Autoignition characteristics of bio-based fuels,farnesane and TPGME,in comparison with fuels of similar cetane rating

Bio-based alternative fuels have received increasing attention with growing concerns about depletion of fossil reserves and environmental deterioration. The development of new combustion concepts in internal combustion engines requires a better understanding of autoignition characteristics of the bio-based alternative fuels. This study investigates two cases of alternative fuels, namely, a kerosene-type fuel farnesane and an oxygenated fuel, TPGME, and compares those fuels with full-boiling range of fuels with similar cetane number. The homogeneous autoignition and spray ignition characteristics of the selected fuels are studied using a modified CFR octane rating engine and a cetane rating instrument, respectively. When comparing farnesane with a full-boiling range counterpart (HRJ8), their similar cetane ratings result in comparable combustion heat release, but the overall ignition reactivity of farnesane is stronger than HRJ8 during the pre-ignition process. Results from a constant volume spray combustion chamber indicate that the spray process of farnesane and HRJ8 strongly influences the overall ignition delay of each fuel. Despite the similar cetane ratings of TPGME and n-heptane, TPGME shows greater apparent low-temperature oxidation reactivity at low compression ratios in the range from CR 4.0-5.5 than n-heptane. A simplified model focused on the key reaction pathways of low-temperature oxidation of TPGME has been applied to account for the stronger low-temperature reactivity of TPGME, supported by density functional theory (DFT) calculations. Regardless of the similar cetane ratings of the fuels, n-heptane and JP-8/SPK lead to similar total ignition delay times, while TPGME shows the shortest overall ignition delay times in the constant volume combustion chamber.     

Experimental and modeling study of the autoignition characteristics of commercial diesel under engine-relevant conditions

Knowledge of the autoignition characteristics of diesel fuels is of great importance for understanding the combustion performance in engines and developing surrogate fuels. Here ignition delays of China's stage 6 diesel, a commercial fuel, were measured in a heated rapid compression machine (RCM) under engine-relevant conditions. Gas-phase autoignition experiments were carried out at equivalence ratios ranging from 0.37 to 1.0, under compressed pressures of 10, 15, and 20?bar, and within a temperature range of 685–865?K. In all investigated conditions, negative temperature coefficient (NTC) behavior of the total ignition delays is observed. The autoignition of the diesel fuel exhibits pronounced two-stage characteristics with strong low-temperature reactivity. Experimental results indicate that the total ignition delays shorten with increasing compressed pressure, oxygen mole fraction and fuel mole fraction. The first-stage ignition delays are mainly controlled by compressed temperature and also affected by oxygen mole fraction and compressed pressure but show a very weak dependence on fuel mole fraction. Correlations describing the first-stage ignition delay and the total ignition delay were proposed to further clarify the ignition delay dependence on the multiple factors. Additionally, it is found that the newly measured ignition delays well coincide with and complement the diesel ignition data in the literature. A recently developed diesel mechanism was used to simulate the diesel autoignition on the RCM. The simulation results are found to agree well the experimental measurements over the whole temperature ranges. Species concentration analysis and brute force sensitivity analysis were also conducted to identify the crucial species and reactions controlling the autoignition of the diesel fuel.     

Global reaction mechanism for the auto-ignition of full boiling range gasoline and kerosene fuels

Compact reaction schemes capable of predicting auto-ignition are a prerequisite for the development of strategies to control and optimise homogeneous charge compression ignition (HCCI) engines. In particular for full boiling range fuels exhibiting two stage ignition a tremendous demand exists in the engine development community. The present paper therefore meticulously assesses a previous 7-step reaction scheme developed to predict auto-ignition for four hydrocarbon blends and proposes an important extension of the model constant optimisation procedure, allowing for the model to capture not only ignition delays, but also the evolutions of representative intermediates and heat release rates for a variety of full boiling range fuels. Additionally, an extensive validation of the later evolutions by means of various detailed n-heptane reaction mechanisms from literature has been presented; both for perfectly homogeneous, as well as non-premixed/stratified HCCI conditions. Finally, the models potential to simulate the auto-ignition of various full boiling range fuels is demonstrated by means of experimental shock tube data for six strongly differing fuels, containing e.g. up to 46.7% cyclo-alkanes, 20% napthalenes or complex branched aromatics such as methyl- or ethyl-napthalene. The good predictive capability observed for each of the validation cases as well as the successful parameterisation for each of the six fuels, indicate that the model could, in principle, be applied to any hydrocarbon fuel, providing suitable adjustments to the model parameters are carried out. Combined with the optimisation strategy presented, the model therefore constitutes a major step towards the inclusion of real fuel kinetics into full scale HCCI engine simulations.     

