High-temperature Ignition Delay Research Articles

Investigation of the injection pressure impact on non-monotonic two-stage ignition delay of diesel engines under cold-start

Poor startability under cold-start conditions is a long-term obstacle of the compression ignition engine and adjustment of the injection pressure is an effective way to improve the startability. Therefore, a detailed investigation of the effect of injection pressure (Pi) on the ignition characteristics of the fuel spray under cold-start conditions is needed. Though numerous studies have been conducted on the effect of Pi on the ignition characteristics of the fuel spray, the two-stage ignition process of the fuel spray under cold-start conditions is still an unknown field. In this paper, the effect of Pi on the two-stage ignition process of the fuel spray under cold-start conditions is investigated in a constant volume combustion chamber through simultaneous Shadowgraphy and high-speed natural luminosity method an analytical model for two-stage ignition delay is established accordingly for further investigation. Based on the experiment results, a monotonic decreasing trend on low-temperature ignition delay time LTI (i.e., form 4.5 ms to 2.5 ms under the ambient temperature of 760 K) and an increasing trend on the cool flame propagation time τ (i.e., form 0.4 ms to 1.6 ms under the ambient temperature of 760 K) are found and finally results in a non-monotonic trend of high-temperature ignition delay (HTI) as the injection pressure raises from 40 MPa to 160 MPa. According to the established model, increased Pi leads to promoted atomization and intensified dilution effect of the fuel spray, which is concluded as the reason for decreased LTI and increased τ, respectively. In this way, the non-monotonic trend of HTI under engine cold-start as Pi increases is quantitatively explained through the promoted model.

Effects of nozzle diameter on the characteristic time scales of diesel spray two-stage ignition under cold-start conditions

Diesel engine cold-start performances are closely related to ignition delay time which in turn is strongly influenced by the nozzle diameter (Dnoz). In this study, ignition delay time and ignition location of No. −50 diesel spray at different Dnoz are investigated by high-speed direct photography in a constant volume combustion chamber (CVCC) under cold-start conditions. The experimental results clarify the non-monotonic variation of the high-temperature ignition delay time (τHTI) with decreasing nozzle diameter. The minimum experimental high-temperature ignition delay time of about 1.85 ms is obtained when Dnoz = 160 μm. To investigate the mechanism that the influence of nozzle diameter on high-temperature ignition delay time, numerical simulations of the n-heptane spray ignition process are performed under the same conditions as optical diagnostics. Five characteristic time scales for the two-stage ignition process are defined as: physical preparation time (τphy), low-temperature pre-reaction time (Δτ1), low-temperature ignition delay time (τLTI), high-temperature pre-reaction time (Δτ2), and high-temperature ignition delay time. The physical preparation time decreases linearly with nozzle diameter caused by better spray atomization, evaporation, and air-fuel mixing. Changes in nozzle diameter barely affect low-temperature pre-reaction time, indicating that the linear shortening of low-temperature ignition delay time is attributed to the acceleration of the physical preparation process. The high-temperature pre-reaction time initially decreases and then increases with decreasing Dnoz, which is the result of a smaller scalar dissipation rate promoting the decomposition of H2O2 and inhibiting flame propagation. The combined effect of decreasing Dnoz at each stage leads to a non-monotonic trend in high-temperature ignition delay time.

