNICORN) is used for simulating flames under different equivalence-ratio conditions. Combustion and PAH formation are modeled using the Wang–Frenklach (99 species and 1066 reactions) mechanism, and soot is simulated using a two-equation model of Lindstedt. A Lagrangian-based particle-tracking model is used for understanding the evolution of soot-like particles. Flame and recirculation-zone structures and soot in the experiments are identified using direct photographs taken with and without Mie scattering from soot particles as well as laser-induced-incandescence (LII) measurements. Calculations predict the structures of the partially premixed centerbody flames for various equivalence ratios reasonably well. Experiments confirm the predicted soot suppression in the RZs and enhancement of soot in the trailing jet flame when air is added to the fuel jet. It is found that flame movement in the RZ increases soot-particle burnout and, thereby, reduces the amount of soot within the RZ. As the flame moves closer to the fuel jet, more soot becomes entrained into the inner vortex. Motion of soot-like particles explained the spiral rings observed in the experiment. Increased particle burnout with partial premixing leads to shrinkage of soot spirals.     

Computational and experimental study of the effects of adding dimethyl ether and ethanol to nonpremixed ethylene/air flames

Two sets of axisymmetric laminar coflow flames, each consisting of ethylene/air nonpremixed flames with various amounts (up to 10%) of either dimethyl ether (CH₃-O-CH₃) or ethanol (CH₃-CH₂-OH) added to the fuel stream, have been examined both computationally and experimentally. Computationally, the local rectangular refinement method, which incorporates Newton's method, is used to solve the fully coupled nonlinear conservation equations on solution-adaptive grids for each flame in two spatial dimensions. The numerical model includes C6 chemical kinetic mechanisms with up to 59 species, detailed transport, and an optically thin radiation submodel. Experimentally, thermocouples are used to measure gas temperatures, and mass spectrometry is used to determine concentrations of over 35 species along the flame centerline. Computational results are examined throughout each flame, and validation of the model occurs through comparison with centerline measurements. Very good agreement is observed for temperature, major species, and several minor species. As the level of additive is increased, temperatures, some major species (CO₂, C₂H₂), flame lengths, and residence times are essentially unchanged. However, peak centerline concentrations of benzene (C₆H₆) increase, and this increase is largest when dimethyl ether is the additive. Computational and experimental results support the hypothesis that the dominant pathway to C₆H₆ formation begins with the oxygenates decomposing into methyl radical (CH₃), which combines with C2 species to form propargyl (C₃H₃), which reacts with itself to form C₆H₆.     

A soot particle surface reactivity model applied to a wide range of laminar ethylene/air flames

The effect of soot surface reactivity, in terms of the evolution of sites on the soot particles’ surface available for reaction with gas phase species, is investigated via modeling numerous ethylene/air flames, using a detailed combustion and sectional soot particle dynamics model. A new definition of a particles’ age is introduced. A methodology has been developed to study soot particle surface reactivity. Subsequently, it is investigated if the surface reactivity can be correlated with the particle age. An exponential function giving a smooth transition of surface activity with particle age is employed to model a variety of ethylene/air flames, which differ in fuel stream dilution levels, fuel stream premixing, and burner configurations. Excellent agreement with measured soot volume fractions of a variety of flames, burners, and datasets could be obtained with this approach. The newly developed function based on particle age eliminates the need to fit soot surface growth parameters to each experimental condition. Finally, the applicability and limitation of the new surface reactivity function for use in detailed soot formation models is discussed.     

Experimental study of soot and temperature field structure of laminar co-flow ethylene–air diffusion flames with nitrogen dilution at elevated pressures

An experimental study has been conducted to investigate soot formation in laminar co-flow ethylene–air diffusion flames with nitrogen dilution from a co-flow circular nozzle at pressures from 10 to 35 atm. Spectral soot emission (SSE) diagnostic technique was used to determine the radially resolved soot and temperature field structure. Constancy of ethylene and nitrogen flow rates were maintained and the flow rates of ethylene and nitrogen were selected such that no smoke was emitted even at the highest soot loadings. The flame height, marked by visible flame radiation, remained constant at about 5.5 mm and the cross-sectional area of the flame decreased with increasing pressure. At 10 atm, the peak soot concentration of less than 8 ppm, was measured near the flame tip. At 35 atm, the peak soot concentration of about 62 ppm, was measured near the mid-height of the flame. The conversion of carbon in the fuel to soot was strongly dependent on pressure particularly in the lower pressure range. At higher pressure this dependence was weaker. The peak carbon conversion to soot, 6.5%, was observed at 30 atm and remained constant to 35 atm. Temperatures increased along the flame axis and the peak temperature was observed near the flame tip to indicate complete soot oxidation.     

