Ignition Delay Time Measurements Research Articles

High temperature oxidation of residual oil pyrolysis intermediates for modeling gasification and combustion processes

Developing chemical kinetic models for residual oil pyrolysis, gasification, and combustion is very challenging due to the large number of components and molecular complexity. This study provides experimental data for model development and validation for two residual oils, heavy fuel oil (HFO) and vacuum residual oil (VRO). This study aims to identify and quantify the HFO and VRO pyrolysis intermediates and validate an oxidation chemical kinetic model of the pyrolysis intermediates to provide data for future residual oil model development using hybrid chemistry (HyChem) and functional groups for mechanism development (FGMech) approaches. The pyrolysis experiments were conducted in a bench-scale tubular reactor at atmospheric pressure and a temperature of 1273 K. Detailed compositions of the yields from the pyrolysis of HFO and VRO were analyzed using gas chromatography-flame ionization detection (GC-FID) for the gas yields and gas chromatography-mass spectrometry/flame ionization detection (GC–MS/FID) for the liquids. Elemental analysis was conducted for the solid residuals. The experiment results show similar pyrolysis products from HFO and VRO. A surrogate of major components of the gas products and representatives of benzene and naphthalene derivatives (major compounds identified in liquid products) of the liquid products was formulated and its chemistry was studied by measuring ignition delay times (IDTs) in a shock tube. IDT measurements were conducted for stoichiometric and rich (ϕ = 1 and 3) mixtures, pressures of 20 and 40 bar, and diluents of nitrogen and carbon dioxide. Brute force IDT sensitivity analyses were used to study the effect of pressure, equivalence ratio and diluents on the reactivity of the mixture.

Ignition delays of two ADN/GAP mixtures irradiated by a CO2 laser: atmospheric experiments and numerical calculations

The ignition experiments of two ADN/GAP mixtures irradiated by a CO2 laser were conducted to investigate the dominant mechanism of ignition induced process. The power law exponents of experimental curves for ignition delay versus laser power density are all closed to -1. Two reduced numerical models were employed to calculate the ignition delay times against the experimental data. The analysis suggested that the ignition delays of ADN/GAP mixtures related to the corresponding burning rates and the ignition delay behaviours followed a fixed energy pattern approximately. The calculation results indicated that the measured ignition delay time might be mainly dominated by the formation of preheating layer for steady state burning.

Experimental Kinetics Study on Diethyl Carbonate Oxidation

Diethyl carbonate (DEC) is a common component of the liquid electrolyte in lithium ion batteries (LIBs). As such, understanding DEC combustion chemistry is imperative to improving chemical kinetic modeling of LIB fires. To this end, a comprehensive experimental study was conducted to collect ignition delay times, CO time histories, and laminar flame speeds during DEC combustion. Ignition delay times were collected using a heated shock tube at real fuel–air conditions for three equivalence ratios (ϕ = 0.5, 1.0, and 2.0) near atmospheric pressure and for temperatures between 1182 and 1406 K. Another shock tube was used to collect CO time histories using a laser absorption diagnostic. These experiments were conducted for the same equivalence ratios, but highly diluted in argon and helium (79.25% Ar + 20% He) at an average pressure of 1.27 atm and a temperature range of 1236–1669 K. Finally, a heated constant-volume vessel was used to collect laminar flame speeds of DEC at an initial temperature and pressure of 403 K and 1 atm, respectively, for equivalence ratios between 0.79 and 1.38. The results are compared with different mechanisms from the literature. Good agreement is seen for the ignition delay time and flame speed measurements. However, significant deviations are observed for the CO time histories. A detailed discussion of the chemical kinetics is presented to elucidate the important reactions and direct future modeling efforts.

