外卖塑料包装热解动力学研究——基于无模型和模型拟合法

尹凤福; 庄虔晓; 常天浩; 孙启坤

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中国环境科学 ›› 2021, Vol. 41 ›› Issue (4) : 1756-1764.

固体废物

外卖塑料包装热解动力学研究——基于无模型和模型拟合法

尹凤福, 庄虔晓, 常天浩, 孙启坤

作者信息 +

Pyrolysis kinetics study of takeaway plastic packaging—Based on model-free and model-fitting method

YIN Feng-fu, ZHUANG Qian-xiao, CHANG Tian-hao, SUN Qi-kun

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文章历史 +

摘要

在非等温条件下对外卖包装中的塑料组分进行热重实验，结果显示单组分聚丙烯（PP）、高密度聚乙烯（HDPE）和聚苯乙烯（PS）及其混合物（PP/HDPE/PS）的热解过程一步完成.针对混合塑料的复杂热解反应过程，提出了一种无模型方法和模型拟合法结合逐步获得完整动力学参数的方法，使结果更具可信度.采用无模型方法（K-A-S、F-W-O和Starink）研究了单组分及其混合物热解过程的动力学参数，得到PP、HDPE、PS和PP/HDPE/PS热解过程的平均活化能（E）分别为224.7，238.5，194.1和179.3kJ/mol.在升温速率为20K/min条件下，以无模型方法得到的活化能和模型拟合法（Malek和C-R）结果作为逻辑判定依据，总结了单组分及其混合物的热解机理均属于随机成核随后生长.分析了动力学参数间存在的补偿效应，并构建了补偿效应方程.本论文的研究可为外卖塑料垃圾热解工艺参数的优化和热解反应器的设计提供有力的支撑.

Abstract

Thermogravimetric analysis for components of takeaway plastic packaging was carried out under non-isothermal conditions. The results showed that the pyrolysis processes of the single components of PP, HDPE, PS, and the mixture (PP/HDPE/PS) were finished in one step. For the complex pyrolysis reaction with mixed plastics, a model-free method combined with the model-fitting method was proposed to obtain the complete set of kinetic parameters, which made the results more reliable. The kinetic parameters of a single component and the mixture in the pyrolysis process were studied with model-free methods (K-A-S, F-W-O and Starink). In pyrolysis processes, the average activation energy (E) of PP, HDPE, PS and PP/HDPE/PS reached 224.7, 238.5, 194.1 and 179.3kJ/mol, respectively. Based on the activation energy obtained by the model-free method and the results of model fitting (Malek and C-R), the pyrolysis mechanism of a single component and the mixture was random nucleation followed by growth when the heating rate was 20K/min. Moreover, the compensation effect between the kinetic parameters was analyzed to establish the compensation effect equations. This study can provide support for the optimization of the pyrolysis process parameters of takeaway plastic waste and the design of the pyrolysis reactor.

导出引用

尹凤福, 庄虔晓, 常天浩, 孙启坤. 外卖塑料包装热解动力学研究——基于无模型和模型拟合法[J]. 中国环境科学. 2021, 41(4): 1756-1764

YIN Feng-fu, ZHUANG Qian-xiao, CHANG Tian-hao, SUN Qi-kun. Pyrolysis kinetics study of takeaway plastic packaging—Based on model-free and model-fitting method[J]. China Environmental Science. 2021, 41(4): 1756-1764

