In-situ debromination mechanism based on self-activation and catalysis of Ca(OH) during pyrolysis of waste printed circuit boards.

Completely and deeply removed bromide from waste printed circuit boards (WPCBs) is necessary due to their toxicity and carcinogenicity. To achieve this purpose, calcium hydroxide (Ca(OH)) as a debromination agent was added during pyrolysis process of WPCBs. The results showed that hydrogen bromide (HBr), 4-bromophenol, 2-bromophenol and 2,4-dibromophenol were the main bromide species in pyrolysis products. The Ca(OH) plays a significant role for removing HBr and organic bromide, but not affects products yield. Optimal removal efficiency for 4-bromophenol, 2-bromophenol and 2,4-dibromophenol reached 87.5 %, 74.6 % and 54.5 %, respectively. And debromination efficiency was related to the steric hindrance caused by bromide atoms. The Ca(OH) can be activated by captured HBr and its thermal decomposition. And the newly-generated calcium bromide and calcium oxide significantly facilitate debromination due to their high surface energy and reactivity. The debromination mechanism was clarified by experiments coupled with computational chemistry: the coordination of bromide and calcium to form [Ph-Br···Ca] or [Ph-Br···Ca]. Then, electrons were delivered form bromide atom to Ca or Ca, which resulted in the stretch and weaken the C-Br bond. Hence, the C-Br bond was more easily to break. This work can provide support for designing novel and efficient debromination agents applied for high-temperature system.