Numerical simulations of soot aggregation in premixed laminar flames

In this paper we make use of a detailed particle model and stochastic numerical methods to simulate the particle size distributions of soot particles formed in laminar premixed flames. The model is able to capture the evolution of mass and surface area along with the full structural detail of the particles. The model is validated against previous models for consistency and then used to simulate flames with bimodal and unimodal soot particle distributions. The change in morphology between the particles from these two types of flames provides further evidence of the interplay among nucleation, coagulation, and surface rates. The results confirm the previously proposed role of the strength of the particle nucleation source in defining the instant of transition from coalescent to fractal growth of soot particles.     

Polycyclic aromatic hydrocarbons from the co-pyrolysis of catechol and 1,3-butadiene

In order to better understand the reactions responsible for the formation and growth of polycyclic aromatic hydrocarbons (PAH) from solid fuels, we have performed pyrolysis experiments in an isothermal laminar-flow reactor (at temperatures of 600-1000 °C and a fixed residence time of 0.3 s) with catechol, a model fuel representative of the aromatic moieties in coal and biomass fuels; 1,3-butadiene, a major product of biomass pyrolysis; and with catechol and 1,3-butadiene together (in a catechol-to-1,3-butadiene molar ratio of 0.83). No PAH of ?3 rings are produced at temperatures <700 °C, but PAH production becomes significant at temperatures ?800 °C. Analysis of the higher-temperature reaction products by high-pressure liquid chromatography with diode-array ultraviolet-visible absorbance detection has led to the identification of over 100 PAH (ranging in size to 10 fused aromatic rings) - 47 of which have never before been reported as products of any phenol-type fuel. Quantification of the product yields shows that a much higher percentage of fed carbon is converted to PAH in the catechol-only pyrolysis experiments than in the 1,3-butadiene-only pyrolysis experiments - a result attributable to catechol’s relatively labile O-H bond and capacity for generating oxygen-containing radicals, which accelerate both fuel conversion and the pyrolysis reactions leading to 1- and 2-ring aromatics and PAH. When the two fuels are co-pyrolyzed, the percentage of the total fed carbon converting to PAH is more than two times higher than the amount calculated for the hypothetical case of the two fuels together behaving as a linear combination of the two fuels individually. This elevated production of PAH from the co-pyrolysis experiments reflects not only the reaction-accelerating role of the oxygen-containing radicals but also the efficacy, as growth agents, of the C₂ - and especially the C₄ - species abundantly present in the catechol/1,3-butadiene co-pyrolysis environment.     

Wall-impinging laminar premixed n-dodecane flames under autoignitive conditions

Laminar one-dimensional (1D) flames in a stagnation flow stabilised at a wall are used to study flame–wall interaction under diesel engine conditions. The thermochemical conditions correspond to that of the Engine Combustion Network (ECN) Spray A reference case. A range of inflow velocities is considered, where the lowest inflow velocity is chosen such that the flame is detached from the inlet. The presence of a wall is shown to have a significant impact on the flame structure and emission formation. The 1D flame and homogeneous reactor results exhibit two distinct reaction zones due to low- and high-temperature chemistry (LTC and HTC, respectively). The burner-stabilised flames are overall dominated by autoignition for all inflow velocities. For the impinging jet flames, the response of the LTC reaction zone follows closely that of the burner-stabilised flames up to relatively high inflow velocities. The HTC reaction zone, however, deviates strongly from the burner-stabilised flames, already at low inflow velocities and quenches at high inflow velocities. A budget analysis revealed a strong contribution from diffusion in the HTC reaction zone, resulting in an increasing importance of deflagrative combustion as opposed to autoignition. This trend was attributed to enhanced strain rates at higher inlet velocity leading to higher gradients. Wall heat transfer was also investigated. The highest wall heat transfer rates were observed for mixtures between $\Phi =1.0$ and $\Phi =1.5$ and for inlet velocities just below the quenching limit. This was attributed jointly to the higher peak product temperatures for these mixtures and to their enhanced resilience to quenching under strain which leads to higher temperature gradients at the wall just before quenching. NO formation was studied. The highest NO formation was observed near $\Phi =1.0,$ though the response to strain rate was different for stoichiometric and rich mixtures, which was attributed to differing NO formation pathways.     

