新型含氮含硫螯合树脂的合成及其在黄芪中稀土金属的检测应用
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摘要
随着中国农用稀土的大量施用,稀土金属的蓄积已经成为食品安全的重大问题,因此植物性食品中稀土含量的检测方法备受关注。在稀土金属检测过程中,存在着分离难、基体干扰效应大、样品使用量受限等问题,近年来虽然出现了很多灵敏度和选择性较高的仪器分析方法,如ICP-OES、ICP-AES法,仍需要对样品进行预富集以达到仪器的检出限。而目前我国国家标准中的分光光度法检出限较高且只能测定稀土氧化物总量,必须对样品中的稀土金属预先进行有效的分离和预富集,以提高分光光度法的时效性、灵敏度和选择性。鉴于此,将以上两种检测方法(即分光光度法和ICP-OES法)与螯合树脂预富集结合,测定样品中稀土金属含量并进行比较,既可拓宽分光光度法的应用领域,也可为国家标准检测的进一步制订提供依据。
本文在综述了螯合树脂及其对稀土金属的吸附研究进展的基础上,以建立稀土金属选择性分离富集测定新方法为目的,合成了五种螯合树脂并对其合成条件和合成路线进行探讨,根据静态吸附和动态吸附研究其对稀土金属的选择吸附性能,据此提出了通过预富集分离-分光光度法和预富集分离-ICP-OES法对比测定黄芪中的稀土铈离子。
主要研究内容如下：
1、以氯甲基化聚苯乙烯(氯球)为母体,与杂环配体发生亲核反应制备了五种螯合树脂。与氯球配位的配位原子是氨基(-NH2)中的氮原子,巯基(-SH)中的硫原子。据此将以上5种螯合树脂分为两类,分别为含氮类螯合树脂和含硫类螯合树脂。从反应溶剂、反应温度、反应摩尔比方面确定了树脂的最佳合成条件。利用元素分析确定树脂的含氮量、功能基含量和功能基转化率；用红外光谱对合成的树脂进行了结构表征；利用热重技术对合成的树脂进行热分解来探讨其热稳定性,并验证其合成路线。
2、采用静态吸附法和动态吸附法详细研究了五种树脂对稀土金属离子的吸附性能。静态研究表明,含有羰基的PAR和IAR均对Ce3+有较好的吸附选择性,最大吸附容量分别为107mg/g、87.3mg/g;含有巯基的2-MPR对Nd3+、Pr3+、Ce3+均有较好的吸附效果,最大吸附容量分别为99.1mg/g、65.5mg/g、56.7mg/g。利用4.0mol/L的HCl对以上3种螯合树脂进行洗脱,均可达到100%解吸效果,且树脂的重复使用性能良好。实验还探讨了不同温度下等温吸附曲线与Langmuir方程和Freundlich方程的吻合性,及吸附过程的动力学和热力学参数。结果表明：树脂对稀土金属的吸附符合二级动力学模型,属于化学吸附。动态研究表明：PAR对Ce3+,IAR对Ce3+的吸附量分别为115mg/g,92.3mg/g; 2-MPR对Nd3+、Pr3+、Ce3+的吸附量分别为102mg/g、77.1mg/g、60.2mg/g。动态吸附过程与Thomas动态吸附方程拟合良好。
3、建立了螯合树脂预富集-分光光度法和螯合树脂预富集-ICP-OES法测定并对比黄芪中的稀土金属铈(Ce)含量的方法。实验结果表明,通过螯合树脂的分离富集后,在分离和检测单一稀土铈时,以上两种方法测定的结果基本一致。
In China, with a large number of applications of agricultural rare earth, rare earth metal accumulation in vegetative foods has cause a major issue of safety. Therefore, detection methods of rare earth content in food are more and more concerned. As difficult separation, serious matrix interference effects as well as limited samples use in detection of rare earth metals, although many instrument analysis methods possess high sensitivity and selectivity such as ICP-OES and ICP-AES, still a need for sample pre-concentration to achieve the instrument detection limit. At present, owning to national standard spectrophotometry in the higher detection limit of rare earth and only detection the total amount of rare earth, samples must be separation and preconcentration to improve the time effectiveness, sensitivity and specificity of the spectrophotometry. In view of this, the combination of chelating resin preconcentration with the above two kinds of detection methods (viz. spectrophotometry and ICP-OES method) are applied and compared in determination of rare earth content of the samples. It not only can widen the spectrophotometric application field, but also provide a basis for the further development of national standards detection.
