微气泡O3/H2O2深度处理某树脂厂二级出水效果与机制

陈洋; 倪鹏飞; 吴春笃; 张波; 征晓勇

doi:10.12153/j.issn.1674-991X.20240201

微气泡O₃/H₂O₂深度处理某树脂厂二级出水效果与机制

doi: 10.12153/j.issn.1674-991X.20240201

陈洋^1,,
倪鹏飞¹,
吴春笃¹,
张波^{1, 2, ,},
征晓勇³

1.
江苏大学环境与安全工程学院
2.
常州江苏大学工程技术研究院
3.
江苏环川环境工程有限公司

基金项目: 常州市应用基础研究计划项目（CJ20220025）

详细信息

作者简介:
陈洋（1999—），男，硕士研究生，主要从事臭氧催化氧化研究，3024836114@qq.com

通讯作者:
张波（1975—），男，副教授，主要从事水污染控制技术及装备、高级氧化技术等方面的研究，tabol@126.com

中图分类号: X703
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出版历程
- 收稿日期: 2024-03-31

Efficiency and mechanism of microbubble O₃/H₂O₂ advanced treatment of secondary effluent from a resin factory

1.
School of Environmental and Safety Engineering, Jiangsu University
2.
Changzhou Engineering and Technology Research Institute of Jiangsu University
3.
Jiangsu Huanchuan Environment Engineering Co., Ltd.

摘要

摘要:
针对传统生物降解对树脂废水中苯系物、聚乙烯醇等大分子有机物降解效果不好、达不到排放标准的问题，构建微气泡O₃/H₂O₂体系，对某树脂厂二级出水进行深度处理。对比了微气泡O₃曝气与普通O₃曝气的化学需氧量（COD）降解效果，考察了进气O₃浓度、H₂O₂浓度、初始pH对微气泡O₃/H₂O₂体系降解COD效果的影响，通过总有机碳验证体系的矿化效果，通过电子顺磁共振谱仪（EPR）检测微气泡O₃/H₂O₂体系中的活性物质，最后通过气相色谱质谱联用仪（GC-MS）分析降解前后废水中主要有机物的种类，并对微气泡O₃/H₂O₂体系降解COD的机制与路径进行分析。结果表明：1）微气泡O₃/H₂O₂体系中微气泡粒径主要分布在10~50 μm，平均粒径为32.82 μm；与普通O₃曝气方式进行对比，微气泡O₃体系对COD降解率更高，说明微气泡可以延长O₃气泡上升时间，增加O₃气泡比表面积，提高O₃传质系数和利用率。2）微气泡O₃/H₂O₂体系降解COD，当O₃浓度为60 mg/L、H₂O₂浓度为29.37 mmol/L、pH为7时，反应60 min后，微气泡O₃/H₂O₂体系对树脂厂二级出水的COD降解率为89.53%，处理后出水COD为15.05 mg/L，可达到GB 31572—2015《合成树脂工业污染物排放标准》。3）EPR试验表明，H₂O₂可以促进微气泡O₃体系产生更多的超氧自由基（$\cdot{\mathrm{O}}_2^- $）和羟基自由基（·OH），从而提高体系的氧化能力和对COD的降解效果。根据GC-MS结果推断O₃/H₂O₂体系降解COD的可能路径，即树脂厂二级出水以长链烷烃和环烷烃类为主的大分子物质在O₃的作用下断链、开环，在·OH等自由基的作用下矿化或降解为以小分子有机酸为主的小分子物质。
- 微气泡O₃ /
- 过氧化氢（H₂O₂） /
- 羟基自由基（·OH） /
- 有机物 /
- 树脂废水 /
- 深度处理
Abstract:
Aiming at the problem that traditional biodegradation can not degrade the chemical oxygen demand (COD) of benzene series, polyvinyl alcohol and other macromolecular organic compounds in resin wastewater, and can not meet the discharge standard, a microbubble O₃/H₂O₂ system was constructed to treat the secondary effluent of a resin factory deeply. The COD degradation effects of microbubble O₃ aeration and ordinary O₃ aeration were compared, and the effects of inlet O₃ concentration, H₂O₂ concentration and initial pH on COD degradation efficiency of microbubble O₃/H₂O₂ system were investigated. The mineralization effect of the system was verified by total organic carbon (TOC), and the active substances in microbubble O₃/H₂O₂ were detected by electron paramagnetic resonance spectrometer (EPR). Finally, the types of main organic substances in wastewater before and after degradation were analyzed by GC-MS, and the mechanism and path of COD degradation by microbubble O₃/H₂O₂ system were analyzed. The results showed that: (1) In the microbubble O₃/H₂O₂ system, the particle size of microbubbles was mainly distributed in the range of 10-50 μm, with an average particle size of 32.82 μm. Compared with ordinary aeration, microbubble O₃ system had a higher degradation rate of COD, which indicated that microbubbles could prolong the rising time of O₃ bubbles, increase the specific surface area of O₃ bubbles, and improve the mass transfer coefficient and utilization rate of O₃. (2) The analysis of influencing factors of COD degradation by microbubble O₃/H₂O₂ system showed that when O₃ concentration was 60 mg/L, H₂O₂ concentration was 29.37 mmol/L, and pH was 7 after 60 minutes of reaction, the COD degradation rate of secondary effluent of the resin factory by microbubble O₃/H₂O₂ system was 89.53%, and the treated effluent COD was 15.05 mg/L, meeting the requirements of Emission Standard of Pollutants for Synthetic Resin Industry (GB 31572-2015). (3) The EPR test showed that H₂O₂ could promote the microbubble O₃ system to produce more superoxide radicals ($\cdot{\mathrm{O}}_2^- $) and hydroxyl radicals (·OH), thus improving the oxidation capacity of the system and the degradation effect of COD. According to the results of GC-MS, the possible degradation path was inferred. Macromolecules in the secondary effluent from the resin factory, mainly composed of long-chain alkanes and cycloalkanes, underwent chain-breaking and ring-opening by O₃, and were mineralized or degraded into micromolecule substances, mainly small-molecule organic acids, under the action of ·OH and other free radicals
- microbubble O₃ /
- hydrogen peroxide(H₂O₂) /
- hydroxyl radicals(·OH) /
- organic compound /
- resin wastewater /
- advanced treatment