中图分类号： X705

参考文献

[1] Chen W Q, Ciacci L, Sun N N, et al. Sustainable cycles and management of plastics:A brief review of RCR publications in 2019 and early 2020[J]. Resources, Conservation and Recycling, 2020, 159.https://doi.org/10.1016/j.resconrec.2020.104822.
[2] 郑仲,何品晶,邵立明.塑料包装物中邻苯二甲酸酯的分布统计分析[J]. 中国环境科学, 2006,(5):637-640. Zheng Z, He P J, Shao L M. Statistical analysis of the distribution of phthalates in plastic packaging[J]. China Environmental Science, 2006,(5):637-640.
[3] Geyer R, Jambeck J R, Law K L. Production, use, and fate of all plastics ever made[J]. Science Advances, 2017,3(7):e1700782-e1700782.
[4] 张清安,祁美琪.外卖餐具所致垃圾发展现状及治理对策[J]. 农产品加工, 2018,(17):77-78. Zhang Q A, Qi M Q. The development status and treatment countermeasures of garbage caused by take-out tableware[J]. Processing of Agricultural Products, 2018,(17):77-78.
[5] 岳倩.外卖餐盒回收带来双重命题[N]. 中国质量报, 2018,(4). Yue Q. Takeaway lunch box recycling brings double proposition[N]. China Quality News, 2018,(4).
[6] 温宗国,张宇婷,傅岱石.基于行业全产业链评估一份外卖订单的环境影响[J]. 中国环境科学, 2019,39(9):4017-4024. Wen Z G, Zhang Y T, Fu D S. Evaluate the environmental impact of a takeaway order based on the entire industry chain[J]. China Environmental Science, 2019,39(9):4017-4024.
[7] Sommerhuber P F, Welling J, Krause A. Substitution potentials of recycled HDPE and wood particles from post-consumer packaging waste in woodeplastic composites[J]. Waste Management, 2015,46:76-85.
[8] 杨凯,徐启新,林逢春,等.包装废物减量及回收体系构建研究[J]. 中国环境科学, 2001,21(2):94-97. Yang K, Xu Q X, Lin F C, et al. Research on the construction of packaging waste reduction and recycling system[J]. China Environmental Science, 2001,21(2):94-97.
[9] 谢明辉,李丽,乔琦,等.塑料牛奶包装及处置方式生命周期环境影响研究[J]. 中国环境科学, 2011,31(11):1924-1930. Xie M H, Li L, Qiao Q, et al. Study on the life cycle environmental impact of plastic milk packaging and disposal methods[J]. China Environmental Science, 2011,31(11):1924-1930.
[10] Liu G, Liao Y, Guo S, et al. Thermal behavior and kinetics of municipal solid waste during pyrolysis and combustion process[J]. Applied Thermal Engineering, 2016,98:400-408.
[11] Xue Y, Kelkar A, Bai X. Catalytic co-pyrolysis of biomass and polyethylene in a tandem micropyrolyzer[J]. Fuel, 2016,166:227-23.
[12] Chattopadhyay J, Pathak T S, Srivastava R, et al. Catalytic co-pyrolysis of paper biomass and plastic mixtures (HDPE (high densitypolyethylene), PP (polypropylene) and PET (polyethylene terephthalate)) and product analysis[J]. Energy, 2016,103:513-521.
[13] Oyedun A O, Lam K L, Gebreegziabher T, et al. Optimization of multi-stage pyrolysis[J]. Applied Thermal Engineering, 2013,61(1):123-127.
[14] Yin S, Rajarao R, Gong B, et al. Thermo-delamination of metallised composite plastic:An innovative approach to generate Aluminium from packaging plastic waste[J]. Journal of Cleaner Production, 2019,211:321-329.
[15] Das P, Tiwari P. Valorization of packaging plastic waste by slow pyrolysis[J]. Resources Conservation and Recycling, 2018,128:69-77.
[16] Zhou R, Huang B Q, Ding Y M, et al. Thermal decomposition mechanism and kinetics study of plastic waste chlorinated polyvinyl chloride[J]. Polymers, 2019,11(12).https://doi.org/10.3390/polym11122080.
[17] Cafiero L, Castoldi E, Tuffi R, et al. Identification and characterization of plastics from small appliances and kinetic analysis of their thermally activated pyrolysis[J]. Polymer Degradation and Stability, 2014,109:307-318.
[18] Liu H, Chen B, Wang C. Pyrolysis kinetics study of biomass waste using shuffled complex evolution algorithm[J]. Fuel Processing Technology, 2020,208.https://doi.org/10.1016/j.fuproc.2020.106509.
[19] Rasam S, Haghighi A M, Azizi K. Thermal behavior, thermodynamics and kinetics of co-pyrolysis of binary and ternary mixtures of biomass through thermogravimetric analysis[J]. Fuel, 2020,280.https://doi.org/10.1016/j.fuel.2020.118665.
[20] Guida M Y, Bouaik H, El Mouden L, et al. Utilization of starink approach and avrami theory to evaluate the kinetic parameters of the pyrolysis of Olive Mill Solid Waste and Olive Mill Wastewater[J]. Journal of Advanced Chemical Engineering, 2017,7(1):1-8.
[21] Chen L, Wang S Z, Meng H Y. Synergistic effect on thermal behavior and char morphology analysis during co-pyrolysis of paulownia wood blended with different plastics waste[J]. Applied Thermal Engineering, 2017,111:834-846.
[22] Conesa J A, Marcilla A, Caballero J A, et al. Comments on the validity and utility of the different methods for kinetic analysis of thermogravimetric data[J]. Analytical and Applied Pyrolysis, 2001,58:617-633.
