Ignition Delay Time Predictions Research Articles

Prediction of Ignition Delay Times for Amine-based Liquid Propellants through a QSPR Approach

Prediction of Ignition Delay Times for Amine-based Liquid Propellants through a QSPR Approach

Laminar flame speed measurement and combustion mechanism optimization of methanol–air mixtures

AbstractLaminar flame speeds of methanol/air mixtures at 338–398 K are measured by the heat flux method, extending the range of equivalence ratio up to 2.1. And a new optimized methanol mechanism with 94 reactions is proposed by using the particle swarm algorithm, adjusting 20 Arrhenius pre‐exponential factors in their uncertainty domains. The optimized model is compared with eight methanol combustion mechanisms and experimental data published in recent years, covering a wide range of initial temperatures (298–1537 K), pressures (0.04–50 atm) and equivalence ratios (0.5–2.1). The results show that the optimized mechanism not only improves the accuracy of ignition delay time with rapid compression machine at low temperature but also moderately improve the description of laminar flame speed in lean and stoichiometric conditions. Meanwhile, the optimized model significantly enhances the prediction accuracy of CH3 and CH2O radical, and perfectly captures the evolution trend of HCO radical in laminar flat flame. Overall, the optimized mechanism provides the best overall description of the currently available measurements, leading to more accurate and comprehensive prediction of ignition delay time, laminar flame speed and species concentration.

An improved particle swarm algorithm-based method for kinetic modeling study of ammonia/air laminar flame speed

In recent years, ammonia has garnered increasing attention as a promising carbon-free fuel. Laminar flame speed is a critical property of ammonia fuel that has been extensively studied by researchers using chemical kinetics mechanisms. However, some deviations still remain in the numerical predictions. To further improve the prediction accuracy of the laminar flame speed for ammonia/air flame, an ammonia kinetic mechanism is developed in this work. Reactions from Gri-Mech 3.0, Li et al. mechanism, and Han et al. mechanism that have significant impact on laminar flame speed were first assembled to the Okafor et al. mechanism, and H/OH sub-mechanisms were merged to establish a kinetic mechanism containing 43 species and 142 reactions. A particle swarm algorithm with improved inertia weights is proposed and the fitness function for outputting laminar flame speed prediction error is customized based on Cantera codes, then forming the algorithm framework used to optimize the kinetic mechanism. The pre-exponential factor A, the temperature exponent n and the activation energy Ea of the four reactions in the merged mechanism that have high sensitivity to the laminar flame speed are selected as the independent variables for optimization, and the reactions rate constants corresponding to the high prediction accuracy of the laminar flame speed is finally obtained. The numerical prediction indicates a reduction in mean absolute percentage error of laminar flame speed from 22.563 % to 10.649 % using the optimization mechanism. The results of the sensitivity and reaction pathways analyses demonstrated that more H-related reactions were considered in the optimized mechanism, and the relative ROP of H-related reactions were adjusted at different equivalence ratios, resulting in higher or lower predictions of laminar flame speed compared with the unoptimized Okafor et al. mechanism. Ignition delay time as well as the species distribution of NH3, NO, and N2O was studied. The ignition delay time predictions using the optimized mechanism are in better agreement with the experiment data at P = 11 atm and 30 atm. The optimization mechanism demonstrated accurate predictions for NH3 and NO while exhibiting an overestimation for N2O, but the N2O prediction error is smaller compared to the Okafor et al. mechanism.

Experimental and modeling study on ignition kinetics of ethyl methyl carbonate

Ethyl methyl carbonate (EMC) is an essential electrolyte of lithium-ion batteries (LIBs), and the spontaneous ignition of electrolyte is considered to be an important inducement for the thermal runaway (TR) combustion of LIBs. To better understand its ignition chemistry and combustion kinetics, the ignition delay times (IDTs) of ethyl methyl carbonate were measured by using a Rapid Compression Machine (RCM) over a wide range of temperatures (810–980 K), pressures (20 and 40 bar), equivalence ratios (φ = 0.5, 1.0, and 2.0), and a fuel concentration of 2 %, yielding results that are in substantial variance with those calculated with detailed kinetics in the literature over the entire range of conditions investigated. An improved chemical kinetic model was developed to simulate the ignition and combustion characteristics of EMC under intermediate-temperature region by employing the updated kinetic parameters. Results show that the overall performance of the present kinetics model is substantially improved with respected to the prediction of ignition delay times, intermediate species profiles, as well as laminar flame speeds across different temperature, pressure, and equivalence ratio conditions. Furthermore, sensitivity and pathway analyses show that the ignition chemistry of EMC is mainly controlled by retro-ene reaction and H abstraction reactions.

