新型磁性树脂的合成及其在水中去除Cu(Ⅱ)的性能

doi:10.16085/j.issn.1000-6613.2022-2103

摘要/Abstract

摘要：

探索了磁性树脂在水体中高效去除Cu(Ⅱ)的吸附机制，制备且表征了一种新型磁性阳离子树脂（MCER），研究了MCER树脂对Cu(Ⅱ)的去除效能和影响因素（pH和离子强度），并利用吸附动力学和颗粒内扩散模型分析了Cu(Ⅱ)在MCER树脂上的吸附行为，最后通过傅里叶变换红外光谱和X-射线光电子能谱验证树脂对Cu(Ⅱ)的吸附机制。结果表明，MCER对Cu(Ⅱ)表现出更好的去除效果，去除率超过86.7%。Cu(Ⅱ)的吸附过程对pH有较强的依赖性，随着pH的增加，树脂对Cu(Ⅱ)的吸附容量明显升高。吸附动力学和颗粒内扩散模型表明吸附过程符合伪一级吸附动力学，其对Cu(Ⅱ)的吸附包括颗粒内扩散和液膜扩散等多种过程。MCER树脂对Cu(Ⅱ)的吸附机制主要包括离子交换和静电吸附作用。最后，评价了树脂的耐酸性和重复利用性，表明MCER树脂具有良好的实际应用潜力。

关键词: 废水, 磁性树脂, 复合材料, 离子交换, 吸附

Abstract:

To explore the feasibility of modified cationic resin for efficient removal of Cu(Ⅱ) from water, a new magnetic cationic resin (MCER) was prepared and characterized in this paper. The removal efficiency and influencing factors (pH and ionic strength) of MCER on Cu(Ⅱ) were investigated. The adsorption behavior of Cu(Ⅱ) on MCER resin was analyzed using adsorption kinetics and intraparticle diffusion models. Finally, the adsorption mechanism of Cu(Ⅱ) on MCER resin was verified by Fourier transform infrared spectrometer and X-ray photoelectron spectroscopy analysis. The results showed that MCER displayed a better removal effect on Cu(Ⅱ) than CER resin with the removal rate over 86.7%. The adsorption process of Cu(Ⅱ) was strongly dependent on the pH, and the adsorption capacity of the resin on Cu(Ⅱ) increased significantly with the increase of pH. The adsorption kinetics and intraparticle diffusion model indicated that the adsorption process was consistent with pseudo first-order adsorption kinetics, and its adsorption of Cu(Ⅱ) included various processes such as intraparticle diffusion and liquid film diffusion. In addition, the acid resistance and reusability of the resin were evaluated, and the MCER resin had good potential for application. The adsorption mechanism of MCER resin for Cu(Ⅱ) mainly involved hydrogen bonding and electrostatic adsorption.

Key words: waste water, magnetic resin, composites, ion exchange, adsorption

中图分类号:

X592

张英杰, 陆加越, 王方刚. 新型磁性树脂的合成及其在水中去除Cu(Ⅱ)的性能[J]. 化工进展, 2023, 42(10): 5558-5566.

ZHANG Yingjie, LU Jiayue, WANG Fanggang. Synthesis of a new MCER and its performance in removing Cu(Ⅱ) from water[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5558-5566.

图/表 11

图1 CER和MCER的扫描电镜图

图2 MCER的表面EDS-mapping结果

图3 MCER的表征结果

图4 CER和MCER对Cu(Ⅱ)的去除效果[树脂投加量为0.5g/L，Cu(Ⅱ)初始浓度为50mg/L]

图5 溶液pH和离子强度对树脂吸附Cu(Ⅱ)的影响[树脂投加量为0.5g/L、吸附时间为90min、Cu(Ⅱ)初始浓度为50mg/L]

图6 MCER对Cu(Ⅱ)吸附模型的拟合曲线

表1 树脂MCER吸附Cu(Ⅱ)的动力学和等温吸附模型拟合参数

模型	参数	结果
伪一级动力学	Q_e/mg·g^-1	110.70
	k₁×10²/min^-1	3.11
	R₁²	0.9991
伪二级动力学	Q_e/mg·g^-1	128.96
	k₂×10²/g·mg^-1·min^-1	0.028
	R₂²	0.9945
颗粒内扩散模型	K_1d, K_2d, K_3d/mg·g^-1·min^-1/2	15.14, 3.54, 0.408
	I₁, I₂, I₃	-17.00, 67.24, 105.52
	R₃²	0.9992, 0.9917,0.9934
Langmuir等温吸附模型	K_L	0.1532
	Q_m/mg·g^-1	449.95
	R₄²	0.9963
Freundlich等温吸附模型	K_F	94.54
	n	2.43
	R₅²	0.9772

