Experimental and modeling studies of C2H4/O2/Ar, C2H4/methylal/O2/Ar and C2H4/ethylal/O2/Ar rich flames and the effect of oxygenated additives

The addition of dimethoxymethane (DMM or methylal) and diethoxymethane (DEM or ethylal) to a rich ethylene/oxygen/argon flame has been investigated by measuring the depletion of soot precursors. Three rich premixed ethylene/oxygen/argon (with and without added methylal or ethylal) flat flames have been stabilized at low-pressure (50 mbar) on a Spalding–Botha type burner with the same equivalence ratio of 2.50. Identification and monitoring of signal intensity profiles of species within the flames have been carried out by using molecular beam mass spectrometry (M.B.M.S.). The replacement of some C₂H₄ by C₃H₈O₂ or C₅H₁₂O₂ is responsible for a decrease of the maximum mole fractions of the detected intermediate species. This phenomenon is noticeable for C₂–C₄ intermediates and becomes more effective for C₅–C₁₀ species, mainly when C₃H₈O₂ added.A new kinetic model has been elaborated and contains 546 reactions and 107 chemical species in order to simulate the three investigated flames: C₂H₄/O₂/Ar, C₂H₄/DMM/O₂/Ar and C₂H₄/DEM/O₂/Ar. The reaction mechanism well reproduces experimental mole fraction profiles of major and intermediate species, and underlines the effect of methylal and ethylal addition on species concentration profiles for these flames.     

Flame propagation enhancement by plasma excitation of oxygen. Part I: Effects of O3

The thermal and kinetic effects of O₃ on flame propagation were investigated experimentally and numerically by using C₃H₈/O₂/N₂ laminar lifted flames. Ozone produced by a dielectric barrier plasma discharge was isolated and measured quantitatively by using absorption spectroscopy. Significant kinetic enhancement by O₃ was observed by comparing flame stabilization locations with and without O₃ production. Experiments at atmospheric pressures showed an 8% enhancement in the flame propagation speed for 1260 ppm of O₃ addition to the O₂/N₂ oxidizer. Numerical simulations showed that the O₃ decomposition and reaction with H early in the pre-heat zone of the flame produced O and OH, respectively, from which the O reacted rapidly with C₃H₈ and produced additional OH. The subsequent reaction of OH with the fuel and fuel fragments, such as CH₂O, provided chemical heat release at lower temperatures to enhance the flame propagation speed. It was shown that the kinetic effect on flame propagation enhancement by O₃ reaching the pre-heat zone of the flame for early oxidation of fuel was much greater than that by the thermal effect from the energy contained within O₃. For non-premixed laminar lifted flames, the kinetic enhancement by O₃ also induced changes to the hydrodynamics at the flame front which provided additional enhancement of the flame propagation speed. The present results will have a direct impact on the development of detailed plasma-flame kinetic mechanisms and provided a foundation for the study of combustion enhancement by O₂(a¹Δ_g) in part II of this investigation.     

Flame propagation enhancement by plasma excitation of oxygen. Part II: Effects of O2(aΔg)

The isolated effect of O₂(a¹Δ_g) on the propagation of C₂H₄ lifted flames was studied at reduced pressures (3.61 kPa and 6.73 kPa). The O₂(a¹Δ_g) was produced in a microwave discharge plasma and was isolated from O and O₃ by NO addition to the plasma afterglow in a flow residence time on the order of 1 s. The concentrations of O₂(a¹Δ_g) and O₃ were measured quantitatively through absorption by sensitive off-axis integrated-cavity-output spectroscopy and one-pass line-of-sight absorption, respectively. Under these conditions, it was found that O₂(a¹Δ_g) enhanced the propagation speed of C₂H₄ lifted flames. Comparison with the results of enhancement by O₃ found in part I of this investigation provided an estimation of 2-3% of flame speed enhancement for 5500 ppm of O₂(a¹Δ_g) addition from the plasma. Numerical simulation results using the current kinetic model of O₂(a¹Δ_g) over-predicts the flame propagation enhancement found in the experiments. However, the inclusion of collisional quenching rate estimations of O₂(a¹Δ_g) by C₂H₄ mitigated the over-prediction. The present isolated experimental results of the enhancement of a hydrocarbon fueled flame by O₂(a¹Δ_g), along with kinetic modeling results suggest that further studies of C_nH_m + O₂(a¹Δ_g) collisional and reactive quenching are required in order to correctly predict combustion enhancement by O₂(a¹Δ_g). The present experimental results will have a direct impact on the development of elementary reaction rates with O₂(a¹Δ_g) at flame conditions to establish detailed plasma-flame kinetic mechanisms.     

