反硫化多孔富硫聚合物在快速汞吸附中的应用

doi:10.19965/j.cnki.iwt.2024-0994

摘要/Abstract

摘要：

通过引入碳酸氢钠作为致孔剂来调控富硫聚合物S-Cy的孔结构，评估其去除废水中Hg²⁺的性能。使用环辛二烯作为交联单体，与硫粉反硫化制备了多孔富硫聚合物S-Cy-A。与未添加碳酸氢钠的S-Cy相比，S-Cy-A的比表面积显著提高，达到5.18 m²/g，是S-Cy的28倍。S-Cy-A在30 s内对Hg²⁺的去除率达到了89.2%，并且吸附速率提高至17.84 mg/min，是S-Cy吸附速率的356.8倍。此外，吸附过程符合准一级和准二级反应动力学模型，XPS显示Hg²⁺以HgS的形式被吸附在S-Cy-A表面。溶液pH=4时对Hg²⁺的吸附性能最好。多元金属离子体系实验证明S-Cy-A对Hg²⁺具有吸附选择性。

关键词: 汞, 反硫化, 富硫聚合物, 多孔材料

Abstract:

The pore structure of S-Cy sulfur-rich copolymer was regulated by sodium bicarbonate as a pore-forming agent, and its performance in removing mercury ions(Hg²⁺) from wastewater was evaluated. In this study, cyclooctadiene was used as a crosslinking monomer to prepare a porous sulfur-rich polymer S-Cy-A by reverse vulcanization with sulfur powder. Compared with S-Cy without sodium bicarbonate, the specific surface area of S-Cy-A was significantly increased to 5.18 m²/g,which was 28 times that of S-Cy. The removal efficiency of Hg²⁺ by S-Cy-A reached 89.2% within 30 s, and the adsorption rate increased to 17.84 mg/min, which was 356.8 times that of S-Cy. In addition, the adsorption process conformed to the pseudo-first-order and pseudo-second-order kinetic models. XPS showed that Hg²⁺ was adsorbed on the surface of S-Cy-A in the form of HgS. When the pH of solution was 4, the adsorption performance of Hg²⁺ was the best. The adsorption selectivity of S-Cy-A for Hg²⁺ was proved by the experiment of multi-metal ion system.

Key words: mercury, inverse vulcanization, sulfur-rich copolymers, porous material

中图分类号:

X703.1

史超宾, 刘瑞琦, 杜江晖, 闫浩冰, 张肖静, 马永鹏. 反硫化多孔富硫聚合物在快速汞吸附中的应用[J]. 工业水处理, 2025, 45(12): 108-115.

Chaobin SHI, Ruiqi LIU, Jianghui DU, Haobing YAN, Xiaojing ZHANG, Yongpeng MA. Application of reverse sulfide porous sulfur-rich copolymer in rapid mercury adsorption[J]. Industrial Water Treatment, 2025, 45(12): 108-115.

https://www.iwt.cn/CN/Y2025/V45/I12/108

图/表 13

图1 吸附剂（富硫聚合物）的FESEM图（a）S-Cy；（b）S-Cy-B；（c）S-Cy-C；（d）S-Cy-A；（e）S-Cy-A-1；（f）S-Cy-A-2。

Fig.1 FESEM images of adsorbents（sulfur-rich copolymers）

图2 硫粉、S-Cy和S-Cy-A的XRD

Fig.2 XRD patterns of sulfur powder，S-Cy，and S-Cy-A

图3 S-Cy、S-Cy-A和环辛二烯的FTIR/ATR光谱

Fig.3 FTIR/ATR spectra of S-Cy，S-Cy-A，and cyclooctene

图4 环辛二烯、S-Cy和S-Cy-A的¹H-NMR光谱

Fig.4 ¹H-NMR spectra of cyclooctene，S-Cy，and S-Cy-A

图5 S-Cy和S-Cy-A的¹³C-NMR光谱

Fig.5 ¹³C-NMR spectra of S-Cy and S-Cy-A

图6 不同致孔剂对S-Cy吸附Hg²⁺性能的影响

Fig.6 Effects of different pore-forming agents on the adsorption of Hg²⁺ by S-Cy

图7 NaHCO₃投加量对S-Cy吸附Hg²⁺性能的影响

Fig.7 The effect of NaHCO₃ dosage on the adsorption of Hg²⁺ by S-Cy

图8 S-Cy-A对工业废水环境中Hg²⁺的吸附

Fig.8 The adsorption of Hg²⁺ by S-Cy-A in industrial wastewater environment

图9 各因素对S-Cy-A吸附性能的影响

Fig.9 Effects of various factors on the adsorption performance of S-Cy-A

图10 Hg²⁺吸附的反应动力学模型拟合和吸附等温线模型

Fig.10 Kinetic and isotherm modeling for Hg²⁺ adsorption

表1 Hg²⁺吸附的反应动力学模型拟合参数

Table 1 Fitting parameters of Hg²⁺ adsorption for the kinetic models

富硫聚合物	q _exp/（mg·g^-1）	准一级反应动力学模型			准二级反应动力学模型
富硫聚合物	q _exp/（mg·g^-1）	q _max/（mg·g^-1）	k ₁/min^-1	R ²	q _max/（mg·g^-1）	k ₂/（g·mg^-1·min^-1）	R ²
S-Cy	8.8	8.78	0.01	0.99	8.68	0.005	0.99
S-Cy-A	8.9	8.79	0.92	1	8.92	0.89	0.99

表2 吸附等温线模型拟合参数

Table 2 Adsorption isotherm model parameters

富硫聚

合物

R _L ²

R _F ²

图11 Hg²⁺吸附机理

Fig.11 Hg²⁺ adsorption mechanism

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