Application of an aerosol shock tube to the measurement of diesel ignition delay times

Shock tube ignition delay times were measured for DF-2 diesel/21% O₂/argon mixtures at pressures from 2.3 to 8.0 atm, equivalence ratios from 0.3 to 1.35, and temperatures from 900 to 1300 K using a new experimental flow facility, an aerosol shock tube. The aerosol shock tube combines conventional shock tube methodology with aerosol loading of fuel-oxidizer mixtures. Significant efforts have been made to ensure that the aerosol mixtures were spatially uniform, that the incident shock wave was well-behaved, and that the post-shock conditions and mixture fractions were accurately determined. The nebulizer-generated, narrow, micron-sized aerosol size distribution permitted rapid evaporation of the fuel mixture and enabled separation of the diesel fuel evaporation and diffusion processes that occurred behind the incident shock wave from the chemical ignition processes that occurred behind the higher temperature and pressure reflected shock wave. This rapid evaporation technique enables the study of a wide range of low-vapor-pressure practical fuels and fuel surrogates without the complication of fuel cracking that can occur with heated experimental facilities. These diesel ignition delay measurements extend the temperature and pressure range of earlier flow reactor studies, provide evidence for NTC behavior in diesel fuel ignition delay times at lower temperatures, and provide an accurate data base for the development and comparison of kinetic mechanisms for diesel fuel and surrogate mixtures. Representative comparisons with several single-component diesel surrogate models are also given.     

Experimental study and modeling of shock tube ignition delay times for hydrogen-oxygen-argon mixtures at low temperatures

Recent literature has indicated that experimental shock tube ignition delay times for hydrogen combustion at low-temperature conditions may deviate significantly from those predicted by current detailed kinetic models. The source of this difference is uncertain. In the current study, the effects of shock tube facility-dependent gasdynamics and localized pre-ignition energy release are explored by measuring and simulating hydrogen-oxygen ignition delay times. Shock tube hydrogen-oxygen ignition delay time data were taken behind reflected shock waves at temperatures between 908 to 1118 K and pressures between 3.0 and 3.7 atm for two test mixtures: 4% H₂, 2% O₂, balance Ar, and 15% H₂, 18% O₂, balance Ar. The experimental ignition delay times at temperatures below 980 K are found to be shorter than those predicted by current mechanisms when the normal idealized constant volume (V) and internal energy (E) assumptions are employed. However, if non-ideal effects associated with facility performance and energy release are included in the modeling (using CHEMSHOCK, a new model which couples the experimental pressure trace with the constant V, E assumptions), the predicted ignition times more closely follow the experimental data. Applying the new CHEMSHOCK model to current experimental data allows refinement of the reaction rate for H + O₂ + Ar ↔ HO₂ + Ar, a key reaction in determining the hydrogen-oxygen ignition delay time in the low-temperature region.     

Ignition and combustion of isopropyl nitrate

The ignition delay times for mixtures of isopropyl nitrate (IPN) with air and argon are measured in a rapid-injection reactor at a pressure of 1 atm and in a shock tube at 2–3 atm. It is shown that the ignition delay time τ of mixtures in which heat is largely released due to oxidation by the oxygen contained in the IPN molecule is determined by the unimolecular decomposition of IPN over the entire temperature range covered (500–730 K). For mixtures in which heat is mainly produced by oxidation reactions involving air oxygen, the ignition delay time at high temperatures is controlled by secondary reactions of oxidation of the hydrocarbon moiety of the IPN molecule, leading to an increase in τ by more than an order of magnitude. Liquid IPN burns in a nitrogen atmosphere only at pressures above 40 atm, at a linear rate of ~4 mm/s. The measured flame temperatures are in close agreement with the respective values calculated using a thermodynamic code.     

