Low-Temperature Flameless Combustion of a Large Drop of <Emphasis Type="Italic">n</Emphasis>-Dodecane under Microgravity Conditions

The forced ignition, combustion, and spontaneous ignition of a drop of n-dodecane in an atmosphere of air at a normal pressure under microgravity conditions were studied based on a physicomathematical model of drop combustion and a detailed kinetic mechanism of the oxidation and combustion of n-dodecane C₁₂H₂₆. The selection of n-dodecane was related to the Russian–American experiment CFI (Cool Flame Investigation) Zarevo performed in 2017 aboard the International Space Station with the use of the large drops of this hydrocarbon. The analysis carried out deepens our knowledge about the flameless combustion of a large drop under the conditions of microgravity. The calculations showed that, after the radiation extinction of a hot flame, the drop can continue to evaporate because of the exothermic low-temperature oxidation of fuel vapor with repeated blue flame flashes at a characteristic temperature of 980–1000 K. A detailed analysis of the calculation results showed that the regular splashes of temperature resulted from the thermal decomposition of hydrogen peroxide—branching with the release of hydroxyl radicals.     

A comprehensive experimental and improved kinetic modeling study on the pyrolysis and oxidation of propyne

To improve our understanding of the combustion characteristics of propyne, new experimental data for ignition delay times (IDTs), pyrolysis speciation profiles and flame speed measurements are presented in this study. IDTs for propyne ignition were obtained at equivalence ratios of 0.5, 1.0, and 2.0 in ‘air’ at pressures of 10 and 30 bar, over a wide range of temperatures (690–1460 K) using a rapid compression machine and a high-pressure shock tube. Moreover, experiments were performed in a single-pulse shock tube to study propyne pyrolysis at 2 bar pressure and in the temperature range 1000–1600 K. In addition, laminar flame speeds of propyne were studied at an unburned gas temperature of 373 K and at 1 and 2 bar for a range of equivalence ratios. A detailed chemical kinetic model is provided to describe the pyrolytic and combustion characteristics of propyne across this wide-ranging set of experimental data. This new mechanism shows significant improvements in the predictions for the IDTs, fuel pyrolysis and flame speeds for propyne compared to AramcoMech3.0. The improvement in fuel reactivity predictions in the new mechanism is due to the inclusion of the propyne + H?₂ reaction system along with ?H radical addition to the triple bonds of propyne and subsequent reactions.     

Detailed investigation of soot formation from jet fuel in a diffusion flame with comprehensive and hybrid chemical mechanisms

A numerical and experimental study is performed to investigate soot formation from jet fuel in a laminar coflow diffusion flame. The combustion chemistry of the fuel is simulated using (1) the MURI jet fuel surrogate (Dooley et al. 2012) with a modestly reduced Ranzi mechanism (Ranzi et al. 2012), and (2) the recently proposed HyChem model (Xu et al. 2018) combined with the KAUST PAH mechanism 2 (Wang et al. 2013). The two reaction mechanisms are coupled with a sectional soot model to simulate a coflow diffusion flame of methane doped with the MURI jet fuel surrogate. The combined laser extinction and two-angle elastic light scattering method is used to perform non-intrusive in situ measurements of soot volume fraction, primary particle diameter and number density. The good agreement including soot particle size and number density between the experimental data and the simulation results computed with the reduced Ranzi mechanism demonstrate the robustness of the soot model to changes in fuel composition, as the model parameters are unchanged with a previous numerical study of soot formation of n-propylbenzene/n-dodecane mixtures (Zhang and Thomson, 2018). The computation with the combined HyChem/KAUST mechanism predicts similar results as the computation with the detailed chemistry of the reduced Ranzi mechanism for fuel breakdown, thus the basic premise of the HyChem model that the fuel decomposition process can be greatly simplified with the lumped reaction steps is supported. The results also show that by adding a PAH growth scheme to the HyChem model, the approach can be used to predict soot formation from jet fuel combustion in a laminar coflow diffusion flame. Finally, the dependency of the soot prediction on PAH chemistry is discussed and it is suggested that more experimental data is needed to validate the PAH mechanism and improve the predictive accuracy of the model.     