Impact of pressure fluctuations on the dynamics of laminar premixed flames

Thermo-acoustic instabilities are problematic in the design of continuous-combustion propulsion systems such as gas turbine engines, rocket motors, jet engine afterburners, and ramjets. Conceptually, the coupling between acoustics and flame dynamics can be divided into two categories: flame area fluctuations and changes in the local flame speed. The latter can be caused by the thermodynamic fluctuations that accompany an acoustic wave. This coupling is the focus of the present work. In this paper, we are concerned with the dynamics of laminar premixed flames involving large hydrocarbon species. Through high-fidelity numerical simulations, we investigate the flame response for a wide range of fuels and acoustic frequencies. The combustion of hydrogen and methane is considered for verification purposes and as baseline cases for comparison with two large hydrocarbon fuels, n-heptane and n-dodecane. We extract the phase and gain of the unsteady heat release response, which are directly related to the Rayleigh criterion and thus the stability of the system. For all fuels, we observe a local peak in the heat release gain. At high frequencies, we find that the fluctuations of the different species mass fractions decrease with the inverse of the acoustic frequency, leading to chemistry being “frozen” in the high-frequency limit. This allows us to predict the flame behavior directly from the steady-state solution.     

Large scale effects in weakly turbulent premixed flames

In this study we numerically investigate large scale premixed flames in weakly turbulent flow fields. A large scale flame is classified as such based on a reference hydrodynamic lengthscale being larger than a neutral (cutoff) lengthscale for which the hydrodynamic or Darrieus–Landau (DL) instability is balanced by stabilizing diffusive effects. As a result, DL instability can develop for large scale flames and is inhibited otherwise. Direct numerical simulations of both large scale and small scale three-dimensional, weakly turbulent flames are performed at constant Karlovitz and turbulent Reynolds number, using two paradigmatic configurations, namely a statistically planar flame and a slot Bunsen flame. As expected from linear stability analysis, DL instability induces its characteristic cusp-like corrugation only on large scale flames. We therefore observe significant morphological and topological differences as well as DL-enhanced turbulent flame speeds in large scale flames. Furthermore, we investigate issues related to reaction rate modeling in the context of flame surface density closure. Thicker flame brushes are observed for large scale flames resulting in smaller flame surface densities and overall larger wrinkling factors.     

A detailed chemical kinetic reaction mechanism for oxidation of four small alkyl esters in laminar premixed flames

A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate, and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low-pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions for each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.     

Experimental counterflow ignition temperatures and reaction mechanisms of 1,3-butadiene

The ignition temperatures of nitrogen-diluted 1,3-butadiene by heated air in counterflow were experimentally determined for pressures up to 5 atmospheres and pressure-weighted strain rates from 100 to 250 s⁻¹. The experimental data were compared with computational results using the mechanism of Laskin et al. [A. Laskin, H. Wang and C.K. Law, Int. J. Chem. Kinet. 32 (10) (2000) 589-614], showing that while the overall prediction is approximately within the experimental uncertainty, the mechanism over-predicts ignition temperature by about 25-40 K, with the differences becoming larger at high pressure/low temperature region. Sensitivity analyses for the near-ignition states were performed for both reactions and diffusion, which identified the importance of H₂/CO chain reactions, three 1,3-butadiene reaction pathways, and the binary diffusion between 1,3-butadiene and N₂ on ignition. The detailed mechanism, consisting of 94 species and 614 reactions, was then simplified to a skeletal mechanism consisting of 46 species and 297 reactions by using a new reduction algorithm combining directed relation graph and sensitivity analysis. The skeletal mechanism was further simplified to a 30-step reduced mechanism by using computational singular perturbation and quasi-steady-state assumptions. Both the skeletal and reduced mechanisms mimic the performance of the detailed mechanism with good accuracy in both homogeneous and heterogeneous systems.     

