Detailed Chemical Kinetic Mechanism Research Articles

Flow-field analysis and performance assessment of rotating detonation engines under different number of discrete inlet nozzles

This study explores in depth rotating detonation engines (RDEs) fueled by premixed stoichiometric hydrogen/air mixtures through two-dimensional numerical simulations including a detailed chemical kinetic mechanism. To model the spatial reactant non-uniformities observed in practical RDE combustors, the referred simulations incorporate different numbers of discrete inlet nozzles. The primary focus here is to analyze the influence of reactant non-uniformities on detonation combustion dynamics in RDEs. By systematically varying the number of reactant injection nozzles (from 15 to 240), while maintaining a constant total injection area, the study delves into how this variation influences the behavior of rotating detonation waves (RDWs) and the associated overall flow field structure. The numerical results obtained here reveal significant effects of the number of inlets employed on both RDE stability (self-sustaining detonation wave) and performance. RDE configurations with a lower number of inlets exhibit a detonation front with chaotic behavior (pressure oscillations) due to an increased amount of unburned gas ahead of the detonation wave. This chaotic behavior can lead to the flame extinguishing or decreasing in intensity, ultimately diminishing the engine's overall performance. Conversely, RDE configurations with a higher number of inlets feature smoother detonation propagations without chaotic transients, leading to more stable and reliable performance metrics. This study uses high-fidelity numerical techniques such as adaptive mesh refinement (AMR) and the PeleC compressible reacting flow solver. This comprehensive approach enables a thorough evaluation of critical RDE characteristics including detonation velocity, fuel mass flow rate, impulse, thrust, and reverse pressure waves under varying reactant injection conditions. The insights derived from the numerical simulations carried out here enhance the understanding of the fundamental processes governing the performance of RDE concepts.

Development of Detailed and Reduced Chemical Kinetic Models for Ammonia Gas Turbines

Abstract The power generation sector has been recently moving towards decarbonization and there is an increased interest in replacing conventional fossil fuels with fuels that produce reduced/zero carbon emissions. One such fuel is ammonia (NH3). However, ammonia is hard to ignite, has a low flame speed, and produces a significantly large amount of nitrogen oxide (NOx) emissions. Hence, using 100% ammonia as fuel in gas turbines requires significant modifications and the development of novel combustors. Blending hydrogen with ammonia, however, helps in having better control over the combustion properties. Before utilizing hydrogen-blended ammonia in an actual gas turbine combustor, thorough simulation studies are required to evaluate its performance, possible hazards, and emissions. The literature lacks well-validated chemical kinetic models for the combustion of hydrogen-blended ammonia for undiluted mixtures at gas turbine-relevant conditions (~20 bar). Hence, in this work, we develop a detailed chemical kinetic model for hydrogen blended ammonia combustion and validate it with a wide range of experimental data for both dilute and undiluted mixtures relevant to gas turbine operating conditions. The detailed chemical kinetic mechanism was reduced to a smaller version (32 species mechanism) without significant loss in accuracy using the direct relation graph with error propagation (DRGEP) and full species sensitivity analysis. The resultant mechanism can predict a wide range of experimental results with the least cumulative error and will be a valuable tool in CFD simulations that will enable the development of gas turbines for zero-carbon power generation.

Numerical study on laminar burning velocity and ignition delay time of ammonia/methanol mixtures

As a carbon-free hydrogen-carrying fuel, ammonia can effectively alleviate the problem of CO2 emissions and has great application potential in marine engines. The low laminar burning velocity and calorific value, and the narrow flammability limit range make the combustion of pure ammonia difficult. Ammonia/methanol mixed combustion is a feasible method to improve ammonia combustion and mitigate CO2 emissions. It is difficult to accurately predict the laminar burning velocity (LBV) and ignition delay time (IDT) of ammonia/methanol combustion simultaneously by the existing chemical kinetic mechanisms. This study aims to develop a detailed chemical kinetic mechanism that can simultaneously predict the LBV and IDT. The new-developed mechanism was fully validated based on experimental data. Furthermore, it was employed to investigate the effects of methanol blending ratios and equivalence ratios on the LBV and IDT in NH3/CH3OH mixed flames. Besides, chemical kinetic analyses were conducted to elucidate the influence of methanol mixing ratios and equivalence ratios on LBV and IDT. Reaction pathway analysis revealed that the NH3 and CH3OH chemistry interacted by the sharing of H, OH and O radicals in fuels’ decomposition, and chemical interactions of N-containing radicals with the C1 species. The reactions involving C-containing species can notably improve the LBV of NH3/CH3OH mixed combustion. At low equivalence ratio, LBV increases in proportion to the fuel proportion. Conversely, at high equivalence ratio, the effect of oxygen concentration on LBV becomes the dominant factor.