Ignition delay times of methyl oleate and methyl linoleate behind reflected shock waves

Ignition delay times for methyl oleate (C₁₉H₃₆O₂, CAS: 112-62-9) and methyl linoleate (C₁₉H₃₄O₂, CAS: 112-63-0) were measured for the first time behind reflected shock waves, using an aerosol shock tube. The aerosol shock tube enabled study of these very-low-vapor-pressure fuels by introducing a spatially-uniform fuel aerosol/4% oxygen/argon mixture into the shock tube and employing the incident shock wave to produce complete fuel evaporation, diffusion, and mixing. Reflected shock conditions covered temperatures from 1100 to 1400 K, pressures of 3.5 and 7.0 atm, and equivalence ratios from 0.6 to 2.4. Ignition delay times for both fuels were found to be similar over a wide range of conditions. The most notable trend in the observed ignition delay times was that the pressure and equivalence ratio scaling were a strong function of temperature, and exhibited cross-over temperatures at which there was no sensitivity to either parameter. Data were also compared to the biodiesel kinetic mechanism of Westbrook et al. (2011) [10], which underpredicts ignition delay times by about 50%. Differences between experimental and computed ignition delay times were strongly related to existing errors and uncertainties in the thermochemistry of the large methyl ester species, and when these were corrected, the kinetic simulations agreed significantly better with the experimental measurements.     

High pressure ignition delay times of H2/CO mixture in carbon dioxide and argon diluent

Ignition Delay Time (IDT) plays a significant role in combustion process of advanced power cycles such as direct-fired supercritical carbon dioxide (sCO₂) cycle. In this cycle, fuel and oxidizer are heavily diluted with carbon dioxide (CO₂) and autoignite at a combustor inlet pressure range of 10–30 MPa and a temperature range of 900–1500 K. A fuel candidate for sCO₂ power cycle applications is syngas (H₂/CO mixture); however, its ignition properties at these conditions are not studied. Moreover, the existing chemical kinetics models have not been evaluated for H₂/CO mixtures applications relevant to elevated pressure conditions and under large dilution levels of CO₂. Therefore, two tasks are performed in this study. First, IDTs of a H₂/CO=95:5 mixture at stoichiometric and rich (Φ=2) conditions are measured in a high-pressure shock tube under 95.5% CO₂ dilution level and at 10 MPa and 20 MPa for a temperature range of 1161–1365 K. For the experimental conditions considered in this work, Aramco 2.0, FFCM-1, HP-Mech and USC Mech II kinetic models are capable of capturing IDT data. Second, similar experiments are conducted by replacing the CO₂ dilute gas with Argon (Ar) to understand the chemical effect of CO₂ on IDT globally. Sensitivity analysis results reveal that for both diluents, reaction H + O₂(+M)=HO₂(+M) is the most important reaction in controlling ignition. Further, a rate of production analysis shows that CO₂ has a competing effect on OH radical production. On one hand, CO₂ accelerates the consumption of H radicals through H + O₂+CO₂→HO₂+CO₂ therefore hindering HO₂+HOH+OH reaction for OH production. On the other hand, CO₂ is shown to enhance OH production through H₂O₂+M=OH+OH+M. These kinetic effects from CO₂ cancel out, therefore CO₂ does not significantly alter the IDT globally when compared to the Ar bath case. This is confirmed by both experimental results and simulation.     

Experimental and modeling study of the low to high-temperature oxidation of the methyl isopropyl ketone in O2/N2/Ar and O2/CO2/Ar atmospheres

Few studies on the low-temperature combustion behavior of MIPK, being a promising fuel additive, have been conducted. In this work, ignition delay times (IDTs) of MIPK were measured in the temperatures ranging between 780–910 K and pressures of 20 and 25 bar using a rapid compression machine (RCM). Oxy-fuel combustion combined with biofuel could remove CO₂ from the atmosphere. The IDTs of MIPK were measured in the temperatures ranging between 1125–1600 K under the O₂/CO₂ atmosphere at the pressures of 1 and 10 bar using a shock tube. A low to high-temperature MIPK kinetic model (HUST-MIPK model) was proposed, in which the low-temperature sub-model consists of 19 low-temperature reaction classes and was constructed by analogy-based method, the high-temperature sub-model was adapted from the works of Cheng et al.. The predictions of HUST-MIPK model are in good agreement with the present low-temperature IDTs, high-temperature O₂/CO₂ atmosphere IDTs, and the literature experimental data. The negative temperature coefficient (NTC) behavior was not observed in the temperature range from 790 to 910 K in the present RCM experiments, but was observed for methyl propyl ketone (MPK) and diethyl ketone (DEK) under similar conditions. The low-temperature chemistry of three pentanone isomers (MIPK, MPK, and DEK) was compared using the flux and sensitivity analysis. The comparison of the experimental high-temperature IDTs between O₂/CO₂ and O₂/Ar atmospheres indicates the IDTs of MIPK under O₂/CO₂ atmosphere are longer than those under O₂/Ar atmosphere at 1 bar, and the effects of CO₂ are almost independent of the pressure. The physical and chemical effects of CO₂ on the ignition were studied in detail.     

