Mechanochemical debromination of waste printed circuit boards with marble sludge in a planetary ball milling process

An effective management of waste printed circuit board (WCB) recycling presents significant advantages of an economic, social, and environmental nature. This is particularly the case when a suitable valorisation is made of the non-metallic parts of the WCBs, well known for their "hidden" toxicological risks. Such benefits motivate research on techniques that could contribute to mitigating their adverse socio-environmental impacts. In this work, waste printed circuit boards (WCBs) containing tetrabromobisphenol A (TBBPA) as a brominated flame retardant (BFR) underwent debromination using a mechanochemical treatment (MCT) and marble sludge, another recoverable waste, as well as pure CaO as additives. All runs in this work were performed at an intermediate rotation speed of 450 rpm, using additive/WCB mass ratios (Rm) of 4:1 and 8:1, ball to powder ratios (BPR) of 20:1 and 50:1, treatment times from 2.5 h to 10 h, two WCB sizes (powder and 0.84 mm) and marble sludge, from original to precalcined conditioning. Stainless steel jars and balls were used to verify the effect of each parameter on the system and to seek an optimum process. Complete debromination of 0.84 mm WCBs was achieved at 450 rpm, using a Rm of 8:1, a BPR of 50:1, a residence time of 10 h (more than 95% in only 5 h), and a precalcined marble sludge as additive. The results revealed that when using a Rm of 4:1 instead of 8:1, more waste could be effectively treated, per batch with a lesser need for additives, at the expense of a slightly lower level of debromination efficiency. In the same way, an appropriate apparent ball diameter (with respect to the volume of the used jar) should be carefully studied in relation to WCB size in order to achieve a beneficial total amount of energy transfer during milling.