Methanol oxidation up to 100 atm in a supercritical pressure jet-stirred reactor

Methanol (CH3OH) has attracted considerable attention as a renewable fuel or fuel additive with low greenhouse gas emissions. Methanol oxidation was studied using a recently developed supercritical pressure jet-stirred reactor (SP-JSR) at pressures of 10 and 100 atm, at temperatures from 550 to 950 K, and at equivalence ratios of 0.1, 1.0, and 9.0 in experiments and simulations. The experimental results show that the onset temperature of CH3OH oxidation at 100 atm is around 700 K, which is more than 100 K lower than the onset at 10 atm and this trend cannot be predicted by the existing kinetics models. Furthermore, a negative temperature coefficient (NTC) behavior was clearly observed at 100 atm at fuel rich conditions for methanol for the first time. To understand the observed temperature shift in the reactivity and the NTC effect, we updated some key elementary reaction rates of relevance to high pressure CH3OH oxidation from the literature and added some new low-temperature reaction pathways such as CH2O + HO2 = HOCH2O2 (RO2), RO2 + RO2 = HOCH2O (RO) + HOCH2O (RO) + O2, and CH3OH + RO2 = CH2OH + HOCH2O2H (ROOH). Although the model with these updates improves the prediction somewhat for the experimental data at 100 atm and reproduces well high-temperature ignition delay times and laminar flame speed data in the literature, discrepancies still exist for some aspects of the 100 atm low-temperature oxidation data. In addition, it was found that the pressure-dependent HO2 chemistry shifts to lower temperature as the pressure increases such that the NTC effect at fuel-lean conditions is suppressed. Therefore, as shown in the experiments, the NTC phenomenon was only observed at the fuel-rich condition where fuel radicals are abundant and the HO2 chemistry at high pressure is weakened by the lack of oxygen resulting in comparatively little HO2 formation.

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

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

Development of a fast-virtual CFR engine model and its use on autoignition studies

Homogenous charge compression ignition engines have been studied as an alternative to the conventional diesel combustion to attain high efficiency with ultra-low NOx and soot emissions for a wide variety of fuels. However, its usage in real applications has been restricted due to the difficulties regarding combustion control and operating range extension. The modification of the fuel characteristics may be a pathway to solve the previous hurdles. Therefore, this research presents a relevant methodology to assess the fuel response to HCCI boundary conditions based on 0-D and 1-D modelling for detailed chemistry solution and state conditions definition, respectively. The results suggest that the methodology can predict the early stages of the fuel oxidation with good accuracy. For the objective of predicting the start of combustion, the best results are obtained using tabulated chemistry when investigating fuels that have pre reactions and a low temperature heat release. As the oxidation process progresses, the deviation of the pressure-temperature trajectory from non-reactive to reactive conditions after the low temperature heat release decreases the predictive capability to some extent. Nonetheless, the methodology outcomes are still valid as a qualitative metric for reactivity determination as well as the intermediate and high temperature ignition delay.

Experimental and Kinetic Study on the Critical Ambient Density for Auto-ignition of the Diesel Spray under Cold-start Conditions

ABSTRACT In the present study, the effect of ambient density () on spray two-stage auto-ignition characteristics under cold-start condition was investigated using both optical and numerical methods. By the high-speed Shadowgraph, the LTI (low-temperature ignition delay) and HTI (high-temperature ignition delay) were obtained and followed an increasing trend with the decreasing . Both experimental and simulated results show that HTI is more sensitive to the than LTI, because the high-temperature chemistry is more suppressed at higher due to the increased scalar dissipation rate . Moreover, the simulation showed that the high-temperature ignition emerges at the same mixture fraction of 0.065, regardless of changes of , which indicates that has little effect on the ignition site in the mixture fraction space. Further kinetic analysis found that as the decreases, the O2 concentration reduces and the reaction rates of both low- and high-temperature reactions reduce, leading to the increased LTI and HTI. When the HTI increases to such a long time that no ignitable mixture exists in the space due to the continuing diffusion after the end of injection, the spray misfire happens.

Measurements of the High Temperature Ignition Delay Times and Kinetic Modeling Study on Oxidation of Nitromethane

ABSTRACTIgnition delay times of the nitromethane (NM)/O2/Ar mixtures were measured behind reflected shock waves in the temperature range of 1200–2000 K, pressures of 2.0 and 10.0 atm, equivalence ratios of 0.5, 1.0, and 2.0, and fuel concentrations of 0.5%, 1.0%, and 2.0%. OH emission intensity and pressure evolution were used for the ignition delay time determination. Two-stage ignition behavior was observed in the experiments. The ignition delay time decreases sharply with pressure increasing and equivalence ratio decreasing. In addition, a sub-model including 24 updated reactions for nitromethane oxidation was proposed based on ab initio calculation with CCSD(T)/CBS//B3LYP/6–311 + G(3DF, 3P) level. The present model and the Mathieu’s model (Mathieu et al. Fuel 182(2016): 597) were then validated against present measured ignition delay times, as well as some laminar flame speed data and ignition data in the literature. The present model shows better or comparable predictions with the experimental data. The main species concentration evolution and reaction analysis were presented, based on which the experimentally observed two-stage ignition behavior was interpreted.

