新塑料和废塑料的热降解:使用无模型等转换法估算动力学和热力学参数

IF 1.5 4区 化学 Q4 CHEMISTRY, PHYSICAL
Rohit Kumar Singh, Prithviraj Gupta, Biswajit Ruj, Anup Kumar Sadhukhan, Parthapratim Gupta
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引用次数: 0

摘要

针对三种原生塑料和废塑料以及混合废塑料的热降解过程,估算了动力学三要素--表观活化能(Ea)、前指数(A)和反应模型。动力学分析采用了无模型等转换 FWO 法、KAS 法、Starink 法、Kissinger 法、Vyzovkin 法和 Friedman 法。用积分法测定的表观活化能分别为:原生高密度聚乙烯(HDPE)206.5-209.1 kJ mol-1 和 195.6-198.8 kJ mol-1,废高密度聚乙烯(HDPE)211.6-214.1 kJ mol-1 和 183.1-186.6 kJ mol-1。原生和废弃聚丙烯 (PP) 分别为 211.6-214.1 kJ mol-1 和 183.1-186.6 kJ mol-1,原生和废弃聚苯乙烯 (PS) 分别为 144.0-163.1 kJ mol-1 和 159.7-167.1 kJ mol-1,混合塑料废弃物分别为 173.6-178.9 kJ mol-1。Ea 值的变化趋势与高密度聚乙烯(HDPE)、聚丙烯(PP)和聚苯乙烯(PS)相同,高密度聚乙烯(HDPE)和聚丙烯(PP)原始样品的 Ea 值高于其废料的 Ea 值,而原始聚苯乙烯(PS)的 Ea 值略低于其废料的 Ea 值。所有塑料样品的降解都遵循阿夫拉米-埃罗费夫方程,n 在 1.0 和 1.8 之间变化。转化率对 Ea 的影响表明,原生高密度聚乙烯和废弃高密度聚乙烯的降解由多个平行反应组成,而其他塑料的降解则更为复杂。傅立叶变换红外光谱分析用来解释可能的反应机理。所有塑料样品的焓变和表观活化能(6-7 kJ mol-1)之间的微小差异表明热解反应是有利的。估算的动力学参数和热力学性质表明,不同塑料如高密度聚乙烯(HDPE)、聚丙烯(PP)和聚苯乙烯(PS)具有稳定性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Thermal degradation of virgin and waste plastics: Estimation of kinetic and thermodynamic parameters using model-free iso-conversional methods

Kinetic triplets—apparent activation energy (Ea), pre-exponential factor (A), and the reaction model—were estimated for the thermal degradation of three primary virgin and waste plastics, as well as mixed plastics waste. Model-free iso-conversional FWO, KAS, Starink, Kissinger and Vyzovkin and Friedman methods were employed for the kinetic analysis. The apparent activation energy was determined by the integral methods as 206.5-209.1 kJ mol−1 and 195.6-198.8 kJ mol−1 for the virgin and waste high-density polyethylene (HDPE), 211.6-214.1 kJ mol−1 and 183.1-186.6 kJ mol−1 for the virgin and waste polypropylene (PP), 144.0-163.1 kJ mol−1 and 159.7-167.1 kJ mol−1 for the virgin and waste polystyrene (PS), and 173.6-178.9 kJ mol−1 for the mixed plastics waste respectively. Ea was found to follow the trend HDPE > PP > PS with higher values for HDPE and PP virgin samples than that for their waste and marginally smaller for the virgin PS than its waste. Degradation of all plastic samples followed Avrami-Erofeev equation with n varying between 1.0 and 1.8. The effect of conversion on Ea suggested the degradation of both virgin and waste HDPE to consist of multiple parallel reactions while that of others to be more complex. FTIR analysis of the evolved gases was used to explain the possible reaction mechanism. A small difference between the enthalpy change and the apparent activation energy (6-7 kJ mol−1) for all plastic samples indicated favourable pyrolysis reactions. The estimated kinetic parameters and thermodynamic properties showed the stability of different plastics as HDPE > PP > PS.

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来源期刊
CiteScore
3.30
自引率
6.70%
发文量
74
审稿时长
3 months
期刊介绍: As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.
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