有机磁性膨润土对环丙沙星和四环素的吸附性能

doi:10.16085/j.issn.1000-6613.2020-2356

化工进展 ›› 2021, Vol. 40 ›› Issue (11): 6235-6245.DOI: 10.16085/j.issn.1000-6613.2020-2356

有机磁性膨润土对环丙沙星和四环素的吸附性能

汤睿¹(), 张寒冰², 陆彩妹², 刘坤¹, 王忠凯², 余思珊², 童张法¹^,³(), 季军荣⁴

^1.广西大学化学化工学院，资源化工应用新技术广西高校重点实验室，广西南宁 530004
^2.广西大学资源环境与材料学院，广西南宁 530004
^3.广西大学，广西碳酸钙产业化工程院，广西南宁 530004
^4.崇左南方水泥有限公司，广西钙基材料协同创新中心，广西崇左 532200

收稿日期:2020-11-25 修回日期:2021-03-10 出版日期:2021-11-05 发布日期:2021-11-19
通讯作者: 童张法
作者简介:汤睿（1994—），男，博士研究生，研究方向为工业废水处理。E-mail：735707457@qq.com。
基金资助:
国家自然科学基金(21576055);广西石化资源加工及过程强化技术重点实验室主任课题(2020Z008)

Adsorption of ciprofloxacin and tetracycline by organically modified magnetic bentonite

TANG Rui¹(), ZHANG Hanbing², LU Caimei², LIU Kun¹, WANG Zhongkai², YU Sishan², TONG Zhangfa¹^,³(), JI Junrong⁴

^1.Guangxi Colleges and Universities, Key Laboratory of New Technology and Application in Resource Chemical Engineering, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
^2.College of Resources, Environment and Materials, Guangxi University, Nanning 530004, Guangxi, China
^3.Guangxi Engineering Academy of Calcium Carbonate Industrialization, Guangxi University, Nanning 530004, Guangxi, China
^4.Guangxi Cooperative Innovation Centre for Calcium-based Materials (GCICCM), Chongzuo South Cement Co. , Ltd. , Chongzuo 532200, Guangxi, China

Received:2020-11-25 Revised:2021-03-10 Online:2021-11-05 Published:2021-11-19
Contact: TONG Zhangfa

摘要/Abstract

摘要：

为了提高磁性膨润土（magnetic bentonite，MB）的磁分离性能，达到高效去除抗生素的目的，本文采用羧甲基纤维素（sodium carboxymethyl cellulose，CMC）和壳聚糖（chitosan，CS）相互作用所生成的有机共聚膜（chitosan/sodium carboxymethyl cellulose copolymer film，CC）对MB进行联合修饰，制得双有机修饰的有机磁性膨润土（magnetic bentonite/carboxymethyl cellulose-chitosen composite，MB-CC），同时进行了MB-CC对环丙沙星（ciprofloxacin，CIP）和四环素（tetracyclines，TC）的吸附性能研究。表征结果表明，磁性Fe₃O₄纳米粒子和有机共聚膜CC成功地固定在MB上；经过CC改性，提高了Fe₃O₄的稳定性和对CIP及TC的去除性能。吸附结果表明，在pH为5、温度为25℃的条件下，MB-CC对CIP和TC的吸附容量（182mg/g和189mg/g）高于MB对CIP和TC的吸附容量（147mg/g和136mg/g）。经过5次循环，MB-CC对CIP和TC的去除率仍然保持在90%以上。与Freundlich模型相比较而言，CIP和TC在MB和MB-CC上的吸附行为更加符合Langmuir模型；吸附过程可由准二级动力学模型描述，说明吸附速率主要由化学吸附控制。MB-CC对CIP和TC的吸附机理主要包括孔扩散、阳离子交换和静电吸引作用。综上所述，MB-CC具有合成简单、高效等优点，是一种很有前途的抗生素废水去除方法。

关键词: 磁性膨润土, 有机修饰, 吸附, 环丙沙星, 四环素

Abstract:

