壳聚糖及其衍生物对放射性核素铀和钍吸附性能的研究
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摘要
核能作为一种清洁能源,应对能源短缺将发挥不可替代的作用。然而,在核能的利用过程中又潜藏着无限危害的可能。因此,在发展核电过程中,始终都迫切要求有更加有效的放射性废水及废液处理技术。壳聚糖及其衍生物作为放射性核素吸附材料,具有无毒,易降解,不会对环境造成二次污染等优点,有望成为一种更为绿色环保的放射性核素去污材料。
目的：
通过探讨不同配体与金属离子的配位关系,筛选出最佳配位基团；利用基团改性方法调节壳聚糖对放射性核素铀和钍的吸附性能,并确定最佳吸附条件；将具有磁性核引入壳聚糖吸附材料,解决吸附材料从去污介质中分离、回收的难题。通过对壳聚糖及改性后的磁性壳聚糖微球的进行理化表征,及这种磁性壳聚糖对放射性核素铀和钍吸附性能的分析测定,为研究新型高效、高选择性并可再利用的固体吸附材料提供理论和实验依据。
方法：
采用酸碱滴定法、红外光谱和质谱分析法确定壳聚糖的脱乙酰度和聚合度信息；通过紫外可见光谱法,对金属离子Cu2+、Ni2+、Co2+与各种配体(氨基酸,壳聚糖,柠檬酸等)的配合物进行光谱分析,选择最佳配位基团；利用铀和钍分析测定方法检测壳聚糖对放射性核素铀和钍的吸附性能,确定最佳吸附条件；采用沉淀法制备磁性壳聚糖微球,利用扫描电镜显示磁性微球的结构及形态,XRD检测分析磁性核的物相；在最佳吸附条件下,对比分析壳聚糖及其磁性微球对放射性核素铀和钍的吸附性能。
结果：
1.通过紫外可见光谱法,对金属离子Cu2+、Ni2+、Co2+与各种配体(氨基酸,壳聚糖,柠檬酸等)的配合物进行可见扫描,通过光谱图的峰形变化,确定Cu2+与各种配体的配位能力,这种配位能力按照壳聚糖、氨基葡萄糖、氨基酸的顺序增强。
2.采用酸碱滴定法测定出壳聚糖的脱乙酰度为90.1%,IR测定结果验证了不同壳聚糖中的乙酰基和氨基,MALDI-FT-MS进一步给出壳聚糖的脱乙酰度及聚合度的信息。
3.通过壳聚糖吸附性能的研究发现,壳聚糖对放射性核素铀具有较强的吸附能力,吸附率在96%以上。即使在大量Cu2+存在情况下,仍可高效吸附放射性核素铀。在壳聚糖对钍吸附性能的研究中,发现壳聚糖对钍也有较好的吸附能力。
4.通过沉淀法制备的磁性壳聚糖微球,电镜观察显示,壳聚糖形状规整,表面致密均匀；Fe3O4的扫描电镜显示多数纳米粒近似球形,整齐规则,大小在200～300nm；Fe3O4@SiO2的扫描电镜显示粒子分布均匀,形状整齐,粒子大小约500m;XRD的衍射结果表明Fe3O4在壳聚糖的包覆中没有受到影响,仍然保持较好的结晶度。
5.通过与壳聚糖的吸附能力对比,磁性壳聚糖虽然对放射性核素铀和钍的吸附率有所降低,但仍然表现出很好的吸附性能。
结论：
1.在过渡金属离子与配体的配位能力的研究中,发现配体中的-NH2、-OH、-COO-等基团都可与过渡金属离子进行配位。在配体与Cu2+离子配位时,含有氨基的配体显示出较强的配位能力,这种配位能力按照壳聚糖、氨基葡萄糖、氨基酸的顺序增强。
2.壳聚糖由于含有大量的氨基,所以对放射性核素铀有很好的吸附性能。即使在Cu2+存在的情况下,仍然有很高的吸附效率；壳聚糖对钍也表现出较好的吸附性能。
3.将磁性核引入壳聚糖吸附材料后,磁性壳聚糖仍然保持较好的对放射性核素铀和钍的吸附能力,同时还能较方便地从去污介质中分离、回收。
Nowdays, nuclear energy as a type of green energy, is treated as a better solution and show important role for energy shortage. However, in the process of its utilization, high risk is hidden around the world. In the development process of nuclear power, the effective disposal technique of radioactive waste which contains wastewater appears especially important. As an adsorbent material, chitosan and its deviants has the advantage of non-toxicity, easy degradation and no extra pollution. All these above advantages are expected chitosan and its deviants to develop as an environmental eradicator.
