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.     

A model for sooting in diffusion flames

For laminar diffusion flames the onset of sooting can be predicted by a simple extension of the Bauke-Schumann theory of such flames. Deviations from these predictions may be caused by effectively finite soot-oxidation rates and by enhanced mixing due to turbulence. Both effects have been enhanced. It is shown that the fraction of carbon in the fuel liberated as soot is determined largely by the physical characteristics of the flame rather than by the detailed chemical nature of the fuel. The effect on soot production of the addition of oxygen to the fuel is studied under conditions for which the physical parameters are carefully controlled.     

Effect of ferrocene addition on sooting limits in laminar premixed ethylene-oxygen-argon flames

The critical sooting C/O ratio was measured for a series of atmospheric-pressure, laminar premixed ethylene-oxygen-argon flames doped with a small amount of ferrocene. Comparisons of the doped and undoped flames show marked increases in sooting tendency for flames doped with ferrocene. Under the same flame conditions, the critical C/O ratios in doped flames were uniformly lower than those of undoped flames. A five-step reaction mechanism of ferrocene decomposition, leading to the formation of the cyclopentadienyl, was proposed. Detailed kinetic modeling of the experimental flames showed little changes in the flame temperature and the aromatic concentration upon ferrocene doping. The experimental and computational results support the early suggestion that in premixed flames the increase in sooting tendency due to ferrocene addition is the result of induced nucleation by iron oxide nanoparticles. These particles provide a surface to initiate soot surface growth.     

Sooting tendencies of primary reference fuels in atmospheric laminar diffusion flames burning into vitiated air

In this study, the sooting tendencies of primary reference fuels (PRFs) are measured in term of yield sooting indices (YSIs) in methane diffusion flames doped with the vapors of PRFs. The present paper represents an incremental advance complementing the original methodology prescribed by McEnally and Pfefferle. The influence of both PRF formulation and CO₂ dilution of the coflowing air on the YSIs is also assessed. The diffusion flames burning in a coflowing oxidizer stream are established over the Santoro’s burner and vapor of the liquid fuel to be investigated is injected into the fuel stream. Laser extinction measurements are performed to map the two-dimensional field of soot volume fraction in the flame. For the pure liquid hydrocarbons investigated, i.e., n-hexane, n-heptane, isooctane, and benzene, the YSI reported in the original paper by McEnally and Pfefferle quantitatively predict the sooting propensities, measured here at much higher dopant concentrations. The present study therefore extends the consistency of the YSI methodology on the Santoro’s burner. For blends of n-heptane and isooctane, the sooting tendency of doped flames exhibits regular and monotonic trends and decreases with increasing n-heptane mole fraction or CO₂ dilution. Interestingly, the evolution of YSI with the isooctane mole fraction exhibits a strong similarity for varying CO₂ mole fraction. A quadratic least-squares fit is then derived, providing a phenomenological model of YSI as a function of both isooctane mole fraction in the fuel stream and CO₂ mole fraction in the oxidizer. A non-negligible cross effect of PRF formulation and CO₂ dilution on YSI is revealed. The method elaborated within the framework of the present paper could be extended to surrogate fuels. This would help develop a comprehensive database and empirical correlations that could predict the sooting propensities of different surrogate fuels, therefore their potentially mitigationed soot production through control of fuel composition and/or exhaust gas recirculation. This database would also be useful for the validation of CFD simulations incorporating sophisticated model of soot production.     

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.     

An assessment of surrogate fuel using Bayesian multiple kernel learning model in sight of sooting tendency

An integrated and systematic database of sooting tendency with more than 190 kinds of fuels was obtained through a series of experimental investigations. The laser-induced incandescence (LII) method was used to acquire the 2D distribution of soot volume fraction, and an apparatus-independent yield sooting index (YSI) was experimentally obtained. Based on the database, a novel predicting model of YSI values for surrogate fuels was proposed with the application of a machine learning method, named the Bayesian multiple kernel learning (BMKL) model. A high correlation coefficient (0.986) between measured YSIs and predicted values with the BMKL model was obtained, indicating that the BMKL model had a reliable and accurate predictive capacity for YSI values of surrogate fuels. The BMKL model provides an accurate and low-cost approach to assess surrogate performances of diesel, jet fuel, and biodiesel in terms of sooting tendency. Particularly, this model is one of the first attempts to predict the sooting tendencies of surrogate fuels that concurrently contain hydrocarbon and oxygenated components and shows a satisfying matching level. During surrogate formulation, the BMKL model can be used to shrink the surrogate candidate list in terms of sooting tendency and ensure the optimal surrogate has a satisfying matching level of soot behaviors. Due to the high accuracy and resolution of YSI prediction, the BMKL model is also capable of providing distinguishing information of sooting tendency for surrogate design.     

