Lean or ultra-lean stretched planar methane/air flames

Lean premixed combustion has potential advantages of reducing pollutants and improving fuel economy. In some lean engine concepts, the fuel is directly injected into the combustion chamber resulting in a distribution of lean fuel/air mixtures. In this case, very lean mixtures can burn when supported by hot products from more strongly burning flames. This study examines the downstream interaction of opposed jets of a lean-limit CH₄/air mixture vs. a lean H₂/air flame. The CH₄ mixtures are near or below the lean flammability limit. The flame composition is measured by laser-induced Raman scattering and is compared to numerical simulations with detailed chemistry and molecular transport including the Soret effect. Several sub-limit lean CH₄/air flames supported by the products from the lean H₂/air flame are studied, and a small amount of CO₂ product (around 1% mole fraction) is formed in a “negative flame speed” flame where the weak CH₄/air mixture diffuses across the stagnation plane into the hot products from the H₂/air flame. Raman scattering measurements of temperature and species concentration are compared to detailed simulations using GRI-3.0, C₁, and C₂ chemical kinetic mechanisms, with good agreement obtained in the lean-limit or sub-limit flames. Stronger self-propagating CH₄/air mixtures result in a much higher concentration of product (around 6% CO₂ mole fraction), and the simulation results are sensitive to the specific chemical mechanism. These model-data comparisons for stronger CH₄/air flames improve when using either the C₂ or the Williams mechanisms.     

Laminar flame propagation of acetone and 2-butanone at normal to high pressures: Insight into fuel molecular structure effects of ketones

This work reports an experimental and kinetic modeling investigation on the laminar flame propagation of acetone and 2-butanone at normal to high pressures. The experiments were performed in a high-pressure constant-volume cylindrical combustion vessel at 1–10 atm, 423 K and equivalence ratios of 0.7–1.5. A kinetic model of acetone and 2-butanone combustion was developed from our recent pentanone model [Li et al., Proc. Combust. Inst. 38 (2021) 2135–2142] and validated against experimental data in this work and in literature. Together with our recently reported data of 3-pentanone, remarkable fuel molecular structure effects were observed in the laminar flame propagation of the three C₃C₅ ketones. The laminar burning velocity increases in the order of acetone, 2-butanone and 3-pentanone, while the pressure effects in laminar burning velocity reduces in the same order. Modeling analysis was performed to provide insight into the key pathways in flames of acetone and 2-butanone. The differences in radical pools are concluded to be responsible for the observed fuel molecular structure effects on laminar burning velocity. The favored formation of methyl in acetone flames inhibits its reactivity and leads to the slowest laminar flame propagation, while the easiest formation of ethyl in 3-pentanone flames results in the highest reactivity and fastest laminar flame propagation. Furthermore, the LBVs of acetone and 3-pentanone exhibit the strongest and weakest pressure effects respectively, which can be attributed to the influence of fuel molecular structures through two crucial pressure-dependent reactions CH₃ + H (+M) = CH₄ (+M) and C₂H₄ + H (+M) = C₂H₅ (+M).     

Spatiotemporal measurements of flame stretch and propagation rates for lean and rich CH4/air premixed flames interacting with a turbulent-wake

A 1.5 m long turbulent-wake combustion vessel with a 0.15 m × 0.15 m cross-sectional area is proposed for spatiotemporal measurements of curvature, strain, dilatation and burning rates along a freely downward-propagating premixed flame interacting with a parallel row of staggered vortex pairs having both compression (negative) and extension (positive) strains simultaneously. The wanted wake is generated by rapidly withdrawing an electrically-controlled, horizontally-oriented sliding plate of 5 mm thickness for flame–wake interactions. Both rich and lean CH₄/air flames at the equivalence ratios  = 1.4 and  = 0.7 with nearly the same laminar burning velocity are studied, where flame–wake interactions and their time-dependent velocity fields are obtained by high-speed, high-resolution DPIV and laser-tomography. Correlations among curvature, strain, stretch, and dilatation rates along wrinkled flame fronts at different times are measured and thus their influences on front propagation rates can be analyzed. It is found that strain-related effects have significant influence on front propagation rates of rich CH₄/air (diffusionally stable) flames even when the curvature weights more in the total stretch than the strain rate does. The local propagation rates along the wrinkled flame front are more intense at negative strain rates corresponding to positive peak dilatation rates but the global propagation rate averaged along the rich flame front remains constant during all period of flame–wake interaction. For lean CH₄/air (diffusionally unstable) flames, the curvature becomes a dominant parameter influencing the structure and propagation of the wrinkled flame front, where both local and global propagation rates increase significantly with time, showing unsteady flame propagation. These experimental results suggest that the theory of laminar flame stretch can be applicable to a more complex flame–wake interaction involving unsteadiness and multitudinous interactions between vortices.     