Development of a reduced biodiesel surrogate model for compression ignition engine modeling

Methylbutanoate (MB), a C₄ methyl ester, represents the simplest surrogate that captures the chemical effects of the ester moiety in biodiesel and biodiesel surrogates. An updated chemical kinetic model has been developed to characterize the ignition and flame characteristics of MB. The mechanistic elements within this model that relate to the MB and smaller ester/oxygenate sub-mechanisms are drawn from the prototypical Fisher et al. model and from more recent theory and modeling efforts. The MB model development which is based on an iterative procedure involving global sensitivity analyses to identify elementary reactions that govern ignition and subsequent high level ab initio based theoretical updates to these reaction rates are presented. The MB model makes reasonable predictions of ignition delays and laminar flame speeds.The C₅–C₇ submechanisms from the LLNL n-heptane (NH) model were merged with the present MB model to obtain a detailed chemical kinetics model for a surrogate blend representing biodiesel. The detailed MB-NH model (661 species) was reduced using graph based techniques. The robust reduction techniques employed result in a reduced model (145 species) that is in good agreement with the detailed model over a wide range of conditions. 3-D compression ignition (CI) engine simulations utilizing this reduced chemistry model for MB-NH blends as a surrogate for biodiesel show good agreement with the experimental data suggesting the utility of this model for predictions of combustion and emission characteristics of biodiesel in realistic CI engine simulations.     

Skeletal mechanism generation with CSP and validation for premixed n-heptane flames

An automated procedure has been previously developed to generate simplified skeletal reaction mechanisms for the combustion of n-heptane/air mixtures at equivalence ratios between 0.5 and 2.0 and different pressures. The algorithm is based on a Computational Singular Perturbation (CSP)-generated database of importance indices computed from homogeneous n-heptane/air ignition solutions. In this paper, we examine the accuracy of these simplified mechanisms when they are used for modeling laminar n-heptane/air premixed flames. The objective is to evaluate the accuracy of the simplified models when transport processes lead to local mixture compositions that are not necessarily part of the comprehensive homogeneous ignition databases. The detailed mechanism was developed by Curran et al. and involves 560 species and 2538 reactions. The smallest skeletal mechanism considered consists of 66 species and 326 reactions. We show that these skeletal mechanisms yield good agreement with the detailed model for premixed n-heptane flames, over a wide range of equivalence ratios and pressures, for global flame properties. They also exhibit good accuracy in predicting certain elements of internal flame structure, especially the profiles of temperature and major chemical species. On the other hand, we find larger errors in the concentrations of many minor/radical species, particularly in the region where low-temperature chemistry plays a significant role. We also observe that the low-temperature chemistry of n-heptane can play an important role at very lean or very rich mixtures, reaching these limits first at high pressure. This has implications to numerical simulations of non-premixed flames where these lean and rich regions occur naturally.     

Experimental and detailed kinetics modeling study of the fire suppressant properties of di(2,2,2trifluoroethyl) carbonate

To reduce the flammability of lithium-ion battery electrolytes, the fire suppressant effect of di(2,2,2trifluoroethyl) carbonate (DtFEC) was investigated experimentally and numerically using a new detailed kinetics model. DtFEC has a structure similar to diethyl carbonate (DEC), which is a very common component of battery electrolytes. This similar structure should allow for an integration of the fire suppressant without excessive degradation of the battery performance. To validate the model and assess the fire suppressant potential of DtFEC, several kinds of experiments were performed around atmospheric pressure. The high-temperature chemistry of DtFEC was investigated in shock tubes by measuring ignition delay times for a DtFEC/O₂/Ar mixture and by measuring the CO formation during its pyrolysis using a laser absorption diagnostic. DtFEC's fire suppressant potential was assessed by measuring the effects of a small DtFEC addition on the ignition delay times and laminar flame speeds of well-known fuels, namely H₂ and CH₄. A model was assembled using a well-validated and modern base mechanism (NUIGMech1.1) coupled with existing chemistry for fluoroalkanes. Using ab-initio calculations, the DtFEC module and corresponding thermodynamics data were implemented. The resulting model performs well at predicting the global kinetics data (ignition delay time, laminar flame speed), but improvements on CO time-history profiles are still necessary.     