Combining genetic algorithm and deep learning to optimize a chemical kinetic mechanism of ammonia under high pressure

Ammonia is a potential zero-carbon fuel, but the difficulties of experimenting at high pressure limit its development of application in power engineering. In this work, deep learning and genetic algorithm are combined to optimize the chemical reaction kinetics mechanism of ammonia under high pressure. The result shows that deep learning model is able to regress experimental data of ignition delay time in the range of less than 0.2% |Elog| (logarithmic absolute error). At the same time, the trained model can be applied to the trend prediction of ignition delay time at high pressure, enriching combustion data of ammonia fuel that is not available from experiments. Optimization of PLOG reactions with a large population size was performed by strengthen elitist genetic algorithm, and the prediction accuracy of ammonia chemical reaction kinetics mechanism was improved by about 5% finally. The application value of artificial intelligence in combustion science is demonstrated.

Comprehensive study of autoignition characteristics of propane

Ignition delay times (IDT) for stoichiometric propane (C3H8) diluted with nitrogen were measured in a shock tube facility under reflected shock wave conditions at pressures ranging from 1 to 10 atm and temperatures between 850 and 1500 K. The experiments were limited to a maximum pressure of 10 atm due to the facility’s constraints. In addition, numerical simulations were conducted using several detailed kinetic mechanisms at pressures from 1 to 30 atm and three equivalence ratios (φ = 0.5, 1, and 2) to provide comparative insights. The results indicated that IDT decreases as pressure increases, with a more significant reduction observed between 1 and 10 atm compared to 10 to 30 atm. While most models exhibited similar trends and minimal discrepancies, the GRI Mech 3.0 mechanism demonstrated a slower prediction of ignition delay times at temperatures below 1250 K. In contrast, the POLIMI model exhibited a relatively faster prediction at temperatures above 1250 K, with the deviation between the two models becoming more pronounced as pressure increased. A comparative analysis revealed that the experimental predictions of propane autoignition behavior were in good agreement with the results obtained using the ARAMCO 3.0 mechanism. To further understand the chemistry governing the autoignition process of C3H8, a sensitivity analysis was performed for a stoichiometric mixture at three distinct temperatures (850 K, 1200 K, and 1550 K).

Reduced ethanol skeleton mechanism for multi-dimensional engine simulation

Ethanol is considered one of the most popular renewable biofuels worldwide. Detailed chemical mechanisms are generated to numerically study the oxidation kinetics of this fuel. Although detailed mechanisms are commonly used in 0D and 1D modeling (e.g., ignition delay time and laminar burning speed), their utilization in multi-dimensional modeling (e.g., 2D and 3D) is rather limited due to a large number of species/reactions which increase the computational time consequently. Therefore, a smaller and accurate chemical mechanism is essential for the proper implementation of fuel-oxidizer kinetics in multi-dimensional modeling. In this work, a detailed ethanol mechanism generated by authors, i.e., PCRL-Mech1 is used to create three sets of reduced skeleton mechanisms at different temperature ranges that enable predicting the results of detailed mechanism within reasonable accuracy. PCRL-Mech1 is a detailed ethanol mechanism with 67 species and 1016 reactions which shows a reasonable accuracy in predicting combustion parameters in a wide range of engine-relevant conditions. The mechanism reduction is performed using the path flux analysis method along with sensitivity analysis. Three sets of skeleton mechanisms including reduced-low, -high, and -wide are generated targeting the temperature range of 700–900 K, 1000–1700 K, and 700–1700 K, respectively. The reduced mechanisms are applicable for lean, stoichiometric, and rich conditions with pressure ranging between 1-80 atm. These three reduced mechanisms are successfully validated by comparing the prediction of ignition delay time, laminar burning speed, and species concentration with the detailed mechanism as well as available experimental data in the literature. The final three mechanisms of low, high, and wide temperature range include 27, 25, and 39 species and 147, 185, and 370 reactions, respectively. These three skeleton mechanisms are used in 3D ethanol spray combustion simulations which predict the temperature profile with an acceptable accuracy compared to the available experimental measurements.