Flame studies of C2 hydrocarbons

The oxidation characteristics of C₂ hydrocarbons were revisited in flames established in the counterflow configuration. Laminar flame speeds of ethane/air, ethylene/air, and acetylene/oxygen/nitrogen mixtures as well as extinction strain rates of non-premixed ethane/air flames were measured using digital particle image velocimetry. The experiments were modeled using three different kinetic models. While the experimental and computed laminar flame speeds agreed closely for all C₂ hydrocarbons under fuel-lean conditions, notable discrepancies were identified under fuel-rich conditions. Using the computed flame structures, insight was provided into the controlling mechanisms that could be responsible for the observed discrepancies. More specifically, the uncertainties associated with the kinetics of the thermal decomposition of the ethyl radical were found to be a potential source of the observed discrepancies for ethane flames. It was shown also by using alternative rate constants for the ethyl radical decomposition, the rate of flame propagation and the extinction propensity are affected notably. Furthermore, the values of the branching ratio of acetylene consumption reactions involving atomic oxygen were found to have a significant effect on the propagation of rich acetylene flames.     

Framework for simulating stationary spherical flames

Understanding and quantifying the effects of flame stretch rate on the laminar flame speed and flame structure plays an important role from interpreting experimentally-measured laminar burning velocities to characterizing the impact of turbulence on premixed flames. Unfortunately, accounting for these effects often requires an unsteady reacting flow solver and may be computationally expensive. In this work, we propose a mathematical framework to perform simulations of stationary spherical flames. The objective is to maintain the flame at a constant radius (and hence a constant stretch rate) by performing a coordinate change. The governing equations in the new flame-attached frame of reference resemble the original equations for freely-propagating spherical flames. The only difference is the presence of additional source terms whose purpose is to drive the numerical solution to a steady state. These source terms involve one free parameter: the flame stretch rate, which may either be computed in real time or imposed by the user. This parameter controls ultimately the steady state flame radius and the steady state flame speed. That is why, at a given stretch rate, the results of the stationary spherical flame simulations match those of a freely-expanding spherical flame. As an illustration, the dependence of the laminar flame speed on the stretch rate is leveraged to extract Markstein lengths for hydrogen/air mixtures at different equivalence ratios, as well as for hydrocarbon/air mixtures (CH₄ and C₇H₁₆). Numerical predictions are in good agreement with experimental measurements (within experimental uncertainties). Finally, the proposed methodology is implemented in the chemical kinetic software FlameMaster. The use of a dedicated steady-state solver with a non-uniform optimized mesh leads to significant reductions in the computational cost, highlighting that the proposed methodology is ideally suited for other chemical kinetic software such as Chemkin/Premix and Cantera.     

