Department of Solid Waste Treatment and Recycling, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085, China; University of Chinese Academy of Sciences, Beijing 100049, China.
Department of Solid Waste Treatment and Recycling, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085, China; University of Chinese Academy of Sciences, Beijing 100049, China.
Waste Manag. 2016 Oct;56:423-30. doi: 10.1016/j.wasman.2016.05.022. Epub 2016 Jun 7.
This work investigated various supercritical water oxidation (SCWO) systems, i.e. SCWO1 (only water), SCWO2 (water+H2O2) and SCWO3 (water+H2O2/NaOH), for waste printed circuit boards (PCBs) detoxification and recycling. Response surface methodology (RSM) was applied to optimize the operating conditions of the optimal SCWO3 systems. The optimal reaction conditions for debromination were found to be the NaOH of 0.21g, the H2O2 volume of 9.04mL, the time of 39.7min, maximum debromination efficiency of 95.14%. Variance analysis indicated that the factors influencing debromination efficiency was in the sequence of NaOH>H2O2>time. Mechanism studies indicated that the dissociated ions from NaOH in supercritical water promoted the debromination of brominated epoxy resins (BERs) through an elimination reaction and nucleophilic substitution. HO2, produced by H2O2 could induce the oxidation of phenol ring to open (intermediates of BERs), which were thoroughly degraded to form hydrocarbons, CO2, H2O and NaBr. In addition, the alkali-silica reaction between OH(-) and SiO2 induced the phase transformation of glass fibers, which were simultaneously converted into anorthite and albite. Waste PCBs in H2O2/NaOH improved SCWO system were fully degraded into useful products and simultaneously transformed into functional materials. These findings are helpful for efficient recycling of waste PCBs.
本研究考察了各种超临界水氧化(SCWO)体系,即 SCWO1(仅水)、SCWO2(水+H2O2)和 SCWO3(水+H2O2/NaOH),用于废弃印刷电路板(PCBs)解毒和回收。响应面法(RSM)用于优化最佳 SCWO3 体系的操作条件。发现脱溴的最佳反应条件为 NaOH 为 0.21g、H2O2 体积为 9.04mL、时间为 39.7min,最大脱溴效率为 95.14%。方差分析表明,影响脱溴效率的因素顺序为 NaOH>H2O2>时间。机理研究表明,NaOH 在超临界水中离解出的离子通过消除反应和亲核取代促进溴化环氧树脂(BERs)的脱溴。H2O2 产生的 HO2 可以诱导酚环开环(BERs 的中间体),BERs 被彻底降解为烃类、CO2、H2O 和 NaBr。此外,OH(-)与 SiO2 之间的碱-硅反应诱导玻璃纤维的相转变,同时转化为钙长石和钠长石。H2O2/NaOH 中的废弃 PCB 提高了 SCWO 体系的降解效率,将其完全转化为有用产物,并同时转化为功能性材料。这些发现有助于高效回收废弃 PCB。