Quantitative evaluation of several chemical mechanisms for gasoline surrogate-ethanol blends and study of dominant chemistry under super-knock relevant conditions

A comprehensive database that covers wide ranges of temperature, pressure and equivalence ratio conditions was established for gasoline surrogate fuels composed of n-heptane, iso-octane, toluene with and without ethanol addition. The database includes ignition delay time measurements in shock tubes and laminar flame velocity measurements which are relevant combustion properties under super-knock relevant conditions. Due to the lack of reaction pathways for low-temperature iso-octane combustion and ethanol oxidation in Caltech mechanism, an updated mechanism has been constructed. The update has been carried out as follows: (i) changing the iso-octane sub-mechanism, (ii) adding an ethanol sub-mechanism, and (iii) modifying thermodynamic and kinetic parameters for few species and reactions for removing collision limit violation. The predictive capabilities of the modified Caltech mechanism and of three reaction models developed for n-heptane/iso-octane/toluene/ethanol based mixtures have been quantified using the model evaluation method of Olm. Significant improvement of the combustion properties predictions by the modified Caltech model has been demonstrated by the lower error value. For the prediction of ignition delay time, the updated Caltech mechanism shows better performance than the other models, especially in the high-temperature regime. Error maps were drawn over wide ranges of thermodynamic conditions to show the overall performance of all the evaluated mechanisms. For the prediction of laminar burning velocity, the modified Caltech mechanism performs better for most cases. Laminar burning velocity is always over-estimated by Livermore’s mechanism. The new mechanism was employed to determine the most important chemical pathways under super-knock relevant conditions corresponding to the following thermodynamic states: (630 K, 2.3 MPa), (750 K, 6.0 MPa), (720 K, 2.8 MPa), and (1000 K, 12.0 MPa). The modified Caltech model, or reduced versions of it, could be employed in future work to investigate super-knock for realistic gasoline surrogate.

Development of a virtual kinetics chemistry for prediction of ignition delay time

The simulation of complex reactive flows in combustion applications generally requires a large amount of computational power, and the reactive part of the solution is usually the most time consuming. Detailed chemical kinetics mechanisms can reach up to tens of thousands species, while numerical simulations of complex reactive flows can handle mechanisms, at most, with a few hundred species. Virtual kinetic mechanisms are a very effective strategy to drastically reduce the computational time spent in the reactive part of numerical simulations. They are formed by artificial species and reaction paths, that are optimized to reproduce the important characteristics of a canonical problem of interest. This work presents the development of a virtual mechanism able to reproduce the temperature evolution and ignition delay times of the thermal ignition of a homogeneous, constant mass, constant pressure, adiabatic, fuel-air mixture. Three different reaction structures are built for a methane-air mixture and their predictions are tested over a range of temperatures from 1000 K to 1500 K and pressures from 1 atm to 3 atm. The limitations observed are due to the small number of reactions and parameters of the kinetic model. However, mechanism reduction methodologies, such as DRG, may present much larger errors if used to achieve the same mechanism size of the virtual mechanisms presented in the current study.

H-abstractions by O2, NO2, NH2, and HO2 from H2NO: Theoretical study and implications for ammonia low-temperature kinetics

Unraveling the low-temperature chemistry of ammonia is still an open challenge in combustion kinetics, yet of primary importance because of the novel combustion concepts operating in these conditions, as well as of the rising interest on ammonia as an energy carrier. In this work, a fundamental investigation of the H-abstraction reactions from H2NO by O2, NO2, NH2, and HO2 was performed. These reactions, which belong to the radical-radical abstraction class, associate a high sensitivity to the key low temperature ammonia combustion parameters, to a high uncertainty in rate constant values. Theoretically, the investigation of reactions belonging to this class is complicated by their intrinsic multireference nature. To address this issue, a structured theoretical methodology that relies heavily on the use of CASPT2 calculations was devised. The predicted rate constants highlighted significant deviations from the rates commonly adopted in the state-of-the-art mechanisms, most often based on analogies and estimations. In order to understand their impact on ammonia low-temperature kinetics, the obtained rates were integrated into a kinetic model, which was used to investigate ammonia oxidation and ignition at low-temperature and oxygen-rich conditions. It was found that O2 and NH2 play the major role, as abstractors, in regulating ammonia oxidation and ignition. In particular, ignition delay time predictions proved extremely sensitive to the adopted rates: modifying each of them within their theoretical uncertainty caused deviations by even an order of magnitude, and totally changed the predictive features of the mechanism. The kinetic analysis highlighted then the need of a targeted optimization of the critical rates, downstream of the present work and within their uncertainty boundaries, to further refine the mechanism capability over a wide range of operating conditions.

