Na2S改性生物炭高效吸附重金属离子：制备及吸附机理

doi:10.11949/0438-1157.20240098

摘要/Abstract

摘要：

以废弃芦苇为原料、硫化钠（Na₂S）为改性剂，制备了对Pb²⁺、Cd²⁺、Zn²⁺具有高效吸附性能的Na₂S改性生物炭（BCS）。通过扫描电镜-能谱（SEM-EDS）、红外光谱（FTIR）、元素分析等手段对改性前后的生物炭进行了表征。结果显示，Na₂S改性能够为生物炭引入多种含硫官能团，提升孔体积并增加比表面积。Langmuir模型拟合结果表明，随着改性剂Na₂S溶液浓度的增加，BCS对重金属离子的吸附能力得到提升。在pH为2.0~6.0的范围内，BCS对重金属离子的吸附能力随pH增加逐步增强。在pH=6.0时，BCS对Pb²⁺、Cd²⁺、Zn²⁺的最大吸附量分别为494.99、131.14、94.89 mg/g。根据动力学实验结果可知，BCS对重金属离子的吸附行为符合伪二级动力学模型。吸附机理主要包括表面官能团的络合、离子交换和静电吸附。本研究可为废弃物的再利用以及废水中的重金属的高效去除提供一种环境友好且可行的解决方案。

关键词: 生物炭, 重金属, Na₂S, 吸附, 废水

Abstract:

In this study, Na₂S modified biochar (BCS) with efficient adsorption properties for Pb²⁺, Cd²⁺, and Zn²⁺ was prepared by using waste reed as raw material and sodium sulfide (Na₂S) as modifier. The biochar before and after modification was characterized by scanning electron microscopy-EDS (SEM-EDS), infrared spectroscopy (FTIR) and elemental analysis. The results showed that the Na₂S modification was able to introduce various sulfur-containing functional groups into the biochar, enhance the pore volume and increase the specific surface area. The Langmuir model fitting results indicated that the adsorption capacity of BCS for heavy metal ions was enhanced with the increase of the concentration of the modifier Na₂S solution. In the pH range of 2.0—6.0, the adsorption capacity of BCS on heavy metal ions was gradually enhanced with the increase of pH. At pH=6.0, the maximum adsorption amounts of BCS on Pb²⁺, Cd²⁺ and Zn²⁺ were 494.99, 131.14 and 94.89 mg/g, respectively. Based on the results of the kinetic experiments, it can be seen that the adsorption behaviors of BCS on heavy metal ions were in accordance with the pseudo-secondary kinetic model. The adsorption mechanism mainly includes complexation of surface functional groups, ion exchange and electrostatic adsorption. Overall, this study provides an environmentally friendly and feasible solution for the reuse of waste and the efficient removal of heavy metals from wastewater.

Key words: biochar, heavy metals, Na₂S, adsorption, wastewater

中图分类号:

X 703

马林峰, 欧爱彤, 李志远, 李垚, 刘润泽, 吴晓乐, 徐景涛. Na₂S改性生物炭高效吸附重金属离子：制备及吸附机理[J]. 化工学报, 2024, 75(7): 2594-2603.

Linfeng MA, Aitong OU, Zhiyuan LI, Yao LI, Runze LIU, Xiaole WU, Jingtao XU. High-efficiency adsorption of heavy metal ions by Na₂S modified biochar: preparation and adsorption mechanism[J]. CIESC Journal, 2024, 75(7): 2594-2603.

图/表 14

表1 改性剂浓度对生物炭中元素含量的影响

Table 1 Effect of modifier concentration on elemental content in biochar

生物炭	元素含量/%						原子比			灰分/%
生物炭	C	H	O	N	S	Na	H/C	O/C	（N+O）/C	灰分/%
BC	62.44	3.44	30.15	3.18	—	—	0.06	0.48	0.53	11.82
BCS（0.1）	63.08	2.48	29.15	2.97	0.89	1.43	0.05	0.46	0.51	12.53
BCS（0.3）	64.58	3.58	28.94	2.48	2.47	5.11	0.04	0.45	0.49	13.35
BCS	58.11	3.15	26.52	2.33	3.46	6.44	0.05	0.46	0.50	14.27

表2 改性剂浓度对改性生物炭孔结构的影响

Table 2 Effect of modifier concentration on the pore structure of modified biochar

生物炭	比表面积/(m²/g)	孔体积/(cm³/g)	平均孔径/nm
BC	46.16	0.049	2.16
BCS（0.1）	49.34	0.066	2.74
BCS（0.3）	52.13	0.089	3.17
BCS	54.45	0.102	3.74