New insights into the pre-ignition behavior of methane behind reflected shock waves

Pre-ignition is an undesired combustion event known to restrict kinetic modeling validation. Previous methane oxidation studies reported premature ignition as part of ignition delay time measurements in shock tubes. In this context, the effect on the pre-ignition propensity and auto-ignition behavior of stoichiometric methane mixtures at different dilution levels of hbox {N}_2, Ar, He, and hbox {CO}_2 was studied at 10 bar and 25 bar and temperatures between 1080 K and 1350 K. In addition to conventional sidewall pressure and endwall light emission measurements, a high-speed imaging setup was utilized to visualize the ignition process. Relevant physicochemical parameters to describe and predict the pre-ignition phenomenon were used. The results suggest that dilution levels up to 80% of bath gas are not successful in mitigating early ignition occurrence and its effects at moderate pressures. Replacing hbox {N}_2 by He was found to suppress early ignition at 10 bar, attributed to an enhanced dissipation of temperature inhomogeneities in the test gas section. The present findings demonstrate that hbox {CO}_2 has potential for pre-ignition heat release mitigation, while Ar was confirmed to promote premature ignition. To the best of our knowledge, we present the first detailed study on pre-ignition mitigation for methane mixtures in shock tubes, where further insights into its ignition non-idealities are given.

Methane and n-hexane ignition in a newly developed diaphragmless shock tube

Shock tubes have been routinely used to generate reliable chemical kinetic data for gas-phase chemistry. The conventional diaphragm-rupture mode for shock tube operation presents many challenges that may ultimately affect the quality of chemical kinetics data. Numerous diaphragmless concepts have been developed to overcome the drawbacks of using diaphragms. Most of these diaphragmless designs require significant alterations in the driver section of the shock tube and, in some cases, fail to match the performance of the diaphragm-mode of operation. In the present work, an existing diaphragm-type shock tube is retrofitted with a fast-acting valve, and the performance of the diaphragmless shock tube is evaluated for investigating the ignition of methane and n-hexane. The diaphragmless shock tube reported here presents many advantages, such as eliminating the use of diaphragms, avoiding substantial manual effort during experiments, automating the shock tube facility, having good control over driver conditions, and obtaining good repeatability for reliable gas-phase chemical kinetic studies. Ignition delay time measurements have been performed in the diaphragmless shock tube for three methane mixtures and two n-hexane mixtures at P5 = 10–20 bar and T5 = 738–1537 K. The results obtained for fuel-rich, fuel-lean, and oxygen-rich (undiluted) mixtures show very good agreement with previously reported experimental data and literature kinetic models (AramcoMech 3.0 [1] for methane and Zhang et al. mechanism [2] for n-hexane). The study presents an easy and simple method to upgrade conventional shock tubes to a diaphragmless mode of operation and opens new possibilities for reliable chemical kinetics investigations.

A Novel Reduced Reaction Mechanism for Diesel/2,5-Dimethylfuran Engine Application

The application of 2,5-dimethylfuran (DMF) as an alternative fuel for internal combustion engines has been gaining popularity. However, it has rarely been studied in previous research on the chemical kinetics of DMF for engine combustion simulations. In the present study, a reduced n-heptane/toluene/DMF-polycyclic aromatic hydrocarbon (PAH) reaction mechanism containing only 78 species amongst 190 reactions was proposed and applied to predict the combustion and emissions of a diesel engine using diesel/DMF blend fuel. First, a detailed reaction mechanism for DMF from the literature was chosen and reduced using combined mechanism reduction methods under engine-relevant conditions. Second, the reduced mechanism of DMF was incorporated into an existing reduced n-heptane/toluene-PAH mechanism to establish a three-component chemistry mechanism. Third, the predictive capability of the combined mechanism was improved by adjusting the rate constants of selected gas-phase reactions. Subsequently, the proposed three-component mechanism was compared and validated with experimental measurements of shock tube ignition delay times and premixed flame species profiles acquired from published papers. Moreover, new experimental data from a conventional diesel engine were used to evaluate the developed mechanism. Overall, the predicted results obtained by this proposed reduced n-heptane/toluene/DMF-PAH mechanism are in reasonable agreement with the available experiments.