Autoignition of varied cetane number fuels at low temperatures

The reactivity of six kerosene based control fuels, specifically formulated for cetane number variation, are investigated by measuring ignition delay time in a heated rapid compression machine. Cetane numbers vary from 30 to 55 (increment of 5) while holding other properties relatively constant by adjusting chemical group composition. Main cetane variation was controlled through the distribution of normal alkanes and isoalkanes, which was fine-tuned using additives. Other fuel properties such as density, viscosity, H/C ratio, etc. were balanced using cyclic compounds and aromatics. Fuels were tested in the RCM at compressed pressures of P_c=?10 and 20?bar, equivalence ratios of ??=?0.25, 0.5 and 1.0, in the low to intermediate temperature range (620?K?≤?T_c?≤?730?K). Relations between cetane number and ignition delay time have been evaluated at multiple test conditions, and further analysis on multistage ignition has been conducted. Ignition delay times of fuels with higher cetane numbers are shorter at these temperatures for most conditions. First stage ignition delay time measurements have been observed to be relatively insensitive to P_c, ?, and fuel type, while deviations in overall ignition delay times are mainly attributed to second stage ignition delay time, impacted by variations in the first stage temperature. Control fuels of this type offer an opportunity to be used in practical experiments to determine the impact of cetane number on combustion dynamics.     

The effect of molecular structures of alkylbenzenes on ignition characteristics of binary n-heptane blends

Alkylbenzenes are major aromatic constituents of real transportation fuels and important surrogate components. In this study, the structural impact of nine alkylbenzenes on their ignition characteristics is experimentally and computationally investigated with particular emphasis on the blending effect with significantly more reactive normal alkanes. Experimental comparisons of mono-alkylbenzenes (toluene, ethylbenzene, n-propylbenzene, iso-propylbenzene) from a modified CFR engine showed that the difference in pure alkylbenzene reactivity significantly diminished when blended with n-heptane, as the strength of the radical scavenging effect of all three alkylbenzenes is similar. Among C₈H₁₀ isomers, the reactivity of pure ethylbenzene and o-xylene and their blends with n-heptane showed a complex competing effect between the difference in CH bond energy and the existence of intermediate/low-temperature chemistry caused by adjacent methyl pairs. A similar structural impact was also observed for C₉H₁₂ isomers and their blends with n-heptane, while the influence of CH bond energy was more noticeable than C₈H₁₀ molecules. Kinetic simulations of the alkylbenzene/n-heptane blends highlighted the effect caused by adjacent methyl pairs that is referred to as the “ortho effect”. Analysis of ethylbenzene and o-xylene showed that o-xylene's intermediate/low-temperature pathways initiated by benzylperoxy radical – benzylhydroperoxide isomerization (RO2 – QOOH) produce additional active radicals such as OH and CH₂O, which accelerates the oxidation chemistry of more reactive n-heptane. This study provides knowledge on the blending effect of alkylbenzene compounds with n-heptane on their ignition characteristics that is useful to develop surrogates that can better mimic the reactivity of real fuels.     

Impact of nitric oxide on n-heptane and n-dodecane autoignition in a new high-pressure and high-temperature chamber