The effects of dimethyl ether and ethanol on benzene and soot formation in ethylene nonpremixed flames

Soot volume fractions, C1-C12 hydrocarbon concentrations, and gas temperature were measured in ethylene/air nonpremixed flames with up to 10% dimethyl ether (CH₃OCH₃) or ethanol (CH₃CH₂OH) added to the fuel. The measurement techniques were laser-induced incandescence, photoionization mass spectroscopy, and thermocouples. Oxygenated hydrocarbons have been proposed as soot-reducing fuel additives, and nonpremixed flames are good laboratory-scale models of the fuel-rich reaction zones where soot forms in many full-scale combustion devices. However, addition of both dimethyl ether and ethanol increased the maximum soot volume fractions in the ethylene flames studied here, even though ethylene is a much sootier fuel than either oxygenate. Furthermore, dimethyl ether produced a larger increase in soot even though neat dimethyl ether flames produce less soot than neat ethanol flames. The detailed species measurements suggest that the oxygenates increase soot concentrations because they decompose to methyl radical, which promotes the formation of propargyl radical (C₃H₃) through C1 + C2 addition reactions and consequently the formation of benzene through propargyl self-reaction. Dimethyl ether has a stronger effect than ethanol because it decomposes more completely to methyl radical. Ethylene does not decompose to methyl, so its flames are particularly sensitive to this mechanism; the alkane-based fuels used in most practical fuels do decompose to methyl radical, so the mechanism will be much less important for practical devices.     

TDLAS-based in situ measurement of absolute acetylene concentrations in laminar 2D diffusion flames

We report the first quantitative and calibration-free in situ C₂H₂ measurement in a flame environment using direct Tunable Diode Laser Absorption Spectroscopy(TDLAS). Utilizing a fiber-coupled Distributed Feedback diode laser near 1535 nm we measured spatially resolved, absolute C₂H₂ concentration profiles in a laminar non-premixed CH₄/air flame supported on a modified Wolfhard-Parker slot burner with N₂ purge slots to minimize end flames. We developed a wavelength tuning scheme combining laser temperature and current modulation to record with a single diode laser a mesh of 37 overlapping spectral windows and generate an ∼7 nm (30 cm⁻¹) wide, high-resolution absorption spectrum centered at 1538 nm. Experimental C₂H₂ spectra in a reference cell showed excellent agreement with simulations using HITRAN2004 data. The enhanced wavelength coverage was needed to establish correct C₂H₂ line identification and selection in the very congested high temperature flame spectra and led to the P17e line as the only candidate for in situ detection of C₂H₂ in the flame. We used highly efficient optical disturbance correction algorithms for treating transmission and background emission fluctuations in combination with a multiple Voigt line Levenberg-Marquardt fitting algorithm and Pt/Rh thermocouple measurements to achieve fractional optical resolutions of up to 4 × 10⁻⁵ OD (1σ) in the flame (T up to 2000 K). Temperature dependent C₂H₂ detection limits for the P17e line were 60 to 480 ppm. By translating the burner through the laser beam with a DC motor we obtained spatially resolved, absolute C₂H₂ concentration profiles along the flame sheet with 0.5 mm spatial resolution as measured with a knife edge technique. The TDLAS-based, transverse C₂H₂ concentration profiles without any scaling are in excellent agreement with published mass spectrometric C₂H₂ data for the same flame supported on a similar burner, thus validating our calibration-free TDLAS measurements.     

The effects of burner stabilization on Fenimore NO formation in low-pressure, fuel-rich premixed CH4/O2/N2 flames