Soot formation in flames of model biodiesel fuels

The sooting propensities of non-premixed flames of a class of model biodiesel fuels, namely fatty acid esters, were studied systematically. Soot volume fractions were measured using the laser extinction method in the counter-flow configuration, for different fuel/N₂ molar ratios and atmospheric pressure. The experimental data were compared against those obtained in flames of n-alkanes with similar carbon numbers and a flame of a surrogate diesel fuel. For all cases considered, it was determined that the soot volume fraction increases with the fuel concentration, as expected. Furthermore, the model biodiesel fuels were shown to produce significantly less soot compared to the corresponding n-alkanes. Additional experimental studies were carried as well, in order to assess the effects of carbon number, type of ester group (methyl or ethyl), and extent of saturation on the sooting propensity of flames of these model biodiesel fuels. Three recently developed chemical kinetic models were utilized to model the flames and thus investigate the kinetic pathways controlling the formation of C₂H₄ and two key soot precursors, namely C₂H₂ and C₃H₃, aiming to provide insight into the experimentally observed differences in the sooting propensity among the flames of the various fuels that were considered.     

Numerical investigation of spherical diffusion flames at their sooting limits

Detailed numerical simulations are presented of laminar microgravity spherical diffusion flames at their experimentally observed sooting limits. Ten normal and inverse flames fueled by ethylene are considered. Observed in a drop tower, these flames were initially sooty but reached their sooting limits 2 s after ignition (or slightly before). The flames span broad ranges of stoichiometric mixture fraction (0.065–0.692), adiabatic flame temperature (2226–2670 K), and stoichiometric scalar dissipation rate (0.013–0.384 s^?1). They were modeled using a one-dimensional, transient diffusion flame code with detailed chemistry (up to toluene) and transport. Radiative losses from products were modeled using a detailed absorption/emission statistical narrow-band model coupled with a discrete-ordinates method. Flame structure at the sooting limits was examined, emphasizing the behavior of carbon to oxygen atom ratio, temperature, and scalar dissipation rate. For ethylene flames with sufficiently long flow times it was found that soot formation coincides with regions where the C/O atom ratio and temperature exceed critical values, specifically 0.53 and 1305 K, respectively. The scatter about these critical values is small, which is noteworthy considering the wide range of flame conditions. These observations are consistent with the expected effects of H radicals on the propargyl soot pathway.     

Sooting behavior in temperature-controlled laminar diffusion flames

The sooting tendency of gaseous and liquid hydrocarbon fuels has been determined systematically in an axisymmetric laminar diffusion flame whose temperature was controlled by nitrogen dilution. Sooting tendency was measured by the minimum mass flow rate of fuel (FFM) at the smoke height. Result, plotted as log 1/FFM versus $\text{1}\text{T}$, where T is a calculated adiabatic flame temperature, show that fuel structure plays a significant role in diffusion flames. Comparison of these flame results with basic pyrolysis studies in the literature supports the concept that pyrolysis of the fuel molecule is a controlling factor in determining the overall tendency to soot, even though such tendency results from the competition of pyrolysis of the fuel and heterogeneous oxidation of the soot particles. The pyrolysis characteristics affecting the sooting process are rate, sequence and nature of products, and pyrolysis mode (pure or oxidative). The aromatics show a temperature sensitivity with respect to sooting tendency significantly lower than the other fuels. Conjugation of the initial fuel molecule and pyrolysis intermediates enhances sooting propensity.     

Structure of incipiently sooting ethylene–nitrogen counterflow diffusion flames at high pressures