Effect of methane on pilot-fuel auto-ignition in dual-fuel engines

The ignition behavior of n-dodecane micro-pilot spray in a lean-premixed methane/air charge was investigated in an optically accessible Rapid Compression-Expansion Machine at dual-fuel engine-like pressure/temperature conditions. The pilot fuel was admitted using a coaxial single-hole 100 µm injector mounted on the cylinder periphery. Optical diagnostics include combined high-speed CH2O-PLIF (10 kHz) and Schlieren (80 kHz) imaging for detection of the first-stage ignition, and simultaneous high-speed OH* chemiluminescence (40 kHz) imaging for high-temperature ignition. The aim of this study is to enhance the fundamental understanding of the interaction of methane with the auto-ignition process of short pilot-fuel injections. Addition of methane into the air charge considerably prolongs ignition delay of the pilot spray with an increasing effect at lower temperatures and with higher methane/air equivalence ratios. The temporal separation of the first CH2O detection and high-temperature ignition was found almost constant regardless of methane content. This was interpreted as methane mostly deferring the cool-flame reactivity. In order to understand the underlying mechanisms of this interaction, experimental investigations were complemented with 1D-flamelet simulations using detailed chemistry, confirming the chemical influence of methane deferring the reactivity in the pilot-fuel lean mixtures. This shifts the onset of first-stage reactivity towards the fuel-richer conditions. Consequently, the onset of the turbulent cool-flame is delayed, leading to an overall increased high-temperature ignition delay. Overall, the study reveals a complex interplay between entrainment, low T and high T chemistry and micro-mixing for dual-fuel auto-ignition processes for which the governing processes were identified.

A phenomenological HCCI combustion model in 0D and 3D-CFD

A phenomenological combustion model for HCCI applications – the 3-Stage heat release model – which predicts low, intermediate and high temperature heat release (LTR, ITR and HTR) is developed and validated for six automotive surrogate fuels. The contribution of all three combustion phases to the overall heat release and their durations are modeled based on rapid compression and expansion (RCEM) single-zone adiabatic simulations with detailed chemical kinetic mechanisms for all six fuels. This allows “pure” chemical effects on combustion to be included in the proposed 3-Stage heat release model, avoiding any combustion chamber related uncertainties such as blow-by, heat losses or trapped mass in crevices. Agreement between the 3-Stage heat release model and virtual RCEM (VRCEM) reference data is good. In a second step, a zero-dimensional HCCI model (0D model) is presented. To predict the onset of combustion, the low temperature ignition term of a previously developed and validated 3-Arrhenius auto-ignition model is employed in conjunction with the ignition integral of Livengood and Wu. Thereafter the 3-Stage heat release model predicts chemical heat release. Results show that the 0D model gives excellent predictions of ignition delays and combustion progress compared to the single-zone RCEM simulations using detailed chemical reaction mechanisms. Furthermore, including ITR in the 0D model is shown to be of essential importance to correctly predict high temperature ignition delay. As a final step a 3D HCCI model (3D model) is presented. The onset of combustion is again predicted by the low temperature ignition term of the 3-Arrhenius auto-ignition model, implemented via the source term of the transport equation into the 3D-CFD code. To predict heat release, the source term of the enthalpy equation is used to incorporate the 3-Stage heat release model into the 3D-CFD code. A simplified RCEM geometry is used for the simulations. Validation of the 3D model is made by a comparison to a chemical kinetic mechanism that is directly integrated into the 3D-CFD code. Combustion progress, temperature stratification in the combustion chamber and ignition delay times agree well with the reference data. The combination of the 3-Arrhenius auto-ignition model and 3-stage heat release model, their integration into 0D or 3D-CFD as a fully predictive HCCI model and their very low computational cost suggest the proposed model constitutes a promising approach for the development of future HCCI combustion engines.

