吸附法去除矿井水中F<sup>−</sup>研究进展

唐佳伟; 张锁; 刘兆峰; 张海琴; 包一翔; 侯福林; 郭强; 曹志国; 李井峰

doi:10.13199/j.cnki.cst.2022-1835

吸附法去除矿井水中F⁻研究进展

唐佳伟^{1, 2,},
张锁³,
刘兆峰^{1, 2},
张海琴^{1, 2},
包一翔^{1, 2},
侯福林³,
郭强^{1, 2},
曹志国^{1, 2},
李井峰¹

1.
国家能源集团煤炭开采水资源保护与利用全国重点实验室, 北京　102211
2.
北京低碳清洁能源研究院, 北京　102211
3.
神华新街能源有限责任公司, 内蒙古鄂尔多斯　017200

基金项目:

国家能源集团科技创新资助项目（GJNY-21-129）；煤炭开采水资源保护与利用全国重点实验室自主研发资助项目（SHGF-16-20）

详细信息

作者简介:
唐佳伟: （1992—），男，北京人，工程师，博士。Tel：010-57337332，E-mail：20062356@ceic.com

中图分类号: X752
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出版历程
- 收稿日期: 2022-11-02
- 网络出版日期: 2023-05-16
- 刊出日期: 2023-05-30

Research progress in the removal of fluoride ions from mine water by adsorption method

TANG Jiawei^{1, 2,},
ZHANG Suo³,
LIU Zhaofeng^{1, 2},
ZHANG Haiqin^{1, 2},
BAO Yixiang^{1, 2},
HOU Fulin³,
GUO Qiang^{1, 2},
CAO Zhiguo^{1, 2},
LI Jingfeng¹

1.
State Key Laboratory of Water Resource Protection and Utilization in Coal Mining, Beijing 102211, China
2.
National Institute of Low Carbon and Clean Energy, Beijing 102211, China
3.
Shenhua Group Xinjie Energy Co., Ltd., Ordos 017200, China

Funds:

Technology Project of China Energy (GJNY-21-129); Independent Research and Development Project of National Key Laboratory of Coal Mining Water Resources Protection and Utilization (SHGF-16-20)

摘要

摘要:
氟离子广泛分布于我国的地表河流与地下水体中，尤其是在西部黄河流域的沿黄矿区，矿井水中普遍存在着氟超标的问题，对当地生态环境和人体健康造成潜在的威胁。我国的氟污染现状多处于低浓度污染水平，常规水处理技术难以有效去除。吸附法凭借其吸附效率高、操作便捷等优点被认为是去除低浓度氟离子的有效方法。综述了目前常用的炭基、矿物类、金属类及金属有机骨架类（MOFs）吸附材料去除氟离子的研究现状，归纳并总结了不同因素对吸附材料的除氟效率和吸附机理的影响。重点分析了吸附法在矿井水处理的应用效果与运行成本，展望了吸附法应用低浓度（<10 mg/L）、大水量的含氟矿井水处理中的发展方向。总体而言，针对吸附法去除氟离子的研究中仍存在较大的改进空间。在吸附机理方面，应从吸附材料特性、氟离子的赋存形态和吸附材料与氟离子之间的相互作用机制等方面继续深入探究。而在吸附法应用方面，应以实际工程需求为导向，开发绿色安全的低成本吸附材料。基于上述研究，提出了吸附法除氟应用矿井水处理的研发方向，在明确当地政策及水质水量的原则下，重点开发以天然/废弃（矿）物和炭基、铝基或其他新型高分子吸附材料为基础的低成本、高效率的环境友好型改性吸附剂。并保证吸附材料在制备加工、投产应用以及循环再生的全生命周期的稳定性、经济性与安全性，从而提高吸附法在实际含氟废水应用的竞争力，提升吸附法的应用潜力。
- 矿井水处理 /
- 吸附法 /
- 氟离子 /
- 吸附机理 /
- 环境友好型改性吸附剂
Abstract:
Fluoride ions are widely distributed in surface rivers and groundwater bodies in China, especially in the mining areas along the Yellow River in the western Yellow River basin that there is a widespread problem of excessive fluoride in the mine water, which poses a potential threat to the local ecological environment and human health. The status quo of fluoride pollution in China is mostly at a low concentration pollution level, which leads to it difficult to remove efficiently through conventional water treatment technologies. The adsorption method is considered to be an effective way to remove low concentration fluoride ions because of its high adsorption efficiency and convenient operation. The research status of fluoride removal by commonly used adsorption materials such as carbon based, minerals, metals and metal organic frameworks (MOFs) was reviewed and summarized before summarizing the influence of different factors on the fluoride removal efficiency and adsorption mechanism of these adsorption materials. Then the application effect and operation cost of adsorption method in mine water treatment were emphatically analyzed, and the development direction of adsorption method in the treatment of low concentration (<10 mg/L) and high water content fluorine-containing mine water was prospected. In general, there are still some deficiencies in the study of fluoride removal by adsorption. In terms of adsorption mechanism, it should be further investigated from three aspects which includes the characteristics of adsorption materials, the occurrence form of fluoride ions and the interaction mechanism between adsorption materials and fluoride ions. For the engineering application of adsorption method, the demand of engineering application should be regarded as the guidance. Based on the above discussion, the research and development direction of removing fluoride ions from mine water by adsorption method is proposed, which is to focus on the development of low cost and high efficiency environment-friendly modified adsorbents based on natural/waste (ore) and carbon-based, aluminum-based or other new polymer adsorption materials under the principle of clarifying local policies and water quality and quantity. In addition, it is necessary not to improve the selective adsorption performance of the modified adsorbent for fluoride ions, but also to ensure the stability, economy and safety of the adsorbent in the whole life cycle of preparation, processing, production and recycling, thereby improving its competitiveness of the adsorption method in the actual application of fluoride containing wastewater and enhancing the application potential of the adsorption method.
- mine water treatment /
- adsorption method /
- fluoride ion /
- adsorption mechanism /
- environmentally friendly modified adsorbent