Diethyl ether oxidation: Revisiting the kinetics of the intramolecular hydrogen abstraction reactions of its primary and secondary peroxy radicals

• Reaction kinetics of intramolecular hydrogen abstraction reactions of peroxy radicals yielded by diethyl ether are revisited with high level ab initio calculations. • The individual role of variational, tunneling and multistructural torsional anharmonicity effect in the calculation of rate constant is analyzed in detail. • The special effects of diastereomers and conformers generated via pseudo-rotations within the saddle point ring are emphasized. • The prediction performances of several representative chemical kinetic models of diethyl ether updated with our calculated rate constants are tested. • 1 Yaozong Duan, M. Monge-Palacios and E. Grajales-Gonzalez contributed equally. Diethyl ether is an attractive alternative to diesel fuel for its high autoignition propensity, high energy density, and potential to reduce pollutant emissions. Low-temperature oxidation kinetics play an important role governing fuel autoignition in engines. Peroxy radical intramolecular hydrogen atom abstraction reactions are key isomerization steps in the chain branching reaction sequence at low temperatures. In this study, the kinetics of intramolecular hydrogen atom abstraction reactions of the primary and secondary peroxy radicals were revisited using the multistructural torsional variational transition state theory with small curvature tunneling corrections. High-pressure limit rate constants within a broad temperature range were obtained, which differ from those previously reported for the investigated reactive systems due to the differences in the estimated barrier heights, the role played by multistructural torsional anharmonicity, and the effects of tunneling. We also observed that some higher energy conformers of the saddle point species, some of which with diastereomers, play a surprisingly large role. Similarly, tunneling is pronounced at low temperature combustion conditions, claiming for robust methods to estimate this effect. Different kinetic models for diethyl ether were used to test our calculated rate constants and NASA polynomials for both diethyl ether peroxy radicals, and the results showed an overall slightly better performance in the prediction of ignition delay times at high pressures.

Prediction of ignition delay times of Jet A-1/hydrogen fuel mixture using machine learning

To control the global warming trends, carbon footprint of all the human activities needs to be restricted, including the aviation industry. Mixing hydrogen with commercial kerosene jet fuels appears as a promising alternative fuel to reduce the carbon dioxide emissions of aviation engines. The addition of hydrogen can significantly impact the auto-ignition process of aviation fuels, which is a key ingredient of engine reliability. However, accurate calculations or measurements of ignition delay times (IDTs) over a wide range of pressures, temperatures and fuel blending ratios are complicated and time-consuming. To achieve real-time prediction of ignition delay time for hydrogen-blended jet fuels under various operating conditions, machine learning methods are introduced to build a data-driven proxy model in this work. First, the ignition delay times of Jet A-1/hydrogen fuel mixture are simulated using the well-known HyChem combustion reaction mechanism under different pressures, temperatures, equivalence ratios and blending molar ratios of hydrogen. After some validation against experimental results, an artificial neural network (ANN) model is trained using the database of ignition delay times. Furthermore, a sub-ANN is nested to the original ANN model as an improvement on certain local conditions. The results show that the single original ANN model leads to a large local relative error for IDT <103μs, generally referring to high temperatures and pressures conditions. With the help of the nested sub-ANN approach, the improved model achieves a significantly better accuracy for very fast ignition. Compared with other machine learning models such as random forest, the nested sub-ANN model is more efficient to predict the ignition delay times of Jet A-1/hydrogen fuel mixture, still mitigating computational cost. The sensitivity analysis shows how the nested sub-ANN model is less sensitive to the uncertainties of the input parameters than the original ANN model.