Effect of silane addition on acetylene ignition behind reflected shock waves

Ignition delay time and species profile measurements are reported for the combustion of C₂H₂/O₂/Ar mixtures with and without the addition of silane for temperatures between 1040 and 2320 K and pressures near 1 atm. Characteristic times, namely ignition time and time to peak, were determined from the time histories of CH* (A²Δ → X²Π) and OH* (A²Σ⁺ → X²Π) emission near 430 and 307 nm, respectively. For the cases without silane, there is good agreement between the present data and some recent acetylene oxidation results. Small SiH₄ additions (<10% of the fuel) reduced the ignition time in stoichiometric mixtures by as much as 75% for shocks near 1800 K. Similar reductions were seen in the fuel-lean mixture, although the effect was less temperature dependent. Several detailed chemical kinetics mechanisms of hydrocarbon oxidation were compared to the ignition delay-time data and species profiles for C₂H₂/O₂/Ar mixtures without silane. All models under-predicted ignition time for the 98% diluted stoichiometric mixture but matched the fuel-lean ignition data somewhat better. Two of the models displayed the shift in activation energy at lower temperatures seen in the data, although no one model was able to reproduce all ignition times over the entire range of mixtures and conditions.     

Ignition of cyclopropane in shock waves

The values of the ignition delay time of cyclopropane–oxygen–argon (cyclo-C₃H₆–O₂–Ar) mixtures of different compositions (φ = 0.333, 1, and 3) behind reflected shock waves at temperatures of 1200–1640 K and a pressure of (0.55 ± 0.05) MPa are measured. A kinetic mechanism of cyclopropane ignition using the known rate constants for the most important elementary reactions is developed. The mechanism closely describes both our own and published experimental data on the delay time of ignition of cyclopropane in shock waves over wide ranges of temperature (1200–2100 K), pressure (0.1–0.55 MPa), cyclopropane concentrations (0.05–11 vol %), and oxygen concentrations (0.25–21 vol %). It is shown that, with increasing fraction of diluent gas in the mixture, the dependence of the ignition delay time on the fuel-to-oxidizer equivalence ratio changes.     

Effects of NO2 addition on hydrogen ignition behind reflected shock waves

Ignition delay time measurements of H₂/O₂/NO₂ mixtures diluted in Ar have been measured in a shock tube behind reflected shock waves. Three different NO₂ concentrations have been studied (100, 400 and 1600 ppm) at three pressure conditions (around 1.5, 13, and 30 atm) and for various H₂–O₂ equivalence ratios for the 100 ppm NO₂ case. Results were compared to some recent ignition delay time measurements of H₂/O₂ mixtures. A strong dependence of the ignition delay time on the pressure and the NO₂ concentration was observed, whereas the variation in the equivalence ratio did not exhibit any appreciable effect on the delay time. A mechanism combining recent H₂/O₂ chemistry and a recent high-pressure NOx sub-mechanism with an updated reaction rate for H₂ + NO₂ ? HONO + H was found to represent correctly the experimental trends over the entire range of conditions. A chemical analysis was conducted using this mechanism to interpret the experimental results. Ignition delay time data with NO₂ and other NOx species as additives or impurities are rare, and the present study provides such data over a relatively wide pressure range.     