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图 1 微气泡O₃协同H₂O₂高级氧化试验装置

Figure 1. Experimental device for synergistic advanced oxidation of microbubble ozone and hydrogen peroxide

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图 2 显微镜下微纳米气泡观测图及尺寸分布

Figure 2. Observation diagram of micro-nano bubbles under microscope and size distribution of micro-nano bubbles

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图 3 微气泡O₃与常规曝气O₃对COD的降解效果以及O₃投加量/COD去除量的影响

注：折线表示降解率，柱状表示O₃投加量/COD去除量。

Figure 3. Effects of microbubble O₃ and conventional aeration O₃on COD removal and the ratio of O₃ dosage /COD removal

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图 4 O₃进气浓度对微气泡O₃/H₂O₂体系降解COD的影响

Figure 4. Effect of O₃ intake concentration on COD degradation in O₃/H₂O₂ microbubble system

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图 5 H₂O₂浓度对微气泡O₃/H₂O₂体系降解COD的影响

Figure 5. Influence of H₂O₂ concentration on COD degradation in O₃/H₂O₂ microbubble system

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图 6 溶液初始pH对微气泡O₃/H₂O₂体系降解COD的影响

Figure 6. Effect of initial pH value of solution on COD degradation in O₃/H₂O₂ microbubble system

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图 7 微气泡O₃/H₂O₂体系中TOC随反应时间变化

Figure 7. TOC changes with reaction time in microbubble O₃/H₂O₂ system.

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图 8 微气泡O₃和微气泡O₃/H₂O₂体系的EPR结果

Figure 8. EPR results of microbubble O₃ and microbubble O₃/H₂O₂ system

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表 1 树脂厂二级废水降解前后各物质成分和相对含量

Table 1. Composition and relative content of each substance in the secondary wastewater from resin plant before and after degradation

原水		反应10 min后溶液		反应60 min后溶液
主要成分	相对含量/%	主要成分	相对含量/%	主要成分	相对含量/%
异丙基环丁烷	25.27	庚酸	29.36	十五烷酸	29.22
二十一烷	8.76	十四烷酸	7.36	十四烷酸	21.84
3,7-二甲基壬烷	6.63	苯甲酸	4.09	十六烷酸	13.41
十四烷	4.52	十二烷酸	3.15	壬基环丙烷	8.55
2-甲基十七烷	3.52	2-十五烷醇	2.75	9-十六碳烯酸	5.07
2-甲基十八烷	3.06	丙二醇甲醚醋酸酯	2.67	8-甲基-9-十四烯酸	2.09
二十烷	2.41	丙醇	2.33	三甲基硅烷醇	1.13
十七烷	2.23	十三烷酸	1.41	2,9-二甲基十一烷	1.05
10-甲基十九烷	2.21	2-十二醇	1.84	十五烷酸	0.88
2-甲基十八烷	1.30	2-十四醇	1.83	2,6,10-三甲基十二烷	0.50
二十五烷	0.97	2-丁氧基乙醇	1.02	丁酸	0.23
2-甲基二十六烷	0.86	丙酮	0.93	十二烷酸	0.10

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