Comprehensive chemical kinetic modeling of the oxidation of 2-methylalkanes from C7 to C20

Conventional petroleum jet and diesel fuels, as well as alternative Fischer–Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed and reduced chemical kinetic mechanism for singly methylated iso-alkanes (i.e., 2-methylalkanes) ranging from C₇ to C₂₀. The mechanism also includes an updated version of our previously published C₈–C₁₆n-alkanes model. The complete detailed mechanism contains approximately 7200 species 31400 reactions. The proposed model is validated against new experimental data from a variety of fundamental combustion devices including premixed and non-premixed flames, perfectly stirred reactors and shock tubes. This new model is used to show how the presence of a methyl branch affects important combustion properties such as laminar flame propagation, ignition, and species formation.     

Experimental and numerical study of the role of NCN in prompt-NO formation in low-pressure CH4-O2-N2 and C2H2-O2-N2 flames

We report an experimental and modeling study on prompt-NO formation in low-pressure (5.3 kPa) premixed flames. Special emphasis is given to the quantitative detection (and prediction) of NCN, whose role in prompt-NO formation has recently been confirmed in alkane flames. Here a rich (Φ = 1.25) CH₄-O₂-N₂ flame and rich (Φ = 1.25) and stoichiometric C₂H₂-O₂-N₂ flames have been investigated. Absolute concentration profiles of CH and NCN radicals and NO species are obtained by combining laser-induced fluorescence (LIF) and cavity ring-down spectroscopy (CRDS). Temperature profile is determined in each flame using OH and NO-LIF thermometry. Flame modeling is performed to determine the role of NCN in prompt-NO formation and to test the capacity of the present chemical mechanisms to predict some intermediate species involved in prompt-NO formation. The methane flame is modeled using GDFkin®3.0_NCN mechanism [El Bakali et al., Fuel 85 (2006), 896-909]. The acetylene flames are modeled using the Lindstedt and Skevis C/H/O mechanism [Lindstedt and Skevis, Proc. Combust. Inst. 28 (2000), 1801-1807], completed by the submechanism issued from GDFkin®3.0_NCN for nitrogen chemistry. This submechanism includes the initiation reaction CH + N₂ = NCN + H. Rate constants of NO-sensitive reactions of the submechanism are modified by taking into account the recent literature. In particular, the C₂O route could be explored thanks to a significant presence of C₂O in acetylene flames. Globally, the modified submechanism of nitrogen chemistry coupled with the two hydrocarbon mechanisms leads to a satisfying prediction of NCN and NO mole fraction profiles, even though refinements of rate constant determination is still required. The role of NCN in prompt-NO formation in acetylene flames is demonstrated.     

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.     

An experimental and numerical study on characteristics of laminar premixed H2/CO/CH4/air flames

The effects of variations in the fuel composition on the characteristics of H₂/CO/CH₄/air flames of gasified biomass are investigated experimentally and numerically. Experimental measurements and numerical simulations of the flame front position and temperature are performed in the premixed stoichiometric H₂/CO/CH₄/air opposed-jet flames with various H₂ and CO contents in the fuel. The adiabatic flame temperatures and laminar burning velocities are calculated using the EQUIL and PREMIX codes of Chemkin collection 3.5, respectively. Whereas the flame structures of the laminar premixed stoichiometric H₂/CO/CH₄/air opposed-jet flames are simulated using the OPPDIF package with the GRI-Mech 3.0 chemical kinetic mechanisms and detailed transport properties. The measured flame front position and temperature of the stoichiometric H₂/CO/CH₄/air opposed-jet flames are closely predicted by the numerical calculations. Detailed analysis of the calculated chemical kinetic structures reveals that the reaction rate of reactions (R38), (R46), and (R84) increase with increasing H₂ content in the fuel mixture. It is also found that the increase in the laminar flame speed with H₂ addition is most likely due to an increase in active radicals during combustion (chemical effect), rather than from changes in the adiabatic flame temperature (thermal effect). Chemical kinetic structure and sensitivity analyses indicate that for the stoichiometric H₂/CO/CH₄/air flames with fixed H₂ concentration in the fuel mixture, the reactions (R99) and (R46) play a dominant role in affecting the laminar burning velocity as the CO content in the fuel is increased.     