Simulation-driven formulation of transportation fuel surrogates

An alternative way to formulate transportation fuel surrogates using model predictions of gas-phase combustion targets is explored and compared to conventional approaches. Given a selection of individual fuel components, a multi-component chemical mechanism describing their oxidation kinetics, and a database of experimental measurements for key combustion quantities such as ignition delay times and laminar burning velocities, the optimal fractional amount of each fuel is determined as the one yielding the smallest error between experiments and model predictions. Using a previously studied three-component jet fuel surrogate containing n-dodecane, methyl-cyclohexane, and m-xylene as a case study, this article investigates in a systematic manner how the surrogate composition affects model predictions for ignition delay time and laminar burning velocities over a wide range of temperature, pressure and stoichiometry conditions, and compares the results to existing surrogate formulation techniques, providing new insights on how to define surrogates for simulation purposes. Finally, an optimisation algorithm is described to accelerate the identification of optimal surrogate compositions in this context.     

Kinetic effects of NO addition on n-dodecane cool and warm diffusion flames

The kinetic effects of NO addition on the flame dynamics and burning limits of n-dodecane cool and warm diffusion flames are investigated experimentally and computationally using a counterflow system. The results show that NO plays different roles in cool and warm flames due to their different reaction pathway sensitivities to the flame temperature and interactions with NO. We observe that NO addition decreases the cool flame extinction limit, delays the extinction transition from warm flame to cool flame, and promotes the ignition transition from warm flame to hot flame. In addition, jet-stirred reactor (JSR) experiments of n-dodecane oxidation with and without NO addition are also performed to develop and validate a n-dodecane/NO_x kinetic model. Reaction pathway and sensitivity analyses reveal that, for cool flames, NO addition inhibits the low-temperature oxidation of n-dodecane and reduces the flame temperature due to the consumption of RO₂ via NO+RO₂?NO₂+RO, which competes with the isomerization reaction that continues the peroxy radical branching sequence. The model prediction captures well the experimental trend of the inhibiting effect of NO on the cool flame extinction limit. For warm flames, two different kinds of warm flame transitions, the warm flame extinction transition to cool flame and the warm flame reignition transition to hot flame, were observed. The results suggest that warm extinction transition to cool flame is suppressed by NO addition while the warm flame reignition transition to hot flame is promoted. The kinetic model developed captures well the experimentally observed warm flame transitions to cool flame but fails to predict the warm flame reignition to hot flame at similar experimental conditions.     

Flame propagation of mixtures of air with high molecular weight neat hydrocarbons and practical jet and diesel fuels

Laminar flame speeds of mixtures of air with n-C₁₄H₃₀, n-C₁₆H₃₄, a petroleum-derived JP-5 jet fuel, a camelina-derived hydrotreated renewable JP-5 jet fuel, a petroleum-derived F-76 diesel fuel, and an algae-derived hydrotreated renewable F-76 diesel fuel, were measured in the counterflow configuration at atmospheric pressure and elevated unburned mixture temperatures. Digital particle image velocimetry was used to measure the axial flow velocities along the stagnation streamline. The experiments for n-C₁₄H₃₀/air and n-C₁₆H₃₄/air mixtures were modeled using recently developed kinetic models, and the experimental data were predicted satisfactorily. Both experiments and simulations revealed that the laminar flame speeds of n-C₁₄H₃₀/air and n-C₁₆H₃₄/air mixtures are very close to each other, as expected. On the other hand, the laminar flame speeds for the four practical fuels were found to be lower than n-C₁₄H₃₀ and n-C₁₆H₃₄, due to the presence of aromatics and branched hydrocarbons. Similarly, the laminar flame speeds for the alternative fuels were found to be higher than the petroleum-derived ones, again due to the presence of aromatic compounds in the latter. Further insight into the effects of kinetics and molecular transport was obtained through sensitivity analysis.     