In order to endow magnetic bentonite (MB) with magnetic separation ability and simultaneously obtain stronger removal capacity of antibiotics, magnetic bentonite/carboxymethylcellulose-chitosan composite (MB-CC) was prepared by modifying previously fabricated MB with carboxymethylcellulose (CMC) and chitosan (CS). The characterization of both MB-CC and MB and their adsorption properties towards ciprofloxacin (CIP) and tetracycline (TC) in aqueous solution were investigated. Textural characterization results revealed that the magnetic nanoparticles (Fe₃O₄) were successfully immobilized onto bentonite and further modified with CC. The surface functionalization with CC concurrently enhanced the stability of Fe₃O₄ and removal capability of CIP and TC for the final product. Adsorption results indicated that MB-CC exhibited superior adsorption performance for CIP and TC (182mg/g and 189mg/g) to MB (147mg/g and 136mg/g) at pH 5.0 and 25℃. Adsorptive removal of CIP and TC by MB-CC was more than 90% even after 5 cycles of adsorption-desorption process. The adsorption isotherms were better described by Langmuir model than Freundlich model. The adsorption process fitted well with pseudo-second order kinetic model, indicating that the rate-determining step for MB-CC was chemical adsorption. The main steps during the successful adsorption process of MB-CC for CIP and TC included pore diffusion, ions exchange and electrostatic interaction. The current approach is credited to the simplified synthesis and high-efficiency of MB-CC which could also be deemed as a promising alternative sorbent for removal antibiotics from wastewater.

Key words: magnetic bentonite, organically modification, adsorption, ciprofloxacin, tetracyclines

中图分类号:

X703

汤睿, 张寒冰, 陆彩妹, 刘坤, 王忠凯, 余思珊, 童张法, 季军荣. 有机磁性膨润土对环丙沙星和四环素的吸附性能[J]. 化工进展, 2021, 40(11): 6235-6245.

TANG Rui, ZHANG Hanbing, LU Caimei, LIU Kun, WANG Zhongkai, YU Sishan, TONG Zhangfa, JI Junrong. Adsorption of ciprofloxacin and tetracycline by organically modified magnetic bentonite[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6235-6245.

图/表 14

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组分	质量分数/%
Al₂O₃	16.84
SiO₂	61.35
Fe₂O₃	3.12
MgO	2.63
Na₂O	4.79
CaO	1.81
K₂O	0.37
其他	9.09

组分	质量分数/%
Al₂O₃	16.84
SiO₂	61.35
Fe₂O₃	3.12
MgO	2.63
Na₂O	4.79
CaO	1.81
K₂O	0.37
其他	9.09

吸附过程	Langmuir模型			Freundlich模型			q_m，exp/mg·g^?1
吸附过程	K_L/L·mg^?1	q_m，cal/mg·g^?1	R²	K_f/mg·g^?1	1/n	R²	q_m，exp/mg·g^?1
MB-CC
CIP	1.27	182	0.999	51.3	0.41	0.939	170
TC	1.31	189	0.999	68.2	0.43	0.955	179
MB
CIP	0.28	147	0.999	36.1	0.37	0.937	127
TC	0.55	136	0.999	45.7	0.39	0.958	126

吸附过程	Langmuir模型			Freundlich模型			q_m，exp/mg·g^?1
吸附过程	K_L/L·mg^?1	q_m，cal/mg·g^?1	R²	K_f/mg·g^?1	1/n	R²	q_m，exp/mg·g^?1
MB-CC
CIP	1.27	182	0.999	51.3	0.41	0.939	170
TC	1.31	189	0.999	68.2	0.43	0.955	179
MB
CIP	0.28	147	0.999	36.1	0.37	0.937	127
TC	0.55	136	0.999	45.7	0.39	0.958	126

吸附材料	准一级动力学模型			准二级动力学模型			q_e，exp/mg·g^?1
吸附材料	k₁×0.01/min^?1	q_e，cal/mg·g^?1	R²	k₂×0.01/g·mg^?1·min^?1	q_e，cal/mg·g^?1	R²	q_e，exp/mg·g^?1
MB-CC
CIP	0.003	92	0.466	0.36	181	0.999	170
TC	0.006	103	0.588	0.41	191	0.999	179
MB
CIP	0.002	68	0.582	0.32	102	0.999	127
TC	0.005	77	0.673	0.35	119	0.999	126

有机磁性膨润土对环丙沙星和四环素的吸附性能

Adsorption of ciprofloxacin and tetracycline by organically modified magnetic bentonite

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样品	比表面积/m²?g^-1	孔容/cm³?g^-1	平均孔径/nm
MB	64	0.26	17
MB-CC	56	0.74	26

样品	比表面积/m²?g^-1	孔容/cm³?g^-1	平均孔径/nm
MB	64	0.26	17
MB-CC	56	0.74	26