非均相催化剂催化臭氧氧化含酚废水的研究进展

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

摘要/Abstract

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

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

中图分类号:

X703

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.

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.

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

图/表 3

参考文献 78

1	MOHAMAD SAID K A， ISMAIL A F， ABDUL KARIM Z，et al. A review of technologies for the phenolic compounds recovery and phenol removal from wastewater［J］. Process Safety and Environmental Protection，2021，151：257-289. doi:10.1016/j.psep.2021.05.015
2	SAPUTERA W H， PUTRIE A S， ESMAILPOUR A A，et al. Technology advances in phenol removals：Current progress and future perspectives［J］. Catalysts，2021，11（8）：998. doi:10.3390/catal11080998
3	CORDOVA VILLEGAS L G， MASHHADI N， CHEN Miao，et al. A short review of techniques for phenol removal from wastewater［J］. Current Pollution Reports，2016，2（3）：157-167. doi:10.1007/s40726-016-0035-3
4	LI Dong， STANFORD B， DICKENSON E，et al. Effect of advanced oxidation on N-nitrosodimethylamine（NDMA） formation and microbial ecology during pilot-scale biological activated carbon filtration［J］. Water Research，2017，113：160-170. doi:10.1016/j.watres.2017.02.004
5	CAI Q Q， WU M Y， LI R，et al. Potential of combined advanced oxidation：Biological process for cost-effective organic matters removal in reverse osmosis concentrate produced from industrial wastewater reclamation：Screening of AOP pre-treatment technologies［J］. Chemical Engineering Journal，2020，389：123419. doi:10.1016/j.cej.2019.123419
6	PRIYADARSHINI M，DAS I， GHANGREKAR M M，et al. Advanced oxidation processes：Performance，advantages，and scale-up of emerging technologies［J］. Journal of Environmental Management，2022，316：115295. doi:10.1016/j.jenvman.2022.115295
7	PELALAK R， ALIZADEH R， GHARESHABANI E. Enhanced heterogeneous catalytic ozonation of pharmaceutical pollutants using a novel nanostructure of iron-based mineral prepared via plasma technology：A comparative study［J］. Journal of Hazardous Materials，2020，392：122269. doi:10.1016/j.jhazmat.2020.122269
8	MA Rui， LIU Guangmin， FENG Sihui，et al. Optimization and effects of catalytic ozonation of actual phenolic wastewater by CuO/Al₂O₃ ［J］. China Petroleum Processing & Petrochemical Technology，2019，21（3）：74-80.
9	CHEN Hai， WANG Jianlong. Catalytic ozonation of sulfamethoxazole over Fe₃O₄/Co₃O₄ composites［J］. Chemosphere，2019，234：14-24. doi:10.1016/j.chemosphere.2019.06.014
10	韦丹，陈捷，孙逊. 非均相催化臭氧氧化同时去除COD和氨氮的研究［J］.工业水处理，2022，42（12）：136-141. doi:10.19965/j.cnki.iwt.2022-0119
	WEI Dan， CHEN Jie， SUN Xun. Study on heterogeneous catalytic ozonation for removalof COD and ammonia nitrogen［J］. Industrial Water Treatment，2022，42（12）：136-141. doi:10.19965/j.cnki.iwt.2022-0119
11	ISSAKA E， AMU-DARKO J N O， YAKUBU S，et al. Advanced catalytic ozonation for degradation of pharmaceutical pollutants：A review［J］. Chemosphere，2022，289：133208. doi:10.1016/j.chemosphere.2021.133208
12	李振邦，颜冰川，王全勇，等. 臭氧催化氧化与耦合工艺处理工业废水的研究进展［J］.工业水处理，2022，42（9）：56-63. doi:10.19965/j.cnki.iwt.2021-0783
	LI Zhenbang， YAN Bingchuan， WANG Quanyong，et al. Research progress of ozone catalytic oxidation and coupling process for industrial wastewater treatment［J］. Industrial Water Treatment，2022，42（9）：56-63. doi:10.19965/j.cnki.iwt.2021-0783
