铁锰氧化膜同步除微污染地表水铁锰氨氮研究进展

doi:10.16085/j.issn.1000-6613.2020-0836

摘要/Abstract

摘要：

近年来，饮用水源水中铁、锰、氨氮复合污染的问题越来越普遍。地表水中铁、锰伴生氨氮超标的现象呈现季节性，且多发生在水库水体中，对人们的日常饮用水安全造成威胁。本文首先分析了复合污染产生的原因、危害，简单介绍了常用的处理方法及局限性，阐述了铁锰活性氧化膜接触催化氧化法的由来、氧化膜的作用机理、成熟滤料的制备过程、对污染物的去除特性及催化活性恢复等内容。重点分析了目前已有的两种反应机理，分别是活化分子氧的氧自由基理论和氧化物表面活性锰的氧化理论。最后，指出了接触催化氧化法形成与作用机理的研究仍需深入，对下一步的探索进行了展望，提出了络合催化加速滤膜成熟的设想，并认为该方法在未来具有较大的发展潜力和广阔的应用前景。

关键词: 化学催化氧化, 铁, 锰, 氨氮, 锰(Ⅲ), 双金属催化

Abstract:

The complex pollution of iron, manganese, and ammonia nitrogen in drinking water sources has become more and more common in recent years. The phenomenon of excessive ammonia nitrogen associated with iron and manganese in the surface water is seasonal, and mostly occurs in reservoir water, posing a threat to people’s daily drinking water safety. In this paper, the causes and hazards of compound pollution were analyzed, the traditional treatment methods and their limitations were briefly introduced. The origin of the iron-manganese active oxide film contacted catalytic oxidation method, the action mechanism of the oxide film, the preparation process of the mature filter material, the removal characteristics of pollutants and the recovery of catalytic activity was described. Two reaction mechanisms, the oxygen free radical theory of activating molecular oxygen and the oxidation theory of active manganese on the oxide surface, were analyzed. Finally, it pointed out that the research on the formation and action mechanism of the contact catalytic oxidation method still needs to be further studied. The further exploration was prospected and the idea of accelerating the start-up of coordination catalysis was proposed. It is believed that the method has great development potential and broad application prospects in the future.

Key words: chemical catalytic oxidation, iron, manganese, ammonia nitrogen, manganese trivalent, bimetallic catalysis

中图分类号:

X524

孙浩, 何雪英, 胡一超, 刘哲艺, 张瑛洁. 铁锰氧化膜同步除微污染地表水铁锰氨氮研究进展[J]. 化工进展, 2021, 40(3): 1634-1642.

SUN Hao, HE Xueying, HU Yichao, LIU Zheyi, ZHANG Yingjie. Research progress of iron-manganese oxide film simultaneous removal of iron manganese and ammonia nitrogen from micro-polluted surface water[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1634-1642.

图/表 2

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除铁除锰常用方法	作用原理	优点	不足
自然氧化法^[10]	通过曝气充氧将Fe²⁺氧化成Fe³⁺后以Fe(OH)₃形式析出；锰的去除还需在曝气的基础上投加碱以提高pH。然后通过沉淀、过滤去除	方法简单	工艺流程复杂，二价锰需在一定pH范围内才能被氧化沉淀去除，水体pH过高，需进行酸化处理，增加了处理成本和管理难度
接触氧化法^[13]	二价铁、锰经曝气后被氧化成高价氢氧化物附着在滤料表面形成活性滤膜，能吸附水中铁锰并溶解氧化而形成新的活性物质	对铁、锰的去除效果好	铁的快速氧化影响锰的氧化过程，设计两级曝气使得流程复杂，运行费用增加；且有效的锰质滤膜难以形成并稳定
生物法^[14]	锰氧化细菌具有氧化锰的能力。培养锰氧化细菌，利用曝气＋生物滤池可以实现铁、锰的同步去除	生物法相对于自然氧化和接触氧化，能实现更好的锰去除效果	功能微生物的生长繁殖易受环境影响；具体成熟的工艺参数还需进一步确定

除铁除锰常用方法	作用原理	优点	不足
自然氧化法^[10]	通过曝气充氧将Fe²⁺氧化成Fe³⁺后以Fe(OH)₃形式析出；锰的去除还需在曝气的基础上投加碱以提高pH。然后通过沉淀、过滤去除	方法简单	工艺流程复杂，二价锰需在一定pH范围内才能被氧化沉淀去除，水体pH过高，需进行酸化处理，增加了处理成本和管理难度
接触氧化法^[13]	二价铁、锰经曝气后被氧化成高价氢氧化物附着在滤料表面形成活性滤膜，能吸附水中铁锰并溶解氧化而形成新的活性物质	对铁、锰的去除效果好	铁的快速氧化影响锰的氧化过程，设计两级曝气使得流程复杂，运行费用增加；且有效的锰质滤膜难以形成并稳定
生物法^[14]	锰氧化细菌具有氧化锰的能力。培养锰氧化细菌，利用曝气＋生物滤池可以实现铁、锰的同步去除	生物法相对于自然氧化和接触氧化，能实现更好的锰去除效果	功能微生物的生长繁殖易受环境影响；具体成熟的工艺参数还需进一步确定

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