A wide range experimental and kinetic modeling study of the oxidation of 2,3-dimethyl-2-butene: Part 1

2,3-Dimethyl-2-butene (TME) is a potential fuel additive with high research octane number (RON) and octane sensitivity (S), which can improve internal combustion engine performance and efficiency. However, the combustion characteristics of TME have not been comprehensively investigated. Thus, it is essential to study the combustion characteristics of TME and construct a detailed chemical kinetic model to describe its combustion. In this paper, two high-pressure shock tubes and a constant-volume reactor are used to measure ignition delay times and laminar flame speeds of TME oxidation. The ignition delay times were measured at equivalence ratios of 0.5, 1.0, and 2.0 in “air”, at pressures of 5 and 10 bar, in the temperature range of 950 – 1500 K. Flame speeds of the TME/ “air” mixtures were measured at atmospheric pressure, at a temperature of 325 K, for equivalence ratios ranging from 0.78 to 1.31. Two detailed kinetic mechanisms were constructed independently using different methodologies; the KAUST TME mechanism was constructed based on NUIGMech1.1, and the MIT TME mechanism was built using the Reaction Mechanism Generator (RMG). Both mechanisms were used to simulate the experimental results using Chemkin Pro. In the present work, reaction flux and sensitivity analyses were performed using the KAUST mechanism to determine the critical reactions controlling TME oxidation at the conditions studied.

NOx formation from ammonia, and its effects on oxy-combustion of hydrocarbon fuels under supercritical-CO2 conditions

NOx formation from ammonia impurities and its effects on fuel oxidation is not well understood for high-pressure supercritical CO2 oxy-combustion conditions. This effect is investigated computationally and experimentally in the present work. A chemical kinetic analysis revealed that the reaction between NH radical and CO2 plays an important role in determining the rate of NOx formation at these conditions. It was also found that a significant reduction in the NOx formation from ammonia oxidation occurs with sCO2 oxy-combustion at 300 atm when compared to traditional gas turbine conditions. A chemical reactor network simulation of realistic sCO2 cycle conditions confirmed the reduced NOx emissions. Monte Carlo simulations used to study the sensitivity of model input variables on the emissions showed that CO2 cooling impacts the CO emissions while most of the NOx are generated in the flame zone. Uncertainty analysis showed that the reaction between NH and CO2 to form HNO radical is an important contributor to the model uncertainty under sCO2 oxy-combustion conditions.The presence of combustion-generated NOx in the recycled-CO2 can impact the fuel oxidation in the primary zone of the combustor. Hence, to understand the effect of NOx on ignition, high-pressure shock tube ignition delay time experiments were performed at conditions relevant to sCO2 oxy-combustion. The ignition delay time measurements were made for syngas and CH4 fuels with and without NO addition under supercritical conditions using CO2 as the bulk diluent at nominal pressures around 100 atm. Experimental data showed that the presence of NO promotes ignition at these conditions. The effect is more pronounced for CH4 compared to syngas. Nitric oxide acts as a chemical catalyst to promote ignition by increasing the combustion radical pool. The catalytic cycle involves the conversion of NO to NO2 which also contributes to CH4 oxidation by H-atom abstraction to generate CH3 radical.

A comprehensive experimental and kinetic modeling study of di-isobutylene isomers: Part 2

A wide variety of high temperature experimental data obtained in this study complement the data on the oxidation of the two di-isobutylene isomers presented in Part I and offers a basis for an extensive validation of the kinetic model developed in this study. Due to the increasing importance of unimolecular decomposition reactions in high-temperature combustion, we have investigated the di-isobutylene isomers in high dilution utilizing a pyrolysis microflow reactor and detected radical intermediates and stable products using vacuum ultraviolet (VUV) synchrotron radiation and photoelectron photoion coincidence (PEPICO) spectroscopy. Additional speciation data at oxidative conditions were also recorded utilizing a plug flow reactor at atmospheric pressure in the temperature range 725–1150 K at equivalence ratios of 1.0 and 3.0 and at residence times of 0.35 s and 0.22 s, respectively. Combustion products were analyzed using gas chromatography (GC) and mass spectrometry (MS). Ignition delay time measurements for di-isobutylene were performed at pressures of 15 and 30 bar at equivalence ratios of 0.5, 1.0, and 2.0 diluted in ‘air’ in the temperature range 900–1400 K using a high-pressure shock-tube facility. New measurements of the laminar burning velocities of di-isobutylene/air flames are also presented. The experiments were performed using the heat flux method at atmospheric pressure and initial temperatures of 298–358 K. Moreover, data consistency was assessed with the help of analysis of the temperature and pressure dependencies of laminar burning velocity measurements, which was interpreted using an empirical power-law expression. Electronic structure calculations were performed to compute the energy barriers to the formation of many of the product species formed. The predictions of the present mechanism were found to be in adequate agreement with the wide variety of experimental measurements performed.

