n-Butane: Ignition delay measurements at high pressure and detailed chemical kinetic simulations

Ignition delay time measurements were recorded at equivalence ratios of 0.3, 0.5, 1, and 2 for n-butane at pressures of approximately 1, 10, 20, 30 and 45 atm at temperatures from 690 to 1430 K in both a rapid compression machine and in a shock tube. A detailed chemical kinetic model consisting of 1328 reactions involving 230 species was constructed and used to validate the delay times. Moreover, this mechanism has been used to simulate previously published ignition delay times at atmospheric and higher pressure. Arrhenius-type ignition delay correlations were developed for temperatures greater than 1025 K which relate ignition delay time to temperature and concentration of the mixture. Furthermore, a detailed sensitivity analysis and a reaction pathway analysis were performed to give further insight to the chemistry at various conditions. When compared to existing data from the literature, the model performs quite well, and in several instances the conditions of earlier experiments were duplicated in the laboratory with overall good agreement. To the authors’ knowledge, the present paper presents the most comprehensive set of ignition delay time experiments and kinetic model validation for n-butane oxidation in air.     

Effects of buffer gas composition on low temperature ignition of iso-octane and n-heptane

Experimental and numerical studies have been performed on the thermal and chemical effects of buffer gas composition on low temperature ignition of iso-octane and n-heptane. Experiments were conducted using a recently developed rapid compression machine in the temperature range of 600–850 K. Three buffer gases were studied including nitrogen (N₂), argon (Ar), and a mixture of Ar and carbon dioxide (CO₂) at a mole ratio of 65.1%/34.9%. Iso-octane was studied at 20 bar, ? = 1, and a dilution level of buffer gas to O₂ of 3.76:1 (mole ratio). n-Heptane was studied at 9 bar, ? = 1, and a dilution level of buffer gas to O₂ of 5.63:1 (mole ratio). For experiments where two-stage ignition was observed, the buffer gas composition had no impact on the first-stage ignition time but, as expected, it caused differences in the total heat release, pressure and temperature rise after the first-stage ignition. As a consequence, significant differences were observed for the total ignition delay time as a function of the buffer gas composition, with up to 40% and 42.5% faster total ignition time for iso-octane and n-heptane, respectively, by using Ar instead of N₂. The chemical effects of the buffer gas composition were studied experimentally by comparing the results of the N₂ and Ar/CO₂ (65.1%/34.9%) mixtures, recognizing that while the Ar/CO₂ mixture has the same heat capacity as N₂, its predicted combined third-body collision efficiency is about 76% higher than N₂. The experimental results showed negligible chemical effects on the first-stage and total ignition delay times. Numerical simulations were carried out over a wider range of temperatures for pure N₂, Ar, and CO₂ as buffer gases. Results showed that thermal effects are very pronounced and dominated at the negative temperature coefficient and two-stage ignition conditions, which is consistent with the experimental results and previous studies in the literature. However, the simulation results also showed at temperatures higher than 850 K, the chemical effects of CO₂ became more important than the thermal effects.     

An experimental and modeling study of iso-octane ignition delay times under homogeneous charge compression ignition conditions

Autoignition of iso-octane was examined using a rapid compression facility (RCF) with iso-octane, oxygen, nitrogen, and argon mixtures. The effects of typical homogeneous charge compression ignition (HCCI) conditions on the iso-octane ignition characteristics were studied. Experimental results for ignition delay times, τ_ign, were obtained from pressure time-histories. The experiments were conducted over a range of equivalence ratios (?=0.25-1.0), pressures (P=5.12-23 atm), temperatures (T=943-1027 K), and oxygen mole fractions (χO₂=9-21%), and with the addition of trace amounts of combustion product gases (CO₂ and H₂O). It was found that the ignition delay times were well represented by the expression

     

An experimental investigation of iso-octane ignition phenomena

High-speed digital imaging has been used in rapid compression facility (RCF) studies to investigate ignition phenomena of iso-octane/air mixtures. Sequential images were captured for each experiment. The results indicate the existence of two ignition regimes. In one domain, ignition is rapid, typically less than 76 μs, and ignition occurs simultaneously throughout the test volume. In the other domain, reaction fronts form and propagate within the test volume prior to volumetric ignition. The data span equivalence ratios from ?=0.20 to 1.98, with inert/O₂ gas ratios from 1.38 to 5.89, pressures from 8.7 to 16.6 atm, and temperatures from 903 to 1020 K. The transition between the two regimes is discussed in the context of the mixture composition and experimental conditions. The analysis shows that the fuel mole fraction is a key parameter dictating the boundary between the modes of ignition. Below a critical mole fraction limit, volumetric ignition is observed; above the critical limit, reaction fronts are consistently present prior to volumetric ignition. The ignition delay times for both ignition regimes are well reproduced using a homogeneous simulation with detailed reaction chemistry, when the state conditions are modified to account for the presence of the reaction fronts. The results are discussed in terms of proposed reaction chemistry, ignition theory, and previous studies of iso-octane ignition.     

