天然沸石对模拟尾矿渗滤液中重金属离子的静、动态吸附研究

杨兰; 李兆明; 梅乐夫; 吕国诚; 廖立兵

doi:10.13779/j.cnki.issn1001-0076.2024.01.016

天然沸石对模拟尾矿渗滤液中重金属离子的静、动态吸附研究

中国地质大学（北京）材料科学与工程学院，矿物材料国家专业实验室，非金属矿物与固废资源材料化利用北京市重点实验室，地质碳储与资源低碳利用教育部工程研究中心，北京 100083

基金项目: 国家自然科学基金重点项目（41831288）

详细信息

作者简介: 杨兰（1997—），女，硕士研究生，E-mail：18810890417@163.com

通讯作者: 梅乐夫（1978—），男，教授，E-mail：mlf@cugb.edu.cn; 廖立兵（1963—），男，教授， E-mail：clayl@cugb.edu.cn。

中图分类号: TD926；TD923

收稿日期: 2023-11-13

刊出日期: 2024-02-15

Study on the Static and Dynamic Adsorption of Heavy Metal Ions in Simulated Tailings Leachate by Natural Zeolite

Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences (Beijing), Beijing 100083, China

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Corresponding authors: MEI Lefu, mlf@cugb.edu.cn ; LIAO Libing, clayl@cugb.edu.cn

Received Date: 13 November 2023

Publish Date: 15 February 2024

摘要

摘要:
沸石具有良好的吸附性能和离子交换特性，对去除水中的重金属离子具有廉价、高效的优点。利用天然沸石矿物作为吸附材料，探讨了在不同条件下对干扰分选过程的多种重金属离子的去除效果和去除机制，研究了其在静、动态条件下去除模拟尾矿渗滤液中重金属离子的性能和机理。单一重金属离子静态吸附实验结果表明，沸石对Pb²⁺、Cu²⁺、Mn²⁺、Zn²⁺均有较好的去除效果，对4种重金属离子的吸附能力大小为Pb²⁺ > Cu²⁺ > Zn²⁺ > Mn²⁺。混合离子静态吸附实验结果表明，在任意初始质量浓度下，Pb²⁺在沸石上的吸附量均远大于Cu²⁺、Zn²⁺和Mn²⁺。4种离子的吸附过程均符合Langmuir等温模型，属于单分子层吸附，准二级动力学模型能较好地描述沸石吸附4种重金属离子的过程，沸石在离子交换、表面静电和断键络合的共同作用下去除重金属离子，由于存在竞争吸附，沸石对相同价态不同阳离子的吸附能力存在较大差异，这主要受不同阳离子的水合半径的影响。动态条件下沸石对Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺ 的去除分别在102 h、64 h、900 h和78 h达到平衡，沸石的有效工作时间较长，可作为渗透反应格栅（PRB）的介质材料用于多金属矿尾矿渗滤液污染地下水的原位修复，具有良好的社会和经济效益。
- 天然沸石 /
- 吸附 /
- 重金属离子
Abstract:
Mineral processing wastewater contains a large amount of heavy metal ions. If not properly treated, it will pollute water sources and soil, and endanger human health. Zeolites possess excellent adsorption properties and ion exchange characteristics, making them cost−effective and highly efficient in removing heavy metal ions from water. This study utilizes natural zeolite minerals as adsorption materials to investigate the removal efficiency and mechanisms of various heavy metal ions in the interference sorting process under different conditions. It discusses the removal effect and mechanism of zeolite and its modified materials on the heavy metal ions that interfere with the separation process under different conditions. The performance and mechanism of removing heavy metal ions in simulated tailings leachate under static and dynamic conditions were studied. The results of the static adsorption experiments on single heavy metal ions indicate that zeolite has good removal efficiency for Cu²⁺, Pb²⁺, Zn²⁺, and Mn²⁺, with the adsorption capacity ranking as Pb²⁺ > Cu²⁺ > Zn²⁺ > Mn²⁺. The adsorption process of four types of ions all conform to the Langmuir isotherm model, which is a monolayer adsorption. The pseudo-second order kinetic model can describe the process of zeolite adsorbing four kinds of heavy metal ions well. Zeolite removes heavy metal ions through the combined action of ion exchange and surface electrostatics. Due to the existence of competitive adsorption, the adsorption capacity of zeolite to different cations with the same valence state is quite different. This is mainly influenced by the hydration radius of the different cations. Under dynamic conditions, the removal of Cu²⁺, Mn²⁺, Pb²⁺, and Zn²⁺ by zeolite reaches equilibrium at 102 h, 64 h, 900 h, and 78 h, respectively. The effective working time of zeolite is longer, and it can be used as the medium material of permeation reaction grid (PRB) It is used for in−situ remediation of groundwater polluted by leachate from polymetallic mine tailings, and has good social and economic benefits.
- zeolite /
- adsorption /
- heavy metals

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图 1 (a)样品的XRD图谱；(b)样品的Rietveld精修图谱

Figure 1.