In this paper, research on chelating resins and these adsorption to reare earth metals were reviewed, and the preparation of a series of crosslinked polystyrene matrix resins as well as these adsorption performance which were studied by researchers were enumerated. Aim at separation and preconcentration of metals, five kinds of resin were synthesized by anchoring heterocyclic into crosslinked polystyrene. The adsorption behaviors to rare earth ions were studied by static and dynamic adsorption. Subsequently, two methods of determination of cerium ion by spectrophotometry and ICP-OES are proposed and compared for using chelating resins in preconcentration and separation in astragalus.
1. In this thesis, five novel chelating resins were synthesized by chloromethylated polystyrene beads as matrix, functionalized with heterocyclic ligands. The nitrogen in amide (-NH2) and sulphur in sulfhydryl (-SH) of ligands coordinated with matrix. Five kinds of chelating resins are divided into N-containing and S-containing based on the above coordination atom. The influences of various reaction conditions such as reaction solvent, reaction temperature and molar ratio of reagents on the quality of resins were studied. The N atom content of the resins, the functional group capacities and percentages of functional group conversation of the resins were determined by elemental analysis. The resin structures were confirmed by IR. The synthetic resins were on the thermal decomposition by TGA instrument to investigate the thermal stability, and verify their synthetic scheme.
2. The adsorption properties of five resins for rare earth metals were systematically investigated by means of static and dynamic method. The experimental results with static method showed that both PAR and IAR with carbonyl group for Ce3+have excellent adsorption selectivity, maximum adsorption capacity is 107mg/g,87.3mg/g, respectively; 2-MPR containing mercapto-group for Nd3+, Pr3+, Ce3+have a good adsorption, the maximum adsorption capacity is 99.1mg/g,65.5mg/g, 56.7mg/g, respectively. Metal ions adsorbed on resins could be eluted completely by 4.0mol/L HC1. And resins had favorable repetitive property. Kinetics functions, thermodynamics functions and the adsorption isotherms in different temperature were studied. The results fitted for Langmuir and Freundlich equations. The adsorption process followed with second-order kinetics. The adsorption process was endothermic and chemical. From the study of dynamic adsorption, the dynamic saturated adsorption capacity of resins as follows:PAR for Ce3+, IAR for Ce3+, 2-MPR for Nd3+, Pr3+, Ce3+were 115mg/g,92.3mg/g,102mg/g,77.1mg/g, 60.2mg/g, respectively. Dynamic adsorption coincided with Thomas model.
3. Two methods of determination of cerium by spectrophotometry and ICP-OES are proposed and compared for using chelating resins in preconcentration and separation in astragalus. Experimental results show that, through the chelating resin separation and enrichment, the data of above two methods are basically the same in the detection of cerium.
本文在综述了螯合树脂及其对稀土金属的吸附研究进展的基础上,以建立稀土金属选择性分离富集测定新方法为目的,合成了五种螯合树脂并对其合成条件和合成路线进行探讨,根据静态吸附和动态吸附研究其对稀土金属的选择吸附性能,据此提出了通过预富集分离-分光光度法和预富集分离-ICP-OES法对比测定黄芪中的稀土铈离子。
主要研究内容如下：
1、以氯甲基化聚苯乙烯(氯球)为母体,与杂环配体发生亲核反应制备了五种螯合树脂。与氯球配位的配位原子是氨基(-NH2)中的氮原子,巯基(-SH)中的硫原子。据此将以上5种螯合树脂分为两类,分别为含氮类螯合树脂和含硫类螯合树脂。从反应溶剂、反应温度、反应摩尔比方面确定了树脂的最佳合成条件。利用元素分析确定树脂的含氮量、功能基含量和功能基转化率；用红外光谱对合成的树脂进行了结构表征；利用热重技术对合成的树脂进行热分解来探讨其热稳定性,并验证其合成路线。
2、采用静态吸附法和动态吸附法详细研究了五种树脂对稀土金属离子的吸附性能。静态研究表明,含有羰基的PAR和IAR均对Ce3+有较好的吸附选择性,最大吸附容量分别为107mg/g、87.3mg/g;含有巯基的2-MPR对Nd3+、Pr3+、Ce3+均有较好的吸附效果,最大吸附容量分别为99.1mg/g、65.5mg/g、56.7mg/g。利用4.0mol/L的HCl对以上3种螯合树脂进行洗脱,均可达到100%解吸效果,且树脂的重复使用性能良好。实验还探讨了不同温度下等温吸附曲线与Langmuir方程和Freundlich方程的吻合性,及吸附过程的动力学和热力学参数。结果表明：树脂对稀土金属的吸附符合二级动力学模型,属于化学吸附。动态研究表明：PAR对Ce3+,IAR对Ce3+的吸附量分别为115mg/g,92.3mg/g; 2-MPR对Nd3+、Pr3+、Ce3+的吸附量分别为102mg/g、77.1mg/g、60.2mg/g。动态吸附过程与Thomas动态吸附方程拟合良好。
3、建立了螯合树脂预富集-分光光度法和螯合树脂预富集-ICP-OES法测定并对比黄芪中的稀土金属铈(Ce)含量的方法。实验结果表明,通过螯合树脂的分离富集后,在分离和检测单一稀土铈时,以上两种方法测定的结果基本一致。
