Effect of radiation emission and reabsorption on flame temperature and NO formation in H2/CO/air counterflow diffusion flames

The radiation effect on flame temperature and NO emission of H₂-lean (0.2H₂ + 0.8CO) and H₂-rich (0.8H₂ + 0.2CO) syngas/air counterflow diffusion flames was numerically investigated using OPPDIF code incorporated with the optical thin model, statistical narrow band model and adiabatic condition. Firstly, the coupled effect of strain rate and radiation was studied. Disparate tendencies of NO emission with an increasing strain rate between H₂-lean and H₂-rich syngas flames were found at very small strain rate, and the effect of radiation reabsorption on NO formation can be neglected when the strain rate was greater than 100 s^?1 for both H₂-lean and H₂-rich syngas flames. Because the radiation effect is vital to flames with small strain rate, its impact on flame temperature and NO emission was investigated in detail at a strain rate of 10 s^?1. The results indicated that NO formation is more sensitive to radiation reabsorption than flame temperature, especially for the H₂-rich syngas flame. The underlying mechanism was discovered by using reaction pathway analysis. Furthermore, the radiation effect under CO₂ dilution of the syngas fuel was examined. It was demonstrated that the radiation effect on flame temperature became more prominent with the increase of CO₂ concentration for both H₂-lean and H₂-rich syngas. The radiation effect on NO emission increased first and then decreased with an increasing CO₂ content for H₂-lean syngas, whereas for H₂-rich syngas the radiation effect is monotonic.     

Negative pressure dependence of mass burning rates of H2/CO/O2/diluent flames at low flame temperatures

Experimental measurements of burning rates, analysis of the key reactions and kinetic pathways, and modeling studies were performed for H₂/CO/O₂/diluent flames spanning a wide range of conditions: equivalence ratios from 0.85 to 2.5, flame temperatures from 1500 to 1800 K, pressures from 1 to 25 atm, CO fuel fractions from 0 to 0.9, and dilution concentrations of He up to 0.8, Ar up to 0.6, and CO₂ up to 0.4. The experimental data show negative pressure dependence of burning rate at high pressure, low flame temperature conditions for all equivalence ratios and CO fractions as high as 0.5. Dilution with CO₂ was observed to strengthen the pressure and temperature dependence compared to Ar-diluted flames of the same flame temperature. Simulations were performed to extend the experimentally studied conditions to conditions typical of gas turbine combustion in Integrated Gasification Combined Cycle processes, including preheated mixtures and other diluents such as N₂ and H₂O.Substantial differences are observed between literature model predictions and the experimental data as well as among model predictions themselves – up to a factor of three at high pressures. The present findings suggest the need for several rate constant modifications of reactions in the current hydrogen models and raise questions about the sufficiency of the set of hydrogen reactions in most recent hydrogen models to predict high pressure flame conditions relevant to controlling NO_x emissions in gas turbine combustion. For example, the reaction O + OH + M = HO₂ + M is not included in most hydrogen models but is demonstrated here to significantly impact predictions of lean high pressure flames using rates within its uncertainty limits. Further studies are required to reduce uncertainties in third body collision efficiencies for and fall-off behavior of H + O₂(+M) = HO₂(+M) in both pure and mixed bath gases, in rate constants for HO₂ reactions with other radical species at higher temperatures, and in rate constants for reactions such as O + OH + M that become important under the present conditions in order to properly characterize the kinetics and predict global behavior of high-pressure H₂ or H₂/CO flames.     

A computational study of combustion and extinction of opposed-jet syngas diffusion flames