An experimental and kinetic modeling study of NOx sensitization on methane autoignition and oxidation

An experimental and kinetic modeling study of the influence of NOx (i.e. NO2, NO and N2O) addition on the ignition behavior of methane/‘air’ mixtures is performed. Ignition delay time measurements are taken in a rapid compression machine (RCM) and in a shock tube (ST) at temperatures and pressures ranging from 900–1500 K and 1.5–3.0 MPa, respectively for equivalence ratios of 0.5–2.0 in ‘air’. The conditions chosen are relevant to spark ignition and homogeneous charge compression ignition engine operating conditions where exhaust gas recirculation can potentially add NOx to the premixed charge. The RCM measurements show that the addition of 200 ppm NO2 to the stoichiometric CH4/oxidizer mixture results in a factor of three increase in reactivity compared to the baseline case without NOx for temperatures in the range 600–1000 K. However, adding up to 1000 ppm N2O does not show any appreciable effect on the measurements. The promoting effect of NO2 was found to increase with temperature in the range 950–1150 K, while the sensitization effect decreases at higher pressures. The experimental results measured are simulated using NUIGMech1.2 comprising an updated NOx sub-chemistry in this work. A kinetic analysis indicates that the competition between the reactions ĊH3 + NO2 ↔ CH3Ȯ + NO and ĊH3 + NO2 (+M) ↔ CH3NO2 (+M), the former being a propagation reaction and the latter being a termination reaction governs NOx sensitization on CH4 ignition. Recent calculations by Matsugi and Shiina (A. Matsugi, H. Shiina, J. Phys. Chem. A. 121 (2017) 4218–4224) for the nitromethane formation reaction CH3 + NO2 (+M) ↔ CH3NO2 (+M), together with the recently calculated rate constants for HONO/HNO2 reactions significantly improve ignition delay time predictions in the temperature range 600–1000 K. Furthermore, the experiments with NO addition reveal a non-monotonous sensitization impact on CH4 ignition at lower temperatures with NO initially acting as an inhibitor at low NO concentrations and then as a promoter as NO concentrations increase in the mixture. This non-monotonous trend is attributed to the role of the chain-termination reaction ĊH3 + NO2 (+M) ↔ CH3NO2 (+M) and the impact of NO on the transition to the chain-branching steps CH2O + HȮ2 ↔ HĊO + H2O2, H2O2 (+M) ↔ ȮH + ȮH (+M), HĊO ↔ CO + Ḣ followed by CO + O2 ↔ CO2 + Ö and Ḣ + O2 ↔ Ö + ȮH. NUIGMech1.2 is systematically validated against the new ignition delay measurements taken here together with species measurements and high temperature ignition delay time data available in the literature for CH4/oxidizer mixtures diluted with NO2/N2O/NO and is observed to accurately capture the sensitization trends.

Kinetic Modeling Study on the Combustion Characterization of Synthetic C3 and C4 Alcohols for Lean Premixed Prevaporized Combustion

To reach sustainable aviation, one approach is to use electro-fuels (e-fuels) within the gas turbine engines. E-fuels are CO2-neutral synthetic fuels which are produced employing electrical energy generated from renewable resources, where the carbon is taken out of the atmosphere or from biomass. Our approach is, to find e-fuels, which can be utilized in the lean premixed prevaporized (LPP) combustion, where most of the non-CO2 emissions are prevented. One of the suitable e-fuel classes is alcohols with a low number of carbons. In this work, the autoignition properties of propanol isomers and butanol isomers as e-fuels were investigated in a high-pressure shock tube (HPST) at temperatures from 1200 to 1500 K, the pressure of 10 bar, and lean fuel-air conditions. Additional investigations on the low-temperature oxidation and flame speed of C3 and C4 alcohols from the literature were employed to develop a comprehensive mechanism for the prediction of ignition delay time (IDT) and laminar burning velocity (LBV) of the above-mentioned fuels. A numerical model based on newly developed chemical kinetics was applied to further study the IDT and LBV of fuels in comparison to the Jet-A surrogate at the engine-related conditions along with the emissions prediction of the model at lean fuel-air conditions.