We investigate the effects of varying the degree of burner stabilization on Fenimore NO formation in fuel-rich low-pressure flat CH₄/O₂/N₂ flames. Towards this end, axial profiles of flame temperature and OH, NO and CH mole fractions are measured using laser-induced fluorescence (LIF). The experiments are performed at equivalence ratios between 1.3 and 1.5. The flame temperature is seen to decrease by 200-300 K, with a concomitant decrease in OH mole fraction, upon reducing the total flow rate from 5 to 3 L/min, thus increasing stabilization. At equivalence ratios between 1.3 and 1.5, this decrease in flow rate lowers the maximum CH mole fraction by a factor of 2, and the NO mole fraction by ∼40% in all flames studied. Integrating the reaction rate for CH + N₂ to estimate Fenimore NO formation, using the rate coefficient in GRI-Mech 3.0, and the measured temperatures and CH profiles show very good agreement with the measured NO mole fraction for ? = 1.3 and 1.4, supporting the current choice for this rate. This agreement also shows that the increase in residence time caused by increased stabilization is an important factor in the ultimate impact of the changes in CH mole fraction on NO formation. The results at ? = 1.5 suggest that substantial quantities of fixed nitrogen species, e.g., HCN, are only slowly oxidized in the post-flame zone under these conditions, leading to a significant discrepancy between the measured NO mole fraction and that obtained by integrating over the CH profile. Detailed calculations using GRI-Mech 3.0 predict the experimental results at ? = 1.3 nearly quantitatively, but show increasing differences with the measurements for both CH and NO profiles with increasing equivalence ratio.     

An apparatus-independent extinction strain rate in counterflow flames

Resistance to extinction by stretch is a key property of any flame, and recent work has shown that this property controls the overall structure of several important types of turbulent flames. Multiple definitions of the critical strain rate at extinction (ESR) have been presented in the literature. However, even if the same definition is used, different experiments report different extinction strain rates for flames burning the same fuel-air mixture at very similar temperatures using similarly constructed opposed-flow instruments. Here we show that at extinction, all these flames are essentially identical, so one would expect that each would be assigned the same value of a parameter representing its intrinsic resistance-to-stretch-induced-extinction, regardless of the specifics of the experimental apparatus. A similar situation arises in laminar flame speed measurements since different apparatuses could result in different strain rate distributions. In that instance, the community has agreed to report the unstretched laminar flame speed, and methods have been developed to translate the experimental (stretched) flame speed into a universal unstretched laminar flame speed. We propose an analogous method for translating experimental measurements for stretch-induced extinction into an unambiguous and apparatus-independent quantity (ESR_∞) by extrapolating to infinite opposing burner separation distance. The uniqueness of the flame at extinction is shown numerically and supported experimentally for twin premixed, single premixed, and diffusion flames at Lewis numbers greater than and less than one. A method for deriving ESR_∞ from finite-boundary experimental studies is proposed and demonstrated for methane and propane experimental diffusion and premixed single flame data. The two values agree within the range of ESR differences typically observed between experimental measurements and simulation results for the traditional ESR definition.     

Structural response of different Lewis number premixed flames interacting with a toroidal vortex

Simultaneous measurements of temperature, CH* and OH* chemiluminescent species are carried out to explore the impact of stretch rate and curvature on the structure of premixed flames. The configuration of an initially flat premixed flame interacting with a toroidal vortex is selected for the present study and reasons for this choice are discussed. Lewis number effects are assessed by comparing methane and propane flames. It is emphasized that the flame structure experiences very strong variations. In particular, the flame is shrunk (broadened) in the initial (final) period of the interaction with the vortex where strain rate (curvature) contribution of the stretch rate is predominant. By further analysing independently the thickness of the preheat and reaction zones, it is shown that for propane flames, not only the former but also the latter is significantly altered in zones where the flame curvature is negative. Changes in the reaction zone properties are further emphasized using CH* and OH* radicals. It is demonstrated that higher thermal diffusivity plays a significant role around curved regions, in which the enhanced diffusion of heat leads to a strong increase of CH* compared to OH* intensity. As an overall conclusion, this study suggests that it would be interesting to reassess the internal flame structure at lower and moderate Karlovitz numbers since changes might appear for a moderate vortex intensity with typical size much larger than the flame thickness.     

