A comparative experimental and computational study of methanol, ethanol, and n-butanol flames

Laminar flame speeds and extinction strain rates of premixed methanol, ethanol, and n-butanol flames were determined experimentally in the counterflow configuration at atmospheric pressure and elevated unburned mixture temperatures. Additional measurements were conducted also to determine the laminar flame speeds of their n-alkane/air counterparts, namely methane, ethane, and n-butane in order to compare the effect of alkane and alcohol molecular structures on high-temperature flame kinetics. For both propagation and extinction experiments the flow velocities were determined using the digital particle image velocimetry method. Laminar flame speeds were derived through a non-linear extrapolation approach based on direct numerical simulations of the experiments. Two recently developed detailed kinetics models of n-butanol oxidation were used to simulate the experiments. The experimental results revealed that laminar flame speeds of ethanol/air and n-butanol/air flames are similar to those of their n-alkane/air counterparts, and that methane/air flames have consistently lower laminar flame speeds than methanol/air flames. The laminar flame speeds of methanol/air flames are considerably higher compared to both ethanol/air and n-butanol/air flames under fuel-rich conditions. Numerical simulations of n-butanol/air freely propagating flames, revealed discrepancies between the two kinetic models regarding the consumption pathways of n-butanol and its intermediates.     

Extinction of premixed H2/air flames: Chemical kinetics and molecular diffusion effects

Laminar flame speed has traditionally been used for the partial validation of flame kinetics. In most cases, however, its accurate determination requires extensive data processing and/or extrapolations, thus rendering the measurement of this fundamental flame property indirect. Additionally, the presence of flame front instabilities does not conform to the definition of laminar flame speed. This is the case for Le<1 flames, with the most notable example being ultralean H₂/air flames, which develop cellular structures at low strain rates so that determination of laminar flame speeds for such mixtures is not possible. Thus, this low-temperature regime of H₂ oxidation has not been validated systematically in flames. In the present investigation, an alternative/supplemental approach is proposed that includes the experimental determination of extinction strain rates for these flames, and these rates are compared with the predictions of direct numerical simulations. This approach is meaningful for two reasons: (1) Extinction strain rates can be measured directly, as opposed to laminar flame speeds, and (2) while the unstretched lean H₂/air flames are cellular, the stretched ones are not, thus making comparisons between experiment and simulations meaningful. Such comparisons revealed serious discrepancies between experiments and simulations for ultralean H₂/air flames by using four kinetic mechanisms. Additional studies were conducted for lean and near-stoichiometric H₂/air flames diluted with various amounts of N₂. Similarly to the ultralean flames, significant discrepancies between experimental and predicted extinction strain rates were also found. To identify the possible sources of such discrepancies, the effect of uncertainties on the diffusion coefficients was assessed and an improved treatment of diffusion coefficients was advanced and implemented. Under the conditions considered in this study, the sensitivity of diffusion coefficients to the extinction response was found to be significant and, for certain species, greater than that of the kinetic rate constants.     

A numerical study of laminar flame speed of stratified syngas/air flames

Numerical simulations are performed to study the flame propagation of laminar stratified syngas/air flames with the San Diego mechanism. Effects of fuel stratification, CO/H₂ mole ratio and temperature stratification on flame propagation are investigated through comparing the distribution of flame temperature, heat release rate and radical concentration of stratified flame with corresponding homogeneous flame. For stratified flames with fuel rich-to-lean and temperature high-to-low, the flame speeds are faster than homogeneous flames due to more light H radical in stratified flames burned gas. The flame speed is higher for case with larger stratification gradient. Contrary to positive gradient cases, the flame speeds of stratified flames with fuel lean-to-rich as well as with temperature low-to-high are slower than homogeneous flames. The flame propagation accelerates with increasing hydrogen mole ratio due to higher H radical concentration, which indicates that chemical effect is more significant than thermal effect. Additionally, flame displacement speed does not match laminar flame speed due to the fluid continuity. Laminar flame speed is the superposition of flame displacement speed and flow velocity.     

