The indicative ability of a gas indicator for the spontaneous combustion of coal is affected by the secondary oxidation of oxidized coal, from old goafs, entering a new goaf through air leakages. This phenomenon can affect the accuracy of early warning systems regarding the spontaneous combustion of coal in a goaf. In this research, three kinds of coal were selected to carry out a spontaneous combustion simulation experiment in which a temperature-programmed experimental device was used to analyze the behavior of the index gas towards raw coal and oxidized coal, for which the latter was oxidized at 70 ¿C, 90 ¿C, 130 ¿C, and 150 ¿C. The results show that the chain alkane ratio in the secondary oxidation process and the trends of oxygen, CO, and C2H4 concentrations are the same as those in the primary oxidation process. On the other hand, the temperature at which C2H4 initially appears, during secondary oxidation, is lower than in primary oxidation. The CO produced in the early stage of secondary oxidation is greater than the CO produced, at the same temperature, in primary oxidation. In this regard, the usage of C2H4 concentration as an indicator with which to judge the occurrence of the spontaneous combustion of coal would allow for an earlier response. In the secondary oxidation process, the temperature of the extreme value of the alkene ratio appears higher than in primary oxidation. The presence of a higher pre-oxidation temperature and a higher proportion of secondary oxidation gas will affect an indicator’s judgement when the primary oxidation enters the severe oxidation stage. The gas produced by secondary oxidation will affect the early warning of the spontaneous combustion of coal in the coal mine goaf, which should be considered in the establishment of an early warning system.