Experimental and modeling study on the pyrolysis and oxidation of n-decane and n-dodecane

High pressure n-decane and n-dodecane shock tube experiments were conducted to assist in the development of a Jet A surrogate kinetic model. Jet A is a kerosene based jet fuel composed of hundreds of hydrocarbons consisting of paraffins, olefins, aromatics and naphthenes. In the formulation of the surrogate mixture, n-decane or n-dodecane represent the normal paraffin class of hydrocarbons present in aviation fuels like Jet A. The experimental work on both n-alkanes was performed in a heated high pressure single pulse shock tube. The mole fractions of the stable species were determined using gas chromatography and mass spectroscopy. Experimental data on both n-decane and n-dodecane oxidation and pyrolysis were obtained for temperatures from 867 to 1739 K, pressures from 19 to 74 atm, reaction times from 1.15 to 3.47 ms, and equivalence ratios from 0.46 to 2.05, and ∞. Both n-decane and n-dodecane oxidation showed that the fuel decays through thermally driven oxygen free decomposition at the conditions studied. This observation prompted an experimental and modeling study of n-decane and n-dodecane pyrolysis using a recently submitted revised n-decane/iso-octane/toluene surrogate model. The surrogate model was extended to n-dodecane in order to facilitate the study of the species and the 1-olefin species quantified during the pyrolysis of n-dodecane and n-decane were revised with additional reactions and reaction rate constants modified with rate constants taken from literature. When compared against a recently published generalized n-alkane model and the original and revised surrogate models, the revised (based on our experimental work) and extended surrogate model showed improvements in predicting 1-olefin species profiles from pyrolytic and oxidative n-decane and n-dodecane experiments. The revised and extended model when compared to the published generalized n-alkane and surrogate models also showed improvements in predicting species profiles from flow reactor n-decane oxidation experiments, but similarly predicted n-decane and n-dodecane ignition delay times.     

A novel linear transformation model for the analysis and optimisation of chemical kinetics

In this study, a novel model for the analysis and optimisation of numerical and experimental chemical kinetics is developed. Concentration–time profiles of non-diffusive chemical kinetic processes and flame speed profiles of fuel–oxidiser mixtures can be described by certain characteristic points, so that relations between the coordinates of these points and the input parameters of chemical kinetic models become almost linear. This linear transformation model simplifies the analysis of chemical kinetic models, hence creating a robust global sensitivity analysis and allowing quick optimisation and reduction of these models. Firstly, in this study the model is extensively validated by the optimisation of a syngas combustion model with a large data set of imitated ignition experiments. The optimisation with the linear transformation model is quick and accurate, revealing the potential for decreasing the numerical costs of the optimisation process by at least one order of magnitude compared to established methods. Additionally, the optimisation on this data set demonstrates the capability of predicting reaction rate coefficients more accurately than by currently known confidence intervals. In a first application, methane combustion models are optimised with a small experimental set consisting of OH(A) and CH(A) concentration profiles from shock tube ignition experiments, species profiles from flow reactor experiments and laminar flame speeds. With the optimised models, especially the predictability for the flame speeds of mixtures of hydrogen, carbon monoxide and methane can be increased compared to established models. With the analysis of the optimised models, new information on the low pressure reaction coefficient of the fall-off reaction H+CH₃(+M)?CH₄(+M) is determined. In addition, the optimised combustion model is quickly and efficiently reduced to validate a new rapid reduction scheme for chemical kinetic models.     