Burning velocities and kinetics of H2/NF3/N2, CH4/NF3/N2, and C3H8/NF3/N2 flames

The combustion characteristics and reaction mechanism of mixtures containing nitrogen trifluoride (NF₃) were investigated. Burning velocities for H₂/NF₃/N₂, CH₄/NF₃/N₂, and C₃H₈/NF₃/N₂ flames were determined for the first time at various equivalence ratios and N₂ mole fractions. The burning velocities of the latter two flames were similar and showed peaks at equivalence ratios of ∼1.0, while those of the H₂/NF₃/N₂ flames had the pronounced peak at low equivalence ratios where the formation of the wrinkled flames was observed. A detailed kinetic model was constructed to simulate the laminar burning velocities of H₂/NF₃/N₂ and CH₄/NF₃/N₂ flames. The model accurately reproduced the experimental results. Analyses of the reaction mechanism revealed the major reaction pathways that involve the decomposition of NF₃, the oxidation and chain-fluoridation of H₂ and CH₄, and the formation of N₂.     

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.     

Structure of a freely propagating rich CH4/air flame containing triphenylphosphine oxide and hexabromocyclododecane

The chemical and thermal structure of a premixed rich CH₄/air/N₂ flame (?=1.18±0.02) that contains either triphenylphosphine oxide [(C₆H₅)₃PO] or hexabromocyclododecane [C₁₂H₁₈Br₆] and that is stabilized on a Mache-Hebra burner was studied experimentally using molecular beam mass spectrometry (MBMS) and the microthermocouple technique. Compounds such as hexabromocyclododecane (HBCD) and triphenylphosphine oxide (TPPO) are representative flame-retardant additives that are added to polymers to reduce the flammability of the base polymer. Both compounds provide flame retardation in the gas phase by the production of active species that effectively scavenge key combustion radicals to shut down the combustion process. The MBMS method was used to determine the concentration profiles of stable and active species directly in the flame, which includes atoms as well as free radicals. Thin thermocouples were employed to determine temperature profiles in a flame stabilized on a Mache-Hebra burner at a pressure of 1 atm. A comparison of the experimental data and simulation results for the flame structure shows that MBMS is suitable for studying the structure of flames that are close to freely propagating conditions. The relative effectiveness of flame inhibition by the compounds tested was estimated from changes in the peak concentrations of H and OH radicals in the flame and from changes in the estimated flame velocity.     

Measurement of propagation speeds in adiabatic flat and cellular premixed flames of C2H6+O2+CO2

Adiabatic burning velocities of premixed flat flames and propagation speeds of adiabatic cellular flames of mixtures of ethane+oxygen+carbon dioxide are reported. The oxygen content O₂/(O₂+CO₂) in the artificial air was varied from 26 to 35%. Nonstretched flames were stabilized on a perforated plate burner at 1 atm. A heat flux method was used to determine burning velocities under conditions when the net heat loss of the flame is zero. Under specific experimental conditions the flames become cellular; this leads to significant modification of the flame propagation speed. Measurements in cellular flames are presented and compared with those for laminar flat flames and also with qualitative predictions of a theoretical model. The onset of cellularity was observed throughout the stoichiometric range of the mixtures studied. Cellularity disappears when the flames become only slightly subadiabatic.     