Effect of steam on the single particle ignition of solid fuels in a drop tube furnace under air and simulated oxy-fuel conditions

This article investigates the effect of steam on the ignition of single particles of solid fuels in a drop tube furnace under air and simulated oxy-fuel conditions. Three solid fuels, all in the size range 125–150 µm, were used in this study; specifically, a low rank sub-bituminous Colombian coal, a low-rank/high-ash sub-bituminous Brazilian coal and a charcoal residue from black acacia. For each solid fuel, particles were burned at a constant drop tube furnace wall temperature of 1475?K, in six different mixtures of O₂/N₂/CO₂/H₂O, which allowed simulating dry and wet conventional and oxy-fuel combustion conditions. A high-speed camera was used to record the ignition process and the collected images were treated to characterize the ignition mode (either gas-phase or surface mode) and to calculate the ignition delay times. The Colombian coal particles ignite predominately in the gas-phase for all test conditions, but under simulated oxy-fuel conditions there is a decrease in the occurrence of this ignition mode; the charcoal particles experience surface ignition regardless of the test condition; and the Brazilian coal particles ignite predominately in the gas-phase when combustion occurs in mixtures of O₂/N₂/H₂O, but under simulated oxy-fuel conditions the ignition occurs predominantly on the surface. The ignition delay times for particles that ignited in the gas-phase are smaller than those that ignited on the surface, and generally the simulated oxy-fuel conditions retard the onset of both gas-phase and surface ignition. The addition of steam decreases the gas-phase and surface ignition delay times of the particles of both coals under simulated oxy-fuel conditions, but has a small impact on the gas-phase ignition delay times when the combustion occurs in mixtures of O₂/N₂/H₂O. The steam gasification reaction is likely to be responsible for the steam effect on the ignition delay times through the production of highly flammable species that promote the onset of ignition.     

Ignition of acetylene-oxygen mixtures behind shock waves

The delay time of ignition of C₂H₂-O₂-Ar mixtures of various compositions behind reflected shock waves were measured at 980–1300 K and 0.65 ± 0.05 MPa. A kinetic scheme of the ignition of acetylene based on the available rate constants of the key elementary reactions was developed. The scheme satisfactorily describes the experimental data from various works over wide temperature, pressure, and concentration ranges: 980–2400 K, 0.01–1.0 MPa, and 0.5–20.3 vol % acetylene and 1.25–20.4 vol% O₂.     

Methane/propane oxidation at high pressures: Experimental and detailed chemical kinetic modeling

Shock tube experiments and chemical kinetic modeling were performed to further understand the ignition and oxidation kinetics of various methane-propane fuel blends at gas turbine pressures. Ignition delay times were obtained behind reflected shock waves for fuel mixtures consisting of CH₄/C₃H₈ in ratios ranging from 90/10% to 60/40%. Equivalence ratios varied from lean (? = 0.5), through stoichiometric to rich (? = 3.0) at test pressures from 5.3 to 31.4 atm. These pressures and mixtures, in conjunction with test temperatures as low as 1042 K, cover a critical range of conditions relevant to practical turbines where few, if any, CH₄/C₃H₈ prior data existed. A methane/propane oxidation mechanism was prepared to simulate the experimental results. It was found that the reactions involving CH₃O˙, CH₃O˙₂, and ?H₃ + O₂/HO˙₂ chemistry were very important in reproducing the correct kinetic behavior.     

The impact of the third O2 addition reaction network on ignition delay times of neo-pentane

We studied the oxidation of neo-pentane by combining experiments, theoretical calculations, and mechanistic developments to elucidate the impact of the 3rd O₂ addition reaction network on ignition delay time predictions. The experiments are based on photoionization mass spectrometry in jet-stirred and time-resolved flow reactors allowing for sensitive detection of the keto-hydroperoxide (KHP) and keto-dihydroperoxide (KDHP) intermediates. With neo-pentane exhibiting a unique symmetric molecular structure, which consequently results only in single KHP and KDHP isomers, theoretical calculations of ionization and fragment appearance energies and of absolute photoionization cross sections enabled the unambiguous identification and quantification of the KHP intermediate. Its temperature and time-resolved profiles together with calculated and experimentally observed KHP-to-KDHP signal ratios were compared to simulation results based on a newly developed mechanism that describes the 3rd O₂ addition reaction network. A satisfactory agreement has been observed between the experimental data points and the simulation results, thus adding confidence to the model's overall performance. Finally, this mechanism was used to predict ignition delay times reported previously in shock tube and rapid compression machine experiments (J. Bugler et al., Combust. Flame 163 (2016) 138–156). While the model accurately reproduces the experimental data, simulations with and without the 3rd O₂ addition reaction network included reveal only a negligible effect on the predicted ignition delay times at 10 and 20 atm. According to model calculations, low temperatures and high pressures promote the importance of the 3rd O₂ addition reactions.     