Objective:
By discussing the coordination between different ligands and metal ions, the perfect coordinating group could be screen out. Through the method of changing the character of the group, the adsorption of radionuclide uranium and thorium with chitosan and its derivants were adjusted and the optimal adsorptive situation was confirmed. By enclosing the magnetic chitosan particle to the adsorbent material, to solve the difficulty of separation and reusing research from different radio eradicator medium. In this paper, the physic-chemical characterization of chitosan and its derivants were analyzed, including their adsorption, which provided not only the theoretical basis but also the experimental evidence of adsorbent material for high-efficiency reusing research.
Method:
Some physico-chemical characteristics of chitosan were studied by several methods to control degree of deacetylation (DD), the degree of polymer (DP) by acid-base titration, infrared spectroscopy and mass spectrometric analysis respectively. By ultraviolet-visible spectrometry, spectrum analysis was performed in composition of Cu2+, Ni2+, Co2+ with different ligands such as amino acid, chitosan and citric acid etc. Combined with the adsorption of radionuclide uranium and thorium with chitosan and its derivants, the best adsorption condition could be confirmed. Magnetic chitosan particle was prepared by precipitation. Through the scan electro-microscope the configuration and the shape of the particle was analyzed. Physical phase of the magnetic characteristic particle was analyzed by XRD. Contrast the adsorption of radionuclide uranium and thorium with chitosan and its magnetic derivants under the best adsorptive condition.
Result:
1. By ultraviolet-visible spectrometry, scan the coordinated composition of Cu2+ Ni2+ and Co2+ with some ligands such as amino acid, chitosan and citric acid etc. By overview the absorb peaks, the perfect coordination was found between Cu2+ and amino acid. The coordinated capability was increased according to the order of chitosan, glucosamine and amino acid.
2. The degree of deacetylation test of chitosan by acid-base titration was detected as 90.1%. IR spectrum analyzed the acetyl and amino group, the degree of deacetylation and degree of polymer were observed by MALDI-FT-MS respectively. Further information was confirmed by these spectra.
3. By the research of the adsorption, chitosan showed high adsorption of radionuclide uranium. The adsorption ratio was obtained more than 96%. Even under the exist condition of large amount of Cu2+, the adsorption was still particularly high. In the meanwhile, chitosan showed high adsorption of radionuclide thorium.
4. The magnetic chitosan particle prepared by precipitation showed regular shape by electro-microscope. Reviewing the scan electric-microscope showed of Fe3O4, most grains were even distributed, and surface smooth, shape similar with roundness, size was about 200～300nm. The scan electric-microscope of Fe3O4@SiO2 showed the grains were even distributed and in good order, homogeneous texture, which size was around 500nm. In the enwraped of the chitosan, Fe3O4 had no effect, which still kept proper crystalization.
5. By the contrast analysis, the adsorption of radionuclide uranium and thorium with magnetic chitosan particle was lowered, but still showed perfect adsorption of these radionuclides.
Conclusion:
1. In the research, the ligands such as -NH2,-OH,-COO- were found to be coordinated with metal ions. The ligand with amino group indicated strong ability of coordination. The coordinated capability was increased according to the order of chitosan, glucosamine and amino acid.
2. Chitosan showed high adsorption of radionuclide uranium. Even under the exist condition of large amount of Cu2+, it still displayed proper adsorption. Meanwhile, it also had good adsorption of thorium.
