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Adsorption and chromatographic separation of rare earths with EDTA- and DTPA-functionalized chitosan biopolymers

机译:EDTA和DTPA功能化的壳聚糖生物聚合物对稀土的吸附和色谱分离

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摘要

Chitosan, which is derived from chitin by deacetylation, is one of the most promising biopolymers for adsorption of metal ions from diluted waste streams. By functionalization of chitosan with ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA) groups, it is possible to obtain a material that is much less soluble in acidic aqueous solutions than native chitosan. The coordinating EDTA and DTPA ligands are very efficient for binding of rare-earth (lanthanide) ions. The functionalization was achieved by reaction of chitosan with EDTA bisanhydride or DTPA bisanhydride. The binding of lanthanide ions to functionalized chitosan was investigated by FTIR (binding of Nd3+) and luminescence spectroscopy (binding of Eu3+). Comparison of the luminescence decaytimes of the europium(III) coordinated chitosan complexes swollen in water and in heavy water allowed determination of the hydration number of the coordinated Eu3+ ion. Batch adsorption tests for the uptake of neodymium(III) from aqueous nitrate solutions were performed for EDTA-chitosan and DTPA-chitosan. Different experimental parameters such as the adsorption kinetics, loading capacity and pH ofthe aqueous feed were investigated. The modified chitosan materials are much more effective for adsorption of rare earths than unmodified chitosan. It was shown that adjustment of the pH of the aqueous feed solution allows achieving selectivity for adsorption of rare-earth ions for mixtures containing two different ions. After stripping of the metal content, the modified chitosans could be reused for new adsorption experiments. Medium pressure liquid chromatography (MPLC) with DTPA-chitosan/silica as the stationary phase and a dilute nitric acid solution as eluent was used for the separation of the following mixtures of rare-earth ions: Nd3+/Ho3+, Pr3+/Nd3+ and Pr3+/Nd3+/Ho3+. The experiments show that separation of the rare-earth ions is feasible with DTPA-chitosan/silica, without the need for using solutions of chelating agents as eluents.
机译:壳聚糖是通过脱乙酰作用从几丁质衍生而来的,是最有希望的生物聚合物之一,可从稀释的废物流中吸附金属离子。通过用乙二胺四乙酸(EDTA)或二亚乙基三胺五乙酸(DTPA)基团对壳聚糖进行官能化,可以获得比天然壳聚糖难溶于酸性水溶液的材料。配合的EDTA和DTPA配体对于结合稀土(镧系元素)离子非常有效。通过使壳聚糖与EDTA二氢酐或DTPA二氢酐反应来实现功能化。通过FTIR(Nd3 +的结合)和发光光谱(Eu3 +的结合)研究了镧系元素离子与功能化壳聚糖的结合。比较在水中和重水中溶胀的coordinate(III)配位的壳聚糖配合物的发光衰减时间,可以确定配位的Eu3 +离子的水合数。对EDTA-壳聚糖和DTPA-壳聚糖进行了批次吸附试验,以测定硝酸盐溶液中钕(III)的吸收。研究了不同的实验参数,如水性饲料的吸附动力学,负载量和pH。改性的壳聚糖材料比未改性的壳聚糖更有效地吸附稀土。已经表明,调节进料水溶液的pH可以实现对于包含两种不同离子的混合物的稀土离子吸附的选择性。去除金属含量后,改性壳聚糖可重新用于新的吸附实验。使用以DTPA-壳聚糖/二氧化硅为固定相,以稀硝酸溶液为洗脱液的中压液相色谱(MPLC)分离以下稀土离子混合物:Nd3 + / Ho3 +,Pr3 + / Nd3 +和Pr3 + / Nd3 + / Ho3 +。实验表明,使用DTPA-壳聚糖/二氧化硅分离稀土离子是可行的,而无需使用螯合剂溶液作为洗脱液。

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