HTML全文

图 1 镧改性活性炭中的镧固定机制及其除氟机理^[14]

Figure 1. The mechanism of lanthanum fixation and fluoride removal in lanthanum modified activated carbon^[14]

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图 2 Al₂O₃-Fe₃O₄-EG吸附剂制备过程及Cu₂O-RGO吸附剂循环除氟性能^[25,27]

Figure 2. Al₂O₃-Fe₃O₄-EG nano interlayer adsorbent and cyclic performance test of fluorine removal of Cu₂O-RGO^[25,27]

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图 3 CNT、HAP及CNT-HAP吸附剂的SEM图像及HA-MWCNTs吸附剂添加量对F⁻去除率影响^[27,32]

Figure 3. SEM images of CNT, HAP and CNT-HAP absorbents and the effect of HA-MWCNTs adsorbent addition on F⁻ removal effiency ^[27,32]

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图 4 FeZr改性天然沸石去除F⁻的性能分析^[33]

Figure 4. Performance analysis of FeZr modified natural zeolite for fluoride removal^[33]

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图 5 磷酸改性方解石的3种氟吸附机制示意^[48]

Figure 5. Schematic of three F adsorption mechanisms of phosphoric acid-modified calcite^[48]

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图 6 LC与Ce和F⁻吸附结合机制示意^[50]

Figure 6. Schematic of the mechanism of LC binding to Ce and F⁻ adsorption^[50]

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图 7 吸附法去除F⁻的吸附机理示意

Figure 7. Schematic of the adsorption mechanism for removal of fluoride by adsorption

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图 8 吸附法应用矿井水除氟技术发展前景

Figure 8. Development prospect of the application of adsorption method in the mine water fluoride removal technology

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表 1 常见吸附材料在实际废水中的应用效果^{[26,29,40,46,80,83-93]}

Table 1 Application effect of common adsorbent materials in actual wastewater^{[26,29,40,46,80,83-93]}

