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基于热重-傅里叶变换红外光谱联用仪(TG-FTIR)和热解气相色谱-质谱联用仪(Py-GC/MS)的废旧汽车漆渣热解动力学、反应机理及气体排放研究

Pyrolytic kinetics, reaction mechanisms and gas emissions of waste automotive paint sludge via TG-FTIR and Py-GC/MS.

作者信息

Tian Lu, Liu Tingting, Yang Jinzhong, Yang Haoyue, Liu Zewei, Zhao Youcai, Huang Qifei, Huang Zechun

机构信息

State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing, 100012, China; State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, 200092, China.

State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing, 100012, China.

出版信息

J Environ Manage. 2023 Feb 15;328:116962. doi: 10.1016/j.jenvman.2022.116962. Epub 2022 Dec 2.

Abstract

The present study experimentally quantified the pyrolysis behaviors of waste solvent-based automotive paint sludge (OAPS) and water-based automotive paint sludge (WAPS) at four different heating rates using thermogravimetric-Fourier transform infrared (TG-FTIR) spectrometry and pyrolysis-gas chromatography-mass (Py-GC/MS) spectrometry analyses. Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods combined with the master-plots method were employed to investigate the pyrolysis kinetics and reaction mechanisms of waste automotive paint sludge. Three reaction stages and three reaction peaks in stage 2 were distinguished for both OAPS and WAPS degradation. The average activation energy (E) estimates for OAPS (FWO: 179.09 kJ/mol; KAS: 168.28 kJ/mol) were slightly higher than WAPS (FWO: 175.90 kJ/mol; KAS: 164.80 kJ/mol) according to FWO and KAS methods. The main pyrolysis reaction mechanisms of both OAPS and WAPS closely matched with the order-based model corresponding to 3rd and 2nd order random nucleation on an individual particle. The evolved gas species of CH, CO, phenols, NH, HO, and CO from OAPS and WAPS pyrolysis were identified by TG-FTIR. According to Py-GC/MS, hydrocarbons (47.2%) and O-components (42.7%) were relatively large after OAPS and WAPS pyrolysis, respectively. Melamine was the most abundant N-component product after pyrolysis of OAPS (5.8%) and WAPS (4.8%).

摘要

本研究采用热重-傅里叶变换红外光谱(TG-FTIR)和热解-气相色谱-质谱联用(Py-GC/MS)分析法,在四种不同加热速率下对废溶剂型汽车漆渣(OAPS)和水基汽车漆渣(WAPS)的热解行为进行了实验量化。采用Flynn-Wall-Ozawa(FWO)和Kissinger-Akahira-Sunose(KAS)方法结合主曲线法,研究了废汽车漆渣的热解动力学和反应机理。OAPS和WAPS的降解均区分出三个反应阶段以及第二阶段的三个反应峰。根据FWO和KAS方法,OAPS的平均活化能(E)估计值(FWO:179.09kJ/mol;KAS:168.28kJ/mol)略高于WAPS(FWO:175.90kJ/mol;KAS:164.80kJ/mol)。OAPS和WAPS的主要热解反应机理与基于单个颗粒上三阶和二阶随机成核的基于反应级数的模型密切匹配。通过TG-FTIR鉴定了OAPS和WAPS热解产生的CH、CO、酚类、NH、HO和CO等气体产物。根据Py-GC/MS分析,OAPS和WAPS热解后,烃类(47.2%)和含氧化合物(42.7%)分别相对较多。三聚氰胺是OAPS(5.8%)和WAPS(4.8%)热解后最丰富的含氮产物。

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