This paper reports a numerical study on the combustion and extinction characteristics of opposed-jet syngas diffusion flames. A model of one-dimensional counterflow syngas diffusion flames was constructed with constant strain rate formulations, which used detailed chemical kinetics and thermal and transport properties with flame radiation calculated by statistic narrowband radiation model. Detailed flame structures, species production rates and net reaction rates of key chemical reaction steps were analyzed. The effects of syngas compositions, dilution gases and pressures on the flame structures and extinction limits of H₂/CO synthetic mixture flames were discussed. Results indicate the flame structures and flame extinction are impacted by the compositions of syngas mixture significantly. From H₂-enriched syngas to CO-enriched syngas fuels, the dominant chain reactions are shifting from OH + H₂→H + H₂O for H₂O production to OH + CO→H + CO₂ for CO₂ production through the key chain-branching reaction of H + O₂→O + OH. Flame temperature increases with increasing hydrogen content and pressure, but the flame thickness is decreased with pressure. Besides, the study of the dilution effects from CO₂, N₂, and H₂O, showed the maximum flame temperature is decreased the most with CO₂ as the dilution gas, while CO-enriched syngas flames with H₂O dilution has highest maximum flame temperature when extinction occurs due to the competitions of chemical effect and radiation effect. Finally, extinction limits were obtained with minimum hydrogen percentage as the index at different pressures, which provides a fundamental understanding of syngas combustion and applications.     

NO mechanisms of syngas MILD combustion diluted with N2, CO2, and H2O

The NO mechanism under the moderate or intense low-oxygen dilution (MILD) combustion of syngas has not been systematically examined. This paper investigates the NO mechanism in the syngas MILD regime under the dilution of N₂, CO₂, and H₂O through counterflow combustion simulation. The syngas reaction mechanism and the counterflow combustion simulation are comprehensively validated under different CO/H₂ ratios and strain rates. The effects of oxygen volume fraction, CO/H₂ ratio, pressure, strain rate, and dilution atmosphere are systematically investigated. For all the MILD cases, the contribution of the prompt and NO-reburning routes to the overall NO emission is less than 0.1% due to the lack of CH₄ in fuel. At atmospheric pressure, the thermal route only accounts for less than 20% of the total NO emission because of the low reaction temperature. Moreover, at atmospheric pressure, the contribution of the NNH route to NO emission is always larger than 55% in the N₂ atmosphere. The N₂O-intermediate route is enhanced in CO₂ and H₂O atmospheres due to the increased third-body effects of CO₂ and H₂O through the reaction N₂ + O (+M) ? N₂O (+M). Especially in the H₂O atmosphere, the N₂O-intermediate route contributes to 60% NO at most. NO production is reduced with increasing CO/H₂ ratio or pressure, mainly due to decreased NO formation from the NNH route. Importantly, a high reaction temperature and low NO emission are simultaneously achieved at high pressure. To minimize NO emission, the reactions should be operated at high values of CO/H₂ ratios (i.e., >4) and pressures (e.g., P > 10 atm), low oxygen volume fractions (e.g., X_O2 < 15%), and using H₂O as a diluent. This study provides a new fundamental understanding of the NO mechanism of syngas MILD combustion in N₂, CO₂, and H₂O atmospheres.     

A detailed numerical study of NOx kinetics in low calorific value H2/CO syngas flames

The present study provides an extensive and detailed numerical analysis of NO_x chemical kinetics in low calorific value H₂/CO syngas flames utilizing predictions by five chemical kinetic mechanisms available out of which four deal with H₂/CO while the fifth mechanism (GRI 3.0) additionally accounts for hydrocarbon chemistry. Comparison of predicted axial NO profiles in premixed flat flames with measurements at 1 bar, 3.05 bar and 9.15 bar shows considerably large quantitative differences among the various mechanisms. However, at each pressure, the quantitative reaction path diagrams show similar NO formation pathways for most of the mechanisms. Interestingly, in counterflow diffusion flames, the quantitative reaction path diagrams and sensitivity analyses using the various mechanisms reveal major differences in the NO formation pathways and reaction rates of important reactions. The NNH and N₂O intermediate pathways are found to be the major contributors for NO formation in all the reaction mechanisms except GRI 3.0 in syngas diffusion flames. The GRI 3.0 mechanism is observed to predict prompt NO pathway as the major contributing pathway to NO formation. This is attributed to prediction of a large concentration of CH radical by the GRI 3.0 as opposed to a relatively negligible value predicted by all other mechanisms. Also, the back-conversion of NNH into N₂O at lower pressures (2–4 bar) was uniquely observed for one of the five mechanisms. The net reaction rates and peak flame temperatures are used to correlate and explain the differences observed in the peak [NO] at different pressures. This study identifies key reactions needing assessment and also highlights the need for experimental data in syngas diffusion flames in order to assess and optimize H₂/CO and nitrogen chemistry.     