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.

Shock-tube study of high-temperature ignition of propane-air mixtures at elevated pressures

Ignition delay time measurements in high-temperature propane-air mixtures have been performed behind reflected shock wave at temperatures T = 1043 ÷ 1778 K, pressures p = 17.7 ÷ 42.8 atm, and equivalence ratios φ = 0.5, 1.0, and 2.0. Simultaneously, the emission characteristics of the flammable mixture associated with the emission of electronically excited OH* radical were recorded. The available detailed kinetic mechanisms of propane ignition were used to describe the obtained experimental data. Sensitivity analyses of the propane-air mixtures with various equivalence ratios was carried out to single out the key reactions proceeded in these mixtures. The data obtained make it possible to specify the available information on the ignition of combustible mixtures and thereby to improve the understanding of the processes occurring in the combustion chambers.

Plasma thermal-chemical instability of low-temperature dimethyl ether oxidation in a nanosecond-pulsed dielectric barrier discharge

Plasma stability in reactive mixtures is critical for various applications from plasma-assisted combustion to gas conversion. To generate stable and uniform plasmas and control the transition towards filamentation, the underlying physics and chemistry need a further look. This work investigates the plasma thermal-chemical instability triggered by dimethyl-ether (DME) low-temperature oxidation in a repetitive nanosecond pulsed dielectric barrier discharge. First, a plasma-combustion kinetic mechanism of DME/air is developed and validated using temperature and ignition delay time measurements in quasi-uniform plasmas. Then the multi-stage dynamics of thermal-chemical instability is experimentally explored: the DME/air discharge was initially uniform, then contracted to filaments, and finally became uniform again before ignition. By performing chemistry modeling and analyzing the local thermal balance, it is found that such nonlinear development of the thermal-chemical instability is controlled by the competition between plasma-enhanced low-temperature heat release and the increasing thermal diffusion at higher temperature. Further thermal-chemical mode analysis identifies the chemical origin of this instability as DME low-temperature chemistry. This work connects experiment measurements with theoretical analysis of plasma thermal-chemical instability and sheds light on future chemical control of the plasma uniformity.

The influence of thermochemistry on the reactivity of propane, the pentane isomers and n-heptane in the low temperature regime

The influence of thermochemistry on the reactivity of fuels at low temperatures (600–1000 K) is studied here. Specifically, the effect of different sets of thermochemistry on chemical model predictions is explored, where various sets are calculated at different levels of theory in addition to recently updated group additivity values. Experimentally measured ignition delay times for propane, the pentane isomers and n-heptane are simulated using NUIGMech1.2 and replacing the thermochemistry of the low-temperature species with the calculated values. For propane, three different thermochemistry sets were calculated, namely CCSD(T)-F12/TZ-F12//B2PLYP-D3/TZ//B2PLYP-D3/TZ (QM1), CCSD(T)-F12/TZ-F12//B2PLYP-D3/TZ//ωB97X-D/TZ (QM2) and B2PLYP-D3/TZ/ωB97X-D/6-31G*//ωB97X-D/6-31G* (QM3). The QM2 results provide parameters to optimize new group additivity (NGA) values which are used to calculate the fourth set of thermochemistry. The model predictions using these four sets are compared to those using NUIGMech1.2 for propane. As the QM1 and QM2 calculations are expensive, the thermochemistry calculated from the QM3 and NGA calculations are used in the pentane isomer and n-heptane models. For all of the models, it is found that the thermochemistry of the species involved in the low-temperature reaction sequence (RH, Ṙ, RO2H, RȮ2, Q˙OOH and Ȯ2QOOH species) significantly affect fuel reactivity. The NGA values were developed based on all of these species except Ȯ2QOOH radicals. The thermochemistry of Ȯ2QOOH species cannot be accurately calculated with the NGA representations due to the importance of non-next-nearest neighbor interactions of –OOH substitution. Further development of the NGA method to capture such interactions is in progress. Overall, the model developed using the NGA thermochemistry shows better agreement with experimental data than the model using thermochemistry from affordable and prominent QM methods, such as QM3. Based on the results presented for propane, the pentane isomers and n-heptane, the thermochemistry calculated using the NGA method can be used to model the oxidation of higher order hydrocarbons at low temperatures.

