Research progress on the treatment of phenol containing wastewater by heterogeneous catalyst ozonation

doi:10.19965/j.cnki.iwt.2022-1313

Abstract

Abstract:

Catalytic ozonation process has the advantages of simple operation，high oxidation efficiency and low secondary pollution in the advanced treatment of phenol containing organic wastewater. However，its large-scale application depends on the development of heterogeneous catalysts with high activity and stability. Herein，the mechanism of hetergeneous catalytic ozone oxidation reaction in catalytic ozonation technology was introduced. The research status of heterogeneous catalysts for catalytic ozonation of phenolic compounds was reviewed from two aspects of non-supported and supported catalysts，and the characteristics and limitations of non-supported catalysts，single active component supported catalysts and multi-component supported catalysts were mainly analyzed. Multi-component supported catalyst is the main research object since its advantages on improving ozone utilization rate，reducing ozone emission and great potential of performance optimization. To develop highly efficient catalysts，the optimization strategy on composition，size and defect site of catalyst was proposed from the perspective of geometric structure and electronic structure. Finally，the research progress of heterogeneous catalytic ozonation catalysts for removal of phenolic compounds was summarized and prospected in order to provide reference for the development of efficient catalysts for catalytic ozonation technology.

Key words: catalytic ozonation, phenolic compounds, catalyst, catalyst support

摘要：

催化臭氧氧化技术在深度处理含酚有机废水方面具有操作简单、氧化效率高、二次污染小等优点。然而，其规模化应用依赖于开发高活性和高稳定性的非均相催化剂。介绍了催化臭氧氧化技术中非均相催化臭氧氧化反应机理。从非负载型和负载型催化剂两方面综述了催化臭氧氧化酚类化合物非均相催化剂的研究现状，重点分析了非负载型催化剂、单活性组分负载型催化剂及多组分负载型催化剂的特点及局限性，指出多组分负载型催化剂由于具有显著提升臭氧利用率、降低臭氧投放量，以及性能可优化潜力大等优势，是当前主要研究对象。针对高效催化剂开发，提出了从几何结构和电子结构角度入手，实现催化剂组分、尺寸和缺陷位调控等性能优化策略。最后对用于酚类化合物去除的非均相催化剂的研究进展进行了总结和展望，以期对催化臭氧氧化技术中高效催化剂的开发提供参考。

关键词: 催化臭氧氧化, 酚类化合物, 催化剂, 催化剂载体

CLC Number:

X703

Longxiang XIA, Haodong HE, Dengfeng WU. Research progress on the treatment of phenol containing wastewater by heterogeneous catalyst ozonation[J]. Industrial Water Treatment, 2024, 44(2): 1-10.

夏龙祥, 何昊东, 吴登峰. 非均相催化剂催化臭氧氧化含酚废水的研究进展[J]. 工业水处理, 2024, 44(2): 1-10.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2022-1313

https://www.iwt.cn/EN/Y2024/V44/I2/1

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References 78

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污染物	催化剂	操作条件	去除率	ROS
苯酚	γ-MnO₂ ^〔28〕	苯酚质量浓度100 mg/L，催化剂质量浓度0.5 g/L	苯酚92.21%， COD 73%	—
苯酚	α-MnO₂ ^〔28〕	苯酚质量浓度100 mg/L，催化剂质量浓度0.5 mg/L	苯酚80%	—
苯酚	β-MnO₂ ^〔41〕	臭氧质量浓度112.5 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度1 g/L，初始pH=6.35	苯酚83.7%， COD 50.4%	—
苯酚	CeO₂ ^〔42〕	臭氧质量浓度25 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度0.1 g/L，pH=3.5	TOC 90%	·OH
苯酚	MgO^〔38〕	臭氧质量浓度72 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度20~40 mg/L，初始pH=6.8	苯酚70.1%	·OH
苯酚	AC^〔43〕	臭氧质量浓度90 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度25 g/L，初始pH=11	苯酚100%， TOC 91%	·OH、O₂ ^·-
苯酚	α-FeOOH^〔44〕	臭氧质量浓度150 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度1 g/L，初始pH=6.3	苯酚66.5%	·OH
4-硝基苯酚	α-MnO₂ ^〔27〕	臭氧质量浓度20 mg/L，4-硝基苯酚质量浓度25 mg/L，催化剂质量浓度0.1 g/L，pH=7	TOC 91%	O₂ ^·-、¹O₂
4-硝基苯酚	Fe^0〔30〕	臭氧质量浓度642 g/L，4-硝基苯酚质量浓度500 mg/L，催化剂质量浓度40 g/L，初始pH=5.3	COD 89.5%	·OH

污染物	催化剂	操作条件	去除率	ROS
苯酚	γ-MnO₂ ^〔28〕	苯酚质量浓度100 mg/L，催化剂质量浓度0.5 g/L	苯酚92.21%， COD 73%	—
苯酚	α-MnO₂ ^〔28〕	苯酚质量浓度100 mg/L，催化剂质量浓度0.5 mg/L	苯酚80%	—
苯酚	β-MnO₂ ^〔41〕	臭氧质量浓度112.5 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度1 g/L，初始pH=6.35	苯酚83.7%， COD 50.4%	—
苯酚	CeO₂ ^〔42〕	臭氧质量浓度25 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度0.1 g/L，pH=3.5	TOC 90%	·OH
苯酚	MgO^〔38〕	臭氧质量浓度72 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度20~40 mg/L，初始pH=6.8	苯酚70.1%	·OH
苯酚	AC^〔43〕	臭氧质量浓度90 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度25 g/L，初始pH=11	苯酚100%， TOC 91%	·OH、O₂ ^·-
苯酚	α-FeOOH^〔44〕	臭氧质量浓度150 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度1 g/L，初始pH=6.3	苯酚66.5%	·OH
4-硝基苯酚	α-MnO₂ ^〔27〕	臭氧质量浓度20 mg/L，4-硝基苯酚质量浓度25 mg/L，催化剂质量浓度0.1 g/L，pH=7	TOC 91%	O₂ ^·-、¹O₂
4-硝基苯酚	Fe^0〔30〕	臭氧质量浓度642 g/L，4-硝基苯酚质量浓度500 mg/L，催化剂质量浓度40 g/L，初始pH=5.3	COD 89.5%	·OH