13	WANG Jianlong， CHEN Hai. Catalytic ozonation for water and wastewater treatment：Recent advances and perspective［J］. Science of the Total Environment，2020，704：135249. doi:10.1016/j.scitotenv.2019.135249
14	李振邦，张欢，王全勇，等. 多元负载型催化剂的制备及臭氧催化氧化性能［J］.工业水处理，2022，42（1）：148-153.
	LI Zhenbang， ZHANG Huan， WANG Quanyong，et al. Preparation and ozonation performance of multicomponent supported catalysts［J］. Industrial Water Treatment，2022，42（1）：148-153.
15	LEE Wen Jie， BAO Yueping， GUAN Chaoting，et al. Ce/TiO _x -functionalized catalytic ceramic membrane for hybrid catalytic ozonation-membrane filtration process：Fabrication，characterization and performance evaluation［J］. Chemical Engineering Journal，2021，410：128307. doi:10.1016/j.cej.2020.128307
16	WANG Yujue， YU Gang. Challenges and pitfalls in the investigation of the catalytic ozonation mechanism：A critical review［J］. Journal of Hazardous Materials，2022，436：129157. doi:10.1016/j.jhazmat.2022.129157
17	ALAMEDDINE M， SIRAKI A， TONOYAN L，et al. Treatment of a mixture of pharmaceuticals，herbicides and perfluorinated compounds by powdered activated carbon and ozone：Synergy，catalysis and insights into non-free OH contingent mechanisms［J］. Science of the Total Environment，2021，777：146138. doi:10.1016/j.scitotenv.2021.146138
18	WEI Xingyue， SHAO Shengjuan， DING Xin，et al. Degradation of phenol with heterogeneous catalytic ozonation enhanced by high gravity technology［J］. Journal of Cleaner Production，2020，248：119179. doi:10.1016/j.jclepro.2019.119179
19	LI Yu， XU Jie， QIAN Mengqian，et al. The role of surface hydroxyl concentration on calcinated alumina in catalytic ozonation［J］. Environmental Science and Pollution Research，2019，26（15）：15373-15380. doi:10.1007/s11356-019-04909-5
20	WANG Ye， YANG Wenzhong， YIN Xiaoshuang，et al. The role of Mn-doping for catalytic ozonation of phenol using Mn/γ-Al₂O₃ nanocatalyst：Performance and mechanism［J］. Journal of Environmental Chemical Engineering，2016，4（3）：3415-3425. doi:10.1016/j.jece.2016.07.016
21	ZHAO Hui， DONG Yuming， WANG Guangli，et al. Novel magnetically separable nanomaterials for heterogeneous catalytic ozonation of phenol pollutant：NiFe₂O₄ and their performances［J］. Chemical Engineering Journal，2013，219：295-302. doi:10.1016/j.cej.2013.01.019
22	QU Zhengjun， XU Xiaoshen， REN Hongfei，et al. Effective mineralization of p-nitrophenol in water by heterogeneous catalytic ozonation using Ce-loaded sepiolite catalyst［J］. Journal of Environmental Chemical Engineering，2022，10（4）：108185. doi:10.1016/j.jece.2022.108185
23	TAN Xiuqin， WAN Yifeng， HUANG Yajing，et al. Three-dimensional MnO₂ porous hollow microspheres for enhanced activity as ozonation catalysts in degradation of bisphenol A［J］. Journal of Hazardous Materials，2017，321：162-172. doi:10.1016/j.jhazmat.2016.09.013
24	CHEN Hua， FANG Cunxia， GAO Xingmin，et al. Sintering- and oxidation-resistant ultrasmall Cu（Ⅰ）/（Ⅱ） oxides supported on defect-rich mesoporous alumina microspheres boosting catalytic ozonation［J］. Journal of Colloid and Interface Science，2021，581：964-978. doi:10.1016/j.jcis.2020.09.002
25	ZHANG Jianlin， ZHUANG Tao， LIU Shanjun，et al. Catalytic ozonation of phenol enhanced by mesoporous MnO₂ prepared through nanocasting method with SBA-15 as template［J］. Journal of Environmental Chemical Engineering，2020，8（4）：103967. doi:10.1016/j.jece.2020.103967