Investigation of cyclohexene thermal decomposition and cyclohexene + OH reactions

Cyclohexene is a common intermediate in the oxidation of cyclohexane and alkyl-substituted cyclohexanes. It also plays an important role in the formation of polycyclic aromatic hydrocarbons (PAHs) by providing a route for the first aromatic ring. Two types of reactions are highly important in cyclohexene kinetics, i.e., H-abstraction by OH radicals and cyclohexene thermal decomposition. In this work, we have investigated these two reactions experimentally by employing sensitive UV diagnostics of OH radicals and 1,3-butadiene. We conducted rate coefficient measurements of cyclohexene + OH reaction (k1) over 933–1259 K and 1–4 bar using a narrow-linewidth UV absorption diagnostic of OH radicals near 306.67 nm. The carefully designed test conditions minimized the influence of secondary reactions such as cyclohexene thermal decomposition. Our determined OH + cyclohexene high-temperature rate coefficients show a positive temperature dependence and a negligible pressure dependence. Our rate values may be fitted with a two-parameter Arrhenius expression (units of cm3molecule−1s−1):k1=1.28×10−10e(−1225T)We also investigated channel-specific competition in OH + cyclohexene reaction. H-abstraction by OH from allylic (kc), alkylic (kb), and vinylic (ka) CH bonds contributes roughly 60%, 35%, and 5% over our temperature range. Our determined kc agrees excellently with literature rate coefficient of H-abstraction from the allylic site of 1-butene.We studied cyclohexene thermal decomposition reaction (k2) by tracing the product 1,3-butadiene near 212.5 nm over 1092–1361 K and 0.82–1 bar. Compared to literature works, our highly sensitive UV diagnostic of 1,3-butadiene enabled time-resolved measurements with low cyclohexene concentration, which guaranteed nearly isothermal conditions despite reaction endothermcity. Our measured rate coefficients may be expressed as (unit of s−1):k2=3.68×1014e(−31,562T)We implemented our determined rate coefficients (k1 and k2) in a literature cyclohexene kinetic model and also updated the 1,3-butadiene sub-mechanism. The updated model shows improved predictions of measured ignition delay times of cyclohexene.

Experimental and chemical kinetic modeling study of trimethoxy methane combustion

The use of oxymethylene ethers (OMEs) as alternative fuels or fuel-additives has motivated the present study on the combustion behavior of trimethoxy methane (TMM), which is a branched version of OMEs. A detailed chemical kinetic model for TMM combustion is provided, which is based on a recent model for the structurally similar dimethoxy methane (DMM) and recent elementary reaction kinetics studies. This model is validated against TMM ignition delay times measured in a shock tube at 20 and 40 bar, under fuel lean, stoichiometric, and fuel rich conditions. Further, the TMM model is validated against laminar burning velocities, which were measured in a heat flux setup for a variation of fuel/air ratios. A good agreement between the TMM model predictions and the measured ignition delay times and laminar burning velocities is observed. At fuel rich conditions in the shock tube, however, the model underestimates the reactivity of TMM by up to 60%, which could not be compensated by physically meaningful modifications of the TMM model. The analysis of the TMM model shows that at low temperatures, TMM is primarily consumed via H-atom abstraction by ȮH radicals, followed by classical β-scission and low-temperature chemistry. At higher temperatures, a significant fraction of TMM is consumed via unimolecular decomposition, leading to a higher reactivity compared to OME2. The present model and experiments lay the foundation for future kinetic modeling of TMM and other branched OME-like compounds.