We report on the structure of C₂H₄/N₂/O₂ counterflow diffusion flames at pressures up to 2.5 MPa. The concentrations of major species, aliphatics up to decane and aromatics up to indene are measured by GC–MS analysis of samples collected along the flame centerline with a capillary probe. The data are compared with results of a computational model with detailed chemistry and transport. A first set of measurements (Series 1) is performed for a fixed stoichiometric mixture fraction Z_st = 0.408, fuel mass fraction Y_F = 0.122, and global strain rate a = 57/s at pressures in the 0.1–0.8 MPa range. The flames are soot-free and permanently blue at all pressures but for the highest value of 0.8 MPa, when visual observation of a faint yellow luminosity reveals incipient sooting. A second set of flames (Series 2) is chosen by a similar criterion, by decreasing the fuel mass fraction to Y_F = 0.0975, lowering the global strain rate to 18.4/s, and covering the 0.855–2.5 MPa pressure range, which also in this case yields incipient sooting only at the highest pressure. In all cases, the flames are immune from buoyancy instabilities. Importantly, the temperature-convective time history is maintained constant in the flames in each series, which allows for a systematic exploration of the influence of only pressure, and indirectly diffusion, on the transition to incipient sooting by monitoring critical soot precursors such as the aromatics. A simple scaling based on Damköhler number suggests that just the increase in concentration of species with pressure suffices to explain the increase in sooting density. Agreement between experiments and computations is very good for major species and C₂H₂, even for the thinnest high-pressure flames. The profiles of these species, methane and temperature collapse for all pressures, once rescaled with a diffusive length δ varying with pressure and strain rate as (p·a)^−1/2. The model properly captures the first steps in fuel consumption by hydrogen abstraction by OH and H. As the pressure rises, the preferential decrease of H mole fraction suggests an increasingly dominant role of OH in an exothermic oxidative process. The observed higher sooting tendency at high pressures correlates with the increase in mole fraction of aromatics, but the model significantly overestimates such an increase. The comprehensive experimental database provides a useful test-bed for further refinements and developments of chemistry models.     

部分预混对扩散火焰中碳烟成核的影响

通过测量扩散火焰中开始形成碳核时的临界气动变形率Ｋｐ,对丙烷中加入空气,氮气和氧气时的碳烟生成进行了实验研究,介绍了利用碳烟颗粒和ＰＡＨ对偏振激光的散射性能差异测量Ｋｐ的方法;通过比较不同条件下的Ｋｐ,得出结论：部分预燃具有遏制扩散燃烧中碳烟成核的作用,有利于减少碳烟的生成。     

A radical index for the determination of the chemical kinetic contribution to diffusion flame extinction of large hydrocarbon fuels

The extinction limits of diffusion flames have been measured experimentally and computed numerically for fuels of three different molecular structures pertinent to surrogate fuel formulation: n-alkanes, alkyl benzenes, and iso-octane. The focus of this study is to isolate the thermal and mass transport effects from chemical kinetic contributions to diffusion flame extinction, allowing for a universal correlation of extinction limit to molecular structure. A scaling analysis has been performed and reveals that the thermal and mass transport effects on the extinction limit can be normalized by consideration of the enthalpy flux to the flame via the diffusion process. The transport-weighted enthalpy is defined as the product of the enthalpy of combustion per unit mole of fuel and the inverse of the square root of fuel molecular weight. The chemical kinetic contribution provided by the specific fuel chemistry has thus been elucidated for tested individual component and multi-component surrogate fuels. A chemical kinetic flux analysis for n-decane flames shows that the production/consumption rates of the hydroxyl (OH) radical govern the heat release rate in these flames and therefore play significant roles in defining the extinction limit. The rate of OH formation has been defined by considering the OH concentration, flame thickness, and flow strain rate. A fuel-specific radical index has been introduced as a concept to represent and quantify the kinetic contribution to the extinction limit owing to the fuel-specific chemistry. A relative radical index scale, centered on the radical index of a series of n-alkanes which are observed and fundamentally explained to be common, is established. A universal correlation of the observed extinction limits of all tested fuels has been obtained through a combined metric of radical index and transport-weighted enthalpy. Finally, evidence as to the validity of the fundamental arguments presented is provided by the success of the universal correlation in predicting the extinction limits of the multi-component mixtures typical of surrogate fuels.     

Methyl butanoate inhibition of n-heptane diffusion flames through an evaluation of transport and chemical kinetics

