Department of Pharmaceutical & Biological Engineering, School of Chemical Engineering, Sichuan University, Chengdu 610065, China.
Department of Pharmaceutical & Biological Engineering, School of Chemical Engineering, Sichuan University, Chengdu 610065, China.
J Hazard Mater. 2023 May 5;449:131049. doi: 10.1016/j.jhazmat.2023.131049. Epub 2023 Feb 20.
Organophosphate esters (OPEs) waste is difficult to dispose effectively because of its stability and the potential risk of P element. In this study, taking one typical organic extractant of tributyl phosphate (TBP) as an example, we proposed a strategy to treat OPEs inspired by chemical looping combustion (CLC) technology-oxygen carrier immobilization process (OCIP), aiming at efficient TBP degradation and simultaneous P immobilization. Adopting Fe-Mn bimetallic oxide (FMBO) as oxygen carrier, an almost 100% P immobilization efficiency was achieved under recommended conditions which were obtained by response surface methodology. Meanwhile, gaseous products released from TBP degradation, e.g., non-methane hydrocarbon, was lower than the maximum allowable emission concentration limit. Further characterizations implied that P-species released from reaction process were mainly immobilized as stable inorganic forms of metaphosphate, phosphate and pyrophosphate. On the basis of identifying degradation intermediates, we proposed a possible degradation pathways. FMBO as an oxygen carrier provided sufficient oxygen molecules for flameless combustion of OCIP process. Electron paramagnetic resonance measurement confirmed the existence of oxygen vacancies on FMBO surface, which contributed to the formation of •O. Oxidation by oxygen molecules and •O attack resulted in the degradation and mineralization of TBP, with simultaneously achieving P stabilization.
有机磷酸酯 (OPE) 废物由于其稳定性和 P 元素的潜在风险,难以有效处理。在这项研究中,我们以三丁基磷酸酯 (TBP) 为典型有机萃取剂为例,提出了一种受化学链燃烧 (CLC) 技术-载氧体固定化过程 (OCIP) 启发的处理 OPE 的策略,旨在有效降解 TBP 并同时固定 P。采用 Fe-Mn 双金属氧化物 (FMBO) 作为载氧体,在响应面法获得的推荐条件下,实现了几乎 100%的 P 固定化效率。同时,从 TBP 降解释放的气态产物,如非甲烷烃,低于最大允许排放浓度限值。进一步的特性表明,从反应过程中释放的 P 物质主要以稳定的焦磷酸盐、磷酸盐和焦磷酸盐的无机形式固定。在确定降解中间体的基础上,我们提出了可能的降解途径。FMBO 作为载氧体为 OCIP 过程的无焰燃烧提供了足够的氧分子。电子顺磁共振测量证实了 FMBO 表面存在氧空位,这有助于 •O 的形成。氧分子的氧化和 •O 的攻击导致 TBP 的降解和矿化,同时实现了 P 的稳定。