A comprehensive kinetic modeling of oxymethylene ethers (OMEn, n=1–3) oxidation - laminar flame speed and ignition delay time measurements

This work reports on the development and experimental validation of a detailed reaction mechanism for the oxidation of polyoxymethylene dimethyl ethers (OMEn, n = 1–3). The validation is done by constant-volume chamber laminar flame speeds (393 K and 443 K, 1 to 5 bar, and equivalence ratio 0.8 to 1.6) and Rapid Compression Machine ignition delay times (550–680 K, 10 and 15 bar, equivalence ratios of 0.5–2.0) in OMEn/air mixtures. Using our new experimental and published data, the validation basis for the new kinetic model comprises the pyrolysis and oxidation of OMEn (n = 1–3) in freely propagating flames, auto-ignition in rapid compression machines and shock tubes, and speciation in jet-stirred and flow reactors as well as burner-stabilized premixed flames. The model provides a reasonable agreement with the experimental data for a broad range of conditions investigated. The performance of the developed model is compared against the recent literature models. OMEn (n = 1–3) all have the same laminar flame speed. The model suggests that the chemistry of OME0 (DME) and CH3OCHO (methyl formate) is the one that dictates the flame chemistry. Under the same pressure and equivalence ratio conditions, ignition delay times of OME2 and OME3 are similar for the investigated temperature range. This work helps to improve the understanding of OMEs chemistry. The model developed in this work will serve as the base mechanism for higher chain length OMEs (n>3).

Experimental and modeling study of acetone combustion

The pyrolysis and oxidation of acetone were studied using three complementary experimental setups. Jet-stirred reactor experiments were performed at four equivalence ratios (ϕ = 0.5, 1, 2, and ∞), at pressure of 1.067 bar (800 Torr) and over the temperature range of 700–1200 K for pyrolysis and 600–1150 K for oxidation. The decomposition of acetone starts around 800 K with a conversion rate of 50% obtained around 1000 K in both pyrolysis and oxidation studies. The main stable products detected in both conditions are small hydrocarbons (methane, ethane, and ethylene), with also acetaldehyde, CO and CO2 for oxidation. Oscillation behavior was detected beyond 1000 K under oxidation conditions and the products were followed with on-line mass spectrometry. Ignition delay times were measured using a rapid compression machine at pressures of 20 and 40 bar under non-diluted stoichiometric conditions over the temperature range 850–1100 K. The ignition delay times measured in the present study, combined with shock tube data of literature, exhibit a slight inflexion to the Arrhenius behavior, but no negative temperature coefficient. Laminar burning velocities were measured using a flat flame burner at atmospheric pressure for three fresh gas temperatures: ambient temperature, 358 and 398 K. A detailed kinetic model of the combustion of acetone including 852 species and 3265 reactions was developed. This new kinetic mechanism predicts relatively well the experimental measurements of ignition delay times, the mole fraction of the products in the jet-stirred reactor including oscillations and laminar burning velocities. Related flow rate and sensitivity analysis are also presented providing new insights into the acetone reaction network.

A computational and experimental study of the effects of thermal boundary layers and negative coefficient chemistry on propane ignition delay times

Experimental measurements of low-temperature ignition often exhibit higher uncertainties and scatter compared with ignition measurements at higher temperatures. One source of experimental variability and uncertainty is the effect of negative temperature coefficient (NTC) chemistry in thermal boundary layers at low-temperature conditions. The objective of the current work was to evaluate the effects of NTC chemistry and thermal boundary layers on propane ignition delay times using a combined modeling and experimental approach. A two-zone “balloon” model was developed where the core zone represented the high-temperature region of an experimental facility and an annulus zone represented the cooler thermal boundary-layer region. Independent initial conditions and elementary reaction chemistry was used in each zone. The effects of boundary-layer size were evaluated using different volume fractions (Vcore/Vtotal). At high initial temperatures (Tcore > 1000 K), there was negligible effect of NTC chemistry on the predicted ignition delay time for propane compared with a single-zone model, and the core region dominated the ignition characteristics for all sizes of thermal boundary layer. However, for lower initial temperature conditions (e.g., Tcore = 800 K), the thermal boundary layer was predicted to ignite first and all ignition delay times, regardless of the size of the boundary layer, were faster than the single-zone prediction for 800 K by up to 25%. Based on the results of the modeling study, propane ignition experiments were conducted using two rapid compression facilities (Vcore/Vtotal ≅ 0.9). at core temperatures of 744–1044 K and pressures of 9.8–25.4 atm for stoichiometric propane-air mixtures. While the measured ignition delay times were within the uncertainties of the both the single- and two-zone model predictions, high-speed imaging showed clear transition from ignition initially in the annulus region at lower temperatures to ignition in the core region at higher temperatures. The results of the study provide important new insights into the effects of NTC chemistry on ignition studies and support the use of diagnostics that can resolve core and boundary layer ignition behavior, particularly for experiments conducted in the NTC region. The two-zone model is also a valuable new tool for assessing the impact of NTC chemistry on previous and planned ignition delay time measurements.