Reduction of a detailed reaction mechanism for hydrogen combustion under gas turbine conditions

The aim of this study is to find a reduced mechanism that accurately represents chemical kinetics for lean hydrogen combustion at elevated pressures, as present in a typical gas turbine combustor. Calculations of autoignition, extinction, and laminar premixed flames are used to identify the most relevant species and reactions and to compare the results of several reduced mechanisms with those of a detailed reaction mechanism. The investigations show that the species OH and H are generally the radicals with the highest concentrations, followed by the O radical. However, the accumulation of the radical pool in autoignition is dominated by HO₂ for temperatures above, and by H₂O₂ below the crossover temperature. The influence of H₂O₂ reactions is negligible for laminar flames and extinction, but becomes significant for autoignition. At least 11 elementary reactions are necessary for a satisfactory prediction of the processes of ignition, extinction, and laminar flame propagation under gas turbine conditions. A 4-step reduced mechanism using steady-state approximations for HO₂ and H₂O₂ yields good results for laminar flame speed and extinction limits, but fails to predict ignition delay at low temperatures. A further reduction to three steps using a steady-state approximation for O leads to significant errors in the prediction of the laminar flame speed and extinction limit.     

Nonlinear effects in the extraction of laminar flame speeds from expanding spherical flames

Various factors affecting the determination of laminar flames speeds from outwardly propagating spherical flames in a constant-pressure combustion chamber were considered, with emphasis on the nonlinear variation of the stretched flame speed to the flame stretch rate, and the associated need to nonlinearly extrapolate the stretched flame speed to yield an accurate determination of the laminar flame speed and Markstein length. Experiments were conducted for lean and rich n-butane/air flames at initial pressure, demonstrating the complex and nonlinear nature of the dynamics of flame evolution, and the strong influences of the ignition transient and chamber confinement during the initial and final periods of the flame propagation, respectively. These experimental data were analyzed using the nonlinear relation between the stretched flame speed and stretch rate, yielding laminar flame speeds that agree well with data determined from alternate flame configurations. It is further suggested that the fidelity in the extraction of the laminar flame speed from expanding spherical flames can be facilitated by using small ignition energy and a large combustion chamber.     

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.     

Investigation on fuel-rich premixed flames of monocyclic aromatic hydrocarbons: Part I. Intermediate identification and mass spectrometric analysis

Fuel-rich premixed flames of seven monocyclic aromatic hydrocarbons (MAHs) including benzene, toluene, styrene, ethylbenzene, ortho-xylene, meta-xylene, and para-xylene were studied at the pressure of 30 Torr and comparable flame conditions (C/O = 0.68). The measurement of photoionization efficiency (PIE) spectra facilitated the comprehensive identification of combustion intermediates from m/z = 15 to 240, while mass spectrometric analysis was performed to gain insight into the flame chemistry. Features of the sidechain structure in fuel molecule affect the primary decomposition and aromatics growth processes, resulting in different isomeric structures or compositions of some primary products. This effect becomes weaker and weaker as both processes proceed. The results indicate that most intermediates are identical in all flames, leading to similar intermediate pools of these fuels. Consequently the chemical structures of flames fueled by different MAHs are almost identical, subsequent to the initial fuel-specific decomposition and oxidation that produce the primary intermediates. On the other hand, special features of the sidechain structure can affect the concentration levels of PAHs by increasing the concentrations of the key intermediates including the benzyl radical and phenylacetylene. Therefore, the total ion intensities of the PAH intermediates in the flames were observed to increase in the order of: benzene < toluene and styrene < four C₈H₁₀, which implies the same order of the sooting tendency.     