图1 BCS的表面形貌和元素含量

Fig.1 Surface morphology and elemental content of BCS

图2 Na2S改性对生物炭表面官能团的影响

Fig.2 Effect of Na2S modification on surface functional groups of biochar

图3 不同浓度Na2S改性对生物炭吸附Pb2+、Cd2+、Zn2+性能的影响

Fig.3 Effect of different concentrations of Na2S modified biochar on adsorption performance of Pb2+, Cd2+ and Zn2+ by biochar

表3 不同浓度Na2S改性生物炭对Pb2+、Cd2+、Zn2+的最大吸附量的影响

Table 3 Effect of different concentrations of Na2S modified biochar on the maximum adsorption capacity of Pb2+， Cd2+ and Zn2+

重金属离子	最大吸附量/(mg/g)
重金属离子	BC	BCS（0.1）	BCS（0.3）	BCS
Pb²⁺	19.69	464.11	477.25	494.99
Cd²⁺	15.63	99.94	121.45	131.14
Zn²⁺	13.98	79.29	81.03	94.89

图4 不同pH条件下BCS对Pb2+、Cd2+、Zn2+的去除率

Fig.4 Removal rates of Pb2+, Cd2+ and Zn2+ by BCS under different pH conditions

图5 BCS对Pb2+、Cd2+、Zn2+的吸附等温模型拟合

Fig.5 Isothermal model fitting of Pb2+, Cd2+, Zn2+ adsorption by BCS

表4 BCS对Pb2+、Cd2+、Zn2+的等温模型拟合参数

Table 4 Isothermal model fitting parameters of BCS for Pb2+， Cd2+， Zn2+

重金属离子	Langmuir			Freundlich
重金属离子	K_L/(L/mg)	Q_m/(mg/g)	R²	K_F	1/n	R²
Pb²⁺	0.05	494.99	0.96	10.19	0.29	0.75
Cd²⁺	0.45	131.14	0.95	4.55	0.33	0.73
Zn²⁺	1.49	94.89	0.93	5.33	0.14	0.72

表5 硫化物改性生物炭吸附去除水体重金属离子研究现状

Table 5 Current status of adsorption and removal of heavy metal ions from water by sulfide modified biochar

重金属离子	生物质	改性剂	吸附量/(mg/g)	文献
Hg²⁺	玉米秸秆	S	268.45	[22]
Hg²⁺	牛粪	S	407.8	[31]
Cu²⁺	花生壳	CH₄N₂S、H₃PO₄	21.20	[32]
Cu²⁺	玉米芯	Na₂S₂O₃	165.00	[33]
Pb²⁺	玉米秸秆	CS₂、FeCl₃·6H₂O	124.62	[34]
Pb²⁺	玉米芯	Na₂S₂O₃	421.80	[33]
Pb²⁺	芦苇秸秆	Na₂S	438.86	本研究
Cd²⁺	玉米秸秆	CS₂、FeCl₃·6H₂O	57.71	[34]
Cd²⁺	玉米秸秆	Fe₂(SO₄)₃	32.55	[35]
Cd²⁺	芦苇秸秆	Na₂S	131.14	本研究
Zn²⁺	甘蔗	Na₂S₂O₃	27.00	[36]
Zn²⁺	芦苇秸秆	Na₂S	94.89	本研究
Ni²⁺	玉米芯	Na₂S	15.40	[8]

图6 BCS对Pb2+、Cd2+、Zn2+的吸附动力学模型拟合

Fig.6 Model fitting of adsorption kinetics of Pb2+, Cd2+ and Zn2+ by BCS

表6 BCS对Pb2+、Cd2+、Zn2+的动力学模型拟合参数

Table 6 Kinetic model fitting parameters of BCS for Pb2+， Cd2+ and Zn2+

重金属离子	伪一级动力学模型			伪二级动力学模型			Elvoich动力学模型
重金属离子	Q_e/(mg/g)	k_l	R²	Q_e/(mg/g)	k₂	R²	α	β	R²
Pb²⁺	475.51	0.22	0.96	514.29	0.10	0.98	2.03	0.73	0.88
Cd²⁺	123.91	0.11	0.96	144.74	0.09	0.98	5.87	0.75	0.97
Zn²⁺	89.22	0.17	0.96	99.97	0.26	0.98	4.23	0.89	0.94

图7 BCS的表面电性与吸附前后官能团变化

Fig.7 Surface electrical properties and functional group changes before and after adsorption of BCS

图8 BCS对M2+（Pb2+、Cd2+、Zn2+）的吸附机理

Fig.8 The adsorption mechanism of M2+ (Pb2+, Cd2+, Zn2+) by BCS

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Na₂S改性生物炭高效吸附重金属离子：制备及吸附机理

High-efficiency adsorption of heavy metal ions by Na₂S modified biochar: preparation and adsorption mechanism

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