污染物	催化剂	操作条件	去除率
甲酚	Fe₃O₄/MnO₂ ^〔59〕	臭氧质量浓度75 mg/L，甲酚浓度1 mmol/L，催化剂质量浓度0.2 g/L，pH=9	甲酚99.5%
苯酚	Fe₃O₄/AC^〔60〕	臭氧质量浓度64.2 g/L，苯酚质量浓度100 mg/L，催化剂质量浓度2 g/L，	苯酚98.5%，COD 69.8%
苯酚	CeO₂-OCNT^〔61〕	臭氧质量浓度12 mg/L，苯酚质量浓度20 mg/L，催化剂质量浓度0.05~0.13 g/L，初始pH=6.2	TOC96%
四氯苯酚	β-FeOOH/NiO^〔62〕	臭氧质量浓度28.24 mg/L，四氯苯酚浓度0.002 mol/L，催化剂质量浓度0.1 g/L，初始pH=7	四氯苯酚85%，COD 66%
对氯苯酚	Fe₂O₃/沸石^〔63〕	臭氧质量浓度2.6 mg/L，对氯苯酚浓度100 mg/L，催化剂质量浓度10 g/L	对氯苯酚87.26%，COD 48.83%
对氯苯酚	Fe₃O₄/MnO₂ ^〔59〕	臭氧质量浓度75 mg/L，对氯苯酚浓度1 mmol/L，催化剂质量浓度0.2 g/L，pH=9	对氯苯酚93.9%

污染物	催化剂	操作条件	去除率
甲酚	Fe₃O₄/MnO₂ ^〔59〕	臭氧质量浓度75 mg/L，甲酚浓度1 mmol/L，催化剂质量浓度0.2 g/L，pH=9	甲酚99.5%
苯酚	Fe₃O₄/AC^〔60〕	臭氧质量浓度64.2 g/L，苯酚质量浓度100 mg/L，催化剂质量浓度2 g/L，	苯酚98.5%，COD 69.8%
苯酚	CeO₂-OCNT^〔61〕	臭氧质量浓度12 mg/L，苯酚质量浓度20 mg/L，催化剂质量浓度0.05~0.13 g/L，初始pH=6.2	TOC96%
四氯苯酚	β-FeOOH/NiO^〔62〕	臭氧质量浓度28.24 mg/L，四氯苯酚浓度0.002 mol/L，催化剂质量浓度0.1 g/L，初始pH=7	四氯苯酚85%，COD 66%
对氯苯酚	Fe₂O₃/沸石^〔63〕	臭氧质量浓度2.6 mg/L，对氯苯酚浓度100 mg/L，催化剂质量浓度10 g/L	对氯苯酚87.26%，COD 48.83%
对氯苯酚	Fe₃O₄/MnO₂ ^〔59〕	臭氧质量浓度75 mg/L，对氯苯酚浓度1 mmol/L，催化剂质量浓度0.2 g/L，pH=9	对氯苯酚93.9%

污染物	催化剂	操作条件	去除效率
双酚A	Mn-Fe/Al₂O₃ ^〔65〕	臭氧质量浓度1.3~6.0 mg/L，双酚A质量浓度10~80 mg/L，催化剂质量浓度1~9 g/L，初始pH 3~11	双酚A 84.1%
苯酚	Fe-MnO_x/AC^〔52〕	臭氧质量浓度60 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度2 g/L	TOC 90.75%
苯酚	Fe-Mn/PAC^〔67〕	臭氧质量浓度50 mg/L，催化剂质量浓度4 g/L	苯酚95%，COD 79%
苯酚	Fe-Ni/MAC^〔68〕	臭氧质量浓度68 mg/L，苯酚质量浓度1 243 mg/L，催化剂质量浓度10 g/L，pH=9	苯酚94.25%
苯酚	Co-Fe/ZSM-5^〔69〕	臭氧质量浓度20 mg/L，苯酚质量浓度100 mg/L，催化剂质量浓度0.2 g/L，pH 6~7	苯酚92.9%，COD 86%
苯酚、苯系物	Zn-Co/ZSM-5^〔70〕	臭氧质量浓度4 mg/L，苯酚、苯系物COD 500 mg/L，催化剂质量浓度0.4 g/L，pH 6.0~6.5	COD 96.1%
苯酚	Mn-Fe-Cu/Al₂O₃ ^〔18〕	臭氧质量浓度60 mg/L，苯酚初始质量浓度100 mg/L，pH=6，催化剂质量浓度5~30 g/L	TOC 96.42%
苯酚	Mn-Fe-Ce/Al₂O₃ ^〔66〕	臭氧质量浓度34 mg/L，苯酚浓度300 mg/L，催化剂质量浓度5 g/L	苯酚去除率87.97%
酚类化合物	Mn-Cu-Ce/Al₂O₃ ^〔71〕	臭氧质量浓度10 mg/L，酚类化合物COD 580 mg/L，催化剂质量浓度2 g/L，pH=8.2	TOC 70.2%

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