Experimental and numerical investigation of atmospheric laminar premixed n-butane flames in sooting conditions

Experimental and numerical investigation of atmospheric laminar premixed n-butane/O2/N2 flames operating at two equivalence ratios (ϕ=2.16 and 2.32) has been performed. Both flames produce soot particles. Mole fraction of reactants, stable intermediate and combustion products have been obtained using a quartz microprobe coupled to gas chromatography and infrared spectroscopy technique analysis. The temperature profiles were obtained by Laser induced fluorescence of nitric oxide. The experimental results showed that a weak variation of equivalence ratio in sooting conditions introduces an increase of benzene and some unsaturated aliphatic species peak mole fraction. Except for benzene, the peak species mole fraction increase does not exceed a factor of two. A new reaction kinetic model is proposed to predict gaseous species mole fraction. In addition to the good agreement observed with our experimental data base, the proposed mechanism predicts well the detailed data obtained in low pressure rich n-butane premixed flames and high temperature ignition delay times reported in the literature.Reactions path analysis revealed that the first aromatic ring is controlled by C4+C2 (nC4H5+C2H2=C6H6+H) and C3+C3 (self recombination of C3H3 radicals) reactions routes. C4+C2 reaction path predominates in the reaction zone while C3+C3 path tends to predominate in the post flame region. The impact of the equivalence ratio on both reactions and the main differences between our and three selected literature models are discussed.

Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ4H7 Potential Energy Surface

The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of polyunsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution toward soot formation. On the basis of our previous work on propene and the butene isomers (1-, 2-, and isobutene), it was found that the reaction kinetics of Ḣ-atom addition to the C═C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations, and flame speed measurements. In this study, the rate constants and thermodynamic properties for Ḣ-atom addition to 1,3-butadiene and related reactions on the Ċ4H7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero-point energies, single-point energies, rate constants, barrier heights, and thermochemistry are systematically compared among the two quantum chemical methods. 1-Methylallyl (Ċ4H71-3) and 3-buten-1-yl (Ċ4H71-4) radicals and C2H4 + Ċ2H3 are found to be the most important channels and reactivity-promoting products, respectively. We calculated that terminal addition is dominant (>80%) compared to internal Ḣ-atom addition at all temperatures in the range 298-2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C4H6 + Ḣ → products and C2H4 + Ċ2H3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C4 species, the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H atom abstraction by Ḣ atoms have also been calculated, and it is found that abstraction from the central carbon atoms is the dominant channel (>70%) at temperatures in the range of 298-2000 K. Finally, by incorporating our calculated rate constants for both Ḣ atom addition and abstraction into our recently developed 1,3-butadiene model, we show that laminar flame speed predictions are significantly improved, emphasizing the value of this study.

Correlations for the ignition characteristics of six different fuels and their application to predict ignition delays under transient thermodynamic conditions

The ignition characteristics of six different fuels have been correlated as a function of the temperature, pressure, equivalence ratio and oxygen molar fraction in this investigation. More specifically, the ignition delay referred to cool flames, the high-temperature ignition delay and the critical concentrations and ignition times of HO2 and CH2O have been parameterized for n-dodecane, PRF0, PRF25, PRF50, PRF75 and PRF100. To do so, a wide database of ignition data of the aforementioned fuels has been generated by means of chemical simulations in CHEMKIN, solving a detailed mechanism for PRF mixtures and a reduced mechanism for n-dodecane. In fact, in-cylinder engine-like conditions reached in a Rapid Compression Expansion Machine (RCEM) have been replicated. The mathematical correlations have shown a relative deviation around 20% with the database in the low-temperature, low-pressure zone, which is the typical accuracy of usual correlations for the ignition delay. Finally, the ignition delay under transient conditions measured in the RCEM has been predicted by means of different integral methods coupled to both the proposed correlations and the generated database. I t has been found that deviations between the predictions obtained with the correlations or with the database are lower than 1%. This means that the correlations are accurate enough to predict the ignition time in spite of showing high deviation with the database, since the low-temperature, low-pressure zone has a minor contribution to the ignition delay.