A New One Shot Engine (NOSE) was designed to simulate the thermodynamic conditions at High Pressure-High Temperature like an actual common-rail diesel engine in order to study the compression ignition of spray. The volume of the combustion chamber provided with large optical windows simplified the implementation of various optical diagnostics. The advantage of this kind of set-up in comparison to pre-burn or flue chambers is that the initial gas mixture can be well controlled in terms of species and mole fraction. The purpose of this work was to investigate the impact of nitric oxide (NO) on ignition delay (ID) for two fuels with different cetane numbers: n-heptane, and n-dodecane. In the thermodynamic conditions chosen (60?bar and over 800–900?K), NO had a strong effect on ID, with increases in NO tending to reduce the ignition delay. Results showed that ID and Lift-Off Length (LOL) presented the same trend as a function of temperature and NO concentration. Experimentally, at 900?K the ignition of n-dodecane was promoted by NO up to 100?ppm, whilst higher NO levels did not further promote ignition and a stabilization of the value has been noticed. For n-heptane, stronger promoting effects were observed in the same temperature conditions: the ignition delays were monotonically reduced with up to 200?ppm NO addition. At a lower temperature (800?K) the inhibiting effect was observed for n-dodecane for [NO] greater than 40?ppm, whereas only a promoting effect was observed for n-heptane. The experimental results of LOL showed that NO shortened LOL in almost all cases, and this varied with both the NO concentration and the mixture temperature. Thus, fuels with shorter ignition delays produce shorter lift-off lengths.     

Three-stage auto-ignition of n-heptane and methyl-cyclohexane mixtures at lean conditions in a flat piston rapid compression machine

One approach to enhancing the thermal efficiency of combustion systems is to burn fuels at ultra-lean conditions (equivalence ratio below 0.5). It has been recently reported that the auto-ignition of some hydrocarbon fuels, under specific temperature, pressure, and mixture conditions, releases heat in three distinctive stages. The three auto-ignition stages can be divided as a first low-temperature auto-ignition stage with conventional low temperature, and a high-temperature stage separated into two sub-stages. This study presents ignition delay time measurements of n-heptane and methyl-cyclohexane (MCH) mixtures in a flat piston rapid compression machine (RCM) under ultra-lean conditions. It provides experimental evidence of three-stage auto-ignition. This phenomenon of delayed high-temperature heat release is seldom reported in the literature and this is the first time to be reported for these types of fuels. The experiments cover two binary n-heptane/MCH mixtures of 15/85 and 70/30 by volume, pressures of 11 bar and 16 bar, temperature range of 700 to 900 K, and equivalence ratio of 0.4. The RCM optical access was utilized for high-speed chemiluminescence imaging. Detailed chemical kinetic simulations in a homogenous batch reactor with variable volume were conducted to further interrogate the three-stage auto-ignition phenomenon. Chemiluminescence shows that three-stage auto-ignition occurs in the adiabatically compressed end-gas, which indicates that this phenomenon is chemically-driven and is not induced by a thermal stratification in the RCM experiments. The model predicts the features of three-stage auto-ignition, which were experimentally observed at temperatures approximately below 750 K. As expected, significant discrepancies are observed in the ignition delays of experiment and simulation in the negative temperature coefficient (NTC) region. The simulation of the n-heptane/MCH 70/30 mixture shows better agreement with experiments in the Positive Temperature Coefficient (PTC) region compared to the 15/85 mixture.     

The oxidation characteristics of furan derivatives and binary TPGME blends under engine relevant conditions

Furan and its derivatives have been receiving attention as next generation alternative fuels, related to advanced bio-oil production. However, the ignition quality of furans allows their use only as an additive to diesel fuel in CI engines, which potentially requires the continued use of a fossil-derived base fuel. This study first adopts tri-propylene glycol mono-methyl ether (TPGME) as a substitute for diesel fuel with addition of furan and furan derivatives, including 2-methylfuran, 2,5-dimethylfuran, and furfural, thereby removing fossil-derived fuels from the mixture. With this motivation, gas-phase ignition characteristics of furans were investigated in a modified CFR motored engine, displaying an absence of low temperature heat release (LTHR), while n-heptane as a reference fuel shows a strong two-stage ignition characteristic under the same condition. The structural impact of furans is represented as global oxidation reactivities that are as follows: furan?<?2-methylfuran?<?2,5-dimethylfuran?<?furfural?<?n-heptane. The ranking of individual furans is supported by bond dissociation energies of each fuel's functional group substituent on the furan-ring. Ignition characteristics of TPGME display a strong low-temperature oxidation reactivity; however, its reactivity rapidly diminishes with increasing amounts of furan, shutting down low-temperature oxidation paths. The structural impact of furan and methyl-substituted furans on reactivity is significantly muted when blended with TPGME, as observed in a motored CFR engine and a constant volume spray combustion chamber.     