Dependence of Biofuel Ignition Chemistry on OH-Initiated Branching Fractions

Abstraction of hydrogen by ȮH is the dominant initiation step in low-temperature oxidation of biofuels. Theoretical chemical kinetics calculations for such reactions provide a direct means of quantifying rates of abstraction, which are critical to modeling biofuel combustion. However, in several cases and despite agreement on total rate coefficients, branching fractions (i.e. the distribution of initial radicals) can vary depending on the level of theory, which leads to variations in ignition delay time predictions. To examine the connection between branching fractions and ignition delay time predictions, simulations were conducted for 1-butanol, cyclopentanone, and methyl propanoate at 10 atm and from 500–1000 K. For each case, the simulations utilized recent combustion mechanisms to produce an initial set of ignition delay time trends. H-abstraction rates were then replaced using rates from the literature to examine the effects of ȮH-initiated branching fractions on ignition chemistry. Branching fractions were found to significantly influence ignition chemistry, specifically in the case of 1-butanol, even when total rate coefficients were relatively consistent. From comparison of site-specific rates in the literature, branching fractions for initiation of 1-butanol and methyl propanoate are not consistent, which resulted in ignition delay times differing by factors of up to 6.3 and 1.2 respectively. Conversely, in the case of cyclopentanone, for which both the total and the site-specific rate coefficients agree, ignition delay times were unaffected. From the observed dependence of ignition delay times on ȮH-initiated branching fractions, an intermediate step in the development of combustion mechanisms is necessary to validate site-specific rate coefficients and ensure accurate model predictions. Speciation measurements are one example that can provide a critical link to radical-specific, fundamental chemical pathways and determine accurate branching fractions.

Study of the reduced kinetic mechanism of methane/dimethyl ether combustion

The development of methane (CH4)/dimethyl ether (DME) combustion systems can reduce fossil energy consumption and pollutant emissions of gas turbines while enhancing fuel diversity. However, employing detailed kinetic mechanisms in the fluid dynamics calculations for the design and optimization of CH4/DME burner configurations is enormously costly for computational resources and time. Therefore, reduced kinetic mechanisms are essential for widespread implementation. In the current work, 1200 + iterations based on the genetic algorithm were performed with 30 target conditions, which extracted a reduced mechanism from the detailed CH4/DME chemical kinetic mechanism. It contained 35 species and 131 reaction steps that reasonably captured the detailed mechanism's main reaction path. Measurements from a shock tube verified that the reduced mechanism provides reasonable predictions of ignition delay times for pure methane, pure DME, and CH4/DME mixtures at T > 1300 K, 1050 K, and 1100 K, respectively. The addition of CH3O2 reaction schemes and modification CH3OCH2 related reactions extended the temperature range to T > 900 K, 700 K, and 760 K under stoichiometric and fuel-rich conditions. The accuracy of the reduced and optimized mechanism was also confirmed by other results obtained from laminar flames, counter-flow diffusion flames, and flow reactors. Accurate replication of the temperature and species profiles was achieved for the numerical simulation of the turbulent flames by the optimization mechanism, which also decreased nearly half the computational time compared to the detailed mechanism. Overall, there is a suitable balance between accuracy and computational efficiency, as shown by the reduced mechanism, promising potential computational cost savings for large-scale numerical combustion simulations.

Experimental and modeling of autoignition of gaseous hydrocarbon fuels in the presence of H2 and C2H4

The focus of the present work is to understand the effect of H2 and C2H4 on the ignition characteristics of other gaseous fuels, namely, CH4, C2H6 and C3H6. Atmospheric-pressure flow reactor experiments were performed to measure the ignition delay times of CH4, C2H6 and C3H6 binary mixtures with H2 or C2H4 between 800 and 950 K. Most of the experiments were conducted at stochiometric conditions with 21% O2. Select tests were performed to examine the effects of equivalence ratios and oxygen concentrations. Ignition delay time were also measured for ternary mixtures of C3H6-C2H4-H2 at select conditions. Based on the experimental data, the overall effectiveness of H2 or C2H4 in reducing the ignition delay time of the binary mixtures can be listed in the following order: CH4 > C3H6 > C2H6. The experimental data were used to refine and validate the chemical kinetic mechanism for allyl-HO2 system relevant to low-temperature ignition chemistry of C3H6. A detailed sensitivity analysis is presented to identify the important reaction pathways, and their implications for the experimental observations are discussed. Monte Carlo simulations were used to quantify the model uncertainty for ignition delay time predictions, and to identify reactions that have significant contribution to the model uncertainty. Among the binary mixtures studied, CH4-H2 mixture produced the largest model uncertainty, primarily due to the sensitive reactions involving HO2 radical.