Structure of propagating edge diffusion flames in hydrocarbon fuel jets

Direct numerical simulations with a C₃-chemistry model have been performed to investigate the transient behavior and internal structure of flames propagating in an axisymmetric fuel jet of methane, ethane, ethylene, acetylene, or propane in normal earth gravity (1g) and zero gravity (0g). The fuel issued from a 3-mm-i.d. tube into quasi-quiescent air for a fixed mixing time of 0.3 s before it was ignited along the centerline where the fuel–air mixture was at stoichiometry. The edge of the flame formed a vigorously burning peak reactivity spot, i.e., reaction kernel, and propagated through a flammable mixture layer, leaving behind a trailing diffusion flame. The reaction kernel broadened laterally across the flammable mixture layer and possessed characteristics of premixed flames in the direction of propagation and unique flame structure in the transverse direction. The reaction kernel grew wings on both fuel and air sides to form a triple-flame-like structure, particularly for ethylene and acetylene, whereas for alkanes, the fuel-rich wing tended to merge with the main diffusion flame zone, particularly methane. The topology of edge diffusion flames depend on the properties of fuels, particularly the rich flammability limit, and the mechanistic oxidation pathways. The transit velocity of edge diffusion flames, determined from a time series of calculated temperature field, equaled to the measured laminar flame speed of the stoichiometric fuel–air mixtures, available in the literature, independent of the gravity level.     

Exploring fuel isomeric effects on laminar flame propagation of butylbenzenes at various pressures

This work reports an experimental and kinetic modeling investigation on the laminar flame propagation of three butylbenzene isomers (n-butylbenzene, iso-butylbenzene and tert-butylbenzene)/air mixtures. The experiments were performed in a high-pressure constant-volume cylindrical combustion vessel at the initial temperature of 423 K, initial pressures of 1–10 atm, and equivalence ratios (?) of 0.7–1.5. The laminar burning velocities of butylbenzene/O₂/He mixtures were also measured at 423 K, 10 atm and ? = 1.5 to provide additional experimental data under conditions that the butylbenzene/air experiments are susceptible of cellular instability. Comparison among the laminar burning velocities of butylbenzenes including both the three isomers investigated in this work and sec-butylbenzene investigated in our recent work [Combust. Flame 211 (2020) 18–31] shows remarkable fuel isomeric effects, that is, iso-butylbenzene has the slowest laminar burning velocities, followed by n-butylbenzene and tert-butylbenzene, while sec-butylbenzene has the fastest laminar burning velocities. A kinetic model for butylbenzene combustion was developed to simulate the laminar flame propagation of butylbenzenes. Sensitivity analysis was performed to reveal important reactions in laminar flame propagation of butylbenzenes, including both small species reactions and fuel-specific reactions. Kinetic effects are concluded to result in the different laminar burning velocities of four butylbenzene isomers. Small species reactions control the laminar flame propagation under lean conditions, which results in small differences of laminar burning velocities. Chain termination reactions, especially fuel-specific reactions, have important contributions to inhibit the laminar flame propagation under rich conditions. The structural features of butylbenzene isomers can significantly affect the formation of some crucial radicals such as methyl, cyclopentadienyl and benzyl radicals under rich conditions, which leads to remarkable fuel isomeric effects on their laminar burning velocities, especially at high pressures.     

On laminar premixed flame propagating into autoigniting mixtures under engine-relevant conditions

Usually premixed flame propagation and laminar burning velocity are studied for mixtures at normal or elevated temperatures and pressures, under which the ignition delay time of the premixture is much larger than the flame resistance time. However, in spark-ignition engines and spark-assisted compression ignition engines, the end-gas in the front of premixed flame is at the state that autoignition might happen before the mixture is consumed by the premixed flame. In this study, laminar premixed flames propagating into an autoigniting dimethyl ether/air mixture are simulated considering detailed chemistry and transport. The emphasis is on the laminar burning velocity of autoigniting mixtures under engine-relevant conditions. Two types of premixed flames are considered: one is the premixed planar flame propagating into an autoigniting DME/air without confinement; and the other is premixed spherical flame propagating inside a closed chamber, for which four stages are identified. Due to the confinement, the unburned mixture is compressed to high temperature and pressure close to or under engine-relevant conditions. The laminar burning velocity is determined from the constant-volume propagating spherical flame method as well as PREMIX. The laminar burning velocities of autoigniting DME/air mixture at different temperatures, pressures, and autoignition progresses are obtained. It is shown that the first-stage and second-stage autoignition can significantly accelerate the flame propagation and thereby greatly increase the laminar burning velocity. When the first-stage autoignition occurs in the unburned mixture, the isentropic compression assumption does not hold and thereby the traditional method cannot be used to calculate the laminar burning velocity. A modified method without using the isentropic compression assumption is proposed. It is shown to work well for autoigniting mixtures. Besides, a power law correlation is obtained based on all the laminar burning velocity data. It works well for mixtures before autoignition while improvement is still needed for mixtures after autoignition.     