Effects of hydrogen addition on laminar flame speeds of methane,ethane and propane: Experimental and numerical analysis

The main purpose of this study is to investigate the effects of hydrogen addition on the laminar flame speeds of methane, ethane and propane. In this work, a flat flame method was used to measure the laminar flame speed in a counter-flow configuration combined with particle image velocimetry (PIV) system. The results indicate that with the increase of hydrogen amount, the laminar flame speeds of methane, ethane and propane increase linearly approximately. In addition, as hydrogen is increased, the flame speed of methane has the maximum increasing amplitude among them, which indicates that methane is more sensitive to hydrogen addition in flame speed than the other two fuels.Simulation analysis finds that the reaction R1: H + O₂ ? OH + O can promote the flame speeds of these three kinds of gaseous fuel obviously, and with the increase of hydrogen amount, the promoting effect is more obviously. Therefore, the main reason why hydrogen addition could increase flame speed is that the increase of H radical prompts reaction R1 to proceed in the forward direction. Comparing the flames of methane, ethane and propane mixed with hydrogen, it was found that the promotion of reaction R1 to the methane/hydrogen mixtures flame speed is strongest, and its free radicals concentration in flame increase more obviously. Therefore, hydrogen addition has a greater effect on the flame speed of methane than on that of ethane and propane.     

Effects of CO addition on the characteristics of laminar premixed CH4/air opposed-jet flames

The effects of CO addition on the characteristics of premixed CH₄/air opposed-jet flames are investigated experimentally and numerically. Experimental measurements and numerical simulations of the flame front position, temperature, and velocity are performed in stoichiometric CH₄/CO/air opposed-jet flames with various CO contents in the fuel. Thermocouple is used for the determination of flame temperature, velocity measurement is made using particle image velocimetry (PIV), and the flame front position is measured by direct photograph as well as with laser-induced predissociative fluorescence (LIPF) of OH imaging techniques. The laminar burning velocity is calculated using the PREMIX code of Chemkin collection 3.5. The flame structures of the premixed stoichiometric CH₄/CO/air opposed-jet flames are simulated using the OPPDIF package with GRI-Mech 3.0 chemical kinetic mechanisms and detailed transport properties. The measured flame front position, temperature, and velocity of the stoichiometric CH₄/CO/air flames are closely predicted by the numerical calculations. Detailed analysis of the calculated chemical kinetic structures reveals that as the CO content in the fuel is increased from 0% to 80%, CO oxidation (R99) increases significantly and contributes to a significant level of heat-release rate. It is also shown that the laminar burning velocity reaches a maximum value (57.5 cm/s) at the condition of 80% of CO in the fuel. Based on the results of sensitivity analysis, the chemistry of CO consumption shifts to the dry oxidation kinetics when CO content is further increased over 80%. Comparison between the results of computed laminar burning velocity, flame temperature, CO consumption rate, and sensitivity analysis reveals that the effect of CO addition on the laminar burning velocity of the stoichiometric CH₄/CO/air flames is due mostly to the transition of the dominant chemical kinetic steps.     

A chemical kinetic study of tertiary-butanol in a flow reactor and a counterflow diffusion flame

The combustion chemistry of tertiary-butanol is studied experimentally in a high pressure flow reactor and in counterflow diffusion flames. Princeton Variable Pressure Flow Reactor results show that t-butanol does not exhibit low temperature chemistry, and thus has no negative temperature coefficient behavior under the studied conditions. The onset of gas phase chemistry at high pressure occurs at ～780 K. Over the temperature range of 780–950 K, t-butanol primarily reacts through hydrogen abstraction ? alkyl or alkoxy radical beta-scission pathways to form methyl and propen-2-ol, which likely tautomerizes in the sampling system to form acetone. A species sampling study of a t-butanol counterflow diffusion flame reveals that the high temperature consumption routes of t-butanol lead to the stable intermediates isobutene, acetone, and methane, with isobutene existing in the highest concentrations. The extinction limits of t-butanol, isobutene, acetone, and methane diffusion flames are also reported. On a transport-weighted enthalpy basis, t-butanol extinguishes more readily than any of its primary intermediates, signifying that it is kinetically less resistant to extinction than the products of its initial reactions. Numerical simulation of these t-butanol flames reveals that the isobutene and acetone chemistry sub-models significantly affect the computed extinction limits. Improvement in the current understanding of isobutene oxidation kinetics, in particular, appears necessary to developing reliable kinetic models for t-butanol combustion.     