Formation and consumption of NO in H2 + O2 + N2 flames doped with NO or NH3 at atmospheric pressure

Flat premixed burner-stabilized H₂ + O₂ + N₂ flames, neat or doped with 300–1000 ppm of NO or NH₃, were studied experimentally using molecular-beam mass-spectrometry and simulated numerically. Spatial profiles of temperature and concentrations of stable species, H₂, O₂, H₂O, NO, NH₃, and of H and OH radicals obtained at atmospheric pressure in lean (? = 0.47), near-stoichiometric (? = 1.1) and rich (? = 2.0) flames are reported. Good agreement between measured and calculated structure of lean and near-stoichiometric flames was found. Significant discrepancy between simulated and measured profiles of NO concentration was observed in the rich flames. Sensitivity and reaction path analyses revealed reactions responsible for the discrepancy. Modification to the model was proposed to improve an overall agreement with the experiment.     

Computational investigation of non-premixed hydrogen-air laminar flames

Laminar diffusion hydrogen/air flames are numerically investigated. Detailed and global mechanisms are compared. NO formation is modelled by full nitrogen chemistry and the extended Zeldovich mechanism. A satisfactory agreement between the present predictions and the experiments of other authors is observed. Significance of different ingredients of mathematical modelling is analyzed. Minor roles of thermal diffusion and radiation, but a significant role of buoyancy is observed. It is observed that the full and quasi multi-component diffusion deliver the same results, whereas assuming Le = 1 to a remarkable difference. NO emissions logarithmically increase with increasing residence time. NO is the dominating nitrogen oxide. Its share increases with residence time, whereby NO₂ and N₂O show a reverse trend. It is observed that the NNH route plays a remarkable role in NO formation, where the share of the Zeldovich mechanism increases with residence time from about 20% to 85%, within the considered range.     

Flame structure and kinetic studies of carbon dioxide-diluted dimethyl ether flames at reduced and elevated pressures

The flame structure and kinetics of dimethyl ether (DME) flames with and without CO₂ dilution at reduced and elevated pressures were studied experimentally and computationally. The species distributions of DME oxidation in low-pressure premixed flat flames were measured by using electron-ionization molecular-beam mass spectrometry (EI-MBMS) at an equivalence ratio of 1.63 and 50 mbar. High-pressure flame speeds of lean and rich DME flames with and without CO₂ dilution were measured in a nearly-constant-pressure vessel between about 1 and 20 bar. The experimental results were compared with predictions from four kinetic models: the first was published by Zhao et al. (2008) [9], the second developed by the Lawrence Livermore National Laboratory (LLNL) (Kaiser et al., 2000) [13], and the third has been made available to us as the Aramco mechanism (Metcalfe et al., 2013) [14]; as the fourth, we have used an updated model developed in this study. Good agreement was found between measurements and predictions from all four models for all major and most typical intermediate species with and without CO₂ addition in low-pressure flat flame experiments. However, none of the models was able to reliably predict high-pressure flame speeds. Although the updated model improved the prediction of flame speeds for lean mixtures, errors remained for rich conditions at elevated pressure, likely due to uncertainty in the rates of CH₃ + H(+M) = CH₄(+M) and the branching and termination reaction pair of CH₃ + HO₂ = CH₃O + OH and CH₃ + HO₂ = CH₄ + O₂. CO₂ addition considerably decreased the flame speed. Kinetic comparisons between inert and chemically active CO₂ in DME flames showed that CO₂ addition affects rich and lean DME flame kinetics differently. For lean flames, both the inert third-body effect and the kinetic effect of CO₂ reduce H-atom production. However, for rich flames, the inert third-body effect increases H-atom production via HCO(+M) = H + CO(+M) and suppression of the kinetic effect of CO₂ by shifting the equilibrium of CO + OH = CO₂ + H.     