A numerical study comparing the performance of a self-aspirating domestic LPG porous burner and that of a conventional LPG burner

The study involves in the design of a domestic two-layer self-aspirating porous burner that operates at a thermal load of 1 kW using liquefied petroleum gas (LPG). The porous burner is intended to function within India’s standard domestic regulator fuel inlet pressure of 3000 Pa. For the same thermal load, this work also provides a numerical comparison between the domestic conventional burner and the designed porous burner. For both porous and conventional burners, a full-scale 3D model is developed to calculate the flow, combustion, heat transfer to the cooking vessel, thermal efficiency, and emissions. The combustion process of both burners is numerically computed using a detailed chemical kinetic mechanism of LPG combustion, the San Diego Mechanism (SDM) with 57 species and 268 reactions are used. The porous burner is simulated using a non-thermal equilibrium condition to better calculate the heat recirculation within the porous domain. The self-aspirated porous burner has an equivalence ratio ϕ of 0.75 at 1 kW and an efficiency of 84.2%; conventional burner at the same load had an efficiency of 68%. 10 and 6 parts per million (ppm), respectively, are the measured CO and NOx emissions from the domestic porous burner and 660 and 80 ppm for domestic conventional burner, respectively.

A shock-tube experimental and kinetic simulation study on the autoignition of methane at ultra-lean and lean conditions

Coalbed methane represents an important kind of natural gas resource in many countries. However, the low-concentration property of coalbed methane limits its applications. To gain insight into the combustion kinetics of coalbed methane and facilitate its combustion utilization, this work reports an experimental and kinetic simulation study on the autoignition properties of methane at ultra-lean and lean conditions. A shock-tube (ST) facility is used for ignition delay time (IDT) measurements with equivalence ratios at 0.5, 0.1, and 0.05 with pressure at 2 and 10 bar under the temperature ranging from 1320 to 1850 K. The measured IDTs can be correlated into a general Arrhenius expression, and the equivalence ratio effect on IDTs is then analyzed. Seven detailed chemical kinetic mechanisms are employed to predict the IDTs and statistical error indicators are used to evaluate their performance. Detailed kinetic analysis via sensitivity and reaction path analysis is performed to uncover the kinetic differences among the seven mechanisms. It is shown that some of the reaction paths only exist in the NUIGMech1.3 mechanism, while the other detailed mechanisms do not consider them. Reaction path analysis indicates that the reactions related to O2, OH and O species become more important compared to the reactions involving CH3 and H radicals as the equivalence ratio decreases from lean to ultra-lean conditions. Detailed chemical kinetics analysis is also conducted to demonstrate the uncertainty of key reactions. The present work should be valuable to gain insight into the methane ignition characteristics and to facilitate kinetic mechanism optimization of methane combustion.

Computational assessment of soot models in ethylene/air laminar diffusion flames

To improve the accuracy of soot formation and evolution predictions, several physical and chemical models have been developed over the last decades. These models include (i) detailed chemical kinetic mechanisms describing both gas-phase chemistry related to combustion processes and reaction pathways leading to large-sized aromatic molecules, which are needed for modelling soot formation, and (ii) soot models providing a comprehensive description of soot particle dynamics and interactions with gas-phase chemical species. Accordingly, in this work, two detailed soot models, the method of moments (MOM) and the discrete sectional method (DSM), are evaluated in ethylene/air laminar diffusion flames, and their corresponding results are compared with experimental measurements. Furthermore, the NBP and KM2 chemical kinetic mechanisms are assessed and compared with each other by examining key chemical species related to soot formation and evolution. To compute gas mixture’s radiative properties, the weighted sum of grey gases model considering a grey medium is also utilised. Finally, the contributions of the soot precursors known as PAH (polycyclic aromatic hydrocarbon) to soot formation are also analysed. The main results show that the discrepancies in PAH concentrations obtained with different chemical kinetic mechanisms can be significant. In addition, compared to MOM ones, DSM results obtained here show a better agreement with experimental data. Finally, the analysis of PAH shows that those with two (A2) to four (A4) aromatic rings impact the most on soot modelling. Specifically, contributions of A4 were found to be more significant at lower heights above the burner, whereas A2 was found to be more impactful downstream as the flame develops. Maximum contributions of A2 and A4 to the soot inception rate were 66% and 85%, respectively, whereas the maximum summed contribution of PAH with five (A4R5) to seven (A7) aromatic rings accounted for only 13% of the inception rate.