3. After cross-linking and enwrapping the magnetic particle, the magnetic chitosan particle still kept proper adsorption of the radionuclide uranium and thorium. The new magnetic material was very convenient to separate and recycle from the decontamination medium.
目的：
通过探讨不同配体与金属离子的配位关系,筛选出最佳配位基团；利用基团改性方法调节壳聚糖对放射性核素铀和钍的吸附性能,并确定最佳吸附条件；将具有磁性核引入壳聚糖吸附材料,解决吸附材料从去污介质中分离、回收的难题。通过对壳聚糖及改性后的磁性壳聚糖微球的进行理化表征,及这种磁性壳聚糖对放射性核素铀和钍吸附性能的分析测定,为研究新型高效、高选择性并可再利用的固体吸附材料提供理论和实验依据。
方法：
采用酸碱滴定法、红外光谱和质谱分析法确定壳聚糖的脱乙酰度和聚合度信息；通过紫外可见光谱法,对金属离子Cu2+、Ni2+、Co2+与各种配体(氨基酸,壳聚糖,柠檬酸等)的配合物进行光谱分析,选择最佳配位基团；利用铀和钍分析测定方法检测壳聚糖对放射性核素铀和钍的吸附性能,确定最佳吸附条件；采用沉淀法制备磁性壳聚糖微球,利用扫描电镜显示磁性微球的结构及形态,XRD检测分析磁性核的物相；在最佳吸附条件下,对比分析壳聚糖及其磁性微球对放射性核素铀和钍的吸附性能。
结果：
1.通过紫外可见光谱法,对金属离子Cu2+、Ni2+、Co2+与各种配体(氨基酸,壳聚糖,柠檬酸等)的配合物进行可见扫描,通过光谱图的峰形变化,确定Cu2+与各种配体的配位能力,这种配位能力按照壳聚糖、氨基葡萄糖、氨基酸的顺序增强。
2.采用酸碱滴定法测定出壳聚糖的脱乙酰度为90.1%,IR测定结果验证了不同壳聚糖中的乙酰基和氨基,MALDI-FT-MS进一步给出壳聚糖的脱乙酰度及聚合度的信息。
3.通过壳聚糖吸附性能的研究发现,壳聚糖对放射性核素铀具有较强的吸附能力,吸附率在96%以上。即使在大量Cu2+存在情况下,仍可高效吸附放射性核素铀。在壳聚糖对钍吸附性能的研究中,发现壳聚糖对钍也有较好的吸附能力。
4.通过沉淀法制备的磁性壳聚糖微球,电镜观察显示,壳聚糖形状规整,表面致密均匀；Fe3O4的扫描电镜显示多数纳米粒近似球形,整齐规则,大小在200～300nm；Fe3O4@SiO2的扫描电镜显示粒子分布均匀,形状整齐,粒子大小约500m;XRD的衍射结果表明Fe3O4在壳聚糖的包覆中没有受到影响,仍然保持较好的结晶度。
5.通过与壳聚糖的吸附能力对比,磁性壳聚糖虽然对放射性核素铀和钍的吸附率有所降低,但仍然表现出很好的吸附性能。
结论：
1.在过渡金属离子与配体的配位能力的研究中,发现配体中的-NH2、-OH、-COO-等基团都可与过渡金属离子进行配位。在配体与Cu2+离子配位时,含有氨基的配体显示出较强的配位能力,这种配位能力按照壳聚糖、氨基葡萄糖、氨基酸的顺序增强。
2.壳聚糖由于含有大量的氨基,所以对放射性核素铀有很好的吸附性能。即使在Cu2+存在的情况下,仍然有很高的吸附效率；壳聚糖对钍也表现出较好的吸附性能。
3.将磁性核引入壳聚糖吸附材料后,磁性壳聚糖仍然保持较好的对放射性核素铀和钍的吸附能力,同时还能较方便地从去污介质中分离、回收。
Nowdays, nuclear energy as a type of green energy, is treated as a better solution and show important role for energy shortage. However, in the process of its utilization, high risk is hidden around the world. In the development process of nuclear power, the effective disposal technique of radioactive waste which contains wastewater appears especially important. As an adsorbent material, chitosan and its deviants has the advantage of non-toxicity, easy degradation and no extra pollution. All these above advantages are expected chitosan and its deviants to develop as an environmental eradicator.