Effects of fuel branching on the propagation of octane isomers flames

Laminar flame speeds of mixtures of air with 3-methylheptane/air, 2,5-dimethylhexane/air, and iso-octane/air, were determined for a wide range of equivalence ratios in the counterflow configuration at atmospheric pressure, and an unburned mixture temperature of 353 K. The results were compared against those obtained in recent investigations for n-octane/air and 2-methylheptane/air flames. It was determined that n-octane/air flames propagate the fastest, followed by 2- and 3-methylheptane/air, 2,5-dimethylhexane/air, and iso-octane/air flames, confirming that the overall reactivity decreases as the extent of fuel branching increases. The experimental data were modeled using a combination of recently developed kinetic models. Detailed sensitivity and reaction path analyses were performed in order to provide further insight into the high temperature oxidation chemistry of the octane isomers. It was determined that for all octane isomers, flame propagation is largely sensitive to H₂/CO and C₁C₄ kinetics, while the effects of fuel-related reactions were found to be minor. Additionally, the analysis of the computed flame structures revealed that the low reactivity of branched isomers could be attributed to the production of unreactive, H-scavenging, resonantly stabilized intermediates such as propene, allyl, and iso-butene. Although fuel specific reactions do not exert a first order effect on flame propagation, the products of the initial fuel decomposition affect the concentrations of C₁C₄ intermediates, whose subsequent reactions are responsible for the observed differences in the overall flame reactivity among all isomers.     

Computational diagnostics for n-heptane flames with chemical explosive mode analysis

Computational flame diagnostics (CFLDs) are systematic tools to extract important information from simulated flames, particularly when detailed chemical kinetic mechanisms are involved. The results of CFLD can be employed for various purposes, e.g. to simplify detailed chemical kinetics for more efficient flame simulations, and to explain flame behaviors associated with complex chemical kinetics. In the present study, the utility of a recently developed method of chemical explosive mode analysis (CEMA) for CFLD will be demonstrated with a variety of flames for n-heptane including auto-ignition, ignition and extinction in steady state perfectly stirred reactors (PSRs) and laminar premixed flames. CEMA was further utilized for analyses and visualization of a direct numerical simulation (DNS) dataset for a 2-D n-heptane–air flame under homogeneous charge compression ignition (HCCI) conditions. CEMA was found to be a versatile method for systematic detection of many critical flame features including ignition, extinction, premixed flame fronts, and flame stabilization mechanisms. The effects of cool flame chemistry for n-heptane on ignition, extinction and flame stability were also investigated with CEMA.     

Effect of the composition of the hot product stream in the quasi-steady extinction of strained premixed flames

The extinction of premixed CH₄/O₂/N₂ flames counterflowing against a jet of combustion products in chemical equilibrium was investigated numerically using detailed chemistry and transport mechanisms. Such a problem is of relevance to combustion systems with non-homogeneous air/fuel mixtures or recirculation of the burnt gases. Contrary to similar studies that were focused on heat loss/gain, depending on the degree of non-adiabaticity of the system, the emphasis here was on the yet unexplored role of the composition of counterflowing burnt gases in the extinction of lean-to-stoichiometric premixed flames. For a given temperature of the counterflowing products of combustion, it was found that the decrease of heat release with increase in strain rate could be either monotonic or non-monotonic, depending on the equivalence ratio φ_b of the flame feeding the hot combustion product stream. Two distinct extinction modes were observed: an abrupt one, when the hot counterflowing stream consists of either inert gas or equilibrium products of a stoichiometric premixed flame, and a smooth extinction, when there is an excess of oxidizing species in the combustion product stream. In the latter case four burning regimes can be distinguished as the strain rate is progressively increased while the heat release decreases smoothly: an adiabatic propagating flame regime, a non-adiabatic propagating flame regime, the so-called partially-extinguished flame regime, in which the location of the peak of heat release crosses the stagnation plane, and a frozen flow regime. The flame structure was analyzed in detail in the different burning regimes. Abrupt extinction was attributed to the quenching of the oxidation layer with the entire H-OH-O radical pool being comparably reduced. Under conditions of smooth extinction, the behavior is different and the concentration of the H radical decreases the most with increasing strain rate, whereas OH and O remain comparatively abundant in the oxidation layer. As the profile of the heat release rate thickens, the oxidation layer is quenched and the attack of the fuel relies more heavily on the OH radicals.     