NO formation of opposed-jet syngas diffusion flames: Strain rate and dilution effects

The NO formation characteristics and reaction pathways of opposed-jet H₂/CO syngas diffusion flames were analyzed with a revised OPPDIF program which coupled a narrowband radiation model with detailed chemical kinetics in this work. The effects of strain rates ranging from 0.1 to 1000 s^?1 and diluents including CO₂, H₂O and N₂ on NO production rates were investigated for three typical syngas compositions. The numerical results demonstrated that NO is produced primary through NNH-intermediate route and thermal route at high strain rates, where the reaction of NH + O = NO + H (R51) also become more active. Near the strain rate of 10 s^?1, the flame temperature is the highest and thermal route is the dominant NO formation route, but NO would be consumed by reburn route where NO is converted to NH through HNO, especially for H₂-rich syngas. At low strain rates, radiative heat loss results in a lower flame temperature and further reduce NO formation, while the reaction of N + CO₂ = NO + CO (R140) become more important, especially for CO-rich syngas. With the diluents, NO production rates decreased with increasing dilution percentages. When the flame temperature is very high as the thermal route is dominant near strain rate of 10 s^?1, CO₂ dilution makes flame temperature and NO production rate the lowest. Toward both lower and higher strain rates, adding H₂O is more effective in reducing NO because R140 and NNH-intermediate route are suppressed the most by H₂O dilution respectively.     

Effects of dilution with carbon dioxide on the laminar burning velocity and flame stability of H2–CO mixtures at atmospheric condition

The objective of this investigation was to study the effect of dilution with CO₂ on the laminar burning velocity and flame stability of syngas fuel (50% H₂–50% CO by volume). Constant pressure spherically expanding flames generated in a 40 l chamber were used for determining unstretched burning velocity. Experimental and numerical studies were carried out at 0.1 MPa, 302 ± 3 K and ? = 0.6–3.0 using fuel-diluent and mixture-diluent approaches. For H₂–CO–CO₂–O₂–N₂ mixtures, the peak burning velocity shifts from ? = 2.0 for 0% CO₂ in fuel to ? = 1.6 for 30% CO₂ in fuel. For H₂–CO–O₂–CO₂ mixtures, the peak burning velocity occurred at ? = 1.0 unaffected by proportion of CO₂ in the mixture. If the mole fraction of combustibles in H₂–CO–O₂–CO₂ mixtures is less than 32%, then such mixtures are supporting unstable flames with respect to preferential diffusion. The analysis of measured unstretched laminar burning velocities of H₂–CO–O₂–CO₂ and H₂–CO–O₂–N₂ mixtures suggested that CO₂ has a stronger inhibiting effect on the laminar burning velocity than nitrogen. The enhanced dilution effect of CO₂ could be due to the active participation of CO₂ in the chemical reactions through the following intermediate reaction CO + OH ? CO₂ + H.     

Influences of different diluents on NO emission characteristics of syngas opposed-flow flame

This paper used the opposed-flow flame model and GRI 3.0 mechanism to investigate NO emission characteristics of H₂-rich and H₂-lean syngas under diffusion and premixed conditions, respectively, and analyzed influences of adding H₂O, CO₂ and N₂ on NO formation from the standpoint of thermodynamics and reaction kinetics. For diffusion flames, thermal route is the dominant pathway to produce NO, and adding N₂, H₂O and CO₂ shows a decreasing manner in lowering NO emission. The phenomenon above is more obvious for H₂-rich syngas because it has higher flame temperature. For premixed flames, adding CO₂ causes higher NO concentration than adding H₂O, because adding CO₂ produces more O radical, which promotes formation of NO through NNH + O = NH + NO, NH + O = NO + H and reversed N + NO = N₂ + O. And in burnout gas, thermal route is the dominant way for NO formation. Under this paper's conditions, adding N₂ increases the formation source of NO as well as decreases the flame temperature, and it reduces the NO formation as a whole. In addition, for H₂-lean syngas and H₂-rich syngas with CO₂ as the diluent, N + CO₂ = NO + CO plays as an important role in thermal route of NO formation.     

