This paper investigates the kinetic behaviour of thermal decomposition of pre-treated pine needles. The model-free methods of Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Kissinger, are used to determine the kinetic parameters of the processed pine needles. For a comparative analysis, the kinetic characteristic of the pre-treated pine needles is equated to the thermal decomposition of the raw pine needles. For torrefaction of the raw substrate, some changes related to the design have been made to the furnace. The raw material has been thermally pre-treated at a temperature of 523 K for 5 minutes. The volumetric rate of nitrogen during the torrefaction process is 42 L · min⁻¹, while the purge flow rate of nitrogen gas is 0.2 L · min⁻¹ for the thermogravimetric analysis. The temperature range for the thermal degradation of the torrefied pine needles is 308 K-873 K. The activation energies determined by the FWO and the KAS methods are 157.08 kJ · mol⁻¹ and 160.54 kJ · mol⁻¹, respectively, whereas it is 137 kJ · mol⁻¹ by the Kissinger method. The activation energy computed by the FWO and the KAS schemes for the raw material is found to be 1.3% less than that of the processed pine needles. The aromaticity of the thermally processed pine needles is increased by 13.61%. Thermal immunity or stability due to the increasing fraction of lignin causes the activation energy and frequency factor of the pre-treated pine needles to slightly elevate. The redistribution of the pyrolysis stages has been observed for the torrefied pine needle sample, the temperature scale at a constant heating rate increases slightly by 0.34% during the char formation.

中文翻译：

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烘焙对热处理黑松热动力学的影响

本文研究了预处理过的松针的热分解动力学行为。Flynn-Wall-Ozawa (FWO)、Kissinger-Akahira-Sunose (KAS) 和 Kissinger 的无模型方法用于确定加工松针的动力学参数。为了进行比较分析，预处理过的松针的动力学特性等同于原始松针的热分解。对于原始基材的烘焙，已对炉子进行了一些与设计相关的更改。原材料已在 523 K 的温度下进行了 5 分钟的热处理。烘焙过程中氮气的体积流量为42 L·min ^-1，而氮气的吹扫流量为0.2 L·min ^-1用于热重分析。焙干后的松针热降解温度范围为 308 K-873 K。 FWO 法和 KAS 法测定的活化能分别为 157.08 kJ · mol ^-1和 160.54 kJ · mol ^-1，而137 kJ·摩尔^-1通过基辛格方法。发现由 FWO 和 KAS 方案计算的原料活化能比加工过的松针低 1.3%。热处理后的松针芳香度提高了13.61%。由于木质素比例增加而产生的热免疫或稳定性导致预处理松针的活化能和频率因子略微升高。已经观察到烘焙松针样品的热解阶段的重新分布，在炭形成过程中，恒定加热速率下的温标略有增加 0.34%。