Counterflow ignition and extinction of FACE gasoline fuels

The demand for petroleum-derived gasoline in the transportation sector is on the rise. For better knowledge of gasoline combustion in practical combustion systems, this study presents experimental measurements and numerical prediction of autoignition temperatures and extinction limits of six FACE (fuels for advanced combustion engines) gasoline fuels in counterflow flames. Extinction limits were measured at atmospheric pressures while the experiments for autoignition temperatures were carried out at atmospheric and high pressures. For atmospheric pressure experiment, the fuel stream consists of the pre-vaporized fuel diluted with nitrogen, while a condensed fuel configuration is used for ignition experiment at higher chamber pressures. The oxidizer stream is pure air. Autoignition temperatures of the tested fuels are nearly the same at atmospheric pressure, while a huge difference is observed as the pressure is increased. Unlike the ignition temperatures at atmospheric pressures, minor difference exists in the extinction limits of the tested fuels. Simulations were carried out using a recently developed gasoline surrogate model. Both multi-component and n-heptane/isooctane mixtures were used as surrogates for the simulations. Overall, the n-heptane/isooctane surrogate mixtures are consistently more reactive as compared the multi-component surrogate mixtures. Transport weighted enthalpy and radical index analysis was used to explain the differences in extinction strain rates for the various fuels.     

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.     

Experimental and kinetic modeling study of the low- temperature and high-pressure combustion chemistry of straight chain pentanol isomers: 1-, 2- and 3-Pentanol

Pentanols have received significant attention as a potential alternative fuel or fuel additive owing to their high energy densities and low vapor pressure. The development of robust chemical kinetic models for alternative fuels which can provide accurate and efficient predictions of combustion performance across a wide range of engine relevant conditions is important in developing cleaner, more efficient combustors. Although the high temperature oxidation kinetics of pentanol isomers has been researched considerably, their low temperature combustion chemistry needs further investigation. While previously proposed low temperature mechanisms for 1-pentanol based on analogy and rate rules need further refinement, the low temperature oxidation kinetics of 2-pentanol and 3-pentanol has not been studied previously by any means, experimentally or theoretically. A newly developed kinetic mechanism is presented in this work for the three straight chain pentanol isomers: 1-, 2- and 3-pentanol. Low temperature kinetics is based on a recent study by Lockwood et al., 2022 [20] involving theoretical calculations at the CCSD(T)/cc-pV∞Z level of theory for the oxidation pathways involving alcohol peroxy radicals. Rate of production analyses performed in this study highlight the importance of the newly added pressure-dependent reactions of the α-alcohol peroxy radical forming an RȮ₂ adduct. While the α-alcohol fuel radical reacts with O₂ to directly decompose via a chemically activated pathway at low pressures, the formation of the RȮ₂ adduct is favored at high pressures. The detailed model is comprehensively validated against new ignition experiments at low temperature and high pressure, together with the wide range of data available in the literature. Both qualitative and quantitative predictions of the experimental data using the proposed kinetic model are satisfactory for all three pentanol isomers studied here.     

Direct observations of single particle fragmentation in the early stages of combustion under dry and wet conventional and oxy-fuel conditions

This article investigates the single particle fragmentation of three solid fuels in the early stages of combustion under dry and wet conventional and oxy-fuel conditions. The three solid fuels studied were a low rank sub-bituminous Colombian coal, a low-rank/high-ash sub-bituminous Brazilian coal, and a charcoal residue from black acacia. Particles, with size in the range 125–150 µm, were burned in a drop tube furnace with a constant wall temperature of 1475?K, under 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 fragmentation process during the early stages of combustion and the collected images were treated to characterize the fragmentation mode, probability and time. The observed fragmentation modes are characterized by the occurrence of exfoliation, radial fragmentation or a combination of both. The results disclose that the fragmentation mode is strongly affected by the fuel type, but less affected by the atmosphere; the fragmentation probability is strongly affected by both the fuel type and the atmosphere; and, finally, fragmentation in air occurs significantly dispersed after ignition, but it tends to cluster closer to the ignition under simulated oxy-fuel conditions.     