26	HE Yuan， WANG Liangjie， CHEN Zhan，et al. Catalytic ozonation for metoprolol and ibuprofen removal over different MnO₂ nanocrystals：Efficiency，transformation and mechanism［J］. Science of the Total Environment，2021，785：147328. doi:10.1016/j.scitotenv.2021.147328
27	NAWAZ F， CAO Hongbin， XIE Yongbing，et al. Selection of active phase of MnO₂ for catalytic ozonation of 4-nitrophenol［J］. Chemosphere，2017，168：1457-1466. doi:10.1016/j.chemosphere.2016.11.138
28	HUANG Xiaoqiao， CUI Wenyao， YU Jianying，et al. Preparation of mesoporous MnO₂ catalysts with different morphologies for catalytic ozonation of organic compounds［J］. Catalysis Letters，2022，152（5）：1441-1450. doi:10.1007/s10562-021-03745-y
29	WANG Jianlong， BAI Zhiyong. Fe-based catalysts for heterogeneous catalytic ozonation of emerging contaminants in water and wastewater［J］. Chemical Engineering Journal，2017，312：79-98. doi:10.1016/j.cej.2016.11.118
30	XIONG Zhaokun， LAI Bo， YUAN Yue，et al. Degradation of p-nitrophenol（PNP） in aqueous solution by a micro-size Fe⁰/O₃ process（mFe⁰/O₃）：Optimization，kinetic，performance and mechanism［J］. Chemical Engineering Journal，2016，302：137-145. doi:10.1016/j.cej.2016.05.052
31	王勇，杜明辉，张宁，等. α-Fe₂O₃催化臭氧氧化处理苯酚废水的效果及机理［J］. 环境科学研究，2022，35（8）：1818-1826.
	WANG Yong， DU Minghui， ZHANG Ning，et al. Degradation effect and mechanism of phenol wastewater by α-Fe₂O₃ catalytic ozone oxidation［J］. Research of Environmental Sciences，2022，35（8）：1818-1826.
32	LI Yu， WU Luchao， WANG Yun，et al. γ-Al₂O₃ doped with cerium to enhance electron transfer in catalytic ozonation of phenol［J］. Journal of Water Process Engineering，2020，36：101313. doi:10.1016/j.jwpe.2020.101313
33	DAI Qiguang， WANG Wei， WANG Xingyi，et al. Sandwich-structured CeO₂@ZSM-5 hybrid composites for catalytic oxidation of 1，2-dichloroethane：An integrated solution to coking and chlorine poisoning deactivation［J］. Applied Catalysis B：Environmental，2017，203：31-42. doi:10.1016/j.apcatb.2016.10.009
34	AFZAL S， QUAN Xie， LU Sen. Catalytic performance and an insight into the mechanism of CeO₂ nanocrystals with different exposed facets in catalytic ozonation of p-nitrophenol［J］. Applied Catalysis B：Environmental，2019，248：526-537. doi:10.1016/j.apcatb.2019.02.010
35	GUZMÁN I C， RODRÍGUEZ J L， POZNYAK T，et al. Catalytic ozonation of 4-chlorophenol and 4-phenolsulfonic acid by CeO₂ films［J］. Catalysis Communications，2020，133：105827. doi:10.1016/j.catcom.2019.105827
36	NAGAPPA B， CHANDRAPPA G T. Mesoporous nanocrystalline magnesium oxide for environmental remediation［J］. Microporous and Mesoporous Materials，2007，106（1/2/3）：212-218. doi:10.1016/j.micromeso.2007.02.052
37	DU Lei， LI Pengyang， GAO Wenqiang，et al. Enhancement degradation of formaldehyde by MgO/γ-Al₂O₃ catalyzed O₃/H₂O₂ in a rotating packed bed［J］. Journal of the Taiwan Institute of Chemical Engineers，2021，118：29-37. doi:10.1016/j.jtice.2021.01.011
38	WANG Bing， XIONG Xingaoyuan， REN Hongyang，et al. Preparation of MgO nanocrystals and catalytic mechanism on phenol ozonation［J］. RSC Advances，2017，7（69）：43464-43473. doi:10.1039/c7ra07553g
39	CHEN Jun， TIAN Shuanghong， LU Jiang，et al. Catalytic performance of MgO with different exposed crystal facets towards the ozonation of 4-chlorophenol［J］. Applied Catalysis A：General，2015，506：118-125. doi:10.1016/j.apcata.2015.09.001
