臭氧催化氧化含AOX染料废水的效能与风险评估  

Efficiency and Environmental Risk Assessment of Catalytic Ozonation in Treating AOX-containing Dye Wastewater

作　　者：迟彤彤 徐冉云 李菲菲[1,2] 陈吕军 Chi Tongtong;Xu Ranyun;Li Feifei;Chen Lvjun(School of Environment,Tsinghua University,Beijing 100084,China;Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology,Guangzhou 510275,China)

机构地区：[1]清华大学环境学院,北京100084 [2]广东省环境污染控制与修复技术重点实验室,广州510275

出　　处：《生态毒理学报》2023年第1期288-297,共10页Asian Journal of Ecotoxicology

基　　金：国家自然科学基金资助项目(52070111,51808313);广东省环境污染控制与修复技术重点实验室开放基金资助项目(2020K0005)。

摘　　要：针对染料废水生物处理效率低、容易经氧化处理生成可吸附有机卤素(AOX)使得出水毒性升高等问题,采用臭氧(催化)氧化工艺处理难降解染料废水生物处理出水,考察工艺对染料废水的处理效能,并通过蛋白核小球藻和青海弧菌Q67评估不同工艺出水生物毒性。结果发现,MnO_(x)-GAC/O_(3)/H_(2)O_(2)工艺对总有机碳(TOC)去除效果最佳,去除率可达67.6%,较O_(3)工艺提高了39.8%;向O_(3)和O_(3)/H_(2)O_(2)体系加入MnO_(x)-GAC不利于去除卤代有机物,而向O_(3)和MnO_(x)-GAC/O_(3)体系加入H_(2)O_(2)能增强对卤代有机物去除效果。通过对物质定性分析,发现MnO_(x)-GAC/O_(3)和MnO_(x)-GAC/O_(3)/H_(2)O_(2)工艺对O_(3)体系难以去除的类蛋白物质和小分子代谢产物具有更好的去除效果。尤其以MnO_(x)-GAC/O_(3)/H_(2)O_(2)工艺去除效果最佳,能够去除大部分卤代芳香族化合物,同时有效减少卤代副产物的生成。对自由基进行定量分析,发现添加MnO_(x)-GAC或H_(2)O_(2)均可以增加体系中·OH含量,进而增强氧化能力。此外,添加MnO_(x)-GAC可以提高O_(2)^(-)·自由基含量,但添加H_(2)O_(2)会降低O_(2)^(-)·自由基含量。出水生物毒性分析结果显示只有O_(3)/H_(2)O_(2)和MnO_(x)-GAC/O_(3)/H_(2)O_(2)工艺出水对蛋白核小球藻和青海弧菌Q67生物毒性有所降低。因此,综合考虑污染物去除效果和出水生物毒性变化,MnO_(x)-GAC/O_(3)/H_(2)O_(2)工艺处理染料废水效能最高,并且能够有效降低出水生物毒性,为难降解染料废水的减毒处理提供了解决方案。In order to improve the treatment efficiency and safety of dye wastewater,reduce the formation of adsorbable organic halogenates(AOX),catalytic ozonation was used to treat the bio-treated effluent of dye wastewater.Efficiencies of different treatments were analyzed,and biological toxicities of effluents were evaluated by C.pyrenoidosa and V.qinghaiensis sp.-Q67.Results showed that MnO_(x)-GAC/O_(3)/H_(2)O_(2) process had the best re-moval effect on TOC(67.6%),which was 39.8%higher than that of O_(3) process.Adding MnO_(x)-GAC to O_(3) and O_(3)/H_(2)O_(2) system could accelerate halogenated organic matter formation,while adding H_(2)O_(2) to O_(3) and MnO_(x)-GAC/O_(3) system could reduce halogenated organic matter formation.Through qualitative analysis of substances,it was found that MnO_(x)-GAC/O_(3) and MnO_(x)-GAC/O_(3)/H_(2)O_(2) processes had the best removal effect on dissolved organic matter(DOM).They had a better effect on removing protein-like substances and small molecule metabolites which were hardly removed by O_(3) system.Moreover,MnO_(x)-GAC/O_(3)/H_(2)O_(2) process had the best degradation effect on or-ganic matter,which could remove most halogenated aromatic compounds and effectively reduce the formation of halogenated byproducts.Through free radical quantitative analysis,it was found that MnO_(x)-GAC and H_(2)O_(2) could increase the content of·OH and enhance system oxidation ability.Moreover,the addition of MnO_(x)-GAC could in-crease the content of·O_(2)^(-) free radical,but the addition of H_(2)O_(2) would reduce·O_(2)^(-) content.Through biological toxicity analysis,it was found that the effluent of O_(3)/H_(2)O_(2) and MnO_(x)-GAC/O_(3)/H_(2)O_(2) process had lower biological toxicity to C.pyrenoidosa and V.qinghaiensis sp.-Q67.Therefore,considering the effect of pollutant removal and effluent biotoxicity alteration,MnO_(x)-GAC/O_(3)/H_(2)O_(2) process was the most efficient way to treat dye wastewater and reduce the effluent toxicity threat.

关 键 词：染料废水 AOX 碳基锰催化剂 臭氧催化氧化 环境风险 

分 类 号：X171.5[环境科学与工程—环境科学]