Numerical modeling for structure and NOx formation characteristics of oxygen-enriched syngas turbulent non-premixed jet flames

The present study numerically investigated the effect of oxygen enrichment on the precise structure and NO_x formation characteristics of turbulent syngas non-premixed flames. The turbulence-chemistry interactions were represented by a Lagrangian flamelet model. In context with the Lagrangian flamelet model, the NO concentration was obtained directly from the flamelet calculation based on full NO_x chemistry, with radiative heat loss being accounted for through the flamelet energy equation. Computations were performed for three different syngas compositions with a designated nitrogen dilution level. Numerical results indicated that, for the CO-rich composition with the lowest LHV yielding the highest scalar dissipation rate and shortest flight time, the flame structure was dominantly influenced by turbulence-chemistry interactions. On the other hand, with regard to the H₂-rich composition with the highest LHV yielding the lowest injection velocity and longest flight time, the flame structure was strongly influenced by radiative cooling. The peak NO level was remarkably elevated by increased oxygen level due to the elevated temperature of the oxygen-enriched flame. In the enhanced oxygen level (30%), the H₂-rich case produced the highest NO level due to a higher temperature and longer residence time within the hot flame zone, while the CO-rich case yielded the lowest NO level due to a lower temperature and shorter residence time. It was also found that, by enhancing the oxygen level, contributions of NNH and N₂O to total NO emission rapidly decreased while the contributions of the thermal NO path were progressively dominant for all cases.     

Effects of hydrogen addition on structure and NO formation of highly CO-Rich syngas counterflow nonpremixed flames under MILD combustion regime

The present study has numerically investigated the Moderate or Intense Low oxygen Dilution (MILD) combustion regime, combustion processes and NO formation characteristics of the highly CO-rich syngas counterflow nonpremixed flames. To realistically predict the flame properties of the highly CO-rich syngas, the chemistry is represented by the modified GRI 3.0 mechanism. Computations are performed to precisely analyze the flame structure, NO formation rate, and EINO of each NO sub-mechanism. Numerical results reveal that the hydrogen enrichment and oxygen augmentation substantially influence the NO emission characteristics and the dominant NO production route in the CO-rich syngas nonpremixed flames under MILD and high temperature combustion regimes. It is found that the most dominant NO production routes are the NNH path for the lowest oxygen level (3%) and the thermal mechanism for the highest O₂ condition (21%). For the intermediate oxygen level (9%), the most dominant NO production routes are the NNH route for the hydrogen fraction up to 5%, the CO₂ path for the hydrogen fraction range from 5% to 10% and the thermal mechanism for the hydrogen fraction higher than 10%, respectively. To evaluate the contribution of the specific reaction on EINO the sensitivity coefficients are precisely analyzed for NO formation processes with the dominance of NNH/CO₂/Thermal mechanism under the highly CO-rich syngas flames.     

Dilution effects analysis on NOx emissions of opposed-jet H2/CO syngas diffusion flames

Syngas is a promising alternative fuel for stationary power generation due to cleaner combustion than convectional fossil fuels. During the gasification processes, the by-products of CO₂, H₂O, or N₂ may be present in the syngas mixture to control the flame temperature and emissions. Several studies indicated that syngas with dilutions is capable of reducing pollutant emissions such as NO_x emissions. This work applied a numerical model of opposed-jet diffusion fames to explore the dilution effects on NO_x formation and differentiate the inert effect, thermal/diffusion effect, chemical effect, and radiation effect from CO₂, H₂O, or N₂ dilutions. The numerical study was performed by a revised OPPDIF program coupling with narrowband radiation model and detail chemical mechanism. The dilution effects on NO_x formation were analyzed by comparing the realistic and hypothetical cases. Regardless the diluent types, the inert effect is the main cause to reduce NO production, followed by chemical effect and radiation effect. The thermal/diffusion effect may promote NO formation because the preferential diffusion due to different diffusivities between diluents and syngas magnifies the reaction rate locally. CO₂ dilution reduces NO by radiation effect at low strain rate, and contributes NO reduction by chemical effect at high strain rate. At the same dilution percentage, CO₂ dilution reduces NO production the most, followed by H₂O and N₂. Besides the thermal/diffusion effect, the chemical effect of H₂O enhances NO production through thermal route and reburn route.     

