Research progress of combined materials applied in permeable reaction barrier technology

doi:10.19965/j.cnki.iwt.2021-1279

Abstract

Abstract:

Groundwater resources has been under serious threat due to their exposure to contaminants emanating from a variety of sources including agriculture，industries，and mines. Permeable reactive barrier（PRB） is an innovative technology for in-situ remediation of contaminated groundwater，the key of which is the choice of suitable reactive materials，such as widely applied zero valent iron（ZVI），carbon materials and zeolite. In this paper，the principle of PRB，types of reactive materials，and factors influencing the choice of reactive media，were introduced. Recent findings of combined materials containing iron，carbon and silicon（minerals） applied in PRB for the remediation of groundwater were reviewed， and the removal efficiency and mechanism of target pollutants in batch and column experiments were highlighted. Aggregation and passivation of ZVI could be solved to some extent in the combined materials by fixation，surface modification or mixing，and new interaction mechanisms might be introduced to facilitate the removal of pollutants. By means of modification or combination，removal potential of carbon- or silicon（minerals）-containing materials for specific pollutants could be enhanced. Finally，the future development and application of combined materials in PRB technology were prospected，collating references for development of long-term efficient and environmentally friendly PRB reactive materials.

Key words: groundwater contamination, permeable reactive barrier, combined materials, remediation

摘要：

因暴露于农业和工矿业等来源的各类污染物，地下水资源受到严重威胁。可渗透反应墙（Permeable reactive barrier，PRB）是一种地下水污染原位修复的创新技术，该技术的关键在于选取适宜的墙体反应介质，如广泛研究的零价铁（ZVI）、碳材料、沸石等。介绍了PRB技术的原理、介质材料类型与选取所需考虑的因素；回顾了含铁、含碳和含硅（矿物）组合材料应用于PRB修复地下水污染的研究进展，并聚焦了批量实验和柱试验中目标污染物的去除效果及作用机理。通过固定、表面修饰与混合等方式，组合材料在一定程度上可解决ZVI的聚集或表面钝化现象，并新增作用机制以助力污染物的去除；通过改性或混合等形式，组合材料还可增强含碳或含硅（矿物）材料对某些特定污染物的去除性能。最后，还展望了未来PRB技术中组合材料的开发和应用方向，以期为研发长效和环境友好型PRB反应介质提供参考。

关键词: 地下水污染, 可渗透反应墙, 组合材料, 修复

CLC Number:

X523

Liang LI, Jian XU. Research progress of combined materials applied in permeable reaction barrier technology[J]. Industrial Water Treatment, 2023, 43(2): 53-60.

李亮, 徐建. 组合材料应用于可渗透反应墙技术的研究进展[J]. 工业水处理, 2023, 43(2): 53-60.

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反应介质	优点	缺点	应用场景
ZVI	比表面积大、还原性强、可吸附和氧化（ZVI表面的氧化铁）污染物	易团聚或钝化、粒径小易导致堵塞	还原环境、低水压工况；最优条件为接近中性或微酸性的环境
碳质材料	比表面积大、多孔结构、官能团丰富、表面带电荷、可吸附和络合污染物	制备成本高、处理效率有限、机械强度弱	各种水力工况、低浓度污染物
矿物材料	多孔结构、机械强度良好、成本低、可维持水力传导率吸附；可与污染物发生离子交换（沸石）、沉淀（羟基磷灰石）、酸中和（石灰石）反应	处理效率有限、化学组分复杂、潜在二次污染、回收困难	各种水力工况、低浓度污染物、酸性条件

反应介质	优点	缺点	应用场景
ZVI	比表面积大、还原性强、可吸附和氧化（ZVI表面的氧化铁）污染物	易团聚或钝化、粒径小易导致堵塞	还原环境、低水压工况；最优条件为接近中性或微酸性的环境
碳质材料	比表面积大、多孔结构、官能团丰富、表面带电荷、可吸附和络合污染物	制备成本高、处理效率有限、机械强度弱	各种水力工况、低浓度污染物
矿物材料	多孔结构、机械强度良好、成本低、可维持水力传导率吸附；可与污染物发生离子交换（沸石）、沉淀（羟基磷灰石）、酸中和（石灰石）反应	处理效率有限、化学组分复杂、潜在二次污染、回收困难	各种水力工况、低浓度污染物、酸性条件