图7 MCER的重复利用性和耐酸性评价(脱附条件为0.1mol/L HCl溶液，脱附时间为120min)

图8 Cu(Ⅱ)吸附前后的傅里叶红外光谱图

图9 MCER吸附Cu(Ⅱ)前后的XPS图谱

图10 MCER吸附重金属离子机理图（M n+代表铜离子）

参考文献 13

1	李征. 重金属污染水体的环境保护处理技术研究[J]. 环境与发展, 2018, 30(11): 110-111.
	LI Zheng. Research on environmental protection treatment technology based on heavy metal polluted water body[J]. Environment and Development, 2018, 30(11): 110-111.
2	雷兆武, 孙颖. 离子交换技术在重金属废水处理中的应用[J]. 环境科学与管理, 2008, 33(10): 82-84.
	LEI Zhaowu, SUN Ying. Application of lon exchange technology in heavy metals wastewater treatment[J]. Environmental Science and Management, 2008, 33(10): 82-84.
3	BERGQUIST Allison M, CHOE Jong Kwon, STRATHMANN Timothy J, et al. Evaluation of a hybrid ion exchange-catalyst treatment technology for nitrate removal from drinking water[J]. Water Research,2016, 96: 177-187.
4	CHANTHAPON Nopphorn, SARKAR Sudipta, KIDKHUNTHOD Pinit, et al. Lead removal by a reusable gel cation exchange resin containing nano-scale zero valent iron[J]. Chemical Engineering Journal, 2018, 331: 545-555.
5	李海斌, 张克华, 陈庆典, 等. 氨基磷酸螯合树脂(D418)高效去除Cu(Ⅱ)的性能与机制[J]. 复合材料学报, 2021, 38(4): 1128-1138.
	LI Haibin, ZHANG Kehua, CHEN Qingdian, et al. Performance and mechanism of the amino methylene phosphonic acid chelating resin(D418) for the efficient removal of Cu(‍Ⅱ)[J]. Acta Materiae Compositae Sinica, 2021, 38(4): 1128-1138.
6	GE Yuru, LI Yushu, ZU Baiyi, et al. AM-DMC-AMPS multi-functionalized magnetic nanoparticles for efficient purification of complex multiphase water system[J]. Nanoscale Research Letters, 2016, 11(1): 217.
7	路翠萍. 磁性聚苯乙烯基大孔树脂的制备及对水溶液中金属离子的吸附性能研究[D]. 兰州: 兰州理工大学, 2014.
	LU Cuiping. Study on the synthesis of magnetic polystyrene based macroporous resins and their adsorption performance to metal ions in aqueous solution[D]. Lanzhou: Lanzhou University of Technology, 2014.
8	LI Qimeng, FU Lichun, Wang Zheng, et al. Synthesis and characterization of a novel magnetic cation exchange resin and its application for efficient removal of Cu²⁺ and Ni²⁺from aqueous solutions[J]. Journal of Cleaner Production, 2017, 165: 801-810.
9	王彤彤, 马江波, 曲东, 等. 两种木材生物炭对铜离子的吸附特性及其机制[J]. 环境科学, 2017, 38(5): 2161-2171.
	WANG Tongtong, MA Jiangbo, QU Dong, et al. Characteristics and mechanism of copper adsorption from aqueous solutio ns on biochar produced from sawdust and apple branch[J]. Environmental Science, 2017, 38(5): 2161-2171.
10	谢超然, 王兆炜, 朱俊民, 等. 核桃青皮生物炭对重金属铅、铜的吸附特性研究[J]. 环境科学学报, 2016, 36(4): 1190-1198.
	XIE Chaoran, WANG Zhaowei, ZHU Junmin, et al. Adsorption of lead and copper from aqueous solutions on biochar produced from walnut green husk[J]. Acta Scientiae Circumstantiae, 2016, 36(4): 1190-1198.
11	ZHENG Xinyu, ZHENG Huaili, XIONG Zikang, et al. Novel anionic polyacrylamide-modify-chitosan magnetic composite nanoparticles with excellent adsorption capacity for cationic dyes and pH-independent adsorption capability for metal ions[J]. Chemical Engineering Journal, 2020, 392: 123706.
12	LIU Biming, LIU Zhenxue, WU Haixia, et al. Effective and simultaneous removal of organic/inorganic arsenic using polymer-based hydrated iron oxide adsorbent: Capacity evaluation and mechanism[J]. The Science of the Total Environment, 2020, 742: 140508.
13	HUANG Feng, LI Wenzhi, LIU Qingchuan, et al. Sulfonated tobacco stem carbon as efficient catalyst for dehydration of C₆ carbohydrate to 5-hydroxymethylfurfural in γ-valerolactone/water[J]. Fuel Processing Technology, 2018, 181: 294-303.

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