含Cl-/Br-体系2,4,6-三氯苯酚的臭氧氧化处理效能及毒性变化研究
Degradation Efficiency and Toxicity Variation in Ozonation of 2,4,6-trichlorophenol with Interference of Cl-/Br-
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摘要: 2，4，6-三氯苯酚（2，4，6-trichlorophenol，2，4，6-TCP）作为典型的工业生产原料，常与无机卤素离子共存于工业废水中，然而目前少有实验报道后者对2，4，6-TCP氧化降解的影响机制。本文探究了在不同卤素离子条件下，2，4，6-TCP的臭氧氧化降解反应动力学及氧化效能变化，并通过模型预测和发光菌毒性实验评估了臭氧氧化处理过程中2，4，6-TCP降解中间体之间的毒性效应和溶液的毒性变化。结果表明，投加低浓度Cl-（20 mmol·L-1）可使2，4，6-TCP的降解速率从0.234 mol·min-1提升为0.237 mol·min-1，然而高浓度的Cl-和Br-会显著抑制2，4，6-TCP的降解。当体系中Cl-和Br-浓度分别从0 mmol·L-1上升至300 mmol·L-1和100 mmol·L-1时，臭氧氧化2 h后2，4，6-TCP溶液的化学需氧量（chemical oxygen demand，COD）去除率下降了17%和18%，可吸附有机卤代物（adsorbable organic halides，AOX）去除率下降了15%和55%。研究表明2，4，6-TCP污染物主要在O3、·OH和O-2·的共同作用下被降解，生成的2，6-二氯-1，4-苯二醇、2，6-二氯-1，4-苯醌和2，4，6-三溴苯酚的急性毒性和慢性毒性都比母体更高，且三元混合毒性实验表明降解中间体2，6-二氯-1，4-苯醌、2，6-二氯苯酚和2-氯苯酚之间存在协同毒性作用。整体上看，臭氧氧化处理过程中的AOX浓度与2，4，6-TCP溶液的毒性单位呈高度正相关关系，说明AOX物质对废水急性毒性的贡献较大，其对生态环境的潜在危害应引起更多关注。
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关键词:
- 2,4,6-三氯苯酚 /
- 臭氧氧化 /
- AOX /
- COD /
- 混合毒性
Abstract: As a typical raw material for industrial production, 2,4,6-trichlorophenol (2,4,6-TCP) commonly coexists with inorganic halogen ions in the industrial wastewater. However, little literature have reported the effect of halogen ions on the oxidative degradation of 2,4,6-TCP. In this paper, the ozonation degradation kinetics and oxidation efficiency of 2,4,6-TCP were investigated under varying halogen ion conditions. Additionally, the toxic effects between 2,4,6-TCP degradation intermediates as well as the alterations of solution toxicity were evaluated. The results showed that adding low concentration of Cl- (20 mmol·L-1) could increase the degradation rate of 2,4,6-TCP from 0.234 mol·min-1 to 0.237 mol·min-1, while high concentration of Cl- and Br- significantly inhibited the degradation of 2,4,6-TCP. When the concentrations of Cl- and Br- respectively increased from 0 mmol·L-1 to 300 mmol·L-1 and 100 mmol·L-1, the chemical oxygen demand (COD) removal rate of 2,4,6-TCP solution decreased by 17% and 18%, and the adsorbable organic halides (AOX) removal rate decreased by 15% and 55% after 2 h of ozone oxidation. The results indicated that 2,4,6-TCP was mainly degraded by the co-oxidation of O3, ·OH and O-2·. Notably, the intermediate 2,6-dichloro-1,4-benzohydroquinone, 2,6-dichloro-1,4-benzoquinone and 2,4,6-tribromophenol exhibited higher acute and chronic toxicity than 2,4,6-TCP. The ternary mixed toxicity test showed a synergistic toxicity effect between 2,6-dichloro-1,4-benzoquinone, 2,6-dichlorophenol and 2-chlorophenol. The concentration of AOX was highly positively correlated with the toxicity unit of the 2,4,6-TCP solution, indicating a substantial contribution of AOX substances to wastewater acute toxicity. Therefore, the potential ecological risks posed by AOX pollutants warrant further attention.-
Key words:
- 2,4,6-trichlorophenol /
- ozone oxidation /
- AOX /
- COD /
- mixed toxicity
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