Chemical effects of added CO2 on the extinction characteristics of H2/CO/CO2 syngas diffusion flames

Chemical effects of added CO₂ on flame extinction characteristics are numerically studied in H₂/CO syngas diffusion flames diluted with CO₂. The two representative syngas flames of 80% H₂ + 20% CO and 20% H₂ + 80% CO are inspected according to the composition of fuel mixture diluted with CO₂ and global strain rate. Particular concerns are focused on impact of chemical effects of added CO₂ on flame extinction characteristics through the comparison of the flame characteristics between well-burning flames far from extinction limit and flames at extinction. It is seen that chemical effects of added CO₂ reduce critical CO₂ mole fraction at flame extinction and thus extinguish the flame at higher flame temperature irrespective of global strain rate. This is attributed by the suppression of the reaction rate of the principal chain branching reaction through the augmented consumption of H-atom from the reaction CO₂ + H→CO + OH. As a result the overall reaction rate decreases. These chemical effects of added CO₂ are similar in both well-burning flames far from extinction limit and flames at extinction. There is a mismatching in the behaviors between critical CO₂ mole fraction and maximum flame temperature at extinction. This anomalous phenomenon is also discussed in detail.     

An experimental and kinetic modeling study of methyl formate low-pressure flames

The oxidation of methyl formate (CH₃OCHO), the simplest methyl ester, is studied in a series of burner-stabilized laminar flames at pressures of 22–30 Torr and equivalence ratios (Φ) from 1.0 to 1.8 for flame conditions of 25–35% fuel. Flame structures are determined by quantitative measurements of species mole fractions with flame-sampling molecular-beam synchrotron photoionization mass spectrometry (PIMS). Methyl formate is observed to be converted to methanol, formaldehyde and methane as major intermediate species of mechanistic relevance. Smaller amounts of ethylene and acetylene are also formed from methyl formate oxidation. Reactant, product and major intermediate species profiles are in good agreement with the computations of a recently developed kinetic model for methyl formate oxidation [S. Dooley, M.P. Burke, M. Chaos, Y. Stein, F.L. Dryer, V.P. Zhukov, O. Finch, J.M. Simmie, H.J. Curran, Int. J. Chem. Kinet. 42 (2010) 527–529] which shows that hydrogen abstraction reactions dominate fuel consumption under the tested flame conditions. Radical–radical reactions are shown to be significant in the formation of a number of small concentration intermediates, including the production of ethyl formate (C₂H₅OCHO), the subsequent decomposition of which is the major source of observed ethylene concentrations. The good agreement of model computations with this set of experimental data provides a further test of the predictive capabilities of the proposed mechanism of methyl formate oxidation. Other salient issues in the development of this model are discussed, including recent controversy regarding the methyl formate decomposition mechanism, and uncertainties in the experimental measurement and modeling of low-pressure flame-sampling experiments. Kinetic model computations show that worst-case disturbances to the measured temperature field, which may be caused by the insertion of the sampling cone into the flame, do not alter mechanistic conclusions provided by the kinetic model. However, such perturbations are shown to be responsible for disparities in species location between measurement and computation.     

Laminar burning velocities and flame instabilities of diluted H2/CO/air mixtures under different hydrogen fractions

An experimental study was conducted using outwardly propagating flame to evaluate the laminar burning velocity and flame intrinsic instability of diluted H₂/CO/air mixtures. The laminar burning velocity of H₂/CO/air mixtures diluted with CO₂ and N₂ was measured at lean equivalence ratios with different dilution fractions and hydrogen fractions at 0.1 MPa; two fitting formulas are proposed to express the laminar burning velocity in our experimental scope. The flame instability was evaluated for diluted H₂/CO/air mixtures under different hydrogen fractions at 0.3 MPa and room temperature. As the H₂ fraction in H₂/CO mixtures was more than 50%, the flame became more unstable with the decrease in equivalence ratio; however, the flame became more stable with the decrease in equivalence ratio when the hydrogen fraction was low. The flame instability of 70%H₂/30%CO premixed flames hardly changed with increasing dilution fraction. However, the flames became more stable with increasing dilution fraction for 30%H₂/70%CO premixed flames. The variation in cellular instability was analyzed, and the effects of hydrogen fraction, equivalence ratio, and dilution fraction on diffusive-thermal and hydrodynamic instabilities were discussed.     