The Influence of Phosphate on the Determination of Calcium by Flame Methods of Analysis—A New Approach

The depression of the analytical signal of calcium by phosphate ion when using turbulent (H₂/0₂ and H₂/A/entrained air) and laminar (C₂/H₂/air) flames in flame spectro-ietry is studied. Measurements of flame emission of calcium as a function of calcium to phosphate and pyrophosphate molar ratios for various flame heights in both turbulent and laminar flames are made. The phosphate interference when using turbulent flames is shown to be a result of a slow vaporization of the calcium phosphate particles. The phosphate interference when using laminar flames with chamber type aspirators is only important at high calcium and phosphate concentrations. The cause of the interference is probably a result of either slow vaporization of the calcium phosphate particles or a slow rate of change of the orthophosphate to pyrophosphate during the decomposition step.     

Characterization of the effects of pressure and hydrogen concentration on laminar burning velocities of methane–hydrogen–air mixtures

The aim of the present work was to characterize both the effects of pressure and of hydrogen addition on methane/air premixed laminar flames. The experimental setup consists of a spherical combustion chamber coupled to a classical shadowgraphy system. Flame pictures are recorded by a high speed camera. Global equivalence ratios were varied from 0.7 to 1.2 for the initial pressure range from 0.1 to 0.5 MPa. The mole fraction of hydrogen in the methane + hydrogen mixture was varied from 0 to 0.2. Experimental results were compared to calculations using a detailed chemical kinetic scheme (GRIMECH 3.0). First, the results for atmospheric laminar CH₄/air flames were compared to the literature. Very good agreements were obtained both for laminar burning velocities and for burned gas Markstein length. Then, increasing the hydrogen content in the mixture was found to be responsible for an increase in the laminar burning velocity and for a reduction of the flame dependence on stretch. Transport effects, through the reduction of the fuel Lewis number, play a role in reducing the sensitivity of the fundamental flame velocity to the stretch. Finally, when the pressure was increased, the laminar burning velocity decreased for all mixtures. The pressure domain was limited to 0.5 MPa due to the onset of instabilities at pressures above this value.     

Effect of Soret diffusion on lean hydrogen/air flames at normal and elevated pressure and temperature

The influence of Soret diffusion on lean premixed flames propagating in hydrogen/air mixtures is numerically investigated with a detailed chemical and transport models at normal and elevated pressure and temperature. The Soret diffusion influence on the one-dimensional (1D) flame mass burning rate and two-dimensional (2D) flame propagating characteristics is analysed, revealing a strong dependency on flame stretch rate, pressure and temperature. For 1D flames, at normal pressure and temperature, with an increase of Karlovitz number from 0 to 0.4, the mass burning rate is first reduced and then enhanced by Soret diffusion of H₂ while it is reduced by Soret diffusion of H. The influence of Soret diffusion of H₂ is enhanced by pressure and reduced by temperature. On the contrary, the influence of Soret diffusion of H is reduced by pressure and enhanced by temperature. For 2D flames, at normal pressure and temperature, during the early phase of flame evolution, flames with Soret diffusion display more curved flame cells. Pressure enhances this effect, while temperature reduces it. The influence of Soret diffusion of H₂ on the global consumption speed is enhanced at elevated pressure. The influence of Soret diffusion of H on the global consumption speed is enhanced at elevated temperature. The flame evolution is more affected by Soret diffusion in the early phase of propagation than in the long run due to the local enrichment of H₂ caused by flame curvature effects. The present study provides new insights into the Soret diffusion effect on the characteristics of lean hydrogen/air flames at conditions that are relevant to practical applications, e.g. gas engines and turbines.     