组合材料		污染物	去除效果	作用机理	参考文献
含铁材料	钠基沸石-nZVI	Cd	Cd吸附量20.6 mg/g	吸附	〔19〕
	柱撑膨润土-ZVI	Cr（Ⅵ）	柱撑膨润土和ZVI等比例均匀混合时，Cr（Ⅵ）去除率为100%维持了近100孔体积	还原、吸附、沉淀	〔20〕
	Cu/nZVI	磷	相较于nZVI，Cu/nZVI的除磷性能提升2.2倍	吸附、共沉淀	〔24〕
	黄铁矿-ZVI	Cr（Ⅵ）	黄铁矿与ZVI均匀混合时，Cr（Ⅵ）去除率可保持90%以上（50~100孔体积），高于ZVI（约30孔体积）	还原、共沉淀	〔26〕
	MnO₂/ZVI	四环素	相比单一ZVI，MnO₂/ZVI对四环素的去除率提高约20%	降解	〔27〕
	SiO₂/nano-FeC₂O₄	Cr（Ⅵ）	90 min后，Cr（Ⅵ）去除率为95.45%	还原、沉淀、表面络合	〔28〕
	活性炭/铸铁	Cr（Ⅵ）	Cr（Ⅵ）去除量为3.806 mg/g	还原、吸附、沉淀	〔29〕
含碳材料	ZVI/GAC	TCE	静态实验中TCE去除率为90%	还原、吸附	〔30〕
	ZVI/二甲基二氯硅烷-GAC	2，4-DCP	相比GAC，改性GAC/ZVI对2，4-DCP的吸附量提升20%	还原、吸附	〔31〕
	Fe-BC	As	Fe-BC对As（Ⅴ）的吸附量为6.80 mg/g；未改性BC为0.017 mg/g	吸附、静电吸引、沉淀	〔32〕
	ZVI/BC	TCE	在快流速和慢流速下，ZVI/BC对TCE的去除率分别为96%和99%	吸附、还原	〔33〕
	MnO₂/AC	As	MnO₂/AC对As（Ⅴ）和As（Ⅲ）的最大吸附量分别为13.30、12.56 mg/g	吸附、氧化	〔39〕
	磁性壳聚糖/BC	As	25 ℃，磁性壳聚糖/BC对As（Ⅴ）最大吸附量为14.928 mg/g	静电吸引、吸附	〔42〕
	La-BC	氟化物	25 ℃，pH=6.5，La-BC对氟化物的最大吸附量为19.86 mg/g	吸附、离子交换	〔43〕
	Cs-BC、Zn-BC和Zr-BC	钒（Ⅴ）	Cs-BC、Zn-BC和Zr-BC对钒（Ⅴ）的吸附量分别为41.07、28.46、23.84 mg/g	离子交换、沉淀、静电吸引	〔44〕
含硅（矿物）材料	堆肥-沸石	Pb（Ⅱ）	堆肥-沸石对Pb（Ⅱ）的最大吸附量为0.151 mg/g；单一沸石为0.097 mg/g	离子交换、吸附	〔49〕
	Fe²⁺-沸石	As（Ⅲ）	35 ℃，Fe²⁺-沸石对As（Ⅲ）的最大吸附量为15.64 mg/g	吸附	〔50〕
	HDTMA-沸石	VOCs和PAHs	HDTMA-沸石对对二甲苯的吸附量为6.82 mg/g，对二苯并［a，h］蒽的吸附量为0.65 mg/g	溶解、渗透	〔51〕
	氯硅烷-铵基沸石	甲苯	氯硅烷-铵基沸石对甲苯的吸附量为9.355 µmol/g	吸附	〔52〕
	CTMAB-膨润土	Cr（Ⅵ）	CTMAB-膨润土对Cr（Ⅵ）的吸附量为1.962 mg/g；天然膨润土为0.101 mg/g	吸附	〔53〕
	壳聚糖-膨润土	As（Ⅴ）	壳聚糖-膨润土对As（Ⅴ）的最大吸附量为1.47 mg/g	吸附	〔56〕