The kinetics of oxidation of Diesel soots by NO2

The kinetics of oxidation of three soots, from a Diesel engine fuelled by either Ultra-Low Sulphur Diesel (ULSD) or biodiesel, by NO₂ have been measured in a packed bed at various temperatures (300–550 °C) and [NO₂] (20–880 ppm) relevant to regenerating a Diesel Particulate Filter. Adsorbed hydrocarbons and oxygen accounted for a significant fraction (～20% by mass) of the otherwise carbonaceous material. After pre-treatment (heating up to 550 °C in a flow of pure Ar and holding the temperature at 550 °C for 1 h) to ensure consistency between samples, they were subsequently burned at a fixed temperature in a flow of NO₂ + Ar. For this, a balance on oxygen atoms entering and leaving the packed bed showed that during oxidation in NO₂ any oxygen remaining in a soot after pre-treatment was not rapidly liberated as CO or CO₂. A mass balance on the element nitrogen demonstrated that no N₂ or N₂O was formed below 550 °C; mass balances on carbon and oxygen demonstrated that all the carbon ended up as CO or CO₂ and below 550 °C the nitrogen yielded only NO. The oxidation of soot in NO₂ was found to be first-order with respect to NO₂. Also, the soot derived from biodiesel was more reactive than soot from ULSD; nevertheless, the apparent activation energies for oxidation by NO₂ were the same (70 ± 18 kJ mol^?1) for each carbon. When the distribution of diameters of the individual spherules of soot was taken into account, it was not possible to tell whether there was internal burning of porous spherules or, on the other hand, non-porous, solid spherules were burning on their exteriors.     

Effect of CO2/N2/CH4 dilution on NO formation in laminar coflow syngas diffusion flames

The effect of CO₂/N_2/CH₄ dilution on NO formation in laminar coflow H₂/CO syngas diffusion flames was experimentally and numerically investigated. The results reveal that the NO emission index increases with H₂/CO mole ratio. In all cases, CO₂/N₂/CH₄ dilution can reduce the peak temperature of syngas flame and have the ability to reduce peak flame temperature is decreased in the following order: CO₂>N₂>CH₄. CO₂/N₂ dilution reduces the NO formation in syngas flame while CH₄ dilution promotes the NO formation. Besides, the dilution of CO₂/N₂/CH₄ can reduce the peak mole fraction of OH and its variations with H₂/CO mole ratio and dilution ratio show the same trend as the peak flame temperature variations. The height of the flame with CO₂ and N₂ dilution increases with dilution ratio. The flame with CH₄ dilution becomes higher and wider with the increase of dilution ratio.     

The effects of N2 and steam dilution on NO emission for a H2/Air micromix flame

The different effects of N₂ and water steam dilution on the NO emission from a micromix H₂/air flame were experimentally and numerically studied. NO emission was measured using Fourier transform infrared spectroscopy gas analyzer (FTIR). Numerical simulation of the H₂/air flame was carried out with realizable k-ε model and the Eddy Dissipation Concept (EDC) model. Two pseudo species were introduced in the simulations to numerically isolate the thermal-dilution, direct chemical and third-body effect of the steam. The experimental and numerical results show that NO emission with steam dilution is about 20%～50% of the emission with N₂ dilution at the same equivalence ratio (φ) and dilution ratio (D). The present simulation results show that the thermal-dilution and direct chemical effects of steam account for 50.8%～92.1% and 5.8%～15.8% of the total NO emission, respectively, while the third-body effect of steam shows less impact on NO emission. Specifically, the third-body effect slightly promotes the formation of H and NO at lower φ (0.6–0.8) and suppresses the formation of H and NO at higher φ (0.9–1.0) through inhibiting the third-body reaction of H + O₂ + M ? HO₂ + M. In addition, the direct chemical and third-body effects of steam always decrease the formation of NO from the NNH route.     

