SCI和EI收录∣中国化工学会会刊

中国化学工程学报 ›› 2024, Vol. 73 ›› Issue (9): 202-211.DOI: 10.1016/j.cjche.2024.04.024

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Effect of copper content on the pyrolysis process of organic components in waste printed circuit boards: Based on experimental and quantum chemical DFT simulations

Bin Li1,2, Biqin Shen1,2, Ran Tao1,2, Chenwei Hu1,2, Yufeng Wu1,2, Haoran Yuan3, Jing Gu3, Yong Chen3   

  1. 1. Institute of Circular Economy, Beijing University of Technology, Beijing 100124, China;
    2. Faculty of Materials and Manufacturing, Beijing University of Technology, Beijing 100124, China;
    3. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
  • 收稿日期:2024-02-25 修回日期:2024-04-10 接受日期:2024-04-15 出版日期:2024-11-21 发布日期:2024-06-08
  • 通讯作者: Yufeng Wu,E-mail:wuyufeng3r@126.com
  • 基金资助:
    This work was supported by the National Key Research and Development Program of China (2018YFC1902504).

Effect of copper content on the pyrolysis process of organic components in waste printed circuit boards: Based on experimental and quantum chemical DFT simulations

Bin Li1,2, Biqin Shen1,2, Ran Tao1,2, Chenwei Hu1,2, Yufeng Wu1,2, Haoran Yuan3, Jing Gu3, Yong Chen3   

  1. 1. Institute of Circular Economy, Beijing University of Technology, Beijing 100124, China;
    2. Faculty of Materials and Manufacturing, Beijing University of Technology, Beijing 100124, China;
    3. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
  • Received:2024-02-25 Revised:2024-04-10 Accepted:2024-04-15 Online:2024-11-21 Published:2024-06-08
  • Contact: Yufeng Wu,E-mail:wuyufeng3r@126.com
  • Supported by:
    This work was supported by the National Key Research and Development Program of China (2018YFC1902504).

摘要: In recent years, scientists have become increasingly concerned in recycling electronic trash, particularly waste printed circuit boards (WPCBs). Previous research has indicated that the presence of Cu impacts the pyrolysis of WPCBs. However, there may be errors in the experimental results, as printed circuit boards (PCBs) with copper and those without copper are produced differently. For this experiment, we blended copper powder with PCB nonmetallic resin powder in various ratios to create the samples. The apparent kinetics and pyrolysis properties of four resin powders with varying copper concentrations were compared using nonisothermal thermogravimetric analysis (TG) and thermal pyrolysis-gas chromatography mass spectrometry (Py-GC/MS). From the perspective of kinetics, the apparent activation energy of the resin powder in the pyrolysis reaction shows a rise (0.1<α<0.2)-stable (0.2<α<0.4)-accelerated increase (0.4<α<0.8)- decrease (0.8<α<0.9) process. After adding copper powder, the apparent activation energy changes more obviously when (0.2<α<0.4). In the early stage of the pyrolysis reaction (0.1<α<0.6), the apparent activation energy is reduced, but when α = 0.8, it is much higher than that of the resin sample without copper. Additionally, it is discovered using thermogravimetric analysis and Py-GC/MS that copper shortens the temperature range of the primary pyrolysis reaction and prevents the creation of compounds containing bromine. This inhibition will raise the temperature at which compounds containing bromine first form, and it will keep rising as the copper level rises. The majority of the circuit board molecules have lower bond energies when copper is present, according to calculations performed using the Gaussian09 software, which promotes the pyrolysis reaction.

关键词: Waste printed circuit boards, Copper, Pyrolysis, Kinetic study, Density functional theory (DFT)

Abstract: In recent years, scientists have become increasingly concerned in recycling electronic trash, particularly waste printed circuit boards (WPCBs). Previous research has indicated that the presence of Cu impacts the pyrolysis of WPCBs. However, there may be errors in the experimental results, as printed circuit boards (PCBs) with copper and those without copper are produced differently. For this experiment, we blended copper powder with PCB nonmetallic resin powder in various ratios to create the samples. The apparent kinetics and pyrolysis properties of four resin powders with varying copper concentrations were compared using nonisothermal thermogravimetric analysis (TG) and thermal pyrolysis-gas chromatography mass spectrometry (Py-GC/MS). From the perspective of kinetics, the apparent activation energy of the resin powder in the pyrolysis reaction shows a rise (0.1<α<0.2)-stable (0.2<α<0.4)-accelerated increase (0.4<α<0.8)- decrease (0.8<α<0.9) process. After adding copper powder, the apparent activation energy changes more obviously when (0.2<α<0.4). In the early stage of the pyrolysis reaction (0.1<α<0.6), the apparent activation energy is reduced, but when α = 0.8, it is much higher than that of the resin sample without copper. Additionally, it is discovered using thermogravimetric analysis and Py-GC/MS that copper shortens the temperature range of the primary pyrolysis reaction and prevents the creation of compounds containing bromine. This inhibition will raise the temperature at which compounds containing bromine first form, and it will keep rising as the copper level rises. The majority of the circuit board molecules have lower bond energies when copper is present, according to calculations performed using the Gaussian09 software, which promotes the pyrolysis reaction.

Key words: Waste printed circuit boards, Copper, Pyrolysis, Kinetic study, Density functional theory (DFT)