Heterogeneous CPU-GPU parallelization for modeling supersonic reacting flows with detailed chemical kinetics

Accurate simulations of complex combustion phenomena associated with supersonic reacting flows require the use of detailed chemical kinetic mechanisms. However, detailed chemical mechanisms may consist of a large number of species and reactions resulting in extremely high computation cost. In order to accelerate the simulations of supersonic reacting flows with detailed chemical mechanisms, a heterogeneous CPU-GPU parallel algorithm and its portable software implementation are presented. The parallel algorithm was broken down into two parts: the CPU handled the computation of fluid dynamics while the GPU evaluated the chemical source terms and gas physical properties. The use of overlapping computations of chemical source terms on GPU and calculations of viscous flux on CPU is also presented. A study of performance tests was conducted. The performance results show that evaluating chemical source terms and gas physical properties on 2 GPUs are about 157.8× and 78.5× faster than running on the 16-core CPU when using the most complex mechanism on a grid of 3.3 million cells, respectively, resulting in an excellent speedup of the whole iteration up to 47. The significant performance improvement provided by the parallel algorithm can provide a significant perspective for designing heterogeneous CPU-GPU algorithms for applications in simulating supersonic reacting flows with detailed chemical kinetics. Program summaryProgram Title: OpenHurricaneCPC Library link to program files:https://doi.org/10.17632/m9pphg9cjj.1Licensing provisions: GPLv3Programming language: C++, CUDANature of problem: The computation cost in evaluating chemical source terms and theirs diagonal Jacobian matrices, and in calculating gas physical properties dominates the simulations of supersonic reacting flows with detailed chemical kinetic models. And the parallelization of these computations can yield great benefits from GPU acceleration.Solution method: The parallel implementation of evaluating the chemical source terms and theirs diagonal Jacobian matrices, and calculating gas physical properties were conducted on GPU to speed up the computation.

Intrinsic instability of lean hydrogen/ammonia premixed flames: Influence of Soret effect and pressure

The addition of hydrogen in ammonia/air mixtures can lead to the onset of intrinsic flame instabilities at conditions of technical relevance. The length and time scales of intrinsic instabilities can be estimated by means of linear stability analysis of planar premixed flames by evaluating the dispersion relation. In this work, we perform such linear stability analysis for hydrogen-enriched ammonia/air flames (50%H2-50%NH3 by volume) using direct numerical simulation with a detailed chemical kinetic mechanism. The impact of pressure and the inclusion of the Soret effect in the governing equations is assessed by comparing the resulting dispersion relation at atmospheric pressure and 10 atm. Our data indicate that both pressure and the Soret effects promote the onset of intrinsic instabilities. Comparisons with available numerical literature data as well as theoretical models are also discussed.

Reduced Chemical Kinetic Models of DME Based on Variance Filtering Method

Based on the variance value of each species concentration during the combustion process, a new chemical mechanism reduction method is proposed. The data sets which are the molar concentration of each species are generated based on numerical results of zero-dimensional homogeneous ignition process using detailed chemical kinetic mechanisms under various operating conditions. By calculating and analyzing the variance value of each species concentration during the combustion process to determine the contribution of each species to the combustion process, and by selecting a suitable threshold value to determine whether the species and elementary reactions are removed or not. The skeletal mechanisms of DME generated by using the present VFM method are compared to those generated by the path flux analysis (PFA) method and the detailed mechanism. The comparisons of the temperature and the concentration of important species showed that with either the same or significantly smaller number of species, the skeletal mechanisms generated by the present VFM method are more accurate than that of PFA in a broad range of initial pressures, temperatures and equivalence ratios. In addition, the reduction speed of VFM is one orders of magnitude faster than that of PFA.