40	OH S Y， NGUYEN T H A. Ozonation of phenol in the presence of biochar and carbonaceous materials：The effect of surface functional groups and graphitic structure on the formation of reactive oxygen species［J］. Journal of Environmental Chemical Engineering，2022，10（2）：107386. doi:10.1016/j.jece.2022.107386
41	DONG Yuming， YANG Hongxiao， HE Kun，et al. β-MnO₂ nanowires：A novel ozonation catalyst for water treatment［J］. Applied Catalysis B：Environmental，2009，85（3/4）：155-161. doi:10.1016/j.apcatb.2008.07.007
42	GUZMÁN I C， RODRÍGUEZ S J L， POZNYAK T，et al. Effect of sulphate and chloride ions on the oxidation of phenolic compounds by ozonation catalyzed with CeO₂ ［J］. Ozone：Science & Engineering，2021，43（6）：592-605. doi:10.1080/01919512.2021.1892475
43	ZHANG Jingwen， SHAO Shengjuan， DING Xin，et al. Removal of phenol from wastewater by high-gravity intensified heterogeneous catalytic ozonation with activated carbon［J］. Environmental Science and Pollution Research，2022，29（23）：34830-34840. doi:10.1007/s11356-021-18093-y
44	董玉明，蒋平平，张爱民. 介孔结构的α-FeOOH对苯酚的催化臭氧化降解［J］. 无机化学学报，2009，25（9）：1595-1600. doi:10.3321/j.issn:1001-4861.2009.09.014
	DONG Yuming， JIANG Pingping， ZHANG Aimin. Catalytic ozonation degradation of phenol in water by mesoporous α-FeOOH［J］. Chinese Journal of Inorganic Chemistry，2009，25（9）：1595-1600. doi:10.3321/j.issn:1001-4861.2009.09.014
45	LI Yangyang， ZHANG Yunshang， QIAN Kun，et al. Metal-support interactions in metal/oxide catalysts and oxide-metal interactions in oxide/metal inverse catalysts［J］. ACS Catalysis，2022，12（2）：1268-1287. doi:10.1021/acscatal.1c04854
46	KEYKAVOOS R， MANKIDY R， MA H，et al. Mineralization of bisphenol A by catalytic ozonation over alumina［J］. Separation and Purification Technology，2013，107：310-317. doi:10.1016/j.seppur.2013.01.050
47	DAI Qizhou， WANG Jiayu， CHEN Jun，et al. Ozonation catalyzed by cerium supported on activated carbon for the degradation of typical pharmaceutical wastewater［J］. Separation and Purification Technology，2014，127：112-120. doi:10.1016/j.seppur.2014.01.032
48	YU Li， HAN Peiwei， JIN Haibo，et al. Catalytic ozonation of three isomeric cresols in the presence of NaCl with nano-mesoporous β-molecular sieves［J］. Process Safety and Environmental Protection，2019，129：63-73. doi:10.1016/j.psep.2019.06.020
49	WEI Kajia， WANG Zhuo， OUYANG Changpei，et al. A hybrid fluidized-bed reactor（HFBR） based on arrayed ceramic membranes（ACMs） coupled with powdered activated carbon（PAC） for efficient catalytic ozonation：A comprehensive study on a pilot scale［J］. Water Research，2020，173：115536. doi:10.1016/j.watres.2020.115536
50	周云瑞，祝万鹏，刘福东，等. Al₂O₃催化剂结构对催化臭氧化活性的影响［J］. 化学学报，2006，64（9）：889-893. doi:10.3321/j.issn:0567-7351.2006.09.012
	ZHOU YunRui， ZHU WanPeng， LIU Fudong WANG，et al. Effect of alumina structure on catalytic ozonation activity［J］. Acta Chimica Sinica，2006，64（9）：889-893. doi:10.3321/j.issn:0567-7351.2006.09.012
51	MARTINS R C， QUINTA-FERREIRA R M. Manganese-based catalysts for the catalytic remediation of phenolic acids by ozone［J］. Ozone：Science & Engineering，2009，31（5）：402-411. doi:10.1080/01919510903170393
52	ZHANG Jingwen， GUO Qiang， WU Wenli，et al. Preparation of Fe-MnO _x /AC by high gravity method for heterogeneous catalytic ozonation of phenolic wastewater［J］. Chemical Engineering Science，2022，255：117667. doi:10.1016/j.ces.2022.117667
