混合金属氧化物在废水处理中的应用研究综述

朱巧灵; 赵晓丹; 刘成瑞; 王正江; 蓝紫薇; 周振

doi:10.13801/j.cnki.fhclxb.20221005.001

混合金属氧化物在废水处理中的应用研究综述

doi: 10.13801/j.cnki.fhclxb.20221005.001

1.
上海电力大学　环境与化学工程学院，上海 201306
2.
西安西热水务环保有限公司，西安 710054
3.
中国电力工程顾问集团华东电力设计院有限公司，上海 200063

基金项目: 国家自然科学基金(51878403)；上海市曙光计划项目(19SG49)

详细信息

通讯作者:
赵晓丹，博士，副教授，硕士生导师，研究方向为水处理技术　E-mail: zhaoxiaodan@shiep.edu.cn

中图分类号: TB331
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出版历程
- 收稿日期: 2022-08-08
- 修回日期: 2022-09-07
- 录用日期: 2022-09-17
- 网络出版日期: 2022-10-09
- 刊出日期: 2023-06-15

Recent development and application of mixed metal oxides in wastewater treatment: A review

1.
College of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 201306, China
2.
Xi’an TPRI Water Treatment & Environmental Protection CO., LTD., Xi’an 710054, China
3.
East China Electric Power Design Institute CO., LTD., of China Power Engineering Consulting Group, Shanghai 200063, China

Funds: National Natural Science Foundation of China (51878403); Dawn Program of Shanghai Education Commission (19SG49)

摘要

摘要: 混合金属氧化物(Mixed metal oxide，MMO)，即一种以上金属的氧化物，因其在水中结构的独特变化，能展现出较强的吸附性能和催化活性，在废水处理方面具有极大应用潜力。本文综述了MMO的制备方法，主要可分为固相烧结法、聚合物前驱体焙烧法、层状双金属氢氧化物(Layered double hydroxides，LDHs)前驱体焙烧法、化学共沉淀法和水热法5种，并详细介绍了通过改变这些合成方法与合成条件实现的MMO元素组成、元素比例、形貌结构等的控制，以调控其性质性能。系统分析了MMO在去除重金属、类金属、有机污染物和阴离子方面的主要机制及研究进展，其中主要机制为在MMO结构重组过程中，伴随有吸附、催化及其协同作用。得益于这3种机制MMO不仅能实现单一污染物的高效脱除，还能实现多污染物的同步去除，在废水处理方面有着显著成效，但目前大多数研究仍停留在实验阶段，在实际废水处理及工程应用上的研究尚少。
- 混合金属氧化物(MMO) /
- 废水处理 /
- 重金属 /
- 有机污染物 /
- 阴离子
Abstract: Mixed metal oxides (MMO) containing more than one type of metal, have shown great application potential to be adsorbents and catalysts due to their unique structural changes in water. Therefore, they have great potential in wastewater treatment. In this paper, the preparation methods of MMO are described, including solid-phase sintering, polymeric precursor calcination, layered double hydroxides precursor calcination, chemical coprecipitation and hydrothermal methods, and control methods of the element composition, element proportion, and structure of MMO to regulate their properties by changing these synthesis methods and conditions are introduced in detail. The main mechanisms of MMO in the removal of heavy metals, metalloids, organic pollutants and anionic are comprehensively analyzed which can be summarized as: in the process of structural reorganization of MMO, adsorption, catalysis and their synergy are accompanied. MMO can not only remove single pollutants efficiently, but also remove multiple pollutants simultaneously due to these three effects, so MMO have significant effects in effluent treatment, but at present most of the research is still at the experimental stage, and there are few studies on effluent treatment and engineering applications.
- mixed metal oxide /
- wastewater treatment /
- heavy metals /
- organic pollutants /
- anionic

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图 1 MMO的结构记忆效应

Figure 1. Structure memory effect of MMO

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图 2 MMO去除的重金属主要机制

Figure 2. Removal mechanism of heavy metal by MMO

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图 3 FeCu-MMO对As的光催化氧化及吸附机制

Figure 3. Photocatalytic oxidation and adsorption mechanism of As removal by FeCu-MMO

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图 4 FeMn-MMO催化降解水中三氯乙烯的反应机制

Figure 4. Reaction mechanism of catalytic degradation of trichloroethylene in water by FeMn-MMO

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图 5 钙铝石对水中阴离子的去除机制

Figure 5. Removal mechanism of anions in water by mayenite

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表 1 混合金属氧化物(MMO)的不同制备方法及条件

Table 1. Different preparation methods and conditions of mixed metal oxide (MMO)