The extinction limits of methyl butanoate, n-heptane, and methyl butanoate/n-heptane diffusion flames have been measured as a function of fuel mole fraction with nitrogen dilution in counterflow with air. On a mole fraction basis, methyl butanoate diffusion flames are observed to have a much lower extinction strain rate than n-heptane diffusion flames and the extinction strain rate of n-heptane/methyl butanoate diffusion flames is observed to increase significantly as the n-heptane fraction is increased.Based on previous works, detailed chemical kinetic models to describe the high temperature oxidation of these fuel mixtures are assembled, tested and reduced. When the transport properties of ester species are re-evaluated by means of a thorough literature review, numerical computations of extinction generally reproduce experimental results for the pure fuels as well as for mixtures. An in-depth analysis of the kinetic model computations reveals that the extinction behaviour of both fuels is due to (1) fuel energy content affects and (2) the chemical kinetic potential of each fuel to produce the hydroperoxy radical. Comparatively, in n-heptane flames reactive ethyl radicals and ethylene are the major intermediates formed, but in methyl butanoate flames the major intermediates are formyl radicals and formaldehyde. In all flames studied, increased strain rates affect an increased interaction of formyl and/or vinyl radicals with molecular oxygen leading to a transition from hydrogen atom production at low strain rates, to the production of large quantities of the hydroperoxy radical at higher strain rates. The formation of the hydroperoxy radical induces extinction in each flame by directly interfering with the important radical chain branching and exothermic elementary reactions of H atoms and OH radicals that are dominant in weakly strained flames.It is postulated that the similar inhibitive effect of methyl butanoate fuelled flames will also be observed for more biodiesel like, larger n-alkyl esters when compared to equivalent n-alkanes. The diffusive extinction limits of methyl decanoate diffusion flames are also measured and show reactivity comparable to n-heptane diffusion flames by a molar comparison.     

Effects of structure and hydrodynamics on the sooting behavior of spherical microgravity diffusion flames

This study is an examination of the sooting behavior of spherical microgravity diffusion flames burning ethylene at atmospheric pressure in a 2.2-s drop tower. In a novel application of microgravity, spherical flames were employed to allow convection across the flame to be either from fuel to oxidizer or from oxidizer to fuel. Thus, spherical microgravity flames are capable of allowing stoichiometric mixture fraction, Z_st, and direction of convection across the flame to be controlled independently. This allowed for a study of the phenomenon of permanently blue diffusion flames—flames that remain blue as strain rate approaches zero. Z_st was varied by changing inert concentrations such that adiabatic flame temperature did not change. At low Z_st, nitrogen was supplied with the oxidizer, and at high Z_st, it was provided with the fuel. Flame structure, quantified by Z_st, was found to have a profound effect on soot production. Soot-free conditions were observed at high Z_st and sooting conditions were observed at low Z_st regardless of convection direction. Convection direction was found to have a smaller impact on soot inception, suppressing formation when convection at the flame sheet was directed towards the oxidizer. A numerical analysis was developed to simulate steady state conditions and aided the interpretation of the results. The analysis revealed that steady state was not achieved for any of the flames, but particularly for those with pure ethylene or oxygen flowing from the porous burner. Furthermore, despite the fact that all flames had the same adiabatic flame temperature, the actual peak temperatures differed considerably. While transient burner heating and burner radiation reduced flame temperature, gas-phase radiative heat loss was the dominant mechanism accounting for these differences.     

Flame temperature, fuel structure, and fuel concentration effects on soot formation in inverse diffusion flames

Insights into soot formation processes are gained from chemical sampling and thermocouple probing of co-flowing inverse diffusion flames (IDFs), with the oxidizer in the center. The transition from near-to slightly sooting flames and the effects of flame temperature, fuel concentration, and fuel structure (using methane, ethene, propene and 1-butene) are investigated. The aromatic content of IDFS scales with the fuel's sooting tendency, and suggests that the formation of the aromatic ring is a controlling step in soot formation. In addition to the relatively well-established reactions involving C4 and C2 species, benzene may form directly from two C3 species for fuels that readily produce C3 species during pyrolysis and/or oxidative pyrolysis. The total concentration of growth species increases almost linearly with fuel concentration, but depends more weakly on flame temperature than would be expected if pure pyrolysis governed the intermediate hydrocarbon behavior.     

Effect of partial premixing on the sooting structure of methane flames

An experimental investigation of the sooting structure of diluted methane–oxygen counterflow flames is reported for partial premixing in the following two nonpremixed flame configurations:

• Case 1:Nonpremixed flame on the oxidizer side of the stagnation plane,
• Case 2:Nonpremixed flame on the fuel side of the stagnation plane.

Effects of both fuel-side and oxidizer-side partial premixing for Cases 1 and 2 were investigated in a low-strain-rate (∼6–8 s⁻¹) counterflow flame. Computations using OPPDIF code were in excellent agreement with the measured concentrations of major species and [OH]. Distribution of measured soot volume fraction and particle sizes are presented along with measured distributions of C₂ hydrocarbon species. Soot loading can increase or decrease depending on (a) the level of partial premixing, (b) the side of partial premixing (fuel side or oxidizer side), and (c) the nonpremixed flame configuration. Of particular interest is the trend for fuel-side partial premixing of Case 1, where the peak soot loading, the peak soot particle diameter, and the thickness of the soot zone initially decrease and then increase with progressive partial premixing. The trends presented are discussed based on chemical, dilution, and flow-field effects of partial premixing on soot growth in counterflow flames. Unlike previous literature, which focused on soot inception, this work emphasizes the role of partial premixing on soot growth by taking into account the changes in the temperature–time history of soot particulates in addition to the previously reported “chemical” and “dilution” effects.     