In China, with a large number of applications of agricultural rare earth, rare earth metal accumulation in vegetative foods has cause a major issue of safety. Therefore, detection methods of rare earth content in food are more and more concerned. As difficult separation, serious matrix interference effects as well as limited samples use in detection of rare earth metals, although many instrument analysis methods possess high sensitivity and selectivity such as ICP-OES and ICP-AES, still a need for sample pre-concentration to achieve the instrument detection limit. At present, owning to national standard spectrophotometry in the higher detection limit of rare earth and only detection the total amount of rare earth, samples must be separation and preconcentration to improve the time effectiveness, sensitivity and specificity of the spectrophotometry. In view of this, the combination of chelating resin preconcentration with the above two kinds of detection methods (viz. spectrophotometry and ICP-OES method) are applied and compared in determination of rare earth content of the samples. It not only can widen the spectrophotometric application field, but also provide a basis for the further development of national standards detection.
In this paper, research on chelating resins and these adsorption to reare earth metals were reviewed, and the preparation of a series of crosslinked polystyrene matrix resins as well as these adsorption performance which were studied by researchers were enumerated. Aim at separation and preconcentration of metals, five kinds of resin were synthesized by anchoring heterocyclic into crosslinked polystyrene. The adsorption behaviors to rare earth ions were studied by static and dynamic adsorption. Subsequently, two methods of determination of cerium ion by spectrophotometry and ICP-OES are proposed and compared for using chelating resins in preconcentration and separation in astragalus.
1. In this thesis, five novel chelating resins were synthesized by chloromethylated polystyrene beads as matrix, functionalized with heterocyclic ligands. The nitrogen in amide (-NH2) and sulphur in sulfhydryl (-SH) of ligands coordinated with matrix. Five kinds of chelating resins are divided into N-containing and S-containing based on the above coordination atom. The influences of various reaction conditions such as reaction solvent, reaction temperature and molar ratio of reagents on the quality of resins were studied. The N atom content of the resins, the functional group capacities and percentages of functional group conversation of the resins were determined by elemental analysis. The resin structures were confirmed by IR. The synthetic resins were on the thermal decomposition by TGA instrument to investigate the thermal stability, and verify their synthetic scheme.
2. The adsorption properties of five resins for rare earth metals were systematically investigated by means of static and dynamic method. The experimental results with static method showed that both PAR and IAR with carbonyl group for Ce3+have excellent adsorption selectivity, maximum adsorption capacity is 107mg/g,87.3mg/g, respectively; 2-MPR containing mercapto-group for Nd3+, Pr3+, Ce3+have a good adsorption, the maximum adsorption capacity is 99.1mg/g,65.5mg/g, 56.7mg/g, respectively. Metal ions adsorbed on resins could be eluted completely by 4.0mol/L HC1. And resins had favorable repetitive property. Kinetics functions, thermodynamics functions and the adsorption isotherms in different temperature were studied. The results fitted for Langmuir and Freundlich equations. The adsorption process followed with second-order kinetics. The adsorption process was endothermic and chemical. From the study of dynamic adsorption, the dynamic saturated adsorption capacity of resins as follows:PAR for Ce3+, IAR for Ce3+, 2-MPR for Nd3+, Pr3+, Ce3+were 115mg/g,92.3mg/g,102mg/g,77.1mg/g, 60.2mg/g, respectively. Dynamic adsorption coincided with Thomas model.
3. Two methods of determination of cerium by spectrophotometry and ICP-OES are proposed and compared for using chelating resins in preconcentration and separation in astragalus. Experimental results show that, through the chelating resin separation and enrichment, the data of above two methods are basically the same in the detection of cerium.
引文
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