Effects of fuel blending on first stage and overall ignition processes

The effects of blending ratio on mixtures of an alcohol-to-jet (ATJ) fuel and a conventional petroleum-derived fuel on first stage ignition and overall ignition delay are examined at engine-relevant ambient conditions. Experiments are conducted in a high-temperature pressure vessel that maintains a small flow of dry air at the desired temperature (825 K and 900 K) and pressure (6 MPa and 9 MPa) for fuel injections from a custom single-hole, axially-oriented injector, representing medium (7.5 mg) and high (10 mg) engine loading. Formaldehyde, imaged using planar laser-induced fluorescence, is measured at discrete time steps throughout the first and second stage ignition process and is used as a marker of unburned short-chain hydrocarbons formed after the initial breakdown of the fuel. The formaldehyde images are used to calculate the first stage ignition delay for each ambient and fuel loading condition. Chemiluminescence imaging of excited hydroxyl radical at 75 kHz is used to determine the overall ignition delay. At all conditions, increased volume fraction of ATJ resulted in longer, but non-linearly increasing, overall ignition delay. Across all of the blends, first stage ignition delay accounted for about 15% of the increase in overall ignition delay compared to the military's aviation kerosene, F-24, which is Jet A with additives, while extended first stage ignition duration accounted for 85% of the increase. It is observed that blends consisting of 0–60% by volume of the low cetane number ATJ fuel produced nearly identical first stage ignition delays. These results will inform the development of ignition models that can capture the non-linear effects of fuel blending on ignition processes.     

Experimental and semi-detailed kinetic modeling study of decalin oxidation and pyrolysis over a wide range of conditions

Decalin is the simplest polycyclic alkane (polynaphtenic hydrocarbon) found in liquid fuels (jet fuels, Diesel). In order to better understand the combustion characteristics of decalin, this study provides new experimental data for its oxidation in a jet-stirred reactor. For the first time, stable species concentration profiles were measured in a jet-stirred reactor at a constant mean residence time of 0.1 s and 0.5 s at respectively 1 and 10 atm, over a range of equivalence ratios (? = 0.5–1.5) and temperatures (750–1350 K). The oxidation of decalin under these experimental conditions was modeled using a semi-detailed chemical kinetic reaction mechanism (11,000 reactions involving 360 species) derived from a previously proposed scheme for the ignition of the same fuel in a shock-tube. The proposed mechanism that includes both low- and high-temperature chemistry shows reasonably good agreement with the present experimental data set. It can also represent well decalin pyrolysis and oxidation data available in the literature. Reaction path analyses and sensitivity analyses were conducted to interpret the results.     

A reduced mechanism for biodiesel surrogates with low temperature chemistry for compression ignition engine applications

Biodiesel is a promising alternative fuel for compression ignition (CI) engines. It is a renewable energy source that can be used in these engines without significant alteration in design. The detailed chemical kinetics of biodiesel is however highly complex. In the present study, a skeletal mechanism with 123 species and 394 reactions for a tri-component biodiesel surrogate, which consists of methyl decanoate, methyl 9-decanoate and n-heptane was developed for simulations of 3-D turbulent spray combustion under engine-like conditions. The reduction was based on an improved directed relation graph (DRG) method that is particularly suitable for mechanisms with many isomers, followed by isomer lumping and DRG-aided sensitivity analysis (DRGASA). The reduction was performed for pressures from 1 to 100 atm and equivalence ratios from 0.5 to 2 for both extinction and ignition applications. The initial temperatures for ignition were from 700 to 1800 K. The wide parameter range ensures the applicability of the skeletal mechanism under engine-like conditions. As such the skeletal mechanism is applicable for ignition at both low and high temperatures. Compared with the detailed mechanism that consists of 3299 species and 10806 reactions, the skeletal mechanism features a significant reduction in size while still retaining good accuracy and comprehensiveness. The validations of ignition delay time, flame lift-off length and important species profiles were also performed in 3-D engine simulations and compared with the experimental data from Sandia National Laboratories under CI engine conditions.     