Prediction of electron and ion concentrations in low-pressure premixed acetylene and ethylene flames

Flame stabilisation and extinction in a number of different flows can be affected by application of electric fields. Electrons and ions are present in flames, and because of charge separation, weak electric fields can also be generated even when there is no externally applied electric field. In this work, a numerical model incorporating ambipolar diffusion and plasma kinetics has been developed to predict gas temperature, species, and ion and electron concentrations in laminar premixed flames without applied electric fields. This goal has been achieved by combining the existing CHEMKIN-based PREMIX code with a recently developed methodology for the solution of electron temperature and transport properties that uses a plasma kinetics model and a Boltzmann equation solver. A chemical reaction set has been compiled from seven sources and includes chemiionisation, ion-molecule, and dissociative–recombination reactions. The numerical results from the modified PREMIX code (such as peak number densities of positive ions) display good agreement with previously published experimental data for fuel-rich, non-sooting, low-pressure acetylene and ethylene flames without applied electric fields.     

Simulations and experiments on the ignition probability in turbulent premixed bluff-body flames

The ignition characteristics of a premixed bluff-body burner under lean conditions were investigated experimentally and numerically with a physical model focusing on ignition probability. Visualisation of the flame with a 5 kHz OH* chemiluminescence camera confirmed that successful ignitions were those associated with the movement of the kernel upstream, consistent with previous work on non-premixed systems. Performing many separate ignition trials at the same spark position and flow conditions resulted in a quantification of the ignition probability P_ign, which was found to decrease with increasing distance downstream of the bluff body and a decrease in equivalence ratio. Flows corresponding to flames close to the blow-off limit could not be ignited, although such flames were stable if reached from a richer already ignited condition. A detailed comparison with the local Karlovitz number and the mean velocity showed that regions of high P_ign are associated with low Ka and negative bulk velocity (i.e. towards the bluff body), although a direct correlation was not possible. A modelling effort that takes convection and localised flame quenching into account by tracking stochastic virtual flame particles, previously validated for non-premixed and spray ignition, was used to estimate the ignition probability. The applicability of this approach to premixed flows was first evaluated by investigating the model's flame propagation mechanism in a uniform turbulence field, which showed that the model reproduces the bending behaviour of the S_T-versus-u′ curve. Then ignition simulations of the bluff-body burner were carried out. The ignition probability map was computed and it was found that the model reproduces all main trends found in the experimental study.     

Stabilization mechanism of turbulent premixed flames in strongly swirled flows

The stabilization of turbulent premixed flames in strongly swirled flows undergoing vortex breakdown is studied in the case of the ALSTOM En-Vironmental (EV) double cone burner using a simple one-dimensional boundary layer type model and computational fluid dynamics, mainly at the level of large-eddy simulation. The analysis shows that, due to flame curvature effects, the flame speed on the combustor axis is 2 D _t/R _F lower than the turbulent burning rate, where D _t is a characteristic turbulent diffusion coefficient and R _F the flame radius of curvature. Flame propagation with negative speed observed in the experiments, i.e. the flame completely embedded in the central recirculation zone on the symmetry axis, is explained with the one-dimensional model as caused by the factor 2 D _t/R _F being larger than the characteristic turbulent burning rate. A peculiar sudden displacement of the flame anchoring location deep into the burner, which takes place experimentally at a critical value of the equivalence ratio, cannot however be explained with the present one-dimensional approach due to the modelling assumptions. The mathematical analysis is supported in this case with large-eddy simulation which can accurately reproduce the flame behaviour across the full operating range. It is finally shown that steady RANS methods cannot cope with the problem due to their inability to correctly predict the velocity flowfield in this burner.     

Benzene precursors and formation routes in a stoichiometric cyclohexane flame

Benzene formation was found to be dominated by stepwise radical dehydrogenation of cyclohexane in a stoichiometric flat flame of cyclohexane/O₂/32.5% Ar, 30.00 Torr pressure, and 35.0 cm s⁻¹ feed velocity. This route, involving H-abstractions and β-scissions, is in contrast to conventional propargyl routes. Three types of analyses lead to this conclusion: identification of key flame species by mass and ionization energy; measurement and use of mole-fraction profiles in the flat flame; and mechanistic reactive-flow modeling of the flame, interpreted by analyzing the dominant reaction steps giving rise to the prediction. For relevant species, profiles of mole fraction were mapped by molecular-beam mass spectrometry in separate apparatuses with identical burners using electron ionization (UMass Amherst) and synchrotron VUV photoionization (LBNL ALS), respectively. In the latter, recently developed apparatus, ionization energies can be measured with greatly enhanced resolution, yielding improvements in species identification that include precise resolution of hydrocarbon isomers, crucial to the findings of this study.     