The response of turbulent premixed flames to normal acoustic excitation

To model the thermo-acoustic excitation of flames in practical combustion systems, it is necessary to know how a turbulent flame front responds to an incident acoustic wave. This will depend partly on the way in which the burning velocity responds to the wave. In this investigation, the response of CH₄/air and CH₄/H₂/air mixtures has been observed in a novel flame stabilisation configuration, in which the premixture of fuel and air is made to decelerate under controlled conditions in a wide-angle diffuser. Control is provided by an annular wall-jet of air and by turbulence generators at the inlet. Ignition from the outlet of the diffuser allows an approximately flat flame to propagate downwards and stabilise at a height that depends on the turbulent burning velocity. When the flow is excited acoustically, the ensemble-averaged height oscillates. The fluctuations in flow velocity and flame height are monitored by phase-locked particle image velocimetry and OH-planar laser induced fluorescence, respectively. The flame stabilised against a lower incident velocity as the acoustic amplitude increased. In addition, at the lowest frequency of 52 Hz, the fluctuations in turbulent burning velocity (as represented by the displacement speed) were out-of-phase with the acoustic velocity. Thus, the rate of displacement of the flame front relative to the flow slowed as the flow accelerated, and so the flame movement was bigger than it would have been if the burning velocity had not responded to the acoustic fluctuation. With an increase in frequency to 119 Hz, the relative flame movement became even larger, although the phase-difference was reduced, so the effect on burning velocity was less dramatic. The addition of hydrogen to the methane, so as to maintain the laminar burning velocity at a lower equivalence ratio, suppressed the response at low amplitude, but at a higher amplitude, the effect was reversed.     

Laminar flame speed and autoignition characteristics of surrogate jet fuel blended with hydrogen

Hydrogen combustion has emerged as one promising option toward the achievement of carbon-neutral in aviation. In this study, the effects of hydrogen addition on laminar flame speeds, autoignition, and the coupling of autoignition and flame propagation for surrogate jet fuel n-dodecane are numerically investigated at representative engine conditions to elucidate the potential challenges for flame stabilization and the autoignition risks in combustor design. Results show that the normalized flame speed increases almost linearly with hydrogen addition for fuel-lean conditions, while for fuel-rich conditions it increases nonlinearly and can be up to 20. This poses great challenges for avoiding flameholding and flashback, particularly for fuel-rich mixtures. Results further show that flame speed enhancement due to the increased flame temperature can be neglected under fuel-lean conditions, but not for fuel-rich mixtures. For the dependence of ignition delay time on temperature, there exists a unique intersection between pure n-dodecane/air and H₂/air mixtures. Near the intersection temperature, there exists subtle kinetic coupling of the two fuels, leading to different H₂ roles, e.g., accelerator or inhibitor, for the autoignition process of n-dodecane/H₂/air mixtures. With this intersection temperature, the diagram for autoignition risks is constructed, which demonstrates that H₂ acts as an inhibitor under subsonic cruise conditions while either an inhibitor or an accelerator under supersonic cruise conditions depending on the combustor inlet temperature and the amount of hydrogen addition. With the potential coupling of autoignition and flame propagation, the 1-D autoignition-assisted flame calculations show that hydrogen addition can alleviate or even eliminate the two-stage ignition characteristics for pure n-dodecane/air flames. For n-dodecane blended with hydrogen, the autoignition-assisted flame propagation speed, as well as the global transition from flame propagation to autoignition, can still be described by an analytic scaling parameterized by the ignition Damkӧhler number.     