Simultaneous side-wall-schlieren and -emission imaging of autoignition phenomena in conventional and constrained-reaction-volume shock-tube experiments

Simultaneous schlieren and emission imaging through the side wall of a round shock tube is reported for application to experimental autoignition studies. A round, optically accessible shock tube featuring windows designed as aberration-corrected cylindrical lenses provides a large side-wall field of view compatible with both emission and schlieren imaging. Autoignition experiments are reported for non-dilute propane–oxygen–argon mixtures (ϕ=1 C3H8 in 21% O2, 79% Ar) at temperatures (T5) spanning the range 1,203–1,438 K and pressures near 1 atm. Experiments are performed using both conventional and constrained-reaction-volume (CRV) filling, allowing for the most detailed comparison to date of ignition dynamics between these two types of experiments. When T5 exceeds 1,290 K, strong ignition is observed to initiate in the immediate proximity of the end wall regardless of the filling strategy. In lower-T5 experiments, mild ignition is observed to initiate spontaneously at remote locations, which often exceeding the imaging FOV in conventional experiments but are constrained within about 5 cm of the end wall in CRV experiments. Measured ignition delay times (IDTs) are compared to predictions from three kinetic mechanisms. IDTs simulated using the San Diego and USC Mech II mechanisms are of the same magnitude as the measurements but exhibit a lower activation energy; the propane submechanism from NUIG 1.1, meanwhile, systematically over predicts observed IDTs by roughly a factor of two. Comparisons are also made between the experimental measurements and predictions from a recently introduced 1-D axial-temperature-gradient model describing remote ignition in shock tubes. Considering the effect of a supposed dT5/dz=150 K/m gradient, the 1-D model functionally predicts the remote ignition observed in T5< 1,290 K experiments and suggests the use of CRV filling may significantly reduce the error introduced into IDT measurements by remote ignition at low-T5 conditions.

An experimental and kinetic modeling study of auto-ignition and flame propagation of ethyl lactate/air mixtures, a potential octane booster

Spark ignition engines are one of the main technologies in the transport sector. The improvement and optimization of the fuels used to empower these engines are of vital importance, both for economic and environmental reasons. In particular, one of the main issues of spark ignition engines is the knock phenomenon; new formulations of fuels are being studied in order to overcome this problem. In this study, a possible innovative anti-knock, octane booster additive is considered: ethyl lactate. This molecule is almost unknown in combustion literature, as it has been used only as green solvent and food additive. The first experimental results under combustion conditions are presented, together with a kinetic mechanism. Two set-ups have been employed: a rapid compression machine, to measure ignition delay times, and an innovative spherical bomb, OPTIPRIME, to obtain laminar flame speeds. The results are encouraging for the expected application and the mechanism shows good performance. Ignition delay times at all conditions are well predicted by the mechanism and, when compared to ethanol, they are longer, implying a greater anti-knock capability. A rate of production analysis has been performed, where the unimolecular reaction leading to ethylene and lactic acid has been proved to be quite important at high temperatures and lean conditions. For laminar flame speeds, the agreement between model and experiments is good, with some discrepancies at lean conditions and high pressures. Compared to ethanol, at rich and stoichiometric conditions ethyl lactate flame speeds are slightly slower except at lean conditions, indicating that under some conditions this molecule could provide better performances than ethanol as an octane booster additive.