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采用模型拟合和无模型方法相结合对塑料废物热解的动力学研究。

Kinetic studies on the pyrolysis of plastic waste using a combination of model-fitting and model-free methods.

机构信息

College of Materials and Environmental Engineering, Hangzhou Dianzi University, China.

Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, China.

出版信息

Waste Manag Res. 2020 May;38(1_suppl):77-85. doi: 10.1177/0734242X19897814. Epub 2020 Jan 20.

Abstract

In this work, the pyrolysis behavior of plastic waste-TV plastic shell-was investigated, based on thermogravimetric analysis and using a combination of model-fitting and model-free methods. The possible reaction mechanism and kinetic compensation effects were also examined. Thermogravimetric analysis indicated that the decomposition of plastic waste in a helium atmosphere can be divided into three stages: the minor loss stage (20-300°C), the major loss stage (300-500°C) and the stable loss stage (500-1000°C). The corresponding weight loss at three different heating rates of 15, 25 and 35 K/min were determined to be 2.80-3.02%, 94.45-95.11% and 0.04-0.16%, respectively. The activation energy () and correlation coefficient () profiles revealed that the kinetic parameters calculated using the Friedman and Kissinger-Akahira-Sunose method displayed a similar trend. The values from the Flynn-Wall-Ozawa and Starink methods were comparable, although the former gave higher values. The values gradually decreased from 269.75 kJ/mol to 184.18 kJ/mol as the degree of conversion () increased from 0.1 to 0.8. Beyond this range, the slightly increased to 211.31 kJ/mol. The model-fitting method of Coats-Redfern was used to predict the possible reaction mechanism, for which the first-order model resulted in higher values than and comparable values to those obtained from the Flynn-Wall-Ozawa method. The pre-exponential factors (ln) were calculated based on the F1 reaction model and the Flynn-Wall-Ozawa method, and fell in the range 59.34-48.05. The study of the kinetic compensation effect confirmed that a compensation effect existed between E and ln during the plastic waste pyrolysis.

摘要

在这项工作中,基于热重分析,采用模型拟合和无模型方法相结合的方法,研究了塑料废物-TV 塑料外壳的热解行为。还研究了可能的反应机理和动力学补偿效应。热重分析表明,在氦气气氛中,塑料废物的分解可以分为三个阶段:小损失阶段(20-300°C)、大损失阶段(300-500°C)和稳定损失阶段(500-1000°C)。在 15、25 和 35 K/min 三个不同的加热速率下,相应的失重率分别为 2.80-3.02%、94.45-95.11%和 0.04-0.16%。活化能(E)和相关系数(α)图谱表明,使用 Friedman 和 Kissinger-Akahira-Sunose 方法计算的动力学参数呈现出相似的趋势。Flynn-Wall-Ozawa 和 Starink 方法得到的值虽然相近,但前者给出的值更高。E 值从 269.75 kJ/mol 逐渐降低到 184.18 kJ/mol,转化率(α)从 0.1 增加到 0.8。超过这个范围后,E 值略有增加到 211.31 kJ/mol。采用 Coats-Redfern 模型拟合方法预测可能的反应机理,其中一级模型得到的 E 值高于和与 Flynn-Wall-Ozawa 方法得到的值相当。根据 F1 反应模型和 Flynn-Wall-Ozawa 方法计算的指前因子(ln)在 59.34-48.05 范围内。对动力学补偿效应的研究证实,在塑料废物热解过程中,E 和 ln 之间存在补偿效应。

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