Effects of Soret diffusion on the laminar flame speed and Markstein length of syngas/air mixtures

The effects of Soret diffusion on premixed syngas/air flames at normal and elevated temperatures and pressures are investigated numerically including detailed chemistry and transport. The emphasis is placed on assessing and interpreting the influence of Soret diffusion on the unstretched and stretched laminar flame speed and Markstein length of syngas/air mixtures. The laminar flame speed and Markstein length are obtained by simulating the unstretched planar flame and positively-stretched spherical flame, respectively. The results indicate that at atmospheric pressure the laminar flame speed of syngas/air is mainly reduced by Soret diffusion of H radical while the influence of H₂ Soret diffusion is negligible. This is due to the facts that the main reaction zone and the Soret diffusion for H radical (H₂) are strongly (weakly) coupled, and that Soret diffusion reduces the H concentration in the reaction zone. Because of the enhancement in the Soret diffusion flux of H radical, the influence of Soret diffusion on the laminar burning flux increases with the initial temperature and pressure. Unlike the results at atmospheric pressure, at elevated pressures the laminar flame speed is shown to be affected by the Soret diffusion of H₂ as well as H radical. For stretched spherical flame, it is shown that the Soret diffusion of both H and H₂ should be included so that the stretched flame speed can be accurately predicted. Similar to the laminar flame speed, the Markstein length is also reduced by Soret diffusion. However, the reduction is found to be mainly caused by Soret diffusion of H₂ rather than that of H radical. Moreover, the influence of Soret diffusion on the Markstein length is demonstrated to decrease with the initial temperature and pressure.     

On the mechanism of inhibition of a hydrogen flame by propane

Numerical simulations demonstrated that small additives of propane to rich hydrogen-air mixtures suppress the formation of HO₂ and OH in the low-temperature region of the flame zone, thereby causing a substantial decrease in the laminar flame speed. In the low-and high-temperature regions, propane interacts predominantly with OH and H, respectively. In the flame zone, propane is completely converted to CO, CO₂, CH₄, C₂H₂, H₂, and H₂O, being oxidized concurrently with hydrogen at that.     

Strain rate and fuel composition dependence of chemiluminescent species profiles in non-premixed counterflow flames: comparison with model results

A detailed comparison has been conducted between chemiluminescence (CL) species profiles of OH^?, CH^?, and C₂ ^?, obtained experimentally and from detailed flame kinetics modeling, respectively, of atmospheric pressure non-premixed flames formed in the forward stagnation region of a fuel flow ejected from a porous cylinder and an air counterflow. Both pure methane and mixtures of methane with hydrogen (between 10 and 30 % by volume) were used as fuels. By varying the air-flow velocities methane flames were operated at strain rates between 100 and 350 s^?1, while for methane/hydrogen flames the strain rate was fixed at 200 s^?1. Spatial profiles perpendicular to the flame front were extracted from spectrograms recorded with a spectrometer/CCD camera system and evaluating each spectral band individually. Flame kinetics modeling was accomplished with an in-house chemical mechanism including C₁–C₄ chemistry, as well as elementary steps for the formation, removal, and electronic quenching of all measured active species. In the CH₄/air flames, experiments and model results agree with respect to trends in profile peak intensity and position. For the CH₄/H₂/air flames, with increasing H₂ content in the fuel the experimental CL peak intensities decrease slightly and their peak positions shift towards the fuel side, while for the model the drop in mole fraction is much stronger and the peak positions move closer to the fuel side. For both fuel compositions the modeled profiles peak closer to the fuel side than in the experiments. The discrepancies can only partly be attributed to the limited attainable spatial resolution but may also necessitate revised reaction mechanisms for predicting CL species in this type of flame.     

Laminar flame speed of methane/air stratified flames under elevated temperature and pressure