Combustion properties of n-heptane/hydrogen mixtures

The possibility to operate current diesel engines in dual-fuel mode with the addition of hydrogen can be limited by the variation in the combustion properties of the fuel mixture. In the present work, n-heptane was selected as a representative fuel to test the effects of hydrogen addition on the laminar flame speeds and ignition delay times. The spherical bomb technique was used to derive the laminar flame speeds of (n-heptane + hydrogen)/air mixtures (0%, 25%, and 50% hydrogen in the fuel) for an initial temperature of 294 K, pressure of 1 bar, and for equivalence ratios between 0.8 and 1.35. The results showed that average increases of 3% and 10% in the flame speeds were obtained with 25% and 50% hydrogen-enrichment, respectively, while a slight decrease of the Markstein length was obtained. Similar laminar flame speed results were predicted numerically with two kinetic models available in the literature with remarkable accuracy, especially for the Cai and Pitsch model [Cai L, Pitsch H. Combust Flame 2015; 162:1623–37]. The kinetic model was subsequently used to perform additional sensitivity and reaction pathway analyses that showed how the chemistry of n-heptane is not substantially influenced by the presence of hydrogen; while the increase in the flame speed is mainly due to the higher concentrations of radical intermediates. The ignition delay times were measured using the reflected shock tube technique for equivalence ratios equal to 0.832, 1.000, and 1.248, initial nominal pressure of 20 bar, temperatures between 730 K and 1200 K, and for different percentages of hydrogen in the fuel (20%, 50%, and 75%). The Cai and Pitsch model once again did a good job of reproducing the experimental data, indicating how at high temperatures the addition of hydrogen does not significantly affect the ignition delay; and in the NTC region (810 K–920 K) the mixtures composed of (50% n-heptane + 50% hydrogen) and (25% n-heptane + 75% hydrogen) are considerably slower than the reference n-heptane case. This is linked to the concentration of the alkane component and the related low temperature chemistry.     

Isobutane ignition delay time measurements at high pressure and detailed chemical kinetic simulations

Rapid compression machine and shock-tube ignition experiments were performed for real fuel/air isobutane mixtures at equivalence ratios of 0.3, 0.5, 1, and 2. The wide range of experimental conditions included temperatures from 590 to 1567 K at pressures of approximately 1, 10, 20, and 30 atm. These data represent the most comprehensive set of experiments currently available for isobutane oxidation and further accentuate the complementary attributes of the two techniques toward high-pressure oxidation experiments over a wide range of temperatures. The experimental results were used to validate a detailed chemical kinetic model composed of 1328 reactions involving 230 species. This mechanism has been successfully used to simulate previously published ignition delay times as well. A thorough sensitivity analysis was performed to gain further insight to the chemical processes occurring at various conditions. Additionally, useful ignition delay time correlations were developed for temperatures greater than 1025 K. Comparisons are also made with available isobutane data from the literature, as well as with 100% n-butane and 50-50% n-butane-isobutane mixtures in air that were presented by the authors in recent studies. In general, the kinetic model shows excellent agreement with the data over the wide range of conditions of the present study.     

An experimental and kinetic modeling study of n-propanol and i-propanol ignition at high temperatures

Ignition delay times of n- and i-propanol mixtures in argon-diluted oxygen were measured behind reflected shocks. Experimental conditions are: temperatures from 1100 and 1500 K, pressures from 1.2 to 16.0 atm, fuel concentrations of 0.5%, 0.75%, 1.0%, and equivalence ratios of 0.5, 1.0 and 2.0. A detailed kinetic model consisting of 238 species and 1448 reactions was developed to simulate the ignition of the two propanol isomers, with the computed ignition delay times agreeing well with the present measured results as well as the literature data at other conditions. Further validation of the kinetic mechanism was conducted by comparing the simulated results with measured JSR data and laminar flame speeds, and reasonable agreements were achieved for all test conditions. Moreover, reaction pathway analysis indicated that n-propanol mainly produces ethenol, ethene and propene, while i-propanol primarily produces acetone and propene. Finally, sensitivity analysis demonstrated that some fuel-species reactions can be found in the most important reactions for both propanols, and these are mainly the H-abstraction reactions.     

