灰岩基缓释材料原位注入修复酸性矿山废水模拟研究

高旭波; 李鸿煜; 龚培俐; 张兴周; 方健聪

doi:10.19509/j.cnki.dzkq.2022.0221

灰岩基缓释材料原位注入修复酸性矿山废水模拟研究

doi: 10.19509/j.cnki.dzkq.2022.0221

中国地质大学(武汉)环境学院，武汉 430078

基金项目:

国家自然科学基金项目 42172288

详细信息

作者简介:
高旭波(1975—), 男，研究员，主要从事岩溶及地下水水资源与水环境污染防治工作。E-mail: Xubo.gao.cug@gmail.com

中图分类号: X141
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出版历程
- 收稿日期: 2022-07-26
- 网络出版日期: 2022-11-10

Simulation study on remediation of acid mine drainage by in-situ injection of limestone based sustained release materials

School of Environmental Studies, China University of Geosciences(Wuhan), Wuhan 430078, China

摘要

摘要:
我国岩溶区分布面积广，生态环境脆弱。岩溶区大量矿山开采活动产生的酸性矿山废水(AMD)严重威胁着区域生态环境安全。以岩溶区广泛分布的碳酸盐岩和玉米棒(生物质炭)等为原料，通过改性、造粒、覆膜的方式制备了一种可用于原位注入修复的碱基缓释材料(ASRM)，并在室内模拟开展了丰水和枯水交替作用下的原位注入修复实验，以验证和查明ASRM原位修复酸性矿井废水中重金属的能力及去除机制。研究结果表明，碱基缓释材料(ASRM)可有效提高水体pH值，酸性矿山废水(AMD)修复后pH值从2.8提高到5~7，并对Fe²⁺, Mn²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Pb²⁺和Cr³⁺等多种有害重金属有良好去除效果。XRD和SEM分析证明，反应沉淀物主要以FeOOH的形式存在。重金属的去除机制主要包括：①部分金属离子被以反应产生的氢氧化物等沉淀的形式去除；②反应体系产生的大量FeOOH可以吸附去除重金属。本模拟实验研究为利用缓释材料原位高效处理岩溶山区矿山AMD提供了可靠的理论和技术依据。
- 缓释材料 /
- 岩溶山区 /
- 酸性矿山废水 /
- 原位注入修复 /
- 重金属
Abstract:
The karst area is widely distributed in China, and the ecological environment is fragile. Acid mine drainage (AMD) produced by mining activities in karst areas seriously threatens the safety of regional ecological environment. In this paper, carbonate rocks and corn cobs (biochar) widely distributed in karst areas were used as raw materials, and an alkaline sustained release material (ASRM) that could be used for in-situ injection and repair was prepared by means of modification, granulation and film coating. In addition, in-situ injection and repair experiments under alternating effects of wet and dry conditions were carried out in the laboratory, to verify and determine the ability and removal mechanism of ASRM in the in-situ remediation of heavy metals in acid mine wastewater. The results showed that ASRM can effectively improve the pH of water, and the pH of AMD can be increased from 2.8 to approximately 5-7, and it had a good removal effect on many harmful heavy metals, such as Fe²⁺, Mn²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Pb²⁺ and Cr³⁺. XRD and SEM analyses showed that the reaction precipitates mainly existed in the form of FeOOH. The removal mechanism of heavy metals mainly includes: ①some metal ions were removed in the form of precipitation, such as hydroxides produced by the reaction; ②a large amount of FeOOH produced by the reaction system can adsorb and remove heavy metals. This experimental study provides a reliable theoretical and technical basis for the in-situ treatment of AMD in karst mountain mines with high efficiency by using slow-release materials.
- sustained release materials /
- karst mountainous area /
- acid mine drainage(AMD) /
- in-situ injection /
- heavy metal

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图 1 原位注入修复模拟装置图(a)和原位注入工程理论应用效果图(b)

Figure 1. Diagram of the in-situ injection and repair simulation device (a) and effect of the in-situ injection engineering application (b)

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图 2 AMD出水pH及Fe、Mn质量浓度变化

Figure 2. Changes of pH and Fe and Mn concentrations in outflow AMD

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图 3 Fe-Eh-pH(a)和Mn-Eh-pH(b)

Figure 3. Fe-Eh-pH(a) and Mn-Eh-pH(b)

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图 4 AMD出水Zn，Cu，Cd，Pb，Cr质量浓度变化

Figure 4. Changes of Zn, Cu, Cd, Pb and Cr concentration in outflow AMD

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图 5 AMD出水Ca²⁺, Mg²⁺质量浓度变化

Figure 5. Changes of Ca²⁺ and Mg²⁺ concentration in outflow AMD

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图 6 ASRM反应沉积物XRD图

Figure 6. XRD diagram of ASRM reaction sediments

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图 7 ASRM反应沉积物SEM-EDS图

Figure 7. SEM-EDS diagram of ASRM reaction sediments

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表 1 模拟酸性矿山废水水质指标(pH=2.8)

Table 1. Water quality index of simulated acid coal mine wastewater (pH=2.8)

成分	模拟AMD质量浓度/(mg·L^-1)	配置药品	天然AMD质量浓度/(mg·L^-1)
Fe²⁺	180	FeSO₄·7H₂O	100~830
Mn²⁺	70	MnCl₂·4H₂O	0.3~160
Zn²⁺	13.8	ZnCl₂	0.1~22
Cu²⁺	30	CuCl₂·2H₂O	0.01~50
Cd²⁺	0.5	CdCl₂	0.1~5
Pb²⁺	1.5	PbCl₂	0.1~30
Cr³⁺	1.2	CrCl₃·6H₂O	0.1~5

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