Influence of Intrinsic Physicochemical Properties of Agroforestry Waste on Its Pyrolysis Characteristics and Behavior

To obtain a comprehensive understanding of the qualitative and quantitative effects of the intrinsic properties of biomass on its pyrolysis characteristics and assess the behavior of agroforestry waste, thermogravimetric analyses of three representative agroforestry wastes, namely rape (Brassica campestris L.) straw (RS), apple (Malus domestica) tree branches (ATB), and pine (Pinus sp.) sawdust (PS), were carried out by pyrolysis under dynamic conditions (30 to 900 °C) at different heating rates of 5, 10, and 15 °C·min(−1). Correlation analysis showed that intrinsic physicochemical properties play distinct roles in different stages of pyrolysis. The ash content was negatively correlated with the temperature range (R(2)) of the second stage (190–380 °C) of pyrolysis. The lignin content and the amount of pyrolysis residues (RSS) were positively correlated. Kinetic triplets, including the activation energy (Ea), pre-exponential factor (A), and reaction model [f(α)], were obtained using different methods, including the Flynn–Wall–Ozawa (FWO), Freidman, Kissinger–Akahira–Sunose (KAS), and Starink methods. The mean activation energy (Ea[mean]) for RS, ATB, and PS calculated by the different methods ranged from 167.15 to 195.58 kJ·mol(−1), 195.37 to 234.95 kJ·mol(−1), and 191.27–236.45 kJ·mol(−1), respectively. Correlation analysis of the intrinsic physicochemical characteristics and kinetic factors of agroforestry waste showed that the minimum Ea (Ea[min]) was significantly positively correlated with heat capacity (C(0)) and negatively correlated with thermal diffusivity (D). The Ea[mean] and the maximum value of Ea (Ea[max]) significantly positively correlated with the sum content of cellulose and lignin, indicating that the contents of cellulose and lignin determines the energy required for the pyrolysis process of agroforestry waste. The mechanism of degradation involves the diffusion model (D1, D2, and D3), the growth model (A4), and the geometrical contraction model (R3). These results indicate that the pyrolysis of agroforestry waste is a complex process due to the heterogeneity of its intrinsic physicochemical properties.