Ethanol ignition in a high-pressure shock tube: Ignition delay time and high-repetition-rate imaging measurements

Ethanol is known to be prone to pre-ignition in internal combustion engines under high-load conditions and its ignition shows large deviations from ideal, spatially, and temporally-homogeneous ignition in shock tubes at moderate temperatures (800–950 K). In this context, the ignition of stoichiometric ethanol/O₂ mixtures with various levels of inert gas dilution was investigated in a high-pressure shock tube at ?20 bar between 800 and 1250 K. Ignition delay times were determined from spatially integral detection of chemiluminescence emission. Additionally, high-repetition-rate color imaging enabled the differentiation of the luminescence in time, space, and spectral range between various ignition modes. In the low-temperature range (800–860 K), different inhomogeneous ignition modes were identified. The addition of small amounts of helium into the undiluted fuel/air mixture was found to be efficient to mitigate pre-ignition, attributed to a variation in heat transfer and thus suppression of the build-up of local temperature inhomogeneities. The experiments in case of spatially homogeneous ignition show very good agreement with the predictions based on three detailed kinetics mechanisms (Zhang et al., CNF 190 (2018) 74, Frassoldati et al., CNF 159 (2012) 2295, and Zhou et al. CNF 197 (2018) 423), inhomogeneities, however, resulted in a shortening of the ignition delay times up to a factor of 2.6.     

A rapid compression machine study of the low temperature combustion of cyclohexane at elevated pressures

Ignition delay times have been measured in a rapid compression machine for cyclohexane/O₂/N₂/Ar mixtures with equivalence ratios of 0.5, 1.0 and 2.0 at elevated pressures of up to 40 bar and temperatures between 680 and 910 K. These data clearly show the negative-temperature-coefficient behavior for cyclohexane in the temperature range investigated. The predictions of several detailed kinetic models are compared to these new experimental validation data and these mechanisms have been analyzed to explain the obtained differences with a focus on the crucial peroxy-chemistry of the primary radicals. The presented data are the first set of ignition delay times at elevated pressures for the low-temperature range.     

An experimental and modeling study of the shock tube ignition of a mixture of n-heptane and n-propylbenzene as a surrogate for a large alkyl benzene

Alkyl aromatics are an important chemical class in gasoline, jet and diesel fuels. In the present work, an n-propylbenzene and n-heptane mixture is studied as a possible surrogate for large alkyl benzenes contained in diesel fuels. To evaluate it as a surrogate, ignition delay times have been measured in a heated high pressure shock tube (HPST) for a mixture of 57% n-propylbenzene/43% n-heptane in air (≈21% O₂, ≈79% N₂) at equivalence ratios of 0.29, 0.49, 0.98 and 1.95 and compressed pressures of 1, 10 and 30 atm over a temperature range of 1000–1600 K. The effects of reflected-shock pressure and equivalence ratio on ignition delay time were determined and common trends highlighted. A combined n-propylbenzene and n-heptane reaction mechanism was assembled and simulations of the shock tube experiments were carried out. The simulation results showed very good agreement with the experimental data for ignition delay times. Sensitivity and reaction pathway analyses have been performed to reveal the important reactions responsible for fuel oxidation under the shock tube conditions studied. It was found that at 1000 K, the main consumption pathways for n-propylbenzene are abstraction reactions on the alkyl chain, with particular selectivity to the allylic site. In comparison at 1500 K, the unimolecular decomposition of the fuel is the main consumption pathway.     

