硫化零价铁及其耦合高级氧化技术在水处理中的研究进展

Review of Recent Advances in Wastewater Treatment with Sulfidated Zero-Valent Iron Coupled with Advanced Oxidation Processes

  • 摘要: 硫化零价铁(S-ZVI)因其电子传递效率高、选择性好,成为近年水处理领域的研究热点. S-ZVI耦合高级氧化技术(S-ZVI/AOPs)能够在保留S-ZVI较强还原性的基础上引入强氧化作用,实现有机污染物的深度氧化与矿化. 本文总结了S-ZVI及其分别耦合过氧化氢(H2O2)、氧气(O2)和过硫酸盐(PS)体系在水处理领域的研究现状,系统介绍了影响污染物去除效果的各种因素,包括S/Fe (摩尔比,下同)、S-ZVI投加量、氧化剂投加量、溶液初始pH等,重点讨论了S-ZVI和S-ZVI/AOPs体系去除污染物的反应机理,并简述了其在工程中的应用,最后对未来的研究方向提出了建议与展望,旨在拓宽S-ZVI/AOPs在环境修复领域中的实际应用. 结果表明:①S-ZVI主要通过吸附和还原作用去除污染物,S-ZVI/AOPs体系主要通过活性物种的氧化作用去除污染物;硫化层可以通过改变电子转移路径提高活性物种产量,同时一些硫物种也可以活化氧化剂. ②耦合体系中的活性物种除常见活性自由基外,如羟基自由基(·OH)、超氧自由基(O2•−)和硫酸根自由基(SO4•−)等,还包含非自由基Fe(Ⅳ),但Fe(Ⅳ)贡献量相对较少. ③氧化剂的活化途径包括Fe2+均相活化和非均相活化以及Fe0直接活化. 现阶段研究缺乏对反应体系中电子转移途径的量化,同时需要考察反应体系中多种污染物共存时的去除效果并厘清相互影响机制以提高实际应用性. 另外,关于O2对S-ZVI去除污染物的促进或抑制作用的影响机制还有待进一步研究.

     

    Abstract: Sulfidated zero-valent iron (S-ZVI) has become a research hotspot in the field of water treatment in recent years due its high electron transfer efficiency and good selectivity. The combination of S-ZVI with advanced oxidation processes (S-ZVI/AOPs) can not only maintain the strong reducibility of S-ZVI, but also induce the generation of reactive oxidative species with strong ability to achieve oxidation and even mineralization of organic pollutants. This review summarizes the research and application of S-ZVI and S-ZVI-based hydrogen peroxide (H2O2), oxygen (O2) and persulfate (PS) activation systems in the field of water treatment. Various factors that affect the removal of pollutants, including S/Fe (mole ratio), dosage of S-ZVI, dosage of oxidant, initial pH of solution, etc. are systematically introduced. The reaction mechanisms involved in S-ZVI and S-ZVI/AOPs systems for pollutant remove are carefully and comprehensively discussed emphatically, and their applications in practical decontamination are described subsequently. Finally, suggestions and perspectives are made for future study on S-ZVI and S-ZVI/AOPs, aiming to improve the applicable feasibility of S-ZVI/AOPs in environmental remediation. It is found that pollutants are mainly removed through adsorption and reduction process in the S-ZVI alone system, while S-ZVI/AOPs are capable of oxidizing contaminants through the generated reactive oxidizing species (ROS). Sulfide layer can improve the yield of active species by changing electron transfer path, and certain sulfur species can also activate some oxidants. Some common ROS like hydroxyl radical (•OH), superoxygen radical (O2▪−) and sulfate radical (SO4•−) can be produced in S-ZVI/AOPs, while non-free radical Fe(Ⅳ) is also frequently detected, but with a relatively limited contribution to contaminant removal. Furthermore, the activation pathways of oxidants include homogeneous and heterogeneous activation of Fe2+ and direct activation of Fe0. However, it should be noted that the quantification of electron transfer pathways in the reaction system is needed but is lack currently. Moreover, in order to improve the practical applicability, it is necessary to investigate the performance and clarify the mechanism of S-ZVI/AOPs in treating wastewater containing multiple pollutants. Additionally, the extent and the corresponding mechanism of O2 effect on the removal of pollutants by S-ZVI need to be further studied.

     

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