Using rapid compression machines for chemical kinetics studies

Rapid compression machines (RCMs) are used to simulate a single compression stroke of an internal combustion engine without some of the complicated swirl bowl geometry, cycle-to-cycle variation, residual gas, and other complications associated with engine operating conditions. RCMs are primarily used to measure ignition delay times as a function of temperature, pressure, and fuel/oxygen/diluent ratio; further they can be equipped with diagnostics to determine the temperature and flow fields inside the reaction chamber and to measure the concentrations of reactant, intermediate, and product species produced during combustion.This paper first discusses the operational principles and design features of RCMs, including the use of creviced pistons, which is an important feature in order to suppress the boundary layer, preventing it from becoming entrained into the reaction chamber via a roll-up vortex. The paper then discusses methods by which experiments performed in RCMs are interpreted and simulated. Furthermore, differences in measured ignition delays from RCMs and shock tube facilities are discussed, with the apparent initial gross disagreement being explained by facility effects in both types of experiments. Finally, future directions for using RCMs in chemical kinetics studies are also discussed.     

A rapid compression facility study of OH time histories during iso-octane ignition

Iso-octane ignition delay times (τign) and hydroxyl (OH) radical mole fraction (χOH) time histories were measured under conditions relevant to homogeneous charge compression ignition engine operating regimes using the University of Michigan rapid compression facility. Absolute quantitative OH mole fraction time histories were obtained using differential narrow-line laser absorption of the R₁(5) line of the A²Σ⁺←X²Πi(0,0) band of the OH spectrum (). Ignition delay times were determined using pressure and OH data. Diluted iso-octane/argon/nitrogen/oxygen mixtures were used with fuel/oxygen equivalence ratios from ?=0.25 to 0.6 for τign measurements and from ?=0.25 to 0.35 for χOH measurements. The pressures and temperatures after compression ranged from 8.5 to 15 atm and from 945 to 1020 K, respectively, for the combined τign and χOH data. The maximum mole fraction of OH during ignition and the plateau value of OH after ignition are compared with model predictions using different iso-octane oxidation mechanisms. Sensitivity and rate of production analyses for OH identify reactions important in iso-octane ignition under these lean, intermediate-temperature conditions. The OH time histories show significant sensitivity to the OH + OH + M = H₂O₂ + M, CH₃ + HO₂ = CH₃O + OH, and CH₃ + HO₂ = CH₄ + O₂ reactions, which have rate coefficients with relatively high uncertainties. Improved predictions of the OH time histories can be achieved by modifying the rate coefficient for these reactions. The enthalpy of formation used for OH also has a significant effect on the predicted ignition delay times.     

Shock tube and kinetic study of C2H6/H2/O2/Ar mixtures at elevated pressures

Using a high-pressure shock tube facility, the ignition delay times of stoichiometric C₂H₆/H₂/O₂ diluted in argon were obtained behind reflected shock wave at elevated pressures (p = 1.2, 4.0 and 16.0 atm) with ethane blending ratios from 0 to 100%. The measured ignition delay times were compared to the previous correlations, and the results show that the ignition delay times of ethane from different studies exhibit an obvious difference. Meanwhile, numerical studies were conducted with three generally accepted kinetic mechanisms and the results show that only NUIG Aramco Mech 1.3 agrees well with the measurements under all test conditions. Sensitivity analysis was made to interpret the poor prediction of the other two mechanisms. Furthermore, the effect of ethane blending ratio on the ignition delay times of the mixtures was analyzed and the results show that ethane blending ratio gives a non-linear effect on the auto-ignition of hydrogen. Finally, chemical interpretations on this non-linear effect were made from the reaction pathway analysis and normalized H radical consumption analysis.     

An experimental study of the autoignition characteristics of conventional jet fuel/oxidizer mixtures: Jet-A and JP-8

Ignition delay times of Jet-A/oxidizer and JP-8/oxidizer mixtures are measured using a heated rapid compression machine at compressed charge pressures corresponding to 7, 15, and 30 bar, compressed temperatures ranging from 650 to 1100 K, and equivalence ratios varying from 0.42 to 2.26. When using air as the oxidant, two oxidizer-to-fuel mass ratios of 13 and 19 are investigated. To achieve higher compressed temperatures for fuel lean mixtures (equivalence ratio of ∼0.42), argon dilution is also used and the corresponding oxidizer-to-fuel mass ratio is 84.9. For the conditions studied, experimental results show two-stage ignition characteristics for both Jet-A and JP-8. Variations of both the first-stage and overall ignition delays with compressed temperature, compressed pressure, and equivalence ratio are reported and correlated. It is noted that the negative temperature coefficient phenomenon becomes more prominent at relatively lower pressures. Furthermore, the first-stage-ignition delay is found to be less sensitive to changes in equivalence ratio and primarily dependent on temperature.     