Ignition delay time correlation of fuel blends based on Livengood-Wu description

In this work, a universal methodology for ignition delay time (IDT) correlation of multicomponent fuel mixtures is reported. The method is applicable over wide ranges of temperatures, pressures, and equivalence ratios. n-Heptane, iso-octane, toluene, ethanol and their blends are investigated in this study because of their relevance to gasoline surrogate formulation. The proposed methodology combines benefits from the Livengood-Wu integral, the cool flame characteristics and the Arrhenius behavior of the high-temperature ignition delay time to suggest a simple and comprehensive formulation for correlating the ignition delay times of pure components and blends. The IDTs of fuel blends usually have complex dependences on temperature, pressure, equivalence ratio and composition of the blend. The Livengood-Wu integral is applied here to relate the NTC region and the cool flame phenomenon. The integral is further extended to obtain a relation between the IDTs of fuel blends and pure components. Ignition delay times calculated using the proposed methodology are in excellent agreement with those simulated using a detailed chemical kinetic model for n-heptane, iso-octane, toluene, ethanol and blends of these components. Finally, very good agreement is also observed for combustion phasing in homogeneous charge compression ignition (HCCI) predictions between simulations performed with detailed chemistry and calculations using the developed ignition delay correlation.

Sensitivity analysis and validation of a predictive procedure for high and low-temperature ignition delays under engine conditions for n-dodecane using a Rapid Compression-Expansion Machine

A predictive procedure for cool flames and high-temperature ignition delays based on the accumulation and consumption of chain carriers has been validated for n-dodecane under engine conditions. To do so, an experimental parametric study has been carried out in a Rapid Compression-Expansion Machine, measuring the ignition times for different compression ratios (14 and 19), initial temperatures (from 403K to 463K), O2 molar fractions (from 0.21 to 0.16) and equivalence ratios (from 0.4 to 0.7). The measured ignition delays have been compared to results from chemical kinetic simulations performed in CHEMKIN using a 0-D reactor that replicates the experimental conditions by solving five different chemical kinetic mechanisms, as a way to evaluate the mechanisms accuracy and variability. In general, all chemical kinetic mechanisms are able to accurately replicate the experimental ignition delays, being the mean relative deviation lower than 1.9% and 1.6% for both ignition stages, cool flames and the high-temperature ignition respectively. Furthermore, small differences have been appreciated between mechanisms in terms of ignition delay. Then, the predictive method has been applied using different databases obtained from each mechanism and a sensitivity analysis has been performed in order to evaluate the effects of the selected database on the predicted ignition delay. It has been found that while cool flames seems to be independent on the selected mechanism, the predicted high-temperature ignition delay is very sensitive to the species selected as chain carrier. Thus, if formaldehyde is assumed as ignition tracer, the predicted ignition time can vary up to 3%, while this percent decreases up to 1.3% when hydrogen peroxide takes the role of chain carrier.