Isomer-specific combustion chemistry in allene and propyne flames

A combined experimental and modeling study is performed to clarify the isomer-specific combustion chemistry in flames fueled by the C₃H₄ isomers allene and propyne. To this end, mole fraction profiles of several flame species in stoichiometric allene (propyne)/O₂/Ar flames are analyzed by means of a chemical kinetic model. The premixed flames are stabilized on a flat-flame burner under a reduced pressure of 25 Torr (=33.3 mbar). Quantitative species profiles are determined by flame-sampling molecular-beam mass spectrometry, and the isomer-specific flame compositions are unraveled by employing photoionization with tunable vacuum-ultraviolet synchrotron radiation. The temperature profiles are measured by OH laser-induced fluorescence. Experimental and modeled mole fraction profiles of selected flame species are discussed with respect to the isomer-specific combustion chemistry in both flames. The emphasis is put on main reaction pathways of fuel consumption, of allene and propyne isomerization, and of isomer-specific formation of C₆ aromatic species. The present model includes the latest theoretical rate coefficients for reactions on a C₃H₅ potential [J.A. Miller, J.P. Senosiain, S.J. Klippenstein, Y. Georgievskii, J. Phys. Chem. A 112 (2008) 9429-9438] and for the propargyl recombination reactions [Y. Georgievskii, S.J. Klippenstein, J.A. Miller, Phys. Chem. Chem. Phys. 9 (2007) 4259-4268]. Larger peak mole fractions of propargyl, allyl, and benzene are observed in the allene flame than in the propyne flame. In these flames virtually all of the benzene is formed by the propargyl recombination reaction.     

Flame front structure of turbulent premixed flames of syngas oxyfuel mixtures

In order to investigate oxyfuel combustion characteristics of typical composition of coal gasification syngas connected to CCS systems. Instantaneous flame front structure of turbulent premixed flames of CO/H₂/O₂/CO₂ mixtures which represent syngas oxyfuel combustion was quantitatively studied comparing with CH₄/air and syngas/air flames by using a nozzle-type Bunsen burner. Hot-wire anemometer and OH-PLIF were used to measure the turbulent flow and detect the instantaneous flame front structure, respectively. Image processing and statistical analyzing were performed using the Matlab Software. Flame surface density, mean progress variable, local curvature radius, mean flame volume, and flame thickness, were obtained. Results show that turbulent premixed flames of syngas possess wrinkled flame front structure which is a general feature of turbulent premixed flames. Flame surface density for the CO/H₂/O₂/CO₂ flame is much larger than that of CO/H₂/O₂/air and CH₄/air flames. This is mainly caused by the smaller flame intrinsic instability scale, which would lead to smaller scales and less flame passivity response to turbulence presented by Markstain length, which reduce the local flame stretch against turbulence vortex. Peak value of Possibility Density Function (PDF) distribution of local curvature radius, R, for CO/H₂/O₂/CO₂ flames is larger than those of CO/H₂/O₂/air and CH₄/air flames at both positive and negative side and the corresponding R of absolute peak PDF is the smallest. This demonstrates that the most frequent scale is the smallest for CO/H₂/O₂/CO₂ flames. Mean flame volume of CO/H₂/O₂/CO₂ flame is smaller than that of CH₄/air flame even smaller than that of CO/H₂/O₂/air flame. This would be due to the lower flame height and smaller flame wrinkles.     

Onset of cellular instability in adiabatic H2/O2/N2 premixed flames anchored to a flat-flame heat-flux burner

The onset of cellular instability in adiabatic H₂/O₂/N₂ premixed flames anchored to a heat-flux burner is investigated numerically. Both hydrodynamic instability and diffusional-thermal instability are shown to play an important role in the onset of cellular flames. The burner can effectively suppress cellular instability when the flames are close to the burner, otherwise the burner can suppress the instabilities only at large wavenumbers. Because of differential diffusion, local extinction can occur in lean H₂/O₂/N₂ flames. When the flames develop to take on cellular shapes, the surface length, the overall heat release rate and the mean burning velocity are all increased. For near stoichiometric fuel-rich flames the mean burning velocity can increase by as much as 20%–30%. For lean flames with an equivalence ratio of 0.56, the mean burning velocity can be 2–3 times of the burning velocity of the corresponding planar flame.     

