State Key Joint Laboratory of Environment Simulation and Pollution Control (SKLESPC), School of Environment, POPs Research Center, Tsinghua University, Beijing 100084, PR China.
J Hazard Mater. 2012 Dec;243:278-85. doi: 10.1016/j.jhazmat.2012.10.034. Epub 2012 Oct 23.
Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant (BFR), which has received more and more concerns due to its high lipophilicity, persistency and endocrine disrupting property in the environment. Considering the possible need for the safe disposal of TBBPA containing wastes in the future, the potential of mechanochemical (MC) destruction as a promising non-combustion technology was investigated in this study. TBBPA was co-ground with calcium oxide (CaO) or the mixture of iron powder and quartz sand (Fe+SiO(2)) in a planetary ball mill at room temperature. The method of Fe+SiO(2) destructed over 98% of initial TBBPA after 3h and acquired 95% debromination rate after 5h, which showed a better performance than the CaO method. Raman spectra and Fourier transform infrared spectroscopy (FTIR) demonstrated the generation of inorganic carbon with the disappearance of benzene ring and CBr bond, indicating the carbonization and debromination process during mechanochemical reaction. LC-MS-MS screening showed that the intermediates of the treatment with Fe+SiO(2) were tri-, bi-, mono-brominated BPA, BPA and other fragments. Finally all the intermediates were also destroyed after 5h grinding. The bromine balance was calculated and a possible reaction pathway was proposed.
四溴双酚 A（TBBPA）是目前应用最广泛的溴系阻燃剂（BFR）之一，由于其在环境中的高亲脂性、持久性和内分泌干扰特性，受到了越来越多的关注。考虑到未来可能需要安全处理含 TBBPA 的废物，本研究考察了机械化学（MC）破坏作为一种有前途的非燃烧技术的潜力。TBBPA 在室温下与氧化钙（CaO）或铁粉和石英砂的混合物（Fe+SiO2）在行星式球磨机中进行共研磨。Fe+SiO2 法在 3 小时后可破坏超过 98%的初始 TBBPA，5 小时后可获得 95%的脱溴率，性能优于 CaO 法。拉曼光谱和傅里叶变换红外光谱（FTIR）表明，在机械化学反应过程中生成了无机碳，同时苯环和 CBr 键消失，表明发生了碳化和脱溴过程。LC-MS-MS 筛选表明，用 Fe+SiO2 处理的中间产物是三溴、二溴、单溴化 BPA、BPA 和其他片段。最后，所有中间产物在 5 小时研磨后也被破坏。计算了溴的平衡，并提出了可能的反应途径。