Advanced numerical simulation of hydrogen/air turbulent non-premixed flame on model burner

A numerical investigation of hydrogen (H2)/air turbulent non-premixed flame on the model burner was conducted. A large eddy simulation of reacting flow with partial and detailed chemical kinetic mechanisms was employed to obtain a high-resolution and accurate prediction of thermochemical states inside the combustion chamber, including pollutant NO, which have not been adequately predicted until now. This study employed temperature and species mass fraction data from two combustion cases of fully developed turbulent and transition regimes with a fuel composition of 50 % H2 and 50 % N2, experimentally measured by the German Aerospace Center (DLR) and TU Darmstadt. A reactor-based partially-stirred reactor (PaSR) model was used to handle the turbulence chemistry interaction. The employed chemical mechanisms included GRI-Mech 3.0 and partial Mevel mechanism. The effects of chemical mechanism and inlet jet velocity on simulation accuracy were discussed. The more elaborative nitrogen reactions in GRI-Mech 3.0 result in a better NO prediction compared to the partial Mevel mechanism. The implementation of finite rate chemistry in a PaSR model yields a significantly improved prediction of NO from the flamelet probability density function approach with less than 1 % root mean square deviation from experimental data. The performed simulation successfully captured the thermochemical profile of a fully developed turbulent flame; however, further improvement on boundary condition modeling is still required for a flame undergoing a transition from laminar to turbulent regimes. Finally, using the partial Mevel mechanism leads to a computational cost reduction of 32.66 % compared to the GRI-Mech 3.0 mechanism, which confirms the proportional relation between the size of the mechanism and computational cost.

Understanding the Nonlinear Reactivity Promoting Effect of n-Heptane Addition on the Binary Mixture From Low to Intermediate Temperature: A Case of Methane/n-Heptane Mixtures

Abstract To understand the effect of n-heptane (NC7H16) addition on the auto-ignition of methane (CH4) at low to intermediate temperatures, the ignition delay times (IDTs) of stoichiometric CH4/NC7H16 blends with varying NC7H16 concentrations were measured at temperatures from 600 to 1000 K, pressures of 20 and 40 bar. Detailed chemical kinetic mechanisms were validated against the newly measured IDTs. Adding NC7H16 in the binary mixture shows a nonlinear promoting effect on the IDTs: micro-addition of NC7H16 can significantly reduce the IDTs of the binary mixture when the NC7H16 is lower than 20%. However, the decrease of the IDTs becomes much slower when further increasing the NC7H16 addition. Affected by the negative temperature coefficient (NTC) behavior of NC7H16, this nonlinear effect is particularly notable at around 795 K, the low boundary of the NTC region. To reveal the nonlinear reactivity-promoting effect of NC7H16 addition on the binary mixture, reaction flux, ignition sensitivity, rate of production of the key radicals along heat production analyses were conducted. Apart from contributing more O˙H production through the low-temperature chain-branching reaction pathways of NC7H16, adding NC7H16 also promotes the pre-ignition heat release of the binary mixture. The heat release raises the system temperature and further promotes the mixture ignition, enhancing the nonlinear effect at low temperatures.

Experimental and Modeling High-Pressure Study of Ammonia-Methane Oxidation in a Flow Reactor.

The present work deals with an experimental and modeling analysis of the oxidation of ammonia-methane mixtures at high pressure (up to 40 bar) in the 550-1250 K temperature range using a quartz tubular reactor and argon as a diluent. The impact of temperature, pressure, oxygen stoichiometry, and CH4/NH3 ratio has been analyzed on the concentrations of NH3, NO2, N2O, NO, N2, HCN, CH4, CO, and CO2 obtained as main products of the ammonia-methane mixture oxidation. The main results obtained indicate that increasing either the pressure, CH4/NH3 ratio, or stoichiometry results in a shift of NH3 and CH4 conversion to lower temperatures. The effect of pressure is particularly significant in the low range of pressures studied. The main products of ammonia oxidation are N2, NO, and N2O while NO2 concentrations are below the detection limit for all of the conditions considered. The N2O formation is favored by increasing the CH4/NH3 ratio and stoichiometry. The experimental results are simulated and interpreted in terms of an updated detailed chemical kinetic mechanism, which, in general, is able to describe well the conversion of both NH3 and CH4 under almost all of the studied conditions. Nevertheless, some discrepancies are found between the experimental results and model calculations.

