微纳米气泡强化臭氧氧化降解含酚废水

doi:10.16085/j.issn.1000-6613.2023-1249

摘要/Abstract

摘要：

为了降解毒性强的含酚工业废水，本文将微纳米气泡与臭氧氧化法相结合，探究了处理温度、溶液pH、苯酚初始浓度和臭氧浓度对苯酚降解的影响。结果表明，相较于传统气泡，微纳米气泡破裂可诱导产生更多的·OH，弥补了臭氧传质效率低和氧化性不足等缺点，使反应体系的氧化还原电位明显提高，并在苯酚降解过程中起到主要作用；相比于臭氧氧化法，苯酚降解效果得到显著提升；提升臭氧浓度、溶液pH及降低苯酚初始浓度均可促进反应体系中生成更多的·OH，进而提升除酚率。通过气相色谱-质谱法（GC-MS）检测苯酚降解的中间产物，分析了苯酚降解的可能路径。总体而言，微纳米气泡结合臭氧氧化法是一种有潜力的除酚技术，研究结果对此技术在工业废水降解中的应用和推广具有指导意义。

关键词: 废水, 微纳气泡, 臭氧氧化, 苯酚, 降解

Abstract:

In order to degrade the highly toxic phenol-containing industrial wastewater, this paper combined micro-nano bubbles with ozone oxidation to investigate the effects of treatment temperature, solution pH, initial phenol concentration and ozone concentration on phenol degradation. The results showed that the rupture of micro-nanobubbles could induce the generation of more ·OH, which could make up for the shortcomings of low mass transfer efficiency and insufficient oxidizability of ozone, so that the redox potential of the reaction system could be significantly increased and played a major role in phenol degradation. Compared with ozone oxidation, the phenol degradation effect was significantly improved. The increase of ozone concentration, the increase of solution pH and the decrease of initial phenol concentration could promote the generation of more ·OH in the reaction system, which could enhance the phenol removal rate. The intermediate products of phenol degradation were detected by gas chromatography-mass spectrometry (GC-MS), and the possible pathways of phenol degradation were speculated. Overall, the combination of micro-nano bubbles with ozone oxidation was a potential phenol removal technology, and the results of this study were of great significance in guiding the application and popularization of this technology in the degradation of industrial wastewater.

Key words: waste water, micro-nano bubbles, ozone oxidation, phenol, degradation

中图分类号:

X742

宋占龙, 汤涛, 潘蔚, 赵希强, 孙静, 毛岩鹏, 王文龙. 微纳米气泡强化臭氧氧化降解含酚废水[J]. 化工进展, 2024, 43(8): 4614-4623.

SONG Zhanlong, TANG Tao, PAN Wei, ZHAO Xiqiang, SUN Jing, MAO Yanpeng, WANG Wenlong. Micro-nano bubbles enhance ozone oxidation and degradation of wastewater containing phenol[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4614-4623.

图/表 16

表1 模拟废水理化性质分析

苯酚浓度/mg·L^-1	pH	电导率/μS·cm^-1	外观特性
40~200	7	698	无色透明

图1 含酚废水处理装置1—氧气瓶；2—流量计；3—循环水；4—循环水泵；5—臭氧发生器；6—臭氧浓度检测仪；7—微气泡发生装置；8—反应容器；9—尾气处理装置

图2 气泡的粒径及分布

图3 微纳米气泡悬浮时间（制备时长20min，空气负载）

图4 微纳米气泡氧化还原电位

图5 处理温度对微纳米气泡除酚效果的影响

图6 溶液初始pH对微纳米气泡除酚效果的影响

图7 臭氧浓度对微纳米气泡除酚效果的影响

图8 苯酚初始浓度对微纳米气泡除酚效果的影响

图9 气泡大小对除酚率的影响

图10 TBA对微纳米气泡臭氧高级氧化的影响

图11 微纳米气泡协同臭氧高级氧化含酚废水示意图

图12 苯酚和TOC去除情况

图13 苯酚降解GC-MS中间产物谱图

表2 苯酚降解中间产物

序号	物质名称及分子式	反应10min		反应30min
序号	物质名称及分子式	保留时间/min	峰面积/×10⁸	保留时间/min	峰面积/×10⁸
1	苯酚（C₆H₆O）	5.83	96.6	5.65	19.40
2	邻苯二酚（C₆H₆O₂）	10.04	1.14	10.03	0.95
3	2,4-二甲基苯甲醛（C₉H₁₀O）	—	—	10.25	1.00
4	邻苯二甲酸二甲酯（C₁₀H₁₀O₄）	—	—	14.46	0.25
5	2,4-二叔丁基酚（C₁₄H₂₂O）	15.38	1.80	15.41	1.38
6	对苯氧基苯酚（C₁₂H₁₀O₂）	—	—	18.51	0.26
7	邻苯二甲酸二丁酯（C₁₆H₂₂O₄）	21.57	4.31	21.59	2.68
8	邻苯甲酸酯化物（C₁₆H₂₂O₄）	—	—	27.93	0.55

图14 微纳米气泡协同臭氧高级氧化苯酚可能路径

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