OXIDATION PERFORMANCE OF NITRILOTRIS (METHYLENE PHOSPHONIC ACID) BY POTASSIUM PERMANGANATE
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摘要: 高锰酸钾(KMnO4)能有效降解水中有机污染物,但其氧化有机膦酸过程尚不明确。以氨基三亚甲基膦酸(NTMP)为例,采用自由基捕获实验和电子顺磁共振波谱(EPR)探究其在KMnO4体系下降解的主要活性氧化物种,并考察了溶液化学性质(如pH、共存物质、实际水体等)对KMnO4氧化降解NTMP的影响。结果表明:KMnO4直接氧化是NTMP降解的主要途径,且NTMP降解受pH影响较大。当pH=5.0时,KMnO4氧化NTMP的效果最佳,其中51.4% NTMP被氧化生成PO3-4,远高于UV/H2O2和UV/过硫酸钾(PDS)体系。水体中共存物质(SO2-4、NO-3、HCO-3和腐植酸)对NTMP的降解抑制作用较小。此外,在实际水体中KMnO4对NTMP仍有较高的降解效率,且其选择性优于自由基体系。研究结果可为实际废水中有机膦酸的高效去除提供重要参考。Abstract: Organic pollutants could be degraded by KMnO4, and the oxidation process of phosphonates by KMnO4 is still unclear. Herein, using nitrilotris (methylene phosphonic acid, NTMP) as a model pollutant, radical capture experiments and electron paramagnetic resonance (EPR) were used to explore the dominant active oxidizing species in KMnO4 system, and the effects of solution chemical properties (such as pH, coexisting substances, actual water body, etc.) on the degradation of NTMP by KMnO4 were investigated. The results showed that direct oxidation of KMnO4 was the dominant pathway for NTMP degradation, and its degradation was greatly influenced by pH value. The best oxidation performance of NTMP by KMnO4 was obtained at pH=5.0, and 51.4% of NTMP was oxidized into PO3-4, much higher than that in UV/H2O2 and UV/potassium persulfate (PDS) system. No obvious inhibition on the degradation of NTMP was observed in the presence of coexisting substances in water (i.e., SO2-4, NO-3, HCO-3, and humic acid). In addition, KMnO4 also showed a high degradation efficiency on NTMP in actual wastewater, and its selectivity was better than that of free radical systems. The results provide an important reference for the efficient removal of phosphonates from actual wastewater.
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