Shock Tube Ignition Delay Data Affected by Localized Ignition Phenomena

ABSTRACTShock tubes have conventionally been used for measuring high-temperature ignition delay times of approximately O(1 ms). In the last decade or so, the operating regime of shock tubes has been extended to lower temperatures by accessing longer observation times. Such measurements may potentially be affected by some non-ideal phenomena. The purpose of this work is to measure long ignition delay times for fuels exhibiting negative temperature coefficient and to assess the impact of shock tube non-idealities on ignition delay data. Ignition delay times of n-heptane and n-hexane were measured over the temperature range of 650–1250 K and pressures near 1.5 atm. Driver gas tailoring and long length of shock tube driver section were utilized to measure ignition delay times as long as 32 ms. Measured ignition delay times agree with chemical kinetic models at high (>1100 K) and low (<700 K) temperatures. In the intermediate temperature range (700–1100 K), however, significant discrepancies are observed between the measurements and homogeneous ignition delay simulations. It is postulated, based on experimental observations, that localized ignition kernels could affect the ignition delay times at the intermediate temperatures, which lead to compression (and heating) of the bulk gas and result in expediting the overall ignition event. The postulate is validated through simple representative computational fluid dynamic simulations of post-shock gas mixtures, which exhibit ignition advancement via a hot spot. The results of the current work show that ignition delay times measured by shock tubes may be affected by non-ideal phenomena for certain conditions of temperature, pressure, and fuel reactivity. Care must, therefore, be exercised in using such data for chemical kinetic model development and validation.

High temperature ignition delay time of DME/n-pentane mixture under fuel lean condition

Ignition delay times were measured behind reflect shock waves for the lean DME/n-pentane fuel blends with DME blending ratios from 0% to 100% over a wide range of conditions: pressures from 2 to 20atm, temperatures from 1100 to 1600K and equivalence ratio of 0.5. Correlations of ignition delay times of DME/n-pentane were deduced from the experimental data using multiple linear regression. Comparison between measured ignition delay times and numerical predictions by five available kinetic mechanisms, namely NUI Galway pentane isomer model, JetSurF2.0 model, LLNL n-alkanes Model, NUI Galway Mech_56.54 Model and Wang’s DME model, were conducted. NUI Galway pentane isomer model shows good predictions for ignition delay times of DME, n-pentane and their blends which was conducted in this study to interpret the effect of DME addition on the ignition chemistry of n-pentane.

N-heptane micro pilot assisted methane combustion in a Rapid Compression Expansion Machine

The autoignition and combustion behaviour of an n-heptane spray in a premixed methane/air charge was investigated. A Rapid Compression Expansion Machine (RCEM) with a free floating piston was employed to reach engine relevant conditions at Start of Injection (SOI) of the micro n-heptane pilot. The methane content in the ambient gas mixture was varied by injecting different amounts of methane directly into the combustion chamber; the ambient equivalence ratio for the methane content ranged from 0.0 to 0.99. Filtered OH∗ chemiluminescence images of the combustion were taken with a UV intensified camera at a rate of 20kHz through the optical access in the piston and schlieren imaging was performed at 20kHz for the detection of density gradients arising from pilot injection, ignition and flame propagation in the unburned mixture. Filtered photomultiplier signals of the total emitted light for OH∗, CH∗ and C2∗ radicals as well as the pressure signal were simultaneously recorded and the effect of methane content, charge temperature and ambient oxygen concentration on ignition locations, ignition timing and combustion behaviour was analysed. It was found that increasing methane contents in the ambient mixture considerably prolongs the ignition delays of the pilot spray due to inhibiting effects of the premixed methane on the reactions leading to high temperature ignition triggered by n-heptane. Longer ignition delays due to lower ambient temperatures or dilution of the ambient oxidizer cause higher heat release during the combustion of the pilot spray, since more methane/air is entrained and mixed with the pilot spray and oxidized simultaneously. This behaviour is reversed with increasing ignition delays arising from increased methane addition. There, lower heat release rates during pilot combustion were observed due to decreased reactivity in the n-heptane spray area. Comparison of different strategies with respect to the determination of high temperature ignition delay highlighted shortcomings as well as the potential in the usage of spectrally filtered chemiluminescence data, since changes in the spectrum of the emitted chemiluminescence are expected to change over time in the case of pilot ignition due to the transition between combustion modes. An assessment of the methane content influence on the ignition reactions by means of homogeneous, adiabatic Perfectly Stirred Reactor (PSR) simulations with a suitable reaction mechanism is further presented which allows for separation of influences and supports the experimental findings.