An experimental and chemical kinetic simulation study of the high-temperature pyrolysis of linear C1–C5 alcohols

The high-temperature pyrolysis characteristics of C1–C5 linear alcohols, including methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol, systematically studied experimentally and the results interpreted using a detailed kinetic model. Specifically, a single-pulse shock tube coupled to a gas chromatography-mass spectrometry (GC-MS) system and a gas chromatograph (GC) is used to conduct a comprehensive experimental study on the high-temperature pyrolysis of the five alcohols, at pressures of 5 and 10 bar, in the temperature range 1000–1800 K at 1% fuel diluted by argon. Qualitative and quantitative analyses are conducted on the reactant, intermediate, and product species involved to determine species distributions as a function of temperature. A detailed chemical kinetic mechanism, NUIGMech1.3, is used to simulate the experimental data under the working conditions. The simulation results are compared with the experimental results, and it is shown that the overall trends between experiments and model predictions are relatively ideal in the comparison of all product and reactant concentrations, even though there is still a phenomenon of inaccurate prediction. Reaction pathway analysis is then conducted on the five alcohols. The present work not only provides additional experimental data for alcohols, but also provides insights into the high-temperature pyrolysis characteristics of the five fuels, which will be valuable for further development and optimization of detailed kinetic mechanisms of these alcohols and promote their practical application.

Reduction of NO[formula omitted] emissions in ammonia combustion using a double-flame premixed co-combustion concept

Ammonia is a carbon-free fuel that can be produced from renewable energy sources and has the potential to replace fossil fuels, exerting a significant impact on the decarbonization of power production and propulsion industries. However, the challenge lies in the high NOx emissions, narrow flammability, and low flame speed of ammonia/air mixtures. In this paper, we study a novel concept of double-flame premixed co-combustion (DFPC) of ammonia and methane in a double-swirl premixed combustion burner, which results in low NOx emissions and high flame stabilization. Large eddy simulations using a detailed chemical kinetic mechanism and planar laser-induced fluorescence imaging of OH and exhaust gas NO emission measurements are employed to investigate the fundamental mechanisms behind flame/flame interactions and NO emissions. The main findings are: (a) NO emissions can be reduced by 90% using the DFPC concept along with a significant broadening of flammability; (b) the outer methane/air flame stabilizes the inner ammonia flame in the shear layer of the two flames; (c) combustion products and excess oxygen leaked across the shear layer decrease the equivalence ratio of the inner ammonia/air mixture, reducing the NO formation of close-to-stoichiometric ammonia/air flame but increasing the NO formation in the fuel-rich ammonia/air flames; (d) mixing of the combustion products from the inner and outer flames reduces the NO emissions in the flue exhaust gas.

Enhancing lithium-ion battery safety: Investigating the flame-retardant efficacy of bis(2,2,2-trifluoroethyl) carbonate during ethyl methyl carbonate combustion