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图 2 沸石的SEM图(a,b)，沸石样品中各元素的Mapping图(c)

Figure 2.

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图 3 沸石样品对Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺的吸附曲线

Figure 3.

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图 4 沸石样品对Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺的吸附量随吸附时间的变化

Figure 4.

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图 5 pH值对沸石样品吸附Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺的影响

Figure 5.

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图 6 沸石样品对Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺混合离子的静态吸附曲线

Figure 6.

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图 7 沸石样品对Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺混合离子的动态吸附曲线

Figure 7.

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图 8 Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺的阳离子交换量

Figure 8.

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图 9 沸石在不同pH值下的Zeta电位值

Figure 9.

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图 10 不同初始质量浓度下总离子交换量在去除量的占比

Figure 10.

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表 1 样品的氧化物成分含量

Table 1. Oxide content of the sample /%

成分	SiO₂	Al₂O₃	K₂O	CaO	Fe₂O₃	Na₂O	MgO	其他
含量	70.37	14.50	5.57	3.87	2.65	1.40	0.66	0.98

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表 2 沸石吸附Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺的Langmuir 和Freundlich等温线拟合相关系数

Table 2. Langmuir and freundlich adsorption isotherms fitting correlation coefficients of Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺ on zeolite

金属离子	Langmuir 方程			Freundlich 方程
金属离子	q_max	K_L	R²	K_F	n	R²
Cu²⁺	14.22	0.0052	0.9801	1.25	3.02	0.9205
Pb²⁺	105.26	0.0028	0.9827	5.86	2.75	0.9789
Zn²⁺	7.30	0.0061	0.9922	3.77	9.38	0.7939
Mn²⁺	12.36	0.0035	0.9886	2.66	2.08	0.9701

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表 3 沸石样品吸附 Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺ 的准一阶和准二阶动力学拟合相关系数

Table 3. Fitting correlation coefficients of quasi−first−order and quasi−second−order kinetics of adsorption of Cu²⁺、Mn²⁺、Pb²⁺、Zn²⁺ by zeolite samples

金属离子	准一级动力学模型			准二级动力学模型
金属离子	K₁	q_e	R²	K₂	q_e	R²
Cu²⁺	0.0076	3.50	0.4509	0.0302	23.25	0.9998
Pb²⁺	0.0125	20.28	0.9820	0.0027	34.48	0.9960
Zn²⁺	0.0029	2.12	0.9695	0.0166	4.10	0.9873
Mn²⁺	0.0069	3.12	0.4382	0.0278	16.83	0.9980

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表 4 重金属初始质量浓度为1000 mg/L时溶液中被交换出的K⁺、Ca²⁺、Na⁺、Mg²⁺的量

Table 4. Heavy metal removal capacity and exchange capacity of K⁺, Ca²⁺, Na⁺, Mg²⁺ at 1000 mg/L

金属离子	交换量/mmol				总交换量/mmol	重金属去除量/mmol	总交换量/去除量/%
金属离子	K⁺	Ca²⁺	Na⁺	Mg²⁺	总交换量/mmol	重金属去除量/mmol	总交换量/去除量/%
Cu²⁺	0.0241	0.0204	0.0403	0.0022	0.0547	0.3556	15.38
Mn²⁺	0.0255	0.0178	0.0308	0.0021	0.0480	0.3308	14.51
Pb²⁺	0.0422	0.0243	0.0446	0.0022	0.0699	0.1066	65.57
Zn²⁺	0.0221	0.0187	0.0289	0.0018	0.0460	0.2806	16.39
注：总交换量=( K⁺+ Na⁺)/2+ Ca²⁺+ Mg²⁺。

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天然沸石对模拟尾矿渗滤液中重金属离子的静、动态吸附研究

中国地质大学（北京） 材料科学与工程学院，矿物材料国家专业实验室，非金属矿物与固废资源材料化利用北京市重点实验室，地质碳储与资源低碳利用教育部工程研究中心，北京 100083

作者简介: 杨兰（1997—），女，硕士研究生，E-mail：18810890417@163.com

通讯作者: 梅乐夫（1978—），男，教授，E-mail：mlf@cugb.edu.cn; 廖立兵（1963—），男，教授， E-mail：clayl@cugb.edu.cn。

Study on the Static and Dynamic Adsorption of Heavy Metal Ions in Simulated Tailings Leachate by Natural Zeolite

Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences (Beijing), Beijing 100083, China

Corresponding authors: MEI Lefu, mlf@cugb.edu.cn ; LIAO Libing, clayl@cugb.edu.cn

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中国地质大学（北京）材料科学与工程学院，矿物材料国家专业实验室，非金属矿物与固废资源材料化利用北京市重点实验室，地质碳储与资源低碳利用教育部工程研究中心，北京 100083