Computed flammability limits of opposed-jet H2/CO syngas diffusion flames

Extensive computations were made to determine the flammability limits of opposed-jet H₂/CO syngas diffusion flames from high stretched blowoff to low stretched quenching. Results from the U-shape extinction boundaries indicate the minimum hydrogen concentrations for H₂/CO syngas to be combustible are larger towards both ends of high strain and low strain rates. The most flammable strain rate is near one s⁻¹ where syngas diffusion flames exist with minimum 0.002% hydrogen content. The critical oxygen percentage (or limiting oxygen index) below which no diffusion flames could exist for any strain rate was found to be 4.7% for the equal-molar syngas fuels (H₂/CO = 1), and the critical oxygen percentage is lower for syngas mixture with higher hydrogen content. The flammability maps were also constructed with strain rates and pressures or dilution gases percentages as the coordinates. By adding dilution gases such as CO₂, H₂O, and N₂ to make the syngas non-flammable, besides the inert effect from the diluents, the chemical effect of H₂O contributes to higher flame temperature, while the radiation effect of H₂O and CO₂ plays an important role in the flame extinction at low strain rates.     

Inhibition of hydrogen oxidation by HBr and Br2

The high-temperature bromine chemistry was updated and the inhibition mechanisms involving HBr and Br₂ were re-examined. The thermochemistry of the bromine species was obtained using the Active Thermochemical Tables (ATcT) approach, resulting in improved data for, among others, Br, HBr, HOBr and BrO. Ab initio calculations were used to obtain rate coefficients for selected reactions of HBr and HOBr, and the hydrogen/bromine/oxygen reaction mechanism was updated. The resulting model was validated against selected experimental data from the literature and used to analyze the effect of HBr and Br₂ on laminar, premixed hydrogen flames. Our work shows that hydrogen bromide and molecular bromine act differently as inhibitors in flames. For HBr, the reaction HBr + H ? H₂ + Br (R2) is rapidly equilibrated, depleting HBr in favor of atomic Br, which is the major bromine species throughout the reaction zone. The chain-breaking steps are then H + Br + M → HBr + M (R1), Br + HO₂ → HBr + O₂ (R7), and Br + Br + M → Br₂ + M (R8). In Br₂-doped flames, the reaction Br₂ + H ? HBr + Br (R9) is far from equilibration and serves to deplete H in the reaction zone by competing with H + O₂ → O + OH. The inhibition is augmented by recombination of Br (R8). If the inlet Br₂ mole fraction exceeds about 20%, reactions (R8), (R2) are both reversed, now acting to promote chain branching and increase the flame speed. According to the present model, cycles involving HOBr are not important for generation or removal of chain carriers in these flames.     

Experimental and kinetic modeling study of methyl butanoate and methyl butanoate/methanol flames at different equivalence ratios and C/O ratios

Premixed laminar methyl butanoate/oxygen/argon and methyl butanoate/methanol/oxygen/argon flames were studied with tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam sampling mass spectrometry at 30 torr (4.0 kPa). Three flames were investigated in the experiment: MB (methyl butanoate) flame F1.54 (? = 1.54, C/O = 0.479), MB flame F1.67 (? = 1.67, C/O = 0.511) and MB/methanol flame F1.67M (? = 1.67, C/O = 0.479). By measuring the signal intensities at different distances from the burner surface, the mole fraction profiles of intermediates are derived. Experimental results show that the flame front shifts downstream and peak mole fractions of intermediates increase remarkably with the increase of equivalence ratio for pure MB fuel. When methanol is added, the peak mole fractions of most intermediates including those of soot precursors decrease remarkably at the same equivalence ratio, while peaks of soot precursors vary little (only slightly decreasing) at same C/O ratio. It is concluded that the formation of soot precursors is more sensitive to C/O ratio than to equivalence ratio. Besides, more CO₂ is produced near the burner surface in MB flame than that in MB/methanol flame, and this validates an early production of CO₂ in methyl ester oxidation. In addition, a modified MB detailed mechanism is used to model flame structure, and improved agreements between the experimental and predicted results are realized. Based on the simulation results, reaction flux and sensitivity are analyzed for CO₂ and C₃H₃, respectively.