Computational fluid dynamics modeling of hydrogen ignition in a rapid compression machine

In modeling a rapid compression machine (RCM) experiment, a zero-dimensional code is commonly used along with an associated heat loss model. However, the applicability of such a zero-dimensional modeling needs to be assessed over a range of accessible experimental conditions. It is expected that when there exists significant influence of the multidimensional effects, including boundary layer, vortex roll-up, and nonuniform heat release, the zero-dimensional modeling may not be adequate. In this work, we simulate ignition of hydrogen in an RCM by employing computational fluid dynamics (CFD) studies with detailed chemistry. Through the comparison of CFD simulations with zero-dimensional results, the validity of a zero-dimensional modeling for simulating RCM experiments is assessed. Results show that the zero-dimensional modeling based on the approach of “adiabatic volume expansion” generally performs very well in adequately predicting the ignition delay of hydrogen, especially when a well-defined homogeneous core is retained within an RCM. As expected, the performance of this zero-dimensional modeling deteriorates with increasing temperature nonuniformity within the reaction chamber. Implications for the species sampling experiments in an RCM are further discussed. Proper interpretation of the measured species concentrations is emphasized and the validity of simulating RCM species sampling results with a zero-dimensional model is assessed.     

Experimental and kinetic study on ignition delay times of DME/H2/O2/Ar mixtures

Ignition delay times of dimethyl ether (DME)/hydrogen/oxygen/argon mixtures (hydrogen blending ratio ranging from 0% to 100%) were measured behind reflected shock waves at pressures of 1.2–10 atm, temperature range of 900–1700 K, and for the lean (? = 0.5), stoichiometric (? = 1.0) and rich (? = 2.0) mixtures. For more understanding the effect of initial parameters, correlations of ignition delay times for the lean mixtures were obtained on the basis of the measured data (X_H2 ? 95%) through multiple linear regression. Ignition delay times of the DME/H₂ mixtures demonstrate three ignition regimes. For X_H2 ? 80%, the ignition is dominated by the DME chemistry and ignition delay times show a typical Arrhenius dependence on temperature and pressure. For 80% ? X_H2 ? 98%, the ignition is dominated by the combined chemistries of DME and hydrogen, and ignition delay times at higher pressures give higher ignition activation energy. However, for X_H2 ? 98%, the transition in activation energy for the mixture was found as decreasing the temperature, indicating that the ignition is dominated by the hydrogen chemistry. Simulations were made using two available models and different results were presented. Thus, sensitivity analysis was performed to illustrate the causes of different simulation results of the two models. Subsequently, chemically interpreting on the effect of hydrogen blending ratio on ignition delay times was made using small radical mole fraction and reaction pathway analysis. Finally, high-pressure simulations were performed, serving as a starting point for the future work.     

Shock tube study on ignition delay of multi-component syngas mixtures – Effect of equivalence ratio

Ignition delays were measured in a shock tube for syngas mixtures with argon as diluent at equivalence ratios of 0.3, 1.0 and 1.5, pressures of 0.2, 1.0 and 2.0 MPa and temperatures from 870 to 1350 K. Results show that the influences of equivalence ratio on the ignition of syngas mixtures exhibit different tendency at different temperatures and pressures. At low pressure, the ignition delay increases with an increase in equivalence ratio at tested temperature. At high pressures, however, an opposite behavior is presented, that is, increasing equivalence ratio inhibits the ignition at high temperature and vice versa at intermediate temperature. The affecting degree of equivalence ratio on ignition delay is different for each mixture at given condition, especially for the syngas with high CO concentration. Sensitivity analyses demonstrate that reaction H + O₂ = O + OH (R1) dominates the syngas oxidation under all conditions. With the increase of CO mole fraction, reactions CO + OH = CO₂ + H (R27) and CO + HO₂ = CO₂ + OH (R29) become more important in the syngas ignition kinetics. With the increase of pressure, the reactions related to HO₂ and H₂O₂ play the dominate role. The opposite influence of equivalence ratio on ignition delay at high- and intermediate-temperatures is chemically interpreted through kinetic analyses.     

