Autoignition behavior of methanol/diesel mixtures: Experiments and kinetic modeling

Methanol is an attractive oxygenate increasingly used as primary fuel for dual-fuel combustion technology yielding beneficial thermal-efficiency and emissions in modern engines. As such, it is significant to fundamentally understand the autoignition behavior of methanol/diesel mixtures. This study measured the ignition delay times (IDTs) of methanol/diesel blends with different mixing ratios (30%, 50%, 70% methanol by mol.) on a heated shock tube and a heated rapid compression machine at temperatures of 650−1450 K, pressures of 6−20 bar, and equivalence ratios of 0.5, 1.0 and 2.0. The typical two-stage ignition characteristics with the negative temperature coefficient response were observed for dual-fuel mixtures. In general, both the total and first-stage IDTs decrease with the increment of pressure and equivalence ratio as well as diesel proportion in mixtures. The simulation results performed with a published detailed mechanism in conjunction with a tri-component diesel surrogate demonstrate generally good agreement with the experimental data at all test conditions. Moreover, a crossover of IDTs occurs at a higher temperature (~1500 K) for varying equivalence ratios, and experiment and simulation both exhibit a non-linear mixing effect of methanol addition on diesel ignition. Interestingly, simulation results clearly suggest a crossover (~940 K) for mixtures with varying methanol content at an intermediate-temperature, where the IDT of the mixture with a lower methanol ratio becomes longer as the temperature is higher than that of the crossover. Furthermore, brute-force sensitivity analyses assisted with reaction path analysis were conducted to gain deeper insights into the autoignition chemistry of dual-fuel mixtures, especially for the chemical interaction between both fuels during the low-temperature oxidation process. It is found that methanol hardly generates •OH, whereas •OH is mainly produced by the low-temperature reaction pathways of diesel. Thus, •OH is the bridge for both fuels during the ignition process. At the high methanol ratio, the H-abstraction of diesel is mainly via •HO2 while CH3OH consumes a large percentage of •OH. Consequently, the competition between methanol and diesel for •OH radicals inhibits the overall reactivity of reaction network. In addition, the original data reported here lay a foundation for the development and validation of more accurate and robust dual-fuel kinetic schemes.