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.     

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.     

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.     

A model of particle nucleation in premixed ethylene flames

A detailed model of particle inception is proposed to delve into the physical structure and chemistry of combustion-formed particles. A sectional method is used, from a previously developed kinetic mechanism of particle formation with a double discretization of the particle phase in terms of C and H atom number. The present model also distinguishes between different particle structures based on their state of aggregation; single high molecular mass molecules, cluster of molecules and aggregates of clusters. The model predicts the mass of particles, hydrogen content and internal structure. It represents a first approach in following the chemical evolution and internal structure of the particles formed in flames, coupled with the main pyrolysis and oxidation of the fuel.The model is tested in atmospheric premixed flat flames of ethylene and the effect of fuel equivalence ratio on particle morphology is analyzed. Molecular weight growth of aromatic compounds and the inception of particles are predicted. The morphology of the particles and the number of molecules in the clusters at particle inception are also indicated.     

Reduction of PAH and soot in premixed ethylene-air flames by addition of ethanol

Results are presented from a combined experimental and modeling study undertaken to understand the pathways by which the addition of ethanol to fuel-rich ethylene flames causes reductions in PAH and soot. The experimental work was conducted in a flat-flame burner at equivalence ratios of 2.34 and 2.64. Ethanol was added to the ethylene at two levels corresponding to 5 and 10% oxygen by weight in the fuel. Soot was measured by laser-induced incandescence calibrated with light extinction, and aromatic species were measured using laser-induced fluorescence. Modeling was based on a 1-D premixed flame model and kinetic mechanisms available in the literature. The modeling work captures the trends in aromatic species with changes in equivalence ratio and oxygen concentration in the fuel. However, the soot predictions do not match the increases observed at the higher equivalence ratio. Analysis of the modeling results for the lower equivalence ratio shows that the addition of ethanol to the ethylene reduces the aromatic species mainly by reducing the amount of carbon that is available to form precursor species.     

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.     

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.     

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.     

A numerical study on the effects of pressure and gravity in laminar ethylene diffusion flames

The effects of pressure and gravity on sooting characteristics and flame structure were studied numerically in coflow ethylene–air laminar diffusion flames between 0.5 and 5 atm. Computations were performed by solving the unmodified and fully-coupled equations governing reactive, compressible, gaseous mixtures which include complex chemistry, detailed radiation heat transfer, and soot formation/oxidation. Soot formation/oxidation was modeled using an acetylene-based, semi-empirical model which has been verified with previously published experimental data to correctly capture many of the observed trends at normal-gravity. Calculations for each pressure considered were performed for both normal- and zero-gravity conditions to help separate the effects of pressure and buoyancy on soot formation. Based on the numerical predictions, pressure and gravity were observed to significantly influence the flames through their effects on buoyancy and reaction rates. The zero-gravity flames have higher soot concentrations, lower temperatures and broader soot-containing zones than normal-gravity flames at the same pressure. The zero-gravity flames were also found to be longer and wider. Differences were observed between the two levels of gravity when pressure was increased. The zero-gravity flames displayed a stronger dependence of the maximum soot yield on pressure from 0.5 to 2 atm and a weaker dependence from 2 to 5 atm as compared to the normal-gravity flames. In addition, flame diameter decreased with increasing pressure under normal-gravity while it increased with pressure in the zero-gravity cases. Changing the prescribed wall boundary condition from fixed-temperature to adiabatic significantly altered the numerical predictions at 5 atm. When the walls were assumed to be adiabatic, peak soot volume fractions and temperatures increased in both the zero- and normal-gravity flames, emphasizing the importance of heat conduction to the burner rim on flame structure.