53	ZHOU Lilong， ZHANG Shanshan， LI Zhengjie，et al. Efficient degradation of phenol in aqueous solution by catalytic ozonation over MgO/AC［J］. Journal of Water Process Engineering，2020，36：101168. doi:10.1016/j.jwpe.2020.101168
54	LI Siyang， ZHAN Shujuan， SUN Jingxiang，et al. Enhanced ozonation of pollutants by MgO nanoclusters/sewage sludge-derived hierarchical porous carbon：Experimental and theoretical study［J］. Environmental Science：Nano，2021，8（9）：2569-2583. doi:10.1039/d1en00481f
55	AMIN N A S， AKHTAR J， RAI H K. Catalytic ozonation of aqueous phenol over metal-loaded HZSM-5［J］. Water Science and Technology，2011，63（8）：1651-1656. doi:10.2166/wst.2011.313
56	崔福旭，张晶，张波，等. 金属负载ZSM-5分子筛催化臭氧化苯酚废水［J］. 辽宁石油化工大学学报，2019，39（2）：10-14. doi:10.3969/j.issn.1672-6952.2019.02.002
	CUI Fuxu， ZHANG Jing， ZHANG Bo，et al. Metal-loaded ZSM-5 molecular sieve catalyzed ozonation of phenol wastewater［J］. Journal of Liaoning Shihua University，2019，39（2）：10-14. doi:10.3969/j.issn.1672-6952.2019.02.002
57	王勇，张耀宗，毕莹莹，等. α-Fe₂O₃催化臭氧氧化耦合陶瓷膜处理含酚废水［J］. 环境工程技术学报，2023，13（1）：232-239.
	WANG Yong， ZHANG Yaozong， BI Yingying，et al. α-Fe₂O₃ catalytic ozonation coupled with ceramic membrane for phenol wastewater treatment［J］. Journal of Environmental Engineering Technology，2023，13（1）：232-239.
58	LEE Wen jie， BAO Yueping， HU Xiao，et al. Hybrid catalytic ozonation-membrane filtration process with CeO _x and MnO _x impregnated catalytic ceramic membranes for micropollutants degradation［J］. Chemical Engineering Journal，2019，378：121670. doi:10.1016/j.cej.2019.05.031
59	NAWAZ F， XIE Yongbing， XIAO Jiadong，et al. Insights into the mechanism of phenolic mixture degradation by catalytic ozonation with a mesoporous Fe₃O₄/MnO₂ composite［J］. RSC Advances，2016，6（35）：29674-29684. doi:10.1039/c6ra03167f
60	SHAHAMAT Y D， FARZADKIA M， NASSERI S，et al. Magnetic heterogeneous catalytic ozonation：A new removal method for phenol in industrial wastewater［J］. Journal of Environmental Health Science and Engineering，2014，12（1）：50. doi:10.1186/2052-336x-12-50
61	WANG Jing， QUAN Xie， CHEN Shuo，et al. Enhanced catalytic ozonation by highly dispersed CeO₂ on carbon nanotubes for mineralization of organic pollutants［J］. Journal of Hazardous Materials，2019，368：621-629. doi:10.1016/j.jhazmat.2019.01.095
62	OPUTU O， CHOWDHURY M， NYAMAYARO K，et al. A novel β-FeOOH/NiO composite material as a potential catalyst for catalytic ozonation degradation of 4-chlorophenol［J］. RSC Advances，2015，5（73）：59513-59521. doi:10.1039/c5ra09177b
63	张兰河，郭琳，李佳宁，等. Fe₂O₃/改性沸石催化剂的制备及其催化臭氧氧化对氯苯酚［J］. 化工进展，2020，39（8）：3086-3094. doi:10.16085/j.issn.1000-6613.2019-1735
	ZHANG Lanhe， GUO Lin， LI Jianing，et al. Preparation of Fe₂O₃/modified natural zeolite catalyst and mechanism study on catalytic ozonation of 4-chlorophenol［J］. Chemical Industry and Engineering Progress，2020，39（8）：3086-3094. doi:10.16085/j.issn.1000-6613.2019-1735
64	ZHANG Jie， DONG Ben， LIU Jing，et al. The role of Mn doping on Ce-based γ-Al₂O₃ catalysts for phenol degradation［J］. Environmental Engineering Science，2022，39（1）：56-63. doi:10.1089/ees.2020.0494
65	LIU Yanfang， LI Guixia， ZHANG Zhili，et al. Catalytic ozonation of bisphenol A in aqueous medium by Mn-Fe/Al₂O₃ catalyst［J］. Journal of Advanced Oxidation Technologies，2016，19（2）：358-365. doi:10.1515/jaots-2016-0220
66	ZHANG Manning， YIN Dulin， GUO Jinjin，et al. Ternary catalyst Mn-Fe-Ce/Al₂O₃ for the ozonation of phenol pollutant：Performance and mechanism［J］. Environmental Science and Pollution Research，2021，28（25）：32921-32932. doi:10.1007/s11356-021-13006-5
