Kinetic and thermodynamic studies on the adsorption of U(VI) ions on densely crosslinked poly(methacrylic acid) from aqueous solutions

C. Özeroğlu, G. Keçeli
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引用次数: 18

Abstract

Abstract In this study, densely crosslinked poly(methacrylic acid) was used to adsorb uranium(VI) ions from aqueous solution. For this purpose, the crosslinked copolymer of ethylene glycol dimethacrylate (EGDM) and methacrylic acid (MA) containing 25% (w/w) methacrylic acid (MA) was synthesized by using dibenzoyl peroxide-N,N-dimethylaniline (BPO-DMA) initiator system at room temperature. The adsorption of uranium(VI) ions on the copolymer sample (0.02 g copolymer/5 mL solution of U(VI) ions) was carried out in a batch reactor. The parameters which effect the uranium adsorption process, such as, contact time, pH of solution, initial uranium(VI) concentration and temperature were investigated. It was observed that an increase in these parameters enhanced the removal of U(VI) ions from aqueous solution. The adsorption data were modelled by the Freundlich, Langmuir and Dubinin–Radushkevich (D–R) isotherms. The adsorption capacity of the crosslinked copolymer and free energy change were calculated by using D–R isotherms. Thermodynamic parameters (ΔH°, ΔS° and ΔG°) were determined for the adsorption of U(VI) ions from aqueous solutions by the crosslinked copolymer bearing methacrylic acid functional groups. Experimental adsorption data were analyzed using sorption kinetic models of the pseudo-first order and pseudo-second order kinetic models. It was observed that pseudo-second order kinetic model provided a high goodness of fit with experimental data for the adsorption of U(VI) ions on the crosslinked copolymer bearing methacrylic acid functional groups. The densely crosslinked poly(methacrylic acid) might be of interest in large scale uranium removals from aqueous solution, since it had high uranyl sorption capacities ranging from 0.16 mmol/g to 2.37 mmol/g copolymer at pH 2.7 (293 K).
密交联聚甲基丙烯酸吸附U(VI)离子的动力学和热力学研究
摘要采用密交联聚甲基丙烯酸吸附水溶液中的铀(VI)离子。为此,采用过氧化二苯甲酰- n, n -二甲苯胺(BPO-DMA)引发剂体系,在室温下合成了含25% (w/w)甲基丙烯酸(MA)的乙二醇二甲基丙烯酸酯(EGDM)与甲基丙烯酸(MA)交联共聚物。在间歇反应器中进行了铀(VI)离子在共聚物样品(0.02 g共聚物/5 mL U(VI)离子溶液)上的吸附。考察了接触时间、溶液pH、初始铀浓度和温度等参数对铀吸附过程的影响。结果表明,这些参数的增加对U(VI)离子的去除率提高。吸附数据采用Freundlich、Langmuir和Dubinin-Radushkevich (D-R)等温线建模。用D-R等温线计算了交联共聚物的吸附量和自由能变化。测定了含甲基丙烯酸官能团的交联共聚物从水溶液中吸附U(VI)离子的热力学参数(ΔH°,ΔS°和ΔG°)。采用拟一级和拟二级吸附动力学模型对实验吸附数据进行了分析。结果表明,含甲基丙烯酸官能团的交联共聚物吸附U(VI)离子的拟二级动力学模型与实验数据拟合度较高。密交联聚(甲基丙烯酸)可能对从水溶液中大规模去除铀感兴趣,因为它在pH 2.7 (293 K)下具有高的铀酰吸附能力,范围为0.16 mmol/g至2.37 mmol/g共聚物。
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