Degradation and phosphorus immobilization treatment of organophosphate esters hazardous waste by Fe-Mn bimetallic oxide

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 •O2−. Oxidation by oxygen molecules and •O2− attack resulted in the degradation and mineralization of TBP, with simultaneously achieving P stabilization. [Display omitted] •Organophosphate esters waste was treated inspired by CLC technology with FMBO as oxygen carrier.•Phosphorus in TBP could be immobilized into Fe/Mn salts with immobilization efficiency of ∼100%.•Gaseous products from TBP degradation fulfilled the requirement of environmental standard.•Flameless combustion and oxygen vacancy-induced •O2- dominated TBP degradation.