Study on the Combustion Behavior and Kinetic Characteristics of Semi-Coke from Oil Shale

This study systematically investigates the combustion behavior and kinetic characteristics of oil shale semi-coke. Thermogravimetric analysis (TGA) experiments, combined with both model-free and model-based methods, were used to explore the thermal characteristics, kinetic parameters, and reaction mechanisms of the combustion process. The results show that the combustion process of oil shale semi-coke can be divided into three stages: a low-temperature stage (50-310 °C), a mid-temperature stage (310-670 °C), and a high-temperature stage (670-950 °C). The mid-temperature stage is the core of the combustion process, accounting for approximately 28%-37% of the total mass loss, with the released energy concentrated and exhibiting significant thermal chemical activity. Kinetic parameters calculated using the model-free methods (OFW and KAS) and the model-based Coats-Redfern method reveal that the activation energy gradually increases with the conversion rate, indicating a multi-step reaction characteristic of the combustion process. The F2-R3-F2 model, with its segmented mechanism (boundary layer + second-order reaction), better fits the physicochemical changes during semi-coke combustion, and the analysis of mineral phase transformations is more reasonable. Therefore, the F2-R3-F2 model is identified as the optimal model in this study and provides a scientific basis for the optimization of oil shale semi-coke combustion processes. Furthermore, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses were conducted on oil shale semi-coke samples before and after combustion to study the changes in the combustion residues. SEM images show that after combustion, the surface of the semi-coke sample exhibits a large number of irregular holes, with increased pore size and a honeycomb-like structure, indicating that the carbonaceous components were oxidized and decomposed during combustion, forming a porous structure. XRD analysis shows that the characteristic peaks of quartz (Q) are enhanced after combustion, while those of calcite (C) and pyrite (P) are weakened, suggesting that the mineral components underwent decomposition and transformation during combustion, particularly the decomposition of calcite into CO₂ at high temperatures. Infrared spectroscopy (IR) analysis reveals that after combustion, the amount of hydrocarbons in the semi-coke decreases, while aromatic compounds and incompletely decomposed organic materials are retained, further confirming the changes in organic matter during pyrolysis.