Minimized Skeletal Mechanism for Methyl Butanoate Oxidation and Its Application to the Prediction of C3–C4Products in Nonpremixed Flames: A Base Model of Biodiesel Fuels

Kinetic database of methyl butanoate (MB) combustion has been widely used as a base component for formulating kinetic mechanisms describing oxidation of larger methyl esters for biodiesel fuel surrogates. In this study, the detailed mechanism of Dooley et al. (Dooley, S.; Curran, H. J.; Simmie, J. M. Combust. Flame 2008, 153, 2–32) is minimized without empirical adjustment of rate constants in elementary reactions, using a combination of methods including a path flux analysis, removal of individual species, and peak molar concentration analysis. In the first phase, a basic skeletal mechanism with 38 species and 170 reactions for the oxidation of MB is developed, toward understanding the capability and limits of the reduced descriptions on high-temperature ignition delay times and major species profiles in 1-D counterflow flames. A comprehensive analysis of the decomposition pathways associated with preserved and removed reactions provides a scheme for mechanism developers with a clear foundation for creating new skeletal mechanisms of large methyl ester combustion. In the second phase, the MB skeletal mechanism takes into account additional 10 species and 33 reactions in order to predict experimentally measured products in a coflow nonpremixed methane/air flame doped with methyl butanoate. This 48-species skeletal mechanism combined with a 2-D computational fluid dynamic (CFD) flamelet model, for the first time, is able to predict the magnitude and shape of seven C3–C4 intermediate products, which are comparable to the experimental results. Moreover, the present skeletal mechanism, compared with published skeletal mechanisms, not only features a significant reduction in computational cost but also retains more significant products mass-spectrometrically determined.

The high-temperature autoignition of biodiesels and biodiesel components

Ignition delay time measurements are reported for two reference fatty-acid methyl ester biodiesel fuels, derived from methanol-based transesterification of soybean oil and animal fats, and four primary constituents of all methyl ester biodiesels: methyl palmitate, methyl stearate, methyl oleate, and methyl linoleate. Experiments were carried out behind reflected shock waves for gaseous fuel/air mixtures at temperatures ranging from 900 to 1350K and at pressures around 10 and 20atm. Ignition delay times were determined by monitoring pressure and ultraviolet chemiluminescence from electronically-excited OH radicals. The results show similarity in ignition delay times for all methyl ester fuels considered, irrespective of the variations in organic structure, at the high-temperature conditions studied and also similarity in high-temperature ignition delay times for methyl esters and n-alkanes. Comparisons with recent kinetic model efforts are encouraging, showing deviations of at most a factor of two and in many cases significantly less.

High temperature ignition delay times of C5 primary alcohols

Ignition delay times of the three C5 primary alcohol isomers (n-pentanol, iso-pentanol and 2-methyl-1-butanol) were measured behind reflected shock waves. Experiments were conducted in the temperature range of 1100–1500K, pressures of 1.0 and 2.6atm, equivalence ratios of 0.25, 0.5 and 1.0, and O2 concentration in the fuel/O2/Ar mixtures varying from 3.75% to 15%. Measurements show that the ignition delay time and the global activation energy of the three isomers both decrease in the order of iso-pentanol, 2-methyl-1-butanol, and n-pentanol. Chemical kinetic mechanisms for n-pentanol (Mech NP) and iso-pentanol (Mech IP), recently developed by Dagaut and co-workers, were used to model the respective ignition delay times. Results show that Mech NP yields close agreement at the equivalence ratio of 0.25, but the agreement is moderated with increasing equivalence ratio. Mech IP yields fairly close agreements at relatively higher temperatures but over-predicts the measurements by 50% at relatively lower temperatures for the three equivalence ratios studied. A new 2-methyl-1-butanol high temperature mechanism was proposed and validated against the ignition delay data. Sensitivity analysis for both n-pentanol and iso-pentanol showed the dominance of small radical reactions. Reaction pathway analysis aided further scrutiny of the fuel-specific reactions in Mech NP, leading to refinement of the kinetic model, and improved agreement between the predicted and measured ignition delay times as well as the jet-stirred reactor results.