Design and simulation of gas burner ejectors

Ignition within gas burner ejectors can lead to off design conditions and has significant influence on the burner behavior. Thus ignition in the ejector should be prevented. In the present study the influence of combustion reactions on the performance of gas burner injectors is investigated. To investigate if ignition is possible, simulated ignition delay times, using a detailed reaction mechanism, are compared to predicted mean residence times of the gas in the ejector. Gas burner ejectors are designed using one dimensional analytic equations, based on energy and momentum conservation equations and conventional isentropic equations. 1D results are compared to 2D computational fluid dynamics (CFD) simulations, to take into account non-ideal mixing effects along the ejector. Results are validated with experiments with air at room temperature. 1D results show very good agreement not only with CFD simulations for the case of non-reactive flows, but also with performed experiments.It is shown that the assumption of ideal mixing along the ejector and thus the comparison of the ignition delay time to the gas mean residence time, to predict ignition in the ejector, is not valid. Ignition in the ejector is possible, even if the ignition delay time is more than thirty times higher than the mean residence time. In addition to that, it is shown, that ignition and the choice of reaction mechanism have significant influence on the predicted gas burner ejector performance. Thus, the accurate prediction of ignition delay time and the use of a detailed reaction kinetic are mandatory to correctly predict the burner ejector behavior.

Effects of stereoisomeric structure and bond location on the ignition and reaction pathways of hexenes

AbstractThe current work presents new experimental autoignition and speciation data on the two cis‐hexene isomers: cis‐2‐hexene and cis‐3‐hexene. The new data provide insights on the effects of carbon‐carbon double bond location and stereoisomeric structures on ignition delay times and reaction pathways for linear hexene isomers. Experiments were performed using the University of Michigan rapid compression facility to determine ignition delay times from pressure‐time histories. Stoichiometric (ϕ = 1.0) mixtures at dilution levels of inert gas to O2 = 7.5:1 (mole basis) were investigated at an average pressure of 11 atm and temperatures from 809 to 1052 K. Speciation experiments were conducted at T = 900 K for the two cis‐hexene isomers, where fast‐gas sampling and gas chromatography were used to identify and quantify the two cis‐hexene isomers and stable intermediate species. The ignition delay time data showed negligible sensitivity to the location of the carbon‐carbon double bond and the stereoisomeric structure (cis‐trans), and the species data showed no correlation with the stereoisomeric structure, but there was a strong correlation of some of the measured species with the location of the double bond in the hexene isomer. In particular, 2‐hexene showed strong selectivity to propene, acetaldehyde, and 1,3‐butadiene, and 3‐hexene showed selectivity to propanal. Model predictions of ignition delay times were in excellent agreement with the experimental data. There was generally good agreement for the model predictions of the species data for 2‐hexene; however, the mechanism overpredicted some of the small aldehyde (C2‐C4) species for 3‐hexene. Reaction pathway analysis indicates the hexenes are almost exclusively consumed by H‐atom abstraction reactions at the conditions studied (P = 11 atm, T &gt; 900 K), and not by C3‐C4 scission as observed in high‐temperature (&gt;1300 K) hexene ignition studies. Improved estimates for 3‐hexene + OH reactions may improve model predictions for the species measured in this work.

The impact of the third O2 addition reaction network on ignition delay times of neo-pentane

We studied the oxidation of neo-pentane by combining experiments, theoretical calculations, and mechanistic developments to elucidate the impact of the 3rd O2 addition reaction network on ignition delay time predictions. The experiments are based on photoionization mass spectrometry in jet-stirred and time-resolved flow reactors allowing for sensitive detection of the keto-hydroperoxide (KHP) and keto-dihydroperoxide (KDHP) intermediates. With neo-pentane exhibiting a unique symmetric molecular structure, which consequently results only in single KHP and KDHP isomers, theoretical calculations of ionization and fragment appearance energies and of absolute photoionization cross sections enabled the unambiguous identification and quantification of the KHP intermediate. Its temperature and time-resolved profiles together with calculated and experimentally observed KHP-to-KDHP signal ratios were compared to simulation results based on a newly developed mechanism that describes the 3rd O2 addition reaction network. A satisfactory agreement has been observed between the experimental data points and the simulation results, thus adding confidence to the model's overall performance. Finally, this mechanism was used to predict ignition delay times reported previously in shock tube and rapid compression machine experiments (J. Bugler et al., Combust. Flame 163 (2016) 138–156). While the model accurately reproduces the experimental data, simulations with and without the 3rd O2 addition reaction network included reveal only a negligible effect on the predicted ignition delay times at 10 and 20 atm. According to model calculations, low temperatures and high pressures promote the importance of the 3rd O2 addition reactions.