Impact of mixing low-reactivity gases on the mechanism of hydrogen spontaneous combustion: A ReaxFF MD study

The phenomenon of spontaneous combustion during the release of high-pressure H2 is critical to the safe storage and transportation. Besides physical methods to suppress self-ignition, the approach of mixing low-reactivity gases has gained increasing attention. Previous work has mainly focused on the flow, physical heating effects, and boundary conditions of self-ignition in mixed gases, while the intrinsic chemical reaction mechanisms of spontaneous combustion remain underexplored. To clear this issue, this work uses the ReaxFF MD simulation method to study the spontaneous combustion process of H2/CO and H2/CH4 mixtures with various concentrations. The results indicate that: (1) in pure H2, H2/CO, and H2/CH4 systems, the primary initial reaction mechanism is H2+O2--HO2+H. Additionally, in some mixed systems, CO + O2--CO2+O and CH4+O2--CH3+HO2 may also serve as initial reaction mechanisms. (2) Under fuel-lean combustion conditions, the RIDTs of the systems decrease, supporting the viewpoint that self-ignition typically occurs first in fuel-lean regions. The addition of CO and CH4 increases the RIDTs, which helps inhibit the development of self-ignition. (3) In H2-rich environments, CO combusts to CO2 through the formation of HOCO, while CH4 undergoes dehydrogenation and oxidation processes through intermediates such as CH3, CH3O, and HCHO, leading to the formation of CO and CO2. The combustion of H2 is also influenced by these processes. (4) The addition of CO and CH4 increases the activation energy of H2 combustion, raising the reaction energy barrier that must be overcome for spontaneous combustion. This effectively helps to suppress the occurrence and development of self-ignition during the release of high-pressure gases.