Hyperacceleration effects on turbulent combustion in premixed step-stabilized flames

Experimental results are presented from an investigation of the effects of large transverse accelerations on flame propagation and blowout limits in premixed step-stabilized flames. The accelerations, which exceed ±10,000 g in the present study, induce large body forces on the high-density reactants and low-density products. These body forces can substantially alter the flame propagation mechanisms and dramatically increase the flame blowout limits. Sustained centripetal accelerations a_c ≡ U²/R are created by flowing a premixed propane–air reactant stream with equivalence ratios 0.7  Φ  1.9 at various speeds U through a semicircular channel with radius R. A backward-facing step of height h on the radially outer (a_c > 0) or inner (a_c < 0) wall stabilizes the flame. For a_c > 0 the acceleration acts to force high-density reactants into the recirculation zone and low-density products into the reactant stream, while a_c < 0 forces hot products into the recirculation zone and impedes cold reactants from entering this zone. An otherwise identical straight channel provides corresponding baseline (a_c = 0) results for comparison. The flow speed U, equivalence ratio Φ, and step height h are systematically varied for a_c = 0, a_c > 0, and a_c < 0. Shadowgraph and chemiluminescence imaging show that as a_c→ +∞ the propagation of the flame across the channel becomes independent of the flame burning velocity and instead is primarily due to large-scale “centrifugal pumping” driven by the induced body forces. For a_c → −∞ the body forces effectively segregate reactants and products to produce a nearly flat flame. In both cases, for large |a_c| values the resulting blowout limits can be substantially higher than those at a_c = 0.     

Gas-phase Raman spectra of hot bands of fundamentals and combinations associated with the torsional vibration of s-trans-1,3-butadiene and its deuterated isotopologues

The gas-phase Raman spectra of 1,3-butadiene and its 2,3-d₂, 1,1,4,4-d₄, and d₆ isotopologues have been recorded with high sensitivity and resolution of 0.7 cm⁻¹. Hot band series of fundamentals and combinations involving the ν₁₃ torsional vibration of the s-trans rotamer have been observed for each of the isotopologues. Modes studied were ν₁₀ (CH wag), ν₁₂ (CH₂ twist), ν₁₀ + ν₁₂, ν₁₅ (CH₂ wag) + ν₁₆ (CH₂ twist), and ν₂₃ (CH₂ rock) + ν₂₄ (CCC deformation). The spacings of the quantum states of the torsional contribution were found to decrease with additional excitation of this mode (ν₁₃) in the upper vibrational states except for the ν₂₃ + ν₂₄ combination state.     

1,3-丁二烯掺混丙炔热解中芳烃生成的协同效应理论研究

A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation.A detailed kinetic model of 1,3-butadiene/propyne co-pyrolysis with the sub-mechanism of aromatic hydrocarbon formation is developed and validated on previous 1,3-butadiene and propyne pyrolysis experiments.The model is able to reproduce both the single component pyrolysis and the co-pyrolysis experiments,as well as the synergistic effect between 1,3-butadiene and propyne on the formation of a series of aromatic hydrocarbons.Based on the rate of production and sensitivity analyses,key reaction pathways in the fuel decomposition and aromatic hydrocarbon formation processes are revealed and insight into the synergistic effect on aromatic hydrocarbon formation is also achieved.The synergistic effect results from the interaction between 1,3-butadiene and propyne.The easily happened chain initiation in the 1,3-butadiene decomposition provides an abundant radical pool for propyne to undergo the H-atom abstraction and produce propargyl radical which plays key roles in the formation of aromatic hydrocarbons.Besides,the 1,3-butadiene/propyne co-pyrolysis includes high concentration levels of C3 and C4 precursors simultaneously,which stimulates the formation of key aromatic hydrocarbons such as toluene and naphthalene.