Bis(2,2,2-trifluoroethyl) carbonate (BtFEC) is a candidate fire suppressant for lithium-ion batteries (LIBs). The high flammability of the electrolyte is the reason behind the frequent fire incidents reported with LIBs. These incidents are due to various factors, such as a default in the conception of the battery or operational abuse. The flame-retardant effectiveness of BtFEC was investigated by measuring its effect on the oxidation of ethyl methyl carbonate (EMC), a common LIB electrolyte component. Laminar flame speed (LFS) measurements for EMC-BtFEC in air mixtures were carried out at 403 K, 1 atm, for equivalence ratios (ϕ) between 0.8 and 1.4, and with 0.5 % vol. BtFEC. Additional measurements were made at ϕ = 1.1 with BtFEC addition ranging from 0.1 up to 1.4 % vol. To further understand the combustion chemistry of the EMC-BtFEC system, ignition delay times (time at the maximum peak production of the excited radical OH*) and CO time histories were measured in a shock tube with temperatures ranging from 1217 to 1732 K, at near-atmospheric pressure (1.24–1.42 atm), and for three equivalence ratios (ϕ = 0.5, 1.0, and 2.0). These new results constitute an experimental database that was used to evaluate the performance of a model assembled for both BtFEC and EMC using previous work from our group. The updated, detailed chemical kinetics mechanism presented in this study consists of 237 species and 1630 reactions. Sensitivity, rate-of-production, and reaction pathway analyses permitted the oxidation of the BtFEC-EMC system to be described. A flame sensitivity analysis exhibited the significant effect from the reactions H + CF2O ⇆ HF + CFO and CF3 + H ⇆ CF2 + HF, which consume H radicals that are involved in the branching reaction H + O2⇆ OH + O, ultimately reducing the LFS. This study shows that improvements in the base fluorine chemistry are still necessary to obtain better agreement with the experiments, especially at the speciation level.

High-pressure study of the conversion of NH3/H2 mixtures in a flow reactor

Carbon free fuels such as hydrogen (H2) and ammonia (NH3) will probably play a fundamental role owing to their potential for clean combustion without CO2 emissions. To contribute to the knowledge and development of technologies based on carbon free combustion, the present work deals with an experimental and kinetic analysis of ammonia oxidation in its mixtures with hydrogen at high pressure (up to 40 bar), in the 250–1250 K temperature range using a quartz tubular reactor and argon as bath gas. The impact of temperature, pressure, stoichiometry and H2/NH3 ratio on the concentrations of NH3, NO, NO2, N2O, and N2 obtained as main products of oxidation has been analyzed. The main results indicate that either increasing pressure, H2/NH3 ratio or oxygen availability results in a shift of NH3 and H2 conversion to lower temperatures. The NH3 and H2 consumptions are promoted by the reactions that produce NH2, H, OH, O, HO2 and HNO species. The pressure effect is particularly significant in the low range of pressures studied. The main ammonia oxidation nitrogen products are N2 and N2O, while NO and NO2 concentrations are below the detection limit under all considered conditions. N2O formation is favored by increasing stoichiometry, pressure and H2/NH3 ratio. The experimental results are simulated and interpreted in terms of a literature detailed chemical kinetic mechanism, which, in general, is able to describe quite well both the H2 and NH3 conversion profiles under the studied conditions.

Probing O2-dependence of cyclopentyl reactions via isomer-resolved speciation

Modeling chemical kinetics relevant to low-temperature combustion requires complete description of reactions involving critical species such as hydroperoxyalkyl radicals, Q˙OOH, which undergo competing unimolecular reactions and bimolecular reactions with O2. The balance of flux across the two pathways affects rates of chain-branching and depends on temperature, pressure, and oxygen concentration. Accordingly, the influence of [O2] on product formation from alkyl + O2 reactions and the subsequent fate of Q˙OOH and related products is central to the development of an accurate chemical kinetics mechanism. However, chemical reactions consuming Q˙OOH-mediated species are often simplified to such a degree that mechanism truncation error (uncertainty derived from incomplete reaction networks) becomes significant.For the specific purpose of determining the extent to which expanded sub-mechanisms ameliorate inaccuracies in model predictions resulting from mechanism truncation error, the present work integrates speciation measurements from jet-stirred reactor experiments on cyclopentane oxidation with modeling using an expanded detailed chemical kinetics mechanism. The experiments utilize vacuum ultraviolet-absorption spectroscopy and mass spectrometry for isomer-resolved speciation of intermediates produced from cyclopentane oxidation at 835 Torr from 500 – 1000 K. [O2]-dependent experiments were also conducted from 0.12 – 3.66 · 1018 molecules cm–3 at 825 K to examine the influence on species profiles. The expanded mechanism is produced by merging detailed sub-mechanisms for Q˙OOH-mediated species (cyclopentene and 1,2-epoxycyclopentane) produced using Reaction Mechanism Generator (RMG) with an existing detailed mechanism for cyclopentane.Model predictions using the expanded mechanism yielded improvements in species mole fractions for both temperature- and O2-dependence. Ignition delay time simulations were also conducted and show appreciable sensitivity in the negative-temperature coefficient region due to incorporation of the detailed sub-mechanisms due to influence on O˙H radical populations. Sensitivity analysis revealed reactions that merit theoretical rate calculations for additional improvements and include species such as H2O2 and species related to R˙ + O2 reactions of cyclopentene and 1,2-epoxycyclopentane.