Catalytic ignition and autothermal combustion of JP-8 and its surrogates over a Pt/γ-Al2O3 catalyst

With the aim of utilizing JP-8 fuel for small scale portable power generation systems, catalytic combustion of JP-8 is studied. The surface ignition, extinction and autothermal combustion of JP-8, of a six-component surrogate fuel mixture, and the individual components of the surrogate fuel over a Pt/γ-Al₂O₃ catalyst are experimentally investigated in a packed bed flow reactor. The surrogate mixture exhibits similar ignition–extinction behavior and autothermal temperatures compared to JP-8 suggesting the possibility of using this surrogate mixture for detailed kinetics of catalytic combustion of JP-8. It is shown that JP-8 ignites at low temperatures in the presence of catalyst. Upon ignition, catalytic combustion of JP-8 and the surrogate mixture is self-sustained and robust combustion is observed under fuel lean as well as fuel rich conditions. It is shown that the ignition temperature of the hydrocarbon fuels increases with increasing equivalence ratio. Extinction is observed under fuel lean conditions, whereas sustained combustion was also observed for fuel rich conditions. The effect of dilution in the air flow on the catalytic ignition and autothermal temperatures of the fuel mixture is also investigated by adding helium to the air stream while keeping the flow rate and the equivalence ratio constant. The autothermal temperature decreases linearly as the amount of dilution in the flow is increased, whereas the ignition temperature shows no dependence on the dilution level under the range of our conditions, showing that ignition is dependent only on the type and relative concentration of the active species.     

Ignition delay measurements of four component model gasolines exploring the impacts of biofuels and aromatics

This study explores the impacts of combinations of biofuel (ethanol, isobutanol and 2-methyl furan) and aromatic (toluene) compounds in a four component fuel blend, at fixed research octane number (RON) on ignition delay measured in an advanced fuel ignition delay analyzer (AFIDA 2805). Ignition delay measurements were performed over a range of temperatures from 400 to 725 °C (673 to 998 K) and two chamber pressures of 10 and 20 bar. The four component mixtures are compared to primary reference fuels at RON values of 90 and 100. The ignition delay measurements show that as the aromatic and biofuel concentrations increased, two stage ignition behavior was suppressed, at both initial chamber pressures. But both RON 100 (isooctane) and RON 90 reference fuels showed two stage ignition behavior, as did fuel mixtures with low biofuel and aromatic content. RON 90 fuels showed stronger two stage ignition behavior than RON 100 fuels, as expected. Depending on the type of biofuel in the mixture, the ignition delay at low chamber temperatures could be far greater than for the reference fuels. In particular, for the RON 100 mixtures at either 10 or 20 bar initial chamber pressure, the ignition delay at 400 °C (673 K) for the high level blend of 2-methyl furan and toluene (30 vol% of each) exhibited an ignition delay that was 10 times longer than for neat isooctane. The results show the strong non-linear octane blending response of these three biofuel compounds, especially in concert with the kinetic antagonism that toluene is known to display in mixtures with isooctane. These results have implications for the formulation of biofuel mixtures for spark ignition and advanced compression ignition engines, where this non-linear octane blending response could be exploited to improve knock resistance, or modulate the autoignition process.     

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 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.     

Surrogate formulation for diesel and jet fuels using the minimalist functional group (MFG) approach

Surrogate fuels aim to reproduce real fuel combustion characteristics in order to enable predictive simulations and fuel/engine design. In this work, surrogate mixtures were formulated for three diesel fuels (Coryton Euro and Coryton US-2D certification grade and Saudi pump grade) and two jet fuels (POSF 4658 and POSF 4734) using the minimalist functional group (MFG) approach, a method recently developed and tested for gasoline fuels. The diesel and jet fuel surrogates were formulated by matching five important functional groups, while minimizing the surrogate components to two species. Another molecular parameter, called as branching index (BI), which denotes the degree of branching was also used as a matching criterion. The present works aims to test the ability of the MFG surrogate methodology for high molecular weight fuels (e.g., jet and diesel). ¹H Nuclear Magnetic Resonance (NMR) spectroscopy was used to analyze the composition of the groups in diesel fuels, and those in jet fuels were evaluated using the molecular data obtained from published literature. The MFG surrogates were experimentally evaluated in an ignition quality tester (IQT), wherein ignition delay times (IDT) and derived cetane number (DCN) were measured. Physical properties, namely, average molecular weight (AMW) and density, and thermochemical properties, namely, heat of combustion and H/C ratio were also compared. The results show that the MFG surrogates were able to reproduce the combustion properties of the above fuels, and we demonstrate that fewer species in surrogates can be as effective as more complex surrogates. We conclude that the MFG approach can radically simplify the surrogate formulation process, significantly reduce the cost and time associated with the development of chemical kinetic models, and facilitate surrogate testing.