Jiang Lin, Yang Xin-Rui, Gao Xu, Xu Qiang, Das Oisik, Sun Jin-Hua, Kuzman Manja Kitek
School of Mechanical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.
The Division of Material Science, Department of Engineering Sciences and Mathematics, Luleå University of Technology, 97187 Luleå, Sweden.
Polymers (Basel). 2020 Feb 12;12(2):421. doi: 10.3390/polym12020421.
This work was motivated by a study of particle size effects on pyrolysis kinetics and models of polystyrene particle. Micro-size polystyrene particles with four different diameters, 5, 10, 15, and 50 µm, were selected as experimental materials. Activation energies were obtained by isoconversional methods, and pyrolysis model of each particle size and heating rate was examined through different reaction models by the Coats-Redfern method. To identify the controlling model, the Avrami-Eroféev model was identified as the controlling pyrolysis model for polystyrene pyrolysis. Accommodation function effect was employed to modify the Avrami-Eroféev model. The model was then modified to () = (1 - )[-ln(1 - )] , by which the polystyrene pyrolysis with different particle sizes can be well explained. It was found that the reaction model cannot be influenced by particle geometric dimension. The reaction rate can be changed because the specific surface area will decrease with particle diameter. To separate each step reaction and identify their distributions to kinetics, distributed activation energy method was introduced to calculate the weight factor and kinetic triplets. Results showed that particle size has big impacts on both first and second step reactions. Smaller size particle can accelerate the process of pyrolysis reaction. Finally, sensitivity analysis was brought to check the sensitivity and weight of each parameter in the model.
这项工作的动机是研究粒径对聚苯乙烯颗粒热解动力学和模型的影响。选择了四种不同直径(5、10、15和50微米)的微米级聚苯乙烯颗粒作为实验材料。通过等转化率方法获得活化能,并采用Coats-Redfern方法通过不同反应模型研究每种粒径和加热速率下的热解模型。为了确定控制模型,将Avrami-Eroféev模型确定为聚苯乙烯热解的控制热解模型。采用适应函数效应来修正Avrami-Eroféev模型。然后将模型修正为() = (1 - )[-ln(1 - )] ,通过该模型可以很好地解释不同粒径的聚苯乙烯热解。研究发现,反应模型不受颗粒几何尺寸的影响。由于比表面积会随着粒径减小而减小,反应速率可能会发生变化。为了分离每个步骤反应并确定它们在动力学中的分布,引入了分布活化能方法来计算权重因子和动力学三元组。结果表明,粒径对第一步和第二步反应都有很大影响。较小尺寸的颗粒可以加速热解反应过程。最后,进行了敏感性分析,以检查模型中每个参数的敏感性和权重。