Autoignition and combustion of hydrocarbon-hydrogen-air homogeneous and heterogeneous ternary mixtures

A numerical simulation of the ignition and combustion of hydrocarbon-hydrogen-air homogeneous and heterogeneous (gas-drop) ternary mixtures for three hydrocarbon fuels (n-heptane, n-decane, and n-dodecane) is for the first time performed. The simulation is carried out based on a fully validated detailed kinetic mechanism of the oxidation of n-dodecane, which includes the mechanisms of the oxidation of n-decane, n-heptane, and hydrogen as constituent parts. It is demonstrated that the addition of hydrogen to a homogeneous or heterogeneous hydrocarbon-air mixture increases the total ignition delay time at temperatures below 1050 K, i.e., hydrogen acts as an ignition inhibitor. At low temperatures, even ternary mixtures with a very high hydrogen concentration show multistage ignition, with the temperature dependence of the ignition delay time exhibiting a negative temperature coefficient region. Conversely, the addition of hydrogen to homogeneous and heterogeneous hydrocarbon-air mixtures at temperatures above 1050 K reduces the total ignition delay time, i.e., hydrogen acts as an autoignition promoter. These effects should be kept in mind when discussing the prospects for the practical use of hydrogen-containing fuel mixtures, as well as in solving the problems of fire and explosion safety.     

Measurements of the critical initiation radius and unsteady propagation of n-decane/air premixed flames

Unsteady flame propagation, the critical radius for flame initiation, and multiple flame regimes of n-decane/air mixtures are studied experimentally and computationally using outwardly propagating spherical flames at various equivalence ratios and pressures. The transient flame speeds, trajectories, and critical radius are measured. The experimental results are compared with direct numerical simulations using detailed high temperature kinetic models. Both experimental and numerical results show that there exist multiple flame regimes in the unsteady spherical flame initiation process. The transition between the flame regimes depends strongly on the mixture equivalence ratio (or Lewis number). It is found that there is a critical flame radius and that it increases dramatically as the mixture equivalence ratio and pressure decrease. The large increase of critical flame radius leads to a dramatic increase of the minimum ignition energy. Furthermore, the flame thickness and the radical pool concentration change significantly during the transition from the ignition flame regime to the self-sustained propagating flame regime. For the same steady state flame speeds, the predicted unsteady flame speeds and the critical flame radius differ significantly from the experimental results. Moreover, different chemical kinetic mechanisms predict different unsteady flame speeds. The existence of multiple flame regimes and the large critical radius of lean liquid fuel mixtures make the ignition of lean mixtures at low pressure and the development of a validated kinetic model more challenging. The unsteady flame regimes, speeds, and critical flame radius should be included as targets of future kinetic model development for turbulent combustion modeling.     

Ab initio evaluation of primary cyclo-hexane oxidation reaction rates

Naphthenes are chemical species that are always present in liquid hydrocarbon fuels and their pyrolysis and oxidation can play an important role in real liquid fuel combustion. In spite of its practical relevance, the chemical kinetics of naphthene pyrolysis and oxidation is not yet thoroughly investigated and there is not a general agreement on the role and rate of several elementary reactions involved. In this paper, the kinetics of the pyrolysis and oxidation of a simple naphthene, namely cyclo-hexane, has been investigated through detailed kinetic modeling. Ab initio calculations were performed to estimate the kinetic parameters of some primary reactions following the oxygen attack to the cyclo-hexane radical. In fact, due to the complex behavior induced by the ring structure of cyclo-hexane, such data were difficult to determine through thermo-chemical methods. Density functional theory (B3LYP/6-31g(d, p)) was adopted to determine structure and vibrational frequencies of transition states and reaction intermediates, while energies were evaluated using the G2MP2 approach. The kinetic parameters of the investigated primary reactions were then introduced in a general detailed kinetic model consisting of elementary reactions whose kinetic constants were taken from the literature. The so obtained kinetic model was used to simulate ignition delay times and species concentrations measured in various experiments reported in the literature. The agreement between experimental data and theoretical predictions shows the validity of the chosen approach and supports the correctness of the proposed kinetic model.     

