Organically modification of magnetic alkaline Ca-bentonite and its adsorption for Cu(Ⅱ) and Mn(Ⅱ)

doi:10.16085/j.issn.1000-6613.2018-0357

Abstract

Abstract: To further improve the adsorption performance and magnetic stability, magnetic alkaline Ca-bentonite (MACB) was organically modified by chitosan/sodium carboxymethyl cellulose copolymer film (CC). CC-modified MACB (MACB/CC) was prepared by one-step coprecipitation process. The characterizations of both MACB/CC and MACB and the adsorption properties of Cu(Ⅱ) and Mn(Ⅱ) from aqueous solution were investigated. The characterization results indicated that the surface of MACB was successfully covered with CC. MACB/CC exhibited rapid solid-liquid separation ability and highly magnetic stability. The adsorption rate of Cu(Ⅱ) and Mn(Ⅱ) on MACB/CC was rapid initially but slowed down thereafter. The respective adsorption of Cu(Ⅱ) and Mn(Ⅱ) on MACB/CC were 97% and 85% with 60min adsorption time. Meanwhile, the adsorption was strongly dependent on the initial pH and Cu(Ⅱ) & Mn(Ⅱ) adsorption on MACB/CC increased with the initial pH increase. Cu(Ⅱ) & Mn(Ⅱ) adsorption reached 99% and 92% at pH 7.0, respectively. The results also showed the competition adsorption ability between Cu(Ⅱ) and Mn(Ⅱ) was in the order of Cu(Ⅱ)>Mn(Ⅱ). After five recycles, Cu(Ⅱ) and Mn(Ⅱ) adsorption on MACB/CC still maintained above 93% and 90%, respectively. The adsorption isotherms were well described by Langmuir model with the respective Langmuir adsorption capacities of Cu(Ⅱ) and Mn(Ⅱ) being 94mg/g and 38mg/g. The adsorption kinetics study demonstrated that the adsorption process fitted the pseudo-second order model well, indicating that the rate-determination step for MACB/CC was chemical adsorption. The main mechanisms of Cu(Ⅱ) and Mn(Ⅱ) removal by MACB/CC were cation exchange, precipitation and complexation. Due to the enhanced adsorption performance, better magnetic stability and separation ability, MACB/CC could be deemed as a potential adsorbent for the removal of heavy metals from wastewater.

Key words: magnetic alkaline Ca-bentonite, organically modification, composites, adsorption, kinetic modeling

摘要： 为提高磁性碱性钙基膨润土（magnetic alkaline Ca-bentonite，MACB）的吸附性能和磁稳定性，以壳聚糖和羧甲基纤维素钠的交联共聚膜（chitosan/sodium carboxymethyl cellulose copolymer film，CC）为改性剂，采用一步共沉淀法制备了CC改性的磁性碱性钙基膨润土MACB/CC（CC-modified magnetic alkaline Ca-bentonite，MACB/CC），对改性前后材料的结构特性进行分析，并进行MACB/CC对Cu（Ⅱ）和Mn（Ⅱ）的吸附性能研究。研究结果表明，有机共聚膜CC已成功负载在MACB表面，有机改性后的MACB/CC具备更好的磁分离性能和磁稳定性；Cu（Ⅱ）和Mn（Ⅱ）在MACB/CC上的吸附是一个先快速而后缓慢的过程，吸附时间为60min时，MACB/CC对Cu（Ⅱ）和Mn（Ⅱ）的吸附率已分别达到97%和85%；溶液的初始pH对MACB/CC吸附的影响明显，随着pH的升高，MACB/CC对Cu（Ⅱ）和Mn（Ⅱ）的吸附率逐渐上升，在pH为7时对两种重金属的吸附率达到99%和92%；当Cu（Ⅱ）和Mn（Ⅱ）共存时，MACB/CC对Cu（Ⅱ）的吸附能力大于Mn（Ⅱ）；经5次循环利用后，MACB/CC对Cu（Ⅱ）和Mn（Ⅱ）的吸附率仍分别保持在93%和90%以上；MACB/CC对Cu（Ⅱ）和Mn（Ⅱ）的吸附符合Langmuir模型，Langmuir吸附容量分别为94mg/g和38mg/g，吸附过程可由准二级动力学模型描述，说明控制吸附速率的主要是化学吸附；MACB/CC对Cu（Ⅱ）和Mn（Ⅱ）的吸附机理主要包括阳离子交换、表面沉淀和络合作用。总之，相对于MACB，经有机修饰的MACB/CC具有更好的吸附性能、磁稳定性和磁分离能力，是一种非常有应用前景的重金属废水吸附材料。

关键词: 磁性碱性钙基膨润土, 有机改性, 复合材料, 吸附, 动力学模型

CLC Number:

X703

SHI Huazhen, LIU Kun, TANG Rui, ZHU Ying, CHEN Ninghua, WANG Yingya, ZHANG Hanbing, TONG Zhangfa, HE Mingyong. Organically modification of magnetic alkaline Ca-bentonite and its adsorption for Cu(Ⅱ) and Mn(Ⅱ)[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4509-4521.

施华珍, 刘坤, 汤睿, 朱颖, 陈宁华, 王迎亚, 张寒冰, 童张法, 閤明勇. 有机改性磁性碱性钙基膨润土的制备及对Cu(Ⅱ)和Mn(Ⅱ)的吸附[J]. 化工进展, 2018, 37(11): 4509-4521.

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