LES model for sooting turbulent nonpremixed flames

In this work, an integrated Large Eddy Simulation (LES) model is developed for sooting turbulent nonpremixed flames and validated in a laboratory scale flame. The integrated approach leverages state-of-the-art developments in both soot modeling and turbulent combustion modeling and gives special consideration to the small-scale interactions between turbulence, soot, and chemistry. The oxidation of the fuel and the formation of gas-phase soot precursors is described by the Flamelet/Progress Variable model, which has been previously extended to account for radiation losses. However, previous DNS studies have shown that Polycyclic Aromatic Hydrocarbons (PAH), the immediate precursors of soot particles, exhibit significant unsteady effects due to relatively slow chemistry. To model these unsteady effects, a transport equation is solved for a lumped PAH species. In addition, due to the removal of PAH from the gas-phase, alternative definitions of the mixture fraction, progress variable, and enthalpy are proposed. The evolution of the soot population is modeled with the Hybrid Method of Moments (HMOM), an efficient statistical model requiring the solution of only a few transport equations describing statistics of the soot population. The filtered source terms in these equations that describe the various formation, growth, and destruction processes are closed with a recently developed presumed subfilter PDF approach that accounts for the high spatial intermittency of soot. The integrated LES model is validated in a piloted natural gas turbulent jet diffusion flame and is shown to predict the magnitude of the maximum soot volume fraction in the flame relatively accurately, although the maximum soot volume fraction is shown to be rather sensitive to the subfilter scalar dissipation rate model.     

Soot formation in aerodynamically strained methane–air and ethylene–air diffusion flames with chloromethane addition

The effects of chloromethane (CH₃Cl) addition on soot inception in methane–air and ethylene–air counterflow diffusion flames were investigated by varying the concentrations of chloromethane and nitrogen in the fuel stream. Experiments showed a monotonic increase in the critical sooting stretch rate for methane–air flames when methane was replaced by chloromethane, while ethylene and chloromethane flames exhibited a larger sooting tendency than flames under comparable conditions and burning either ethylene or chloromethane alone. For the conditions investigated, the critical sooting stretch rates of methane–chloromethane–nitrogen flames were shown to be primarily a function of the chloromethane loading in the fuel stream. The structure of these flames was modeled using detailed chemistry and transport. Modeling results suggested that the enhancement of soot formation in ethylene–chloromethane flames may be a combined result of increased concentrations of C₂ species and chlorinated C₁ radicals (CH₂Cl and CHCl). A large rate of the reactions among these species may be the first steps in the molecular growth processes, which leads to the inception of soot particles.     

Experimental study of ethylene counterflow diffusion flames perturbed by trace amounts of jet fuel and jet fuel surrogates under incipiently sooting conditions

The structure of an ethylene counterflow diffusion flame doped with 2000 ppm on a molar basis of either jet fuel or two jet fuel surrogates is studied under incipient sooting conditions. The doped flames have identical stoichiometric mixture fractions (z_f = 0.18) and strain rates (a = 92 s⁻¹), resulting in a well-defined and fixed temperature/time history for all of the flames. Gas samples are extracted from the flame with quartz microprobes for subsequent GC/MS analysis. Profiles of critical fuel decomposition products and soot precursors, such as benzene and toluene, are compared.The data for C7-C12 alkanes are consistent with typical decomposition of large alkanes with both surrogates showing good qualitative agreement with jet fuel in their pyrolysis trends. Olefins are formed as the fuel alkanes decompose, with agreement between the surrogates and jet fuel that improves for small alkenes, probably because of an increase in kinetic pathways which makes the specifics of the alkane structure less important.Good agreement between jet fuel and the surrogates is found with respect to critical soot precursors such as benzene and toluene. Although the six-component Utah/Yale surrogate performs better than the Aachen surrogate, the latter performs adequately and retains the advantage of simplicity, since it consists of only two components.The acetylene profiles present a unique multimodal behavior that can be attributed to acetylene’s participation in early stages of formation of soot precursors, such as benzene and other large pyrolysis products, as well as in the surface growth of soot particles.