Rapid compression machines (RCMs) are widely used to investigate gas phase reaction kinetics of various kind of fuels at application relevant conditions. In principle, the operation of an RCM is based on the idea of compressing a homogenous pre-mixed fuel-air mixture by a piston. Usually creviced pistons ensure a homogenous adiabatic core in the center of the reaction chamber which permits the assumption of an isentropic relation between the measured pressure and gas temperature. Despite the ideal core gas compression, non-ideal effects such as heat loss, differences in the compression behavior, and ultimately non-standardized design and operation of rapid compression machines lead to different experimental results in different facilities at nominally the same end of compression conditions.

In this study ignition delay times of ethanol are investigated at four different conditions in five independent RCMs. As expected, the raw results of the different facilities indeed show notable differences at the same end of compression conditions. However, according to the adiabatic core hypothesis the agreement between kinetic simulations and experiments should be consistent for all facilities provided that the facility effects are correctly accounted for. To elaborate upon this hypothesis, a kinetic mechanism is optimized to reflect the experimental results of all facilities. In the end, the optimized mechanism predicts all experimental data within the expected uncertainty. This confirms the reliability of RCM experiments for kinetic investigations and the validity of the effective volume approach in simulating RCM data.

A comprehensive understanding of the combustion chemistry of methyl tert‑butyl ether (MTBE) is of key importance in its application as an additive in gasoline fuels. Ignition delay times (IDTs) of MTBE/air mixtures have been measured in both a high-pressure shock tube (HPST) and in a rapid compression machine (RCM) at equivalence ratios of 0.5, 1.0, and 2.0 in air, at pressures of 10 and 30 bar over the temperature range 600 – 1350 K. Species profiles for MTBE oxidation were obtained in a jet-stirred reactor (JSR) at 1 bar, at equivalence ratios of 0.5, 1.0, and 2.0 in the temperature range 700 – 1100 K.

A detailed reaction mechanism, comprising 813 species and 4319 reactions, has been developed and predicts well all of the experimental data obtained in this work and also texisitng literature data. Pressure- and temperature-dependent rate constants for the MTBE unimolecular elimination reaction producing isobutene and methanol were calculated using high-level ab-initio calculations. A sensitivity analysis reveals that this elimination reaction is important, and significantly inhibits fuel reactivity at temperatures above 1300 K. At intermediate temperatures (850 – 1300 K), the reaction MTBE + ȮH = TĊ₄H₈OCH₃ + H₂O plays a crucial role in promoting the reactivity of MTBE oxidation, whereas the reaction MTBE + ȮH = TC₄H₉OĊH₂ + H₂O is the most inhibiting reaction. At low temperatures (600 – 850 K), the isomerization reaction of TC₄OCȮ₂–1 ⇌ TĊ₄OCO₂H-2 significantly promotes the reactivity. Conversely, the reaction 2TC₄OCȮ₂–1 ↔ 2TC₄OCȮ-1 + O₂ inhibits reactivity the most. The NTC behavior in MTBE oxidation can be explained by the competition between the reactions involving the formation and consumption of cyclic ethers from TĊ₄H₈OCH₃ radicals and the reactions associated with the formation and consumption of carbonyl hydroperoxide species.

Exhaust gas recirculation (EGR) and NO_x affect the autoignition of gasoline in internal combustion engines. In this work, ignition delay times of an oxygenated gasoline (Euro 6 E10) are investigated with EGR and NO_x addition. The experimental data are of interest for gasoline surrogate modeling and for predicting fuel ignition behavior in various engine combustion modes. We studied Euro 6 E10 reactivity with EGR additions of 20 % and 40 % (by mass) doped, in select cases, with high levels of NO_x (874, 1501, 3174, and 5568 ppm, by mol%). Experiments were performed in two high-pressure shock tubes (HPSTs) and two rapid compression machines (RCMs) over a wide range of temperature (658–1610 K), equivalence ratio (0.5, 1.0) and at pressures of 20 and 30 bar. Results show that EGR addition inhibits Euro 6 E10 gasoline reactivity in the intermediate- and low-temperature regimes, while it is minimally affected at high-temperatures. In contrast, a strong reactivity-promoting effect of NO_x is observed at temperatures greater than 825 K for all equivalence ratios investigated, while an inhibiting effect is seen at lower temperatures with a high doping of NO_x (1501 ppm). For fuel-lean cases, where Euro 6/EGR mixtures are sensitized with 3174 – 5568 ppm NO_x, a significant reactivity-promoting effect is observed across the entire range of conditions investigated, except at temperatures below 830 K, where the NO_x-inhibiting effect dominates. A gasoline surrogate model is developed by combining a detailed gasoline surrogate mechanism with appropriate sub-models and making minor updates. The proposed model captures well the influence of EGR and EGR/NO_x on Euro 6 E10 autoignition over the wide range of conditions studied here. Finally, sensitivity analyses were conducted to identify key reactions contributing to the perturbative effects of EGR and EGR/NO_x on oxygenated gasoline ignition.

Despite the widespread use of renewable and green energy, the demand for fossil fuels is also rising due to increasing global energy demand. Therefore, unconventional solutions, with safe environmental impacts, are being pursued to solve this problem. Instead of getting rid of the exhaust gases in the surroundings, one solution might be to inject them with the oxidizer into the oil reservoir, to initiate an in-situ combustion (ISC) process to enhance oil recovery. A numerical study of a 1-D combustion tube has been conducted and validated to simulate the in-situ combustion process using enriched air as the oxidizer. The effects of injecting exhaust gases with the oxidizer are studied. Different ratios of oxygen to nitrogen are used in the enriched air as well as different ratios of exhaust gases. If enriched air which is mostly oxygen, i.e. 95% O₂ +5%N₂, is used, it is found that replacing 10% of the enriched air with exhaust gases can increase the oil recovery factor (ORF) from 94.7% to 94.9% and replacing 20% can improve oil recovery to 95.1%. For another enriched air, 60% O₂ +30% N₂, it is found that replacing portions of the enriched air with exhaust gases will reduce the oil recovery factor. In all previous cases, it was found that replacing the proportions of enriched air with exhaust gases reduces the amount of fuel burned and increases hydrogen production.