Co-Pyrolysis Behavior of Energetic Materials and Pine Sawdust

Incineration is a widely adopted method for the disposal of waste energetic materials (SP). Nevertheless, this approach is associated with considerable thermal energy loss and significant environmental pollution. To address these limitations, this study proposes a co-pyrolysis process incorporating pine sawdust (SD) with SP. This technique utilizes the exothermic decomposition of energetic substances and the endothermic pyrolysis of biomass. Through this synergistic thermal interaction, the process enables efficient energy recovery and facilitates the resource valorization of SP. The pyrolysis kinetics and thermodynamics of SP, SD, and their blends were investigated. Synchronous thermal analysis examined the co-pyrolysis reaction heat at varying blend ratios, while the temperature’s effects on the gas–liquid–solid product distribution were explored. The results indicate that the apparent activation energy (Ea) required for co-pyrolysis of the SP and SD exhibits an initial increase followed by a decrease in both Stage 1 and Stage 2. Furthermore, the mean apparent activation energy (Eavg) during Stage 1 (FWO: 101.87 kJ/mol; KAS: 94.02 kJ/mol) is lower than that in Stage 2 (FWO: 110.44 kJ/mol; KAS: 100.86 kJ/mol). Co-pyrolysis reaction heat calculations indicated that SD addition significantly mitigates the exothermic intensity, shifts decomposition to higher temperatures (the primary exothermic zone shifted from 180–245 °C to 265–400 °C), and moderates heat release. Elevated temperatures increase the gas yield (CO and H2 are dominant). High temperatures promote aromatic bond cleavage and organic component release; the char’s calorific value correlates positively with the carbon content. Higher co-pyrolysis temperatures increase the nitrogenous compounds in the oil, while the aldehyde content peaks then declines. This work proposes a resource recovery pathway for SP, providing fundamental data for co-pyrolysis valorization or the development of catalytic conversion precursors.