Experimental and modeling study of the combustion of ethyl methyl carbonate, a battery electrolyte

Ethyl methyl carbonate (EMC) is one of the main constituents of the electrolyte in lithium-ion batteries (LIBs). To understand better fire events involving LIBs and try to prevent them, the combustion of EMC was studied experimentally, and the results were analyzed using modern detailed kinetics models. Shock tubes were used to collect ignition delay times (IDTs) and CO time histories, while laminar flame speeds were measured in a closed vessel. All experiments were carried out near atmospheric pressure. The shock tube experiments were performed for three equivalence ratios (0.5, 1.0, and 2.0) with the IDTs measured with “fuel-air” mixtures and the CO spectroscopic laser measurements in mixtures highly diluted in 99.25% He/Ar. Comparisons with results obtained for other linear carbonates typically found in LIBs, such as dimethyl carbonate and diethyl carbonate, are also presented. Numerical predictions from recent detailed chemical kinetics mechanisms (Takahashi et al., 2022, Grégoire et al., 2023) did not capture well the combustion behavior of EMC in some of our conditions. Sensitivity analyses suggest that EMC decomposition reactions and subsequent combustion chemistry of the formed intermediates, i.e. methanol and ethylene, still need improvement.

A wide ranging experimental and kinetic modeling study of TMEDA pyrolysis and oxidation

Traditional liquid propellants like unsymmetrical dimethylhydrazine include several issues, such as toxicity, short storage time and preservation difficulty at low temperatures. For this reason, exploring green and stable propellant fuels is imperative in the development of propellants. Tetramethyl ethylenediamine (TMEDA) is considered to be a promising green propellant fuel with high specific impulse, non-toxicity, and long-term storage stability. Thus, investigating the combustion characteristics of TMEDA and constructing a detailed chemical kinetic mechanism are of fundamental importance in describing its combustion in computational fluid simulation. For this work, ignition delay times of TMEDA were measured in a shock tube at equivalent ratios of 0.5, 1.0 and 2.0, at pressures of 2, 10, and 20 bar, and in the temperature range of 870–1500 K with fixed fuel concentration at 2 %. After the reflected shock at 990–1500 K, the pyrolysis products of 2000 and 5000 ppm TMEDA in Argon were also measured at 5 and 10 bar conditions in a single pulse shock tube. In addition, laminar flame speeds of TMEDA were measured at initial pressures of 1 bar, initial temperatures of 333 and 353 K, and equivalence ratios ranging from 0.8 to 1.5 in a constant volume reactor. The experimental results were simulated using a detailed TMEDA kinetic mechanism. Reaction path analysis and sensitivity analysis were provided to clarify the chemical kinetics of TMEDA oxidation and pyrolysis. The current work provides new experimental data and fundamental analyses for understanding the oxidation and pyrolysis characteristics of TMEDA, and sheds light on optimal directions for future models.

Shock-tube CO measurements during the pyrolysis of ethylene carbonate

Ethylene carbonate (EC) is a key component of the flammable electrolyte in lithium-ion batteries. In this study, the pyrolysis of ethylene carbonate was investigated by measuring CO time histories near atmospheric pressure and in highly diluted conditions (0.999 He/Ar). The performance of a recent detailed chemical kinetics mechanism from Kanayama et al., 2022, was evaluated, and noticeable discrepancies were found, possibly indicating missing reaction pathways. A tentative model was proposed by merging the EC sub-mechanism from the Kanayama study with a recent model for linear carbonate pyrolysis from the authors (Grégoire et al., 2023). This tentative model includes the addition of several missing reactions for oxirane pyrolysis, and a couple of reactions for acetaldehyde and EC thermal decomposition were modified within their error uncertainties. The resulting model presents better predictions overall, but room for improvement remains. This study highlights the need to further study the pyrolysis chemistry of EC as well as acetaldehyde, which is a major intermediate component from EC pyrolysis under our conditions.