Important role of chemical interaction on flame extinction in downstream interaction between stretched premixed H2-air and CO-air flames

Important role of chemical interaction in flame extinction is numerically investigated in downstream interaction among lean (rich) and lean (rich) premixed as well as partially premixed H₂- and CO-air flames. The strain rate varies from 30 to 5917 s⁻¹ until interacting flames cannot be sustained anymore. Flame stability diagrams mapping lower and upper limit fuel concentrations for flame extinction as a function of strain rate are presented. Highly stretched interacting flames are survived only within two islands in the flame stability map where partially premixed mixture consists of rich H₂-air flame, extremely lean CO-air flame, and a diffusion flame. Further increase in strain rate finally converges to two points. It is found that hydrogen penetrated from H₂-air flame (even at lean flame condition) participates in CO oxidation vigorously due to the high diffusivity such that it modifies the slow main reaction route CO + O₂ → CO₂ + O into the fast cyclic reaction route involving CO + OH → CO₂ + H. These chemical interactions force even rich extinction boundaries with deficient reactant Lewis numbers larger than unity to be slanted at high strain rate. Appreciable amount of hydrogen in the side of lean H₂-air flame also oxidizes the CO penetrated from CO-air flame, and this reduces flame speed of the H₂-air flame, leading to flame extinction. At extremely high strain rates, interacting flames are survived only by a partially premixed flame such that it consists of a very rich H₂-air flame, an extremely lean CO-air flame, and a diffusion flame. In such a situation, both the weaker H₂- and CO-air flames are parasite on the stronger diffusion flame such that it can lead to flame extinction in the situation of weakening the stronger diffusion flame. Important role of chemical interaction in flame extinction is discussed in detail.     

NOx emission characteristics of partially premixed laminar flames of H2/CO/CO2 mixtures

NO_x emission indices were experimentally measured for partially premixed laminar flames of five different H₂/CO/CO₂ fuels over a wide range of equivalence ratios. Through those fuels, the effects of H₂/CO ratio and CO₂ concentration on NO_x emissions, flame appearance, visible flame height and flame temperature are presented. EINO_x values increase when 1.0 ≤ Φ ≤ 1.6, then remain near the highest value, before decreasing slowly when 3.85 ≤ Φ ≤ ∞. The increase of the CO₂ concentration reduces the EINO_x for the whole range of equivalence ratios, while the increase in the H₂/CO ratio reduces the EINO_x when Φ ≤ 2.0 and is inconsequential for richer mixtures. The variation in flame temperatures approximates EINO_x trends. The variation of flame color from blue to orange when the H₂/CO ratio is increased might be explained by higher CO levels in by-product combustion.     

Study on stretch extinction limits of CH4/CO2 versus high temperature O2/CO2 counterflow non-premixed flames

Extinction limits of counterflow non-premixed flames with normal and high temperature oxidizers were studied experimentally and numerically for development of new-type oxygen-enriched mild combustion furnace. Extinction stretch rates of CH₄/CO₂ (at 300 K) versus O₂/CO₂ flames at oxygen mole fractions of 0.35 and 0.40 and oxidizer temperatures of 300 K, 500 K, 700 K and 1000 K were obtained. Investigation was also conducted for CH₄/N₂ (at 300 K) versus air (O₂/N₂) flames at the same oxidizer temperatures. An effect of radiative heat loss on stretch extinction limits of oxygen-enriched flames and air flames was investigated by computations with optical thin model (OTM) and adiabatic flame model (ADI). The results show influence of radiative heat loss on stretch extinction limits was not significant in relative high fuel mole fraction regions. The extinction curve of the oxygen-enriched flames with oxygen mole fraction of 0.35 was close to that of the air flames at the oxidizer temperature of 300 K. However, the extinction curve of air flames with high temperature oxidizer was comparable with that of oxygen-enriched flames with oxygen mole fraction of 0.40. Scaling analysis based on asymptotic solution of stretch extinction was applied and it was found that stretch extinction limits can be expressed by two terms. The first term is total enthalpy flux of fuel stream based on thermo-physical parameters. The second term is a kinetic term which reflects an effect of the chemical reaction rate on stretch extinction limits. OH radicals which play important roles in chain propagating and main endothermic reactions were used to represent the kinetic term of both oxygen-enriched and air flames. The global rates of OH formation in these two cases were compared to understand the contribution of kinetic term to stretch extinction limits. Variation of extinction curves of oxygen-enriched flames and air flames was well explained by the present scaling analysis. This offers an effective approach to estimate stretch extinction limits of oxygen-enriched flames based on those of air flames at the same oxidizer temperature.