67	JOTHINATHAN L， CAI Q Q， ONG S L，et al. Fe-Mn doped powdered activated carbon pellet as ozone catalyst for cost-effective phenolic wastewater treatment：Mechanism studies and phenol by-products elimination［J］. Journal of Hazardous Materials，2022，424：127483. doi:10.1016/j.jhazmat.2021.127483
68	YANG Yunlong， SHI Xianwei， ZHAO Min，et al. Heterogeneous catalytic ozonation of phenol by a novel binary catalyst of Fe-Ni/MAC［J］. Catalysts，2020，10（10）：1123. doi:10.3390/catal10101123
69	徐增益，余金鹏，郝敏，等. Co-Fe/ZSM-5催化臭氧化降解废水中苯酚的性能研究［J］. 肥料与健康，2020，47（6）：39-45. doi:10.3969/j.issn.2096-7047.2020.06.009
	XU Zengyi， YU Jinpeng， HAO Min，et al. Study on the performance of Co-Fe/ZSM-5 catalytic ozonation to degrade phenol in wastewater［J］. Fertilizer & Health，2020，47（6）：39-45. doi:10.3969/j.issn.2096-7047.2020.06.009
70	徐增益，余金鹏，李森，等. Zn-Co/ZSM-5催化臭氧氧化处理精细化工废水［J］. 化工环保，2021，41（5）：589-594. doi:10.3969/j.issn.1006-1878.2021.05.008
	XU Zengyi， YU Jinpeng， LI Sen，et al. Treatment of fine chemical wastewater by catalytic ozonation with Zn-Co/ZSM-5［J］. Environmental Protection of Chemical Industry，2021，41（5）：589-594. doi:10.3969/j.issn.1006-1878.2021.05.008
71	ZHAO Kanghe， MA Yulong， LIN Feng，et al. Refractory organic compounds in coal chemical wastewater treatment by catalytic ozonation using Mn-Cu-Ce/Al₂O₃ ［J］. Environmental Science and Pollution Research，2021，28（30）：41504-41515. doi:10.1007/s11356-021-13629-8
72	SHAO Shengjuan， LI Zhixing， ZHANG Jingwen，et al. Preparation of Ce-MnO _x /γ-Al₂O₃ by high gravity-assisted impregnation method for efficient catalytic ozonation［J］. Chemical Engineering Science，2022，248：117246. doi:10.1016/j.ces.2021.117246
73	MARTINS R C， QUINTA-FERREIRA R M. Catalytic ozonation of phenolic acids over a Mn-Ce-O catalyst［J］. Applied Catalysis B：Environmental，2009，90（1/2）：268-277. doi:10.1016/j.apcatb.2009.03.023
74	MA Dingren， LIU Weiqi， HUANG Yajing，et al. Enhanced catalytic ozonation for eliminating CH₃SH via stable and circular electronic metal-support interactions of Si—O—Mn bonds with low Mn loading［J］. Environmental Science & Technology，2022，56（6）：3678-3688. doi:10.1021/acs.est.1c07065
75	KUANG Panyong， WANG Yaru， ZHU Bicheng，et al. Pt single atoms supported on N-doped mesoporous hollow carbon spheres with enhanced electrocatalytic H₂-evolution activity［J］. Advanced Materials，2021，33（18）：e2008599. doi:10.1002/adma.202008599
76	NAWAZ F， XIE Yongbing， XIAO Jiadong，et al. The influence of the substituent on the phenol oxidation rate and reactive species in cubic MnO₂ catalytic ozonation［J］. Catalysis Science & Technology，2016，6（21）：7875-7884. doi:10.1039/c6cy01542e
77	YANG Wenwen， LU Zheng， VOGLER B，et al. Enhancement of copper catalyst stability for catalytic ozonation in water treatment using ALD overcoating［J］. ACS Applied Materials & Interfaces，2018，10（50）：43323-43326. doi:10.1021/acsami.8b18299
78	楚天成，纪相宇，李小雨，等. Mn-Ce/C-Al₂O₃催化剂制备及其处理含苯酚废水研究［J］. 能源环境保护，2021，35（5）：29-36. doi:10.3969/j.issn.1006-8759.2021.05.005
	CHU Tiancheng， JI Xiangyu， LI Xiaoyu，et al. Preparation of Mn-Ce/C-Al₂O₃ catalyst and its application in phenol wastewater treatment［J］. Energy Environmental Protection，2021，35（5）：29-36. doi:10.3969/j.issn.1006-8759.2021.05.005

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%

选择文件类型/文献管理软件名称

选择包含的内容