Synthetic method	MMO	Raw material	pH	Other conditions	Calcination temperature/℃	Preparation time/h	Ref.
Solid-phase sintering	CaAl-MMO	CaO, Al₂O₃	—	—	1200	4-5	[15]
Polymer precursor calcination method	ZnAlNiZr-MMO	Zn(NO₃)₂·6H₂O, Al(NO₃)₃·9H₂O, Ni(NO₃)₂·6H₂O, Zr(NO₃)₄·5H₂O, C₆H₈O₇·H₂O, HOCH₂CH₂OH	—	Stir at 60-70℃, stir at 80- 90℃ and heat treat at 300℃	550	18-24	[16]
Polymer precursor calcination method	CoCu-MMO	Co(NO₃)₂·6H₂O, Cu(NO₃)₂·3H₂O, C₆H₈O₇·H₂O, CH₃CH₂OH	—	Stir at normal atmospheric temperature and heat to 80℃	500	53-55	[17]
LDHs precursor calcination method	MgAl-MMO	Mg(NO₃)₂·6H₂O, Al(NO₃)₃·9H₂O, NaOH, Na₂CO₃	9.0	Refluxing crystallization	500	13-15	[18]
LDHs precursor calcination method	CoCr-MMO	Co(NO₃)₂·6H₂O, Cr(NO₃)₃·9H₂O, NaOH, Na₂CO₃	9.0	Age at 80℃ for 24 h, stir, 60℃ drying	400	40-42	[19]
Chemical coprecipitation	FeSn-MMO	Na₂SnO₃, FeCl₃, NaOH	5.3	Stir, precipitate, 70℃ drying	250	11-13	[20]
Chemical coprecipitation	FeZr-MMO	Zr(SO₄)₂·4H₂O, FeSO₄·7H₂O, NaOH	7.5	Stir, precipitate, aging, 65℃ drying	—	—	[21]
Hydrothermal method	SbMo-MMO	SbCl₃, NaMoO₆·2H₂O, CH₃CH₂OH	—	Magnetic stir, pressure cooker 180℃ for 24 h	—	>24	[22]
Note: LDHs—Layered double hydroxides.

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表 2 MMO处理水中污染物的应用

Table 2. Application of MMO in the wastewater treatment

Contaminant	MMO	Application	Adsorption capacity/(mg·g⁻¹)	Removal efficiency/%	Mechanism	Ref.
Heavy metal	ZnSn-MMO	Cu²⁺, Pb²⁺, Zn²⁺	38.9, 117.2, 29.1	—	Surface complexation and adsorption	[50]
	FeMn-MMO	Pb²⁺	108.1	—	Surface complexation and adsorption	[51]
	MgAl-MMO	Cd²⁺, Pb²⁺	386.1, 359.7	—	Surface complexation and adsorption	[52]
	FeZr-MMO	Cr(Ⅵ)	59.9	—	Reorganization and surface adsorption	[53]
	MgAl-MMO	Cr(Ⅵ)	94.6	—	Reorganization and surface adsorption	[54]
Metalloid	FeZr-MMO	Se(IV)	277.0	—	Reorganization and surface adsorption	[55]
	MgAl₂O₄	Se(IV)	179.6	—	Reorganization and surface adsorption	[49]
	FeZr-MMO	Sb(V)	51.0	—	Reorganization and surface adsorption	[21]
	FeMn-MMO	Sb(V)	95.0	—	Reorganization and surface adsorption	[37]
	FeMn-MMO	As(V)	132.8	—	Reorganization and surface adsorption	[56]
	FeAl-MMO	As(III)	314.9	>99.0	Catalysis and adsorption	[57]
	CuFe-MMO	As(III)	118.1	—	Catalysis and adsorption	[58]
Organic pollutants	FeMn-MMO	TCE	—	100	Catalysis	[59]
	NiCo₂O₄	AP	—	99.5	Catalysis	[60]
	CoNi-MMO	PR	—	70.0	Adsorption	[61]
	FeMn-MMO	RBK5	—	88.0	Catalysis	[62]
	1D ZnO-ZnFe₂O₄	CR	263.0	—	Adsorption	[13]
	Nd-CoAl-MMO	AR	—	100	Catalysis	[63]
Halogen ion	MgAl-MMO	Br^–, I^–	362.3	—	Reorganization and surface adsorption	[47]
	MgZr-MMO	F^–	144.1	—	Reorganization and surface adsorption	[64]
	LaZr-MMO	F^–	—	97.0	Reorganization and surface adsorption	[65]
	CaAl-MMO	Cl^–	105.9, 96.0	—	Reorganization and surface adsorption	[15]
Oxyanion	ZnAl−MMO	SO₄^2–	62.5	—	Reorganization and surface adsorption	[66]
	CeAl-MMO	PO₄^3–	70.4	—	Reorganization and surface adsorption	[67]
	CeAl-MMO	PO₄^3–	249.3	—	Reorganization and surface adsorption	[68]
Other anions	MgAl-MMO	S^2–	—	82.0	Reorganization and surface adsorption	[69]
Notes: TCE—Trichloroethylene; AP—4−acetaminophenol; PR—Procion red; RBK5—Reactive black 5; CR—Congo red; AR14—Acid red 14.

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