CERI Materials & Processes, IMT Lille Douai, 941 Rue Charles Bourseul, 59500 Douai, France; Institut Supérieur de Plasturgie d'Alençon (ISPA), Pôle Universitaire d'Alençon, Campus de Damigny, 61250 Damigny, France.
Institut Supérieur de Plasturgie d'Alençon (ISPA), Pôle Universitaire d'Alençon, Campus de Damigny, 61250 Damigny, France; College of Natural and Health Sciences, Zayed University, P.O. Box 144534, Abu Dhabi, United Arab Emirates.
Waste Manag. 2021 Jul 15;131:313-322. doi: 10.1016/j.wasman.2021.06.020. Epub 2021 Jul 1.
Persistent organic pollutants such as brominated flame retardants represent a major problem in the end-of-life of polymer materials. This study investigates the extraction of brominated flame retardants (BFR) from real waste electrical and electronic equipment (WEEE) using supercritical carbon dioxide (sc-CO). Sc-CO is a non-toxic solvent which possesses intermediate properties between liquids and gases which confer it high diffusivity and solubility. A batch of WEEE-derived acrylonitrile-butadienestyrene (ABS) was first characterized to determine its bromine and BFR composition which was found to be four times higher than the regulation limit set in 2019. Then, different parameters of the sc-CO process such as temperature, pressure, granulometry and the use of a co-solvent were studied to estimate the effect of each one on the BFR extraction efficiency. With the view to determine the recyclability of the treated polymer, the impact of the extraction process on the polymer material was also studied by Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and Size Exclusion Chromatography (SEC). The extraction process performed on <500 µm particle size sample at 40 °C and 500 bars during 6 h and using ethanol as a co-solvent allowed to remove 43.5 ± 0.9% of bromine, which was the maximum extraction rate obtained. Sc-CO extraction was found to be an efficient technique to remove tetrabromobisphenol A (TBBPA) but the tested conditions did not allow to remove enough polybromodiphenylethers (PBDE) to satisfy the regulation. Sc-CO process seems to be a promising pre-treatment method prior to mechanical recycling as no degradation effect on the polymer matrix was observed.
持久性有机污染物,如溴系阻燃剂,是聚合物材料生命周期结束时面临的一个主要问题。本研究采用超临界二氧化碳(sc-CO)从实际的废旧电子电气设备(WEEE)中提取溴系阻燃剂(BFR)。sc-CO 是一种无毒溶剂,具有介于液体和气体之间的中间特性,使其具有高扩散性和溶解度。首先对一批源自 WEEE 的丙烯腈-丁二烯-苯乙烯(ABS)进行了特性分析,以确定其溴和 BFR 组成,结果发现其溴和 BFR 组成比 2019 年规定的限值高出四倍。然后,研究了 sc-CO 过程的不同参数,如温度、压力、粒度和使用共溶剂,以评估它们对 BFR 萃取效率的影响。为了确定处理后的聚合物的可回收性,还通过热重分析(TGA)、差示扫描量热法(DSC)和尺寸排阻色谱法(SEC)研究了萃取过程对聚合物材料的影响。在 40°C 和 500 巴的条件下,对 <500 µm 粒径的样品进行 6 小时的萃取,使用乙醇作为共溶剂,可以去除 43.5±0.9%的溴,这是获得的最大萃取率。sc-CO 萃取是一种去除四溴双酚 A(TBBPA)的有效技术,但测试条件无法去除足够的多溴二苯醚(PBDE)以满足法规要求。sc-CO 工艺似乎是机械回收前的一种有前途的预处理方法,因为没有观察到对聚合物基质的降解影响。