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.     

Molecular transport effects on turbulent flame propagation and structure

Various experimental and DNS data show that premixed combustion is affected by the differences between the coefficients of molecular transport of fuel, oxidant, and heat not only at weak but also at moderate and high turbulence. In particular, turbulent flame speed increases with decreasing the Lewis number of the deficient reactant, the effect being very strong for lean hydrogen mixtures. Various concepts; flame instability, flame stretch, local extinction, leading point, that aim at describing the effects of molecular transport on turbulent flame propagation and structure are critically discussed and the results of relevant studies of perturbed laminar flames (unstable flames, flame balls, flames in vortex tubes) are reviewed. The crucial role played by extremely curved laminar flamelets in the propagation of moderately and highly turbulent flames is highlighted and the relevant physical mechanisms are discussed.     

Experimental and kinetic modeling study of PAH formation in methane coflow diffusion flames doped with n-butanol

In order to understand the interactions between butanol and hydrocarbon fuels in the PAH formation, experimental and kinetic modeling investigations were combined to study methane laminar coflow diffusion flames doped with two inlet mole fractions of n-butanol (1.95% and 3.90%) in this work. Mole fractions of flame species along the flame centerline were measured using synchrotron VUV photoionization mass spectrometry. A detailed kinetic model of n-butanol combustion, extended from a recent published n-butanol model, was provided in this work to reproduce the fuel decomposition and the formation of benzene and PAHs in the investigated flames. Numerical simulations were performed with laminarSMOKE code, a CFD code specifically conceived to handle large kinetic mechanisms. The simulation results were able to follow the observed effects of n-butanol addition from the experimental results. In particular, unsaturated hydrocarbons, especially C6–C16 aromatics, were predicted satisfactorily. The reaction flux analysis revealed that benzene precursors, especially C3 radicals, increase significantly with increasing inlet mole fraction of n-butanol. This enhances the formation of phenyl and benzyl radicals, which are important PAH precursors. Reactions of benzyl, phenyl radicals and benzene with C2–C3 species are the major formation pathways for indene and naphthalene. And PAHs with more carbon atoms are dominantly formed from naphthyl and indenyl radicals.     

Investigating the role of methane on the growth of aromatic hydrocarbons and soot in fundamental combustion processes

Experimental results are presented on the effect of methane content in a non-aromatic fuel mixture on the formation of aromatic hydrocarbons and soot in various fundamental combustion configurations. The systems considered consist of a laminar flow reactor, a laminar co-flow diffusion flame burner, and a laminar, premixed flame burner, all of which operate at atmospheric pressure. In the flow reactor, the experiments are performed at 1430 K, constant C-atom flow rates, 98% nitrogen dilution, C/O ratio = 2, and with fuel mixtures consisting of ethylene and methane. The diffusion flames are performed with fuel mixtures of methane and ethylene diluted in nitrogen to maintain a constant adiabatic flame temperature. The premixed flame experiments are performed with n-heptane and methane mixtures at a C/O ratio = 0.67 with nitrogen-impoverished air. The results show the existence of synergistic chemical effects between methane and other alkanes in the production of aromatics, despite reduced acetylene concentrations. This effect is attributable to the ability of methane to enhance the production of methyl radicals that will then promote production channels of aromatics that rely on odd-carbon-numbered species. Benzene, naphthalene, and pyrene show the strongest sensitivity to the presence of added methane. This synergy on aromatics trickles down to soot via enhanced inception and surface growth rates by polycyclic aromatic hydrocarbon condensation, but the overall effects on soot volume-fraction are smaller due to a compensating reduction in surface growth from acetylene. These results are observed under the very fuel-rich environments existing in the flow reactor and diffusion flames. In the premixed flames, however, instabilities did not permit investigation of conditions with sufficiently high equivalence ratios to perturb the aromatic and soot-growth regions.