Insight into the inner structure of stretched premixed ammonia-air flames

Ammonia as a fuel has sparked significant interest in the combustion community. Although, using ammonia has a lot of advantages including no carbon emissions, ammonia-air flames are characterized as thick flames with low flame speeds. It is important to understand the flame structure to know the combustion process better. Flame thickness is an important property of the flame which characterizes the reactivity of the flame. Identifying the preheat zone is necessary to determine the fresh gas surface which is used to determine flame speed. Also, understanding the behavior of the important species emitted helps to demonstrate the reaction pathway which may be implemented in chemical kinetics schemes. Further, it is interesting to know the effect of curvature on the emission of excited species which gives direct knowledge on the influence of curvature on the flame reactivity. It was seen that the change in reactivity was manifested as a change in thickness of the species. The experiments presented here were performed on a Bunsen burner at atmospheric conditions. The laminar flame speeds have been evaluated over a range of equivalence ratios by choosing the isotherm as specified by the definition of the flame speed which are slightly higher than the values obtained from the literature. Chemiluminescence from NH* and NH₂* was studied for different equivalence ratios. A 1D simulation performed in Chemkin-Pro-was used to compare the behavior of the counterpart non-excited species. This comparison helps to correlate excited and non-excited species and also to define the structure of the ammonia-air flame. Both NH* and NH₂* have been determined as heat release rate markers.     

n-Dodecane oxidation at high-pressures: Measurements of ignition delay times and OH concentration time-histories

Ignition delay times and OH concentration time-histories were measured during n-dodecane oxidation behind reflected shocks waves using a heated, high-pressure shock tube. Measurements were made over temperatures of 727-1422 K, pressures of 15-34 atm, and equivalence ratios of 0.5 and 1.0. Ignition delay times were measured using side-wall pressure and OH^∗ emission diagnostics, and OH concentration time-histories were measured using narrow-linewidth ring-dye laser absorption near the R-branchhead of the OH A-X (0, 0) system at 306.47 nm. Shock tube measurements were compared to model predictions of four current n-dodecane oxidation detailed mechanisms, and the differences, particularly in the low-temperature negative-temperature-coefficient (NTC) region where the influence of non-ideal facility effects can be significant, are discussed. To our knowledge, the current measurements provide the first gas-phase shock tube ignition delay times (at pressures above 13 atm) and quantitative OH concentration time-histories for n-dodecane oxidation under practical engine conditions, and hence provide benchmark validation targets for refinement of jet fuel detailed kinetic modeling, since n-dodecane is widely used as the principal representative for n-alkanes in jet fuel surrogates.     

Effects of cryogenic temperature on premixed hydrogen/air flame propagation in a closed channel

As a carbon-free fuel, hydrogen has received significant attention recently since it can help enable low-carbon-economy. Hydrogen has very broad flammability range and very low minimum ignition energy, and thereby there are severe safety concerns for hydrogen transportation and utilization. Cryo-compressed hydrogen is popularly used in practice. Therefore, it is necessary to investigate the combustion properties of hydrogen at extremely low or cryogenic temperatures. This study aims to assess and interpret the effects of cryogenic temperature on premixed hydrogen/air flame propagation and acceleration in a thin closed channel. Different initial temperatures ranging from normal temperature (T₀ = 300 K) to cryogenic temperature (T₀ = 100 K) are considered. Both one- and two-dimensional hydrogen/air flames are investigated through transient simulations considering detailed chemistry and transport. It is found that when the initial temperature decreases from T₀ = 300 K to T₀ = 100 K, the expansion ratio and equilibrium pressure both increase substantially while the laminar flame speeds relative to unburned and burned gasses decrease moderately. The one-dimensional flame propagation is determined by laminar flame speed and thereby the combustion duration increases as the initial temperature decreases. However, the opposite trend is found to happen to two-dimensional flame propagation, which is mainly controlled by the flame surface area increase due to the no-slip side wall constraint and flame instability. Based on the change in flame surface area, three stages including the initial acceleration, steady burning and rapid acceleration are identified and investigated. It is demonstrated that the large expansion ratio and high pressure rise at cryogenic temperatures can significantly increase the flame surface area in early stage and promote both Darrieus-Landau instability (hydrodynamic instability) and Rayleigh-Taylor instability in later stage. These two instabilities can substantially increase the flame surface area and thereby accelerate flame propagation in hydrogen/air mixtures at cryogenic temperatures. The present study provides useful insights into the fundamental physics of hydrogen flames at extremely low temperatures, and is closely related to hydrogen safety.     

