Ministry of Education Key Laboratory of Pollution Control and Ecological Remediation for Industrial Agglomeration Area, College of Environment and Energy, South China University of Technology, Guangzhou, 510006, People's Republic of China.
Zhujianghai Institute of Salty Water Desalination, Dongguan, 523000, People's Republic of China.
Environ Sci Pollut Res Int. 2019 Jan;26(2):1015-1025. doi: 10.1007/s11356-016-8216-6. Epub 2016 Dec 29.
Internal micro-electrolysis (IE) coupled with Fenton oxidation (IEF) was a very effective technology for copper (Cu)-ethylenediaminetetraacetic acid (EDTA) wastewater treatment. However, the mechanisms of Cu removal and EDTA degradation were scarce and lack persuasion in the IEF process. In this paper, the decomplexation and removal efficiency of Cu-EDTA and the corresponding mechanisms during the IEF process were investigated by batch test. An empirical equation and the oxidation reduction potential (ORP) index were proposed to flexibly control IE and the Fenton process, respectively. The results showed that Cu, total organic carbon (TOC), and EDTA removal efficiencies were 99.6, 80.3, and 83.4%, respectively, under the proper operation conditions of iron dosage of 30 g/L, Fe/C of 3/1, initial pH of 3.0, Fe/HO molar ratio of 1/4, and reaction time of 20 min, respectively for IE and the Fenton process. The contributions of IE and Fenton to Cu removal were 91.2 and 8.4%, respectively, and those to TOC and EDTA removal were 23.3, 25.1, and 57, 58.3%, respectively. It was found that Fe-based replacement-precipitation and hydroxyl radical (•OH) were the most important effects during the IEF process. •OH played an important role in the degradation of EDTA, whose yield and productive rate were 3.13 mg/L and 0.157 mg/(L min), respectively. Based on the intermediates detected by GC-MS, including acetic acid, propionic acid, pentanoic acid, amino acetic acid, 3-(diethylamino)-1,2-propanediol, and nitrilotriacetic acid (NTA), a possible degradation pathway of Cu-EDTA in the IEF process was proposed. Graphical abstract The mechanism diagram of IEF process.
内电解(IE)耦合 Fenton 氧化(IEF)是处理铜(Cu)-乙二胺四乙酸(EDTA)废水的一种非常有效的技术。然而,在 IEF 过程中,Cu 去除和 EDTA 降解的机制还很少,缺乏说服力。本文通过批试验研究了 IEF 过程中 Cu-EDTA 的解络合和去除效率及其相应的机制。提出了一个经验方程和氧化还原电位(ORP)指数,分别灵活地控制 IE 和 Fenton 过程。结果表明,在适当的操作条件下,铁投加量为 30 g/L、Fe/C 为 3/1、初始 pH 值为 3.0、Fe/HO 摩尔比为 1/4、反应时间为 20 min 时,Cu、总有机碳(TOC)和 EDTA 的去除率分别为 99.6%、80.3%和 83.4%。IE 和 Fenton 对 Cu 去除的贡献分别为 91.2%和 8.4%,对 TOC 和 EDTA 去除的贡献分别为 23.3%、25.1%和 57%、58.3%。结果表明,Fe 基置换沉淀和羟基自由基(•OH)是 IEF 过程中最重要的影响因素。•OH 在 EDTA 的降解中起重要作用,其产率和生成速率分别为 3.13 mg/L 和 0.157 mg/(L·min)。基于 GC-MS 检测到的中间体,包括乙酸、丙酸、戊酸、氨基乙酸、3-(二乙基氨基)-1,2-丙二醇和氮川三乙酸(NTA),提出了 IEF 过程中 Cu-EDTA 的可能降解途径。