Flame propagation under mixture stratification is relevant to a wide range of applications including gas turbine combustors and internal combustion engines. One of the local stratification effects is known as the back-support effect, where the laminar flame speed is modified when a premixed flame propagates into gradually richer or leaner mixtures. A majority of previous studies have focused on the propagation of methane/air stratified flames under standard temperature and pressure. However, stratified combustion often occurs under elevated temperature and pressure in practical applications, which may influence the characteristics of the back support effect through modified reaction pathways. This study performs numerical simulations of stratified laminar counterflow flames under an Atmospheric Temperature and Pressure (ATP) condition and an Elevated Temperature and Pressure (ETP) condition and examines the influence of elevated temperature and pressure on the back-support effect. Reaction flow analyses were extensively conducted to elucidate the difference in the primary reaction pathway between the two conditions. When scaled by the stratification Damköhler number, the back-support effect on the rich-to-lean stratified flame is weaker under the ETP condition than the ATP condition in the stoichiometric to lean region. This is due to increased contribution from reactions involved with OH radicals under the ETP condition, which leads to lower H₂ reproduction in the reaction zone than under the ATP condition. The contribution from OH radicals is increased under the ETP condition because the conversion of H into OH is enhanced. These results suggest that the back-support effect may become negligibly small in practical combustors operating under elevated temperature and pressure due to (1) the flame being less sensitive to stratification because of the thinner flame, and (2) the lower H₂ reproduction that deteriorates the radical production that drives the back-support effect.     

Further studies of the reaction kernel structure and stabilization of jet diffusion flames

The structure of axisymmetric laminar jet diffusion flames of ethane, ethylene, acetylene, and propane in quasi-quiescent air has been studied numerically in normal earth gravity (1g) and zero gravity (0g). The time-dependent full Navier–Stokes equations with buoyancy were solved using an implicit, third-order accurate numerical scheme, including a C₃-chemistry model and an optically thin-media radiation model for heat losses. Observations of the flames were also made at the NASA Glenn 2.2-Second Drop Tower. For all cases of the fuels and gravity levels investigated, a peak reactivity spot, i.e., reaction kernel, was formed in the flame base, thereby holding a trailing diffusion flame. The location of the reaction kernel with respect to the burner rim depended inversely on the reaction-kernel reactivity or velocity. In the C₂ and C₃ hydrocarbon flames, the H₂–O₂ chain reactions were important at the reaction kernel, yet the CH₃ + O → CH₂O + H reaction, a dominant contributor to the heat-release rate in methane flames studied previously, did not outweigh other exothermic reactions. Instead of the C₁-route oxidation pathway in methane flames, the C₂ and C₃ hydrocarbon fuels dehydrogenated on the fuel side and acetylene was a major hydrocarbon fragment burning at the reaction kernel. The reaction-kernel correlations between the reactivity (the heat-release or oxygen-consumption rate) and the velocity, obtained previously for methane, were developed further for various fuels in more universal forms using variables related to local Damköhler numbers and Peclet numbers.     

Exploration on laminar flame propagation of 3,3-dimethyl-1-butene, 2,3-dimethyl-1-butene and 2,3-dimethyl-2-butene

Laminar flame propagation of branched hexene isomers/air mixtures including 3,3-dimethyl-1-butene (NEC₆D3), 2,3-dimethyl-1-butene (XC₆D1) and 2,3-dimethyl-2-butene (XC₆D2) was investigated using a high-pressure constant-volume cylindrical combustion vessel at 1–10 atm, 373 K and equivalence ratios of 0.7–1.5. The measured laminar burning velocity (LBV) decreases in the order of NEC₆D3, XC₆D1 and XC₆D2, which indicates distinct fuel molecular structure effects. A kinetic model was constructed and examined using the new experimental data. Modeling analyses were performed to reveal fuel-specific flame chemistry of branched hexene isomers. In the NEC₆D3 and XC₆D1 flames, the allylic CC bond dissociation reaction plays the most crucial role in fuel decomposition under rich conditions, while its dominance is replaced by H-abstraction reactions under lean conditions. The H-abstraction and H-assisted isomerization reactions are concluded to govern fuel consumption in the XC₆D2 flame under all investigated conditions. Both C₀C₃ reactions and fuel-specific reactions are found to be influential to the laminar flame propagation of the three branched hexene isomers. Fuel molecular structure effects were analyzed with special attentions on key intermediates distributions and fuel-specific reactions in all flames. Due to the formation selectivity of key intermediates such as 2-methyl-1,3-butadiene and 2,3-dimethyl-1,3-butadiene, the production of reactive radicals especially H follows the order of NEC₆D3 > XC₆D1 > XC₆D2, which results in the same order of fuel reactivities and LBVs.