废弃印刷线路板的热解试验研究
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摘要
随着科学技术的飞速发展,电子产品的数量急剧增加而且使用周期不断缩短,产生了大量的电子废弃物。作为一种数目庞大的典型电子废弃物,废弃印刷线路板的合理处理及回收是一个相当复杂的问题,亟待解决。
采用热解技术处理废弃印刷线路板,不仅能回收线路板中的金属,同时也能实现非金属成分的资源化。但是其中溴化阻燃剂在热解过程中产生的HBr和溴代有机物严重腐蚀热解设备,并且影响热解产物的利用,不利于印刷线路板的热解处理。
本文分别对具有代表性的FR-4型印刷线路板、阻燃剂四溴双酚A和十溴联苯醚进行氮气气氛下热重及热重—红外联用实验,研究其热解特性及热解过程中气体产物。采用多种添加剂如聚丙烯、聚丙烯塑料、CaCO_3和Ca(OH)_2与印刷线路板进行不同添加剂组合的混合热重—红外联用实验研究,分析其热解特性及热解过程中气体产物的变化,为后续管式炉混合热解实验奠定基础。
通过加入一定的添加剂与印刷线路板进行管式炉混合热解实验及离子色谱实验,来研究不同添加剂、不同Ca/Br摩尔比、不同热解温度的HBr的脱除率和溴的转化率,从而得出了较好的溴的转化工况。并研究在此工况下,溴在各产物中的分配情况。
采用多种分析测试方法对本文所得到的印刷线路板样品混合热解最优工况下热解所得到的三种热解产物的组成成分进行分析,并探讨其资源化利用。
With the development of the technology, the number of new applications for electronics increases rapidly and the service life become even shorter than before, which results in a large number of waste electronic and electric equipments. Waste printed wiring boards (PWB) are recognized as a typical kind of electronic waste and are numerous. Treatment and recycling of this kind of waste is a complex problem and needs to be solved urgently.
The metal components and non-metal components of PWB can be recycled by pyrolysis. However, HBr and brominated organic compounds which are pollutants and can cause the equipment corrosion are generated during the pyrolysis of the brominated flame retardants, which exists in the PWB. Therefore, the brominated flame retardant has negative effect on the pyrolysis of PWB.
A typical kind of FR-4 PWB, tetrabromobisphenol A and the decabromodiphenyl oxide are chosen as the experimental materials. The characteristics and products during the pyrolysis of the samples have been investigated by using TG-FTIR method under N_2 atmosphere. Polypropylene, plastic, calcium hydroxide and calcium carbonate have been used as additives with PWB in co-pyrolysis experiments, which have also used the TG-FTIR mean to study the characteristics and pyrolysis products. It is helpful for the co-pyrolysis experiments in quartz tube furnace.
The effects of additives, Ca/Br molar ratio and the co-pyrolysis temperature on the HBr removal and the bromine conversion have been studied in quartz tube furnace co-pyrolysis experiments and ion chromatography experiments. Consequently, a better bromine conversion condition has been found and the bromine distribution in the pyrolysis products has been investigated.
The gas phase, liquid phase and solid phase pyrolysis products generated in the best operation condition have been determined and analyzed by several methods, and the possible resource utilization of pyrolysis product has been discussed.
采用热解技术处理废弃印刷线路板,不仅能回收线路板中的金属,同时也能实现非金属成分的资源化。但是其中溴化阻燃剂在热解过程中产生的HBr和溴代有机物严重腐蚀热解设备,并且影响热解产物的利用,不利于印刷线路板的热解处理。
本文分别对具有代表性的FR-4型印刷线路板、阻燃剂四溴双酚A和十溴联苯醚进行氮气气氛下热重及热重—红外联用实验,研究其热解特性及热解过程中气体产物。采用多种添加剂如聚丙烯、聚丙烯塑料、CaCO_3和Ca(OH)_2与印刷线路板进行不同添加剂组合的混合热重—红外联用实验研究,分析其热解特性及热解过程中气体产物的变化,为后续管式炉混合热解实验奠定基础。
通过加入一定的添加剂与印刷线路板进行管式炉混合热解实验及离子色谱实验,来研究不同添加剂、不同Ca/Br摩尔比、不同热解温度的HBr的脱除率和溴的转化率,从而得出了较好的溴的转化工况。并研究在此工况下,溴在各产物中的分配情况。
采用多种分析测试方法对本文所得到的印刷线路板样品混合热解最优工况下热解所得到的三种热解产物的组成成分进行分析,并探讨其资源化利用。
With the development of the technology, the number of new applications for electronics increases rapidly and the service life become even shorter than before, which results in a large number of waste electronic and electric equipments. Waste printed wiring boards (PWB) are recognized as a typical kind of electronic waste and are numerous. Treatment and recycling of this kind of waste is a complex problem and needs to be solved urgently.
The metal components and non-metal components of PWB can be recycled by pyrolysis. However, HBr and brominated organic compounds which are pollutants and can cause the equipment corrosion are generated during the pyrolysis of the brominated flame retardants, which exists in the PWB. Therefore, the brominated flame retardant has negative effect on the pyrolysis of PWB.
A typical kind of FR-4 PWB, tetrabromobisphenol A and the decabromodiphenyl oxide are chosen as the experimental materials. The characteristics and products during the pyrolysis of the samples have been investigated by using TG-FTIR method under N_2 atmosphere. Polypropylene, plastic, calcium hydroxide and calcium carbonate have been used as additives with PWB in co-pyrolysis experiments, which have also used the TG-FTIR mean to study the characteristics and pyrolysis products. It is helpful for the co-pyrolysis experiments in quartz tube furnace.
The effects of additives, Ca/Br molar ratio and the co-pyrolysis temperature on the HBr removal and the bromine conversion have been studied in quartz tube furnace co-pyrolysis experiments and ion chromatography experiments. Consequently, a better bromine conversion condition has been found and the bromine distribution in the pyrolysis products has been investigated.
The gas phase, liquid phase and solid phase pyrolysis products generated in the best operation condition have been determined and analyzed by several methods, and the possible resource utilization of pyrolysis product has been discussed.
引文
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