废水类别	F⁻初始质量浓度/ （mg·L⁻¹）	吸附材料	应用效果	参考文献	废水类别	F⁻初始质量浓度/ （mg·L⁻¹）	吸附材料	应用效果	参考文献
工业废水	550	氢氧化钙纳米棒	处理了高酸性电镀工业废水，可以达到99.27%的F⁻去除效率	[83]	工业废水	5	改性膨润土	处理了含氟矿井水，当吸附剂剂量为1 g/L时，去除率可以达到87.8%，氟化物浓度为0.63 mg/L	[90]
工业废水	148.2	铝土矿纳米复合材料	在高酸性铅锌冶炼废水中进行了评估，结果表明，当Cl⁻、SO₄ ²⁻浓度超过1 000 mg/L和其他重金属（Zn、Pb和Mn）共存时，初始F⁻的吸附量也能达到80 mg/g	[84]	工业废水	5	辉沸石	处理了埃塞俄比亚地区的高浓度含氟废水，去除率可以达到30%	[86]
工业废水	98.05	镧改性沸石	处理了工业硫酸锌废水，当吸附剂用量为15 g/L时，可以使初始F⁻浓度从98.05 mg/L降低至 44.09 mg/L	[80]	地下水	> 4000	AC/Al₂O₃ 复合材料	吸附容量和去除效率仅为0.48 mg/g和5.05%	[91]
工业废水	24.38	活性炭	处理了玻璃行业废水，除氟效率为66.11%	[85]	地下水	29.05	镧改性膨润土	处理了天然地下水，使F⁻浓度从29.05 mg/L降低至1.61 mg/L	[40]
工业废水	20.6	辉沸石	处理了埃塞俄比亚地区的高浓度含氟废水，去除率可以达到20%	[86]	地下水	4	AC-Al(OH)₃（AC由枣茎合成）	处理了地下水，可使F⁻浓度降低至0.98 mg/L	[92]
工业废水	20	改性沸石	处理了矿井水，氟化物去除率达72.7%	[87]	地下水	3.10	胺官能化GO	处理了实际地下水样品，使实际F⁻浓度从3.10 mg/L降低至1.24 mg/L	[26]
工业废水	11	活性炭	处理了造船行业废水，除氟效率为65.45%	[85]	地表水	3.29	壳基HAP吸附剂	当吸附剂剂量为6 g/L，吸附时间为12 h时，去除效率65%	[46]
工业废水	8.79	HA-MWCNTs	处理了兰州铀浓缩厂的实际废水，可使F⁻浓度由8.79 mg/L降低至 0.25 mg/L	[88]	饮用水	4.50	GO/纳米复合材料	F⁻浓度从4.50 mg/L降低至(0.202 ± 0.05) mg/L	[88]
工业废水	8.79	羟基磷灰石/多壁碳纳米管	处理了实际核工业废水，从8.79 mg/L降低至0.25 mg/L（去除率为97.15%）	[29]	饮用水	0.2～1.2	多壁碳纳米管	去除效率为 71.8%～83.3%	[93]
工业废水	7.59	沸石−锆粉	处理了玻璃工业废水，用沸石−锆粉在脉冲超声、连续超声和搅拌的模式下，分别使F⁻浓度降低至1.48、1.59和1.71 mg/L	[89]	饮用水	0.2～1.2	多壁碳纳米管	去除效率为 71.8%～83.3%	[93]

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表 2 除氟实际工程应用案例分析

Table 2 Practical engineering application of defluorination

来水水质	出水水质	吸附材料	工艺流程	工艺规模及成本分析	评价	参考文献
矿井水，C(F⁻)> 1 mg/L	C(F⁻) > 1 mg/L	活性氧化铝		总投资2 870.11万元，占地面积2 025 m²，运行成本1.959 元/t，再生成本0.825 3 元/t	易受水中HCO₃ ⁻的干扰，出水F⁻浓度难以达到《地表水环境质量标准》(GB3838—2002)Ⅲ类标准	[94]
矿井水，C(F⁻)> 1 mg/L	C(F⁻) < 1 mg/L	羟基磷灰石		总投资1 872.66万，占地面积1 055.25 m²，运行成本1.159 元/t，再生成本0.004 7 元/t	占地面积更小，一次性投资成本低，出水F⁻浓度可达到《地表水环境质量标准》(GB3838—2002)Ⅲ类标准	[94]
含氟矿井水，C(F⁻) > 8 mg/L，水量2万 m³/d	C(F⁻) < 1 mg/L	聚合氯化铝		单独使用聚合氯化铝，达标排放成本 2.6元/t	可能产生水中TDS 质量浓度超过1 000 mg /L	[95]
		羟基磷灰石		单独使用羟基磷灰石，达标排放成本3.39 元/t	羟基磷灰石吸附能力有限，可能造成水质波动时出水不达标的问题，需设置二级吸附系统
		聚合氯化铝+羟基磷灰石		聚合氯化铝+羟基磷灰石梯级联用，综合运行成本3.76 元/t	可避免过量加药导致的TDS显著增高和水质波动导致出水不达标的问题
矿井水，C(F⁻) >1 mg/L，水量 5 000 m³/d	C(F⁻) < 1 mg/L	高效碳基磷石灰石		全工艺综合运行成本1.5 元/t，其中需要配备除氟调酸系统、除氟再生系统、高氟废水化学预沉器、再生废水钙基化除氟加药装置等配套设施，一次投资费用较高		[5]

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