Objective:
By discussing the coordination between different ligands and metal ions, the perfect coordinating group could be screen out. Through the method of changing the character of the group, the adsorption of radionuclide uranium and thorium with chitosan and its derivants were adjusted and the optimal adsorptive situation was confirmed. By enclosing the magnetic chitosan particle to the adsorbent material, to solve the difficulty of separation and reusing research from different radio eradicator medium. In this paper, the physic-chemical characterization of chitosan and its derivants were analyzed, including their adsorption, which provided not only the theoretical basis but also the experimental evidence of adsorbent material for high-efficiency reusing research.
Method:
Some physico-chemical characteristics of chitosan were studied by several methods to control degree of deacetylation (DD), the degree of polymer (DP) by acid-base titration, infrared spectroscopy and mass spectrometric analysis respectively. By ultraviolet-visible spectrometry, spectrum analysis was performed in composition of Cu2+, Ni2+, Co2+ with different ligands such as amino acid, chitosan and citric acid etc. Combined with the adsorption of radionuclide uranium and thorium with chitosan and its derivants, the best adsorption condition could be confirmed. Magnetic chitosan particle was prepared by precipitation. Through the scan electro-microscope the configuration and the shape of the particle was analyzed. Physical phase of the magnetic characteristic particle was analyzed by XRD. Contrast the adsorption of radionuclide uranium and thorium with chitosan and its magnetic derivants under the best adsorptive condition.
Result:
1. By ultraviolet-visible spectrometry, scan the coordinated composition of Cu2+ Ni2+ and Co2+ with some ligands such as amino acid, chitosan and citric acid etc. By overview the absorb peaks, the perfect coordination was found between Cu2+ and amino acid. The coordinated capability was increased according to the order of chitosan, glucosamine and amino acid.
2. The degree of deacetylation test of chitosan by acid-base titration was detected as 90.1%. IR spectrum analyzed the acetyl and amino group, the degree of deacetylation and degree of polymer were observed by MALDI-FT-MS respectively. Further information was confirmed by these spectra.
3. By the research of the adsorption, chitosan showed high adsorption of radionuclide uranium. The adsorption ratio was obtained more than 96%. Even under the exist condition of large amount of Cu2+, the adsorption was still particularly high. In the meanwhile, chitosan showed high adsorption of radionuclide thorium.
4. The magnetic chitosan particle prepared by precipitation showed regular shape by electro-microscope. Reviewing the scan electric-microscope showed of Fe3O4, most grains were even distributed, and surface smooth, shape similar with roundness, size was about 200～300nm. The scan electric-microscope of Fe3O4@SiO2 showed the grains were even distributed and in good order, homogeneous texture, which size was around 500nm. In the enwraped of the chitosan, Fe3O4 had no effect, which still kept proper crystalization.
5. By the contrast analysis, the adsorption of radionuclide uranium and thorium with magnetic chitosan particle was lowered, but still showed perfect adsorption of these radionuclides.
Conclusion:
1. In the research, the ligands such as -NH2,-OH,-COO- were found to be coordinated with metal ions. The ligand with amino group indicated strong ability of coordination. The coordinated capability was increased according to the order of chitosan, glucosamine and amino acid.
2. Chitosan showed high adsorption of radionuclide uranium. Even under the exist condition of large amount of Cu2+, it still displayed proper adsorption. Meanwhile, it also had good adsorption of thorium.
3. After cross-linking and enwrapping the magnetic particle, the magnetic chitosan particle still kept proper adsorption of the radionuclide uranium and thorium. The new magnetic material was very convenient to separate and recycle from the decontamination medium.
引文
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