Methyl concentration time-histories during iso-octane and n-heptane oxidation and pyrolysis

Methyl radical concentration time-histories were measured during the oxidation and pyrolysis of iso-octane and n-heptane behind reflected shock waves. Initial reflected shock conditions covered temperatures of 1100-1560 K, pressures of 1.6-2.0 atm and initial fuel concentrations of 100-500 ppm. Methyl radicals were detected using cw UV laser absorption near 216 nm; three wavelengths were used to compensate for time- and wavelength-dependent interference absorption. Methyl time-histories were compared to the predictions of several current oxidation models. While some agreement was found between modeling and measurement in the early rise, peak and plateau values of methyl, and in the ignition time, none of the current mechanisms accurately recover all of these features. Sensitivity analysis of the ignition times for both iso-octane and n-heptane showed a strong dependence on the reaction C₃H₅ + H = C₃H₄ + H₂, and a recommended rate was found for this reaction. Sensitivity analysis of the initial rate of CH₃ production during pyrolysis indicated that for both iso-octane and n-heptane, reaction rates for the initial decomposition channels are well isolated, and overall values for these rates were obtained. The present concentration time-history data provide strong constraints on the reaction mechanisms of both iso-octane and n-heptane oxidation, and in conjunction with OH concentration time-histories and ignition delay times, recently measured in our laboratory, should provide a self-consistent set of kinetic targets for the validation and refinement of iso-octane and n-heptane reaction mechanisms.     

Exploring fuel isomeric effects on laminar flame propagation of butylbenzenes at various pressures

This work reports an experimental and kinetic modeling investigation on the laminar flame propagation of three butylbenzene isomers (n-butylbenzene, iso-butylbenzene and tert-butylbenzene)/air mixtures. The experiments were performed in a high-pressure constant-volume cylindrical combustion vessel at the initial temperature of 423 K, initial pressures of 1–10 atm, and equivalence ratios (?) of 0.7–1.5. The laminar burning velocities of butylbenzene/O₂/He mixtures were also measured at 423 K, 10 atm and ? = 1.5 to provide additional experimental data under conditions that the butylbenzene/air experiments are susceptible of cellular instability. Comparison among the laminar burning velocities of butylbenzenes including both the three isomers investigated in this work and sec-butylbenzene investigated in our recent work [Combust. Flame 211 (2020) 18–31] shows remarkable fuel isomeric effects, that is, iso-butylbenzene has the slowest laminar burning velocities, followed by n-butylbenzene and tert-butylbenzene, while sec-butylbenzene has the fastest laminar burning velocities. A kinetic model for butylbenzene combustion was developed to simulate the laminar flame propagation of butylbenzenes. Sensitivity analysis was performed to reveal important reactions in laminar flame propagation of butylbenzenes, including both small species reactions and fuel-specific reactions. Kinetic effects are concluded to result in the different laminar burning velocities of four butylbenzene isomers. Small species reactions control the laminar flame propagation under lean conditions, which results in small differences of laminar burning velocities. Chain termination reactions, especially fuel-specific reactions, have important contributions to inhibit the laminar flame propagation under rich conditions. The structural features of butylbenzene isomers can significantly affect the formation of some crucial radicals such as methyl, cyclopentadienyl and benzyl radicals under rich conditions, which leads to remarkable fuel isomeric effects on their laminar burning velocities, especially at high pressures.