A shock tube and modeling study on ignition delay times of pyridine under O2/CO2 atmospheres at elevated pressures

Pressurized oxy-fuel combustion has been attracting increasing attentions due to its improved efficiency and low cost. The present study reports ignition delay times (IDTs) of pyridine under O₂/CO₂ atmospheres within a temperature range from 1202 to 1498 K at pressures from 2.2 to 10 bar for equivalence ratios of 0.5, 1.0, and 2.0. The experimental results were compared with the IDTs of pyridine under O₂/Ar atmospheres from MacNamara et al.. The comparison results indicate that the IDTs of pyridine under O₂/CO₂ atmospheres are evident longer than those under O₂/Ar atmospheres even at low pressure. A modified kinetic model (HUST pyridine Model) was proposed based on our previous mechanism. HUST pyridine Model predicted well the IDTs under both O₂/CO₂ and O₂/Ar atmospheres obtained in shock tubes and the species profiles under both O₂/CO₂ and O₂/N₂ atmospheres obtained in plug flow reactors. HUST pyridine Model, Alzueta Model, and Pyridine LTO Model were evaluated. The results show that the performance of HUST pyridine Model is much better than Alzueta Model, and Pyridine LTO Model. The main reason is that the net reaction rate of C₅H₅N + O = C₅H₄N + OH in HUST pyridine Model is much faster than that in Aluzeta Model. The effect of CO₂ on the ignition of pyridine at elevated pressures has been analyzed in detail. The oxidation pathways of pyridine are also analyzed at different pressures.     

Reactions of initiation of the autoignition of H<Subscript>2</Subscript>–O<Subscript>2</Subscript> mixtures in shock waves

The initiation of the autoignition of hydrogen–oxygen–argon mixtures behind reflected shock waves is studied by absorption and emission spectrophotometry in the temperature range of 960 < T < 1670 K at pressures of ~0.1 MPa. Introduction of Mo(CO)₆ additive in an amount of ~80 ppm made it possible to study the effect of O atoms on the shortening of the ignition delay time of H₂–O₂–Ar mixtures. A kinetic modeling of our own and published experimental data at temperatures of 930 < T < 2500 K and pressures of 0.05 < P < 8.7 MPa enabled to establish how the initiation reactions influence the process of self-ignition and to evaluate the rate constant for one of the initiation reactions: k(H₂ + O₂ → 2OH) = (3 ± 1) × 10¹¹exp(–E _a/RT), cm³ mol^–1 s^–1, where E _a = (40 ± 2) kcal/mol.     

Shock tube measurements of ignition delay times and OH time-histories in dimethyl ether oxidation

Ignition delay times and OH concentration time-histories were measured in DME/O₂/Ar mixtures behind reflected shock waves. Initial reflected shock conditions covered temperatures (T₅) from 1175 to 1900 K, pressures (P₅) from 1.6 to 6.6 bar, and equivalence ratios (?) from 0.5 to 3.0. Ignition delay times were measured by collecting OH^∗ emission near 307 nm, while OH time-histories were measured using laser absorption of the R₁(5) line of the A-X(0,0) transition at 306.7 nm. The ignition delay times extended the available experimental database of DME to a greater range of equivalence ratios and pressures. Measured ignition delay times were compared to simulations based on DME oxidation mechanisms by Fischer et al. [7] and Zhao et al. [9]. Both mechanisms predict the magnitude of ignition delay times well. OH time-histories were also compared to simulations based on both mechanisms. Despite predicting ignition delay times well, neither mechanism agrees with the measured OH time-histories. OH Sensitivity analysis was applied and the reactions DME ↔ CH₃O + CH₃ and H + O₂ ↔ OH + O were found to be most important. Previous measurements of DME ↔ CH₃O + CH₃ are not available above 1220 K, so the rate was directly measured in this work using the OH diagnostic. The rate expression k[1/s] =  1.61 × 10⁷⁹T^−18.4 exp(−58600/T), valid at pressures near 1.5 bar, was inferred based on previous pyrolysis measurements and the current study. This rate accurately describes a broad range of experimental work at temperatures from 680 to 1750 K, but is most accurate near the temperature range of the study, 1350-1750 K. When this rate is used in both the Fischer et al. and Zhao et al. mechanisms, agreement between measured OH and the model predictions is significantly improved at all temperatures.