Experimental and kinetic study on ignition delay times of lean n-butane/hydrogen/argon mixtures at elevated pressures

Measurements on ignition delay times of n-butane/hydrogen/oxygen mixtures diluted by argon were conducted using the shock tube at pressures of 2, 10 and 20 atm, temperatures from 1000 to 1600 K and hydrogen fractions (${\mathrm{X}}_{{\mathrm{H}}_2}$) from 0 to 98%. It is found that hydrogen addition has a non-linear promoting effect on ignition delay of n-butane. Results also show that for ${\mathrm{X}}_{{\mathrm{H}}_2}$ less than 95%, ignition delay time shows an Arrhenius type dependence and the increase of pressure and temperature lead to shorter ignition delay times. However, for ${\mathrm{X}}_{{\mathrm{H}}_2}$ = 98% and 100% mixtures, non-monotonic pressure dependence of ignition delay time were observed. The performances of the Aramco2.0 model, San Diego 2016 model and USC2.0 model were evaluated against the experimental data. Only the Aramco2.0 model gives a reasonable agreement with all the measurements, which was conducted in this study to interpret the effect of pressure and hydrogen addition on the ignition chemistry of n-butane.     

A comprehensive combustion chemistry study of 2,5-dimethylhexane

Iso-paraffinic molecular structures larger than seven carbon atoms in chain length are commonly found in conventional petroleum, Fischer–Tropsch (FT), and other alternative hydrocarbon fuels, but little research has been done on their combustion behavior. Recent studies have focused on either mono-methylated alkanes and/or highly branched compounds (e.g., 2,2,4-trimethylpentane). In order to better understand the combustion characteristics of real fuels, this study presents new experimental data for the oxidation of 2,5-dimethylhexane under a wide variety of temperature, pressure, and equivalence ratio conditions. This new dataset includes jet stirred reactor speciation, shock tube ignition delay, and rapid compression machine ignition delay, which builds upon recently published data for counterflow flame ignition, extinction, and speciation profiles. The low and high temperature oxidation of 2,5-dimethylhexane has been simulated with a comprehensive chemical kinetic model developed using established reaction rate rules. The agreement between the model and data is presented, along with suggestions for improving model predictions. The oxidation behavior of 2,5-dimethylhexane is compared with oxidation of other octane isomers to confirm the effects of branching on low and intermediate temperature fuel reactivity. The model is used to elucidate the structural features and reaction pathways responsible for inhibiting the reactivity of 2,5-dimethylhexane.     

Detailed chemical kinetic reaction mechanisms for soy and rapeseed biodiesel fuels

A detailed chemical kinetic reaction mechanism is developed for the five major components of soy biodiesel and rapeseed biodiesel fuels. These components, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate, and methyl palmitate, are large methyl ester molecules, some with carboncarbon double bonds, and kinetic mechanisms for them as a family of fuels have not previously been available. Of particular importance in these mechanisms are models for alkylperoxy radical isomerization reactions in which a CC double bond is embedded in the transition state ring. The resulting kinetic model is validated through comparisons between predicted results and a relatively small experimental literature. The model is also used in simulations of biodiesel oxidation in jet-stirred reactor and intermediate shock tube ignition and oxidation conditions to demonstrate the capabilities and limitations of these mechanisms. Differences in combustion properties between the two biodiesel fuels, derived from soy and rapeseed oils, are traced to the differences in the relative amounts of the same five methyl ester components.     

Simplified correlation models for CO/H2 chemical reaction times

This paper provides simplified correlation models for CO/H₂ chemical reaction times. The procedure used for the CO/H₂ simplified modeling utilized the full chemical kinetics mechanism run over a range of temperatures from 700 to 1800 K, pressures from 0.5 to 50 atm, mixtures from 0% to 95% CO, and equivalence ratios from 0.2 to 2.0 to determine ignition (or reaction) time. The correlations for ignition times are given in formulas as functions of equivalence ratio, temperature, and pressure. Two different forms of correlations were obtained, one being a single, overall correlation and the other a two-stage correlation representing regions of high and low temperatures. These correlations are shown to work well over a range of chemical time scales spanning ten orders of magnitude. The correlations are also compared with measured data from the literature.     

柴油喷雾着火过程的化学动力学模拟

在直喷式柴油机准维燃烧模型的基础上,建立了能描述柴油机着火前燃油的氧化历程及着火滞燃期的多步着火化学动力学子模型,它不仅可以很好地模拟实际柴油机的燃油氧化过程,而且可以较好地反映着火滞燃期随各种因素的变化关系,比以往的描述着火滞燃期的经验模型更具有合理性和先进性。整个燃烧模型的计算结果及其与试验结果的对比还表明,本模型能够合理地预测柴油机的燃烧过程。