<p>Fire zone coal is an important product formed in the process of spontaneous combustion of coal; due to the timeliness of physical fire prevention materials, the secondary oxidation of coal in the fire zone is unavoidable, which results in the formation of the process of initial heating–cooling–secondary heating. The cooling process of coal is often neglected; however, the changes occurring in coal during the cooling process cannot be ignored, which puts forward a severe test for predicting the secondary oxidation characteristics of coal in the fire zone. The fire zone coal (initial heating up to 180 °C) was subjected to slow cooling and fact cooling to obtain SC and FC. The micro- and macro-changes of the raw coal, SC and FC during the secondary heating process were analysed by FTIR, TG experiments and kinetic methods. It was found that –CH₂, –CH₃, –OH and –COOH production &gt; consumption during the initial heating process of the coal; during the cooling process, –CH₂ and –CH₃ production &lt; consumption, and –OH and –COOH production &gt; consumption. The reactivities of SC and FC exceeded those of the raw coal after the thermal decomposition temperature point. The apparent activation energy of SC was 29.43&#xa0;kJ&#xa0;mol⁻¹ lower than that of FC in the thermal decomposition stage, and FC was 17.38&#xa0;kJ&#xa0;mol⁻¹ lower than that of SC in the combustion stage. By fitting the combustion characteristic index, it was found that FC showed more sensitivity to the change in the rate of temperature increase.</p>