组合材料		污染物	去除效果	作用机理	参考文献
含铁材料	钠基沸石-nZVI	Cd	Cd吸附量20.6 mg/g	吸附	〔19〕
	柱撑膨润土-ZVI	Cr（Ⅵ）	柱撑膨润土和ZVI等比例均匀混合时，Cr（Ⅵ）去除率为100%维持了近100孔体积	还原、吸附、沉淀	〔20〕
	Cu/nZVI	磷	相较于nZVI，Cu/nZVI的除磷性能提升2.2倍	吸附、共沉淀	〔24〕
	黄铁矿-ZVI	Cr（Ⅵ）	黄铁矿与ZVI均匀混合时，Cr（Ⅵ）去除率可保持90%以上（50~100孔体积），高于ZVI（约30孔体积）	还原、共沉淀	〔26〕
	MnO₂/ZVI	四环素	相比单一ZVI，MnO₂/ZVI对四环素的去除率提高约20%	降解	〔27〕
	SiO₂/nano-FeC₂O₄	Cr（Ⅵ）	90 min后，Cr（Ⅵ）去除率为95.45%	还原、沉淀、表面络合	〔28〕
	活性炭/铸铁	Cr（Ⅵ）	Cr（Ⅵ）去除量为3.806 mg/g	还原、吸附、沉淀	〔29〕
含碳材料	ZVI/GAC	TCE	静态实验中TCE去除率为90%	还原、吸附	〔30〕
	ZVI/二甲基二氯硅烷-GAC	2，4-DCP	相比GAC，改性GAC/ZVI对2，4-DCP的吸附量提升20%	还原、吸附	〔31〕
	Fe-BC	As	Fe-BC对As（Ⅴ）的吸附量为6.80 mg/g；未改性BC为0.017 mg/g	吸附、静电吸引、沉淀	〔32〕
	ZVI/BC	TCE	在快流速和慢流速下，ZVI/BC对TCE的去除率分别为96%和99%	吸附、还原	〔33〕
	MnO₂/AC	As	MnO₂/AC对As（Ⅴ）和As（Ⅲ）的最大吸附量分别为13.30、12.56 mg/g	吸附、氧化	〔39〕
	磁性壳聚糖/BC	As	25 ℃，磁性壳聚糖/BC对As（Ⅴ）最大吸附量为14.928 mg/g	静电吸引、吸附	〔42〕
	La-BC	氟化物	25 ℃，pH=6.5，La-BC对氟化物的最大吸附量为19.86 mg/g	吸附、离子交换	〔43〕
	Cs-BC、Zn-BC和Zr-BC	钒（Ⅴ）	Cs-BC、Zn-BC和Zr-BC对钒（Ⅴ）的吸附量分别为41.07、28.46、23.84 mg/g	离子交换、沉淀、静电吸引	〔44〕
含硅（矿物）材料	堆肥-沸石	Pb（Ⅱ）	堆肥-沸石对Pb（Ⅱ）的最大吸附量为0.151 mg/g；单一沸石为0.097 mg/g	离子交换、吸附	〔49〕
	Fe²⁺-沸石	As（Ⅲ）	35 ℃，Fe²⁺-沸石对As（Ⅲ）的最大吸附量为15.64 mg/g	吸附	〔50〕
	HDTMA-沸石	VOCs和PAHs	HDTMA-沸石对对二甲苯的吸附量为6.82 mg/g，对二苯并［a，h］蒽的吸附量为0.65 mg/g	溶解、渗透	〔51〕
	氯硅烷-铵基沸石	甲苯	氯硅烷-铵基沸石对甲苯的吸附量为9.355 µmol/g	吸附	〔52〕
	CTMAB-膨润土	Cr（Ⅵ）	CTMAB-膨润土对Cr（Ⅵ）的吸附量为1.962 mg/g；天然膨润土为0.101 mg/g	吸附	〔53〕
	壳聚糖-膨润土	As（Ⅴ）	壳聚糖-膨润土对As（Ⅴ）的最大吸附量为1.47 mg/g	吸附	〔56〕

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