[23] Branca C, Albano A, Di Blasi C. Critical evaluation of global mechanisms of wood devolatilization[J]. Thermochim. Acta, 2005, 429(2):133-141.
[24] 刘振海,张洪林.分析化学手册[M]. 北京:化学工业出版社, 2016,64:56-79. Liu Z H, Zhang H L. Thermal analysis and calorimetry[M]. Beijing:Chemical Industry Press, 2016,64:56-79.
[25] 胡荣祖,高胜利,赵凤起,等.热分析动力学[M]. 北京:科学出版社, 2008. Hu R Z, Gao S L, Zhao F Q, et al. Thermal analysis kinetics[M]. Beijing:Science Press, 2008.
[26] Zhu Y L, An J, Chang H. An analytical method for overlapping of the melting and decomposition of 2-oximemalononitrile[J]. Journal of Thermal Analysis and Calorimetry, 2020.https://doi.org/10.1007/s10973-020-10141-y.
[27] Chen J B, Wang Y H, Lang X M, et al. Comparative evaluation of thermal oxidative decomposition for oil-plant residues via thermogravimetric analysis:Thermal conversion characteristics, kinetics, and thermodynamics[J]. Bioresource Technology, 2017,243:37-46.
[28] Yun Y M, Seo M W, Koo G H, et al. Pyrolysis characteristics of GFRP (Glass Fiber Reinforced Plastic) under non-isothermal conditions[J]. Fuel, 2014,137:321-327.
[29] Yu B, Vallée T, Thomas K. Modeling of thermo-physical properties for FRP composites under elevated and high temperature[J]. Composites Science and Technology, 2007,67(15/16):3098-3109.
[30] Mishra G, Bhaskar T. Non isothermal model free kinetics for pyrolysis of rice straw[J]. Bioresource Technology, 2014,169:614-621.
[31] Tondl G, Bonell L, Pfeifer C. Thermogravimetric analysis and kinetic study of marine plastic litter[J]. Marine Pollution Bulletin. 2018,133:472-477.
[32] Hu Q, Tang Z Y, Yao D D. Thermal behavior, kinetics and gas evolution characteristics for the co-pyrolysis of real-world plastic and tyre wastes[J]. Journal of Cleaner Production. 260.https://doi.org/10.1016/j.jclepro.2020.1211.02.
[33] Tuffi R, D'Abramo S, Cafiero L M, et al. Thermal behavior and pyrolytic degradation kinetics of polymeric mixtures from waste packaging plastics[J]. Polymer Science. 2018,7:82-99.
[34] Westerhout R W J, Waanders J, Kuipers J A M, et al. Kinetics of the low-temperature pyrolysis of polyethene, polypropene, and polystyrene modeling, experimental determination, and comparison with literature models and data[J]. Industrial & Engineering Chemistry Research, 1997,36(6):1955-1964.
[35] 刘义彬,马晓波,陈德珍,等.废塑料典型组分共热解特性及动力学分析[J]. 中国电机工程学报, 2010,30(23):56-61. Liu Y B, Ma X B, Chen D Z, et al. Co-pyrolysis characteristics and kinetic analysis of typical components of waste plastics[J]. Chinese Society for Electrical Engineering, 2010,30(23):56-61.
[36] Vyazovkin S, Burnham A K, Criado J M, et al. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J]. Thermochimica Acta, 2011,520:1-19.
[37] Diaz Silvarrey L S, Phan A N. Kinetic study of municipal plastic waste[J]. International Journal of Hydrogen Energy, 2016,41(37):16352-16364.
[38] 马大朝,高伟康,孙翔,等.稻壳与聚氯乙烯共热解的特性及动力学[J]. 环境工程, 2020,38(1):135-140. Ma D C, Gao W K, Sun X, et al. The characteristics and kinetics of co-pyrolysis of rice husk and polyvinyl chloride[J]. Environmental Engineering, 2020,38(1):135-140.
[39] Chowlu A C K, Reddy P K, Ghoshal A K. Pyrolytic decomposition and model-free kinetics analysis of mixture of polypropylene (PP) and low-density polyethylene (LDPE)[J]. Thermochimica Acta, 2009,485:20-25.
[40] Xu F F, Wang B, Yang D, et al. Thermal degradation of typical plastics under high heating rate conditions by TG-FTIR:Pyrolysis behaviors and kinetic analysis[J]. Energy Conversion and Management, 2018, 171:1106-1115.
[41] Slopieca K, Bartocci P, Fantozzi F. Thermogravimetric analysis and kinetic study of poplar wood pyrolysis[J]. Applied Energy, 2012, 97:491-497.
[42] Vyazovkin S, Burnham A K, Criado J M, et al. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J]. Thermochimica Acta, 2011,520:1-19.
[43] Das P, Tiwari P. Thermal degradation kinetics of plastics and model selection[J]. Thermochimica Acta, 2017,654:191-202.
[44] 张大磊,李公伟,李卫华,等.聚乙烯塑料/铬渣共热解还原Cr(Ⅵ)的实验研究[J]. 中国环境科学, 2017,37(5):1852-1857. Zhang D L, Li G W, Li W H, et al. Experimental study on reduction of Cr(Ⅵ) by polyethylene plastic/chromium slag co-pyrolysis[J]. China Environmental Science, 2017,37(5):1852-1857.
[45] Qiao Y Y, Wang B, Zong P J, et al. Thermal behavior, kinetics and fast pyrolysis characteristics of palm oil:Analytical TG-FTIR and Py-GC/MS study[J]. Energy Conversion and Management, 2019, 199,111964.