分子组装无机—聚胺材料分离稀土金属离子
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摘要
“中东有石油，中国有稀土”。我国稀土资源丰富，现已成为世界稀土产品的生产大国。稀土是高技术领域中的重要材料，在高科技光电磁材料中，稀土已成为各国竞相关注的21世纪重要的基础材料。单一、高纯稀土是稀土材料的研究及其开发应用的基础。由于稀土元素之间的物理和化学性质十分相似，分离系数很小，稀土矿物共生，稀土精矿分解后所得到的混合稀土化合物中伴生的杂质元素较多。因此，在分离稀土元素的工艺流程中，不但要考虑这十几个化学性质极其相近的稀土元素之间的分离，而且还必须考虑稀土元素同伴生的杂质元素之间的分离。从稀土矿物中制备分离出高纯、单一的稀土是最具有挑战性的研究课题。目前工业化稀土分离方法主要采用液—液萃取法和固—液萃取法。液—液萃取法具有分离速度快、处理量大等优点，但因受目前分离方法的二出口或三出口的限制，每通过一次分离，最多只能获得出口数目的纯稀土，因此，为获得全部纯稀土，需要反复将中间富集物再进萃取槽分离，同时部分有机溶剂残留在水相中，引起污染；而且在技术和经济上限制了对低浓度稀土溶液处理。固—液萃取法包括离子交换法和萃取树脂色层法，因为生产周期长，离子交换法不适合工业生产。萃取树脂把含有萃取剂的载体作为固定相代替离子交换树脂，稀土随流动相在填充床内流动时经过多次的萃取、反萃取和交换等过程，流出液经分部收集，可达到同时获得多个纯稀土的目的。萃取剂的高选择性与树脂填充床的高效性相结合，是萃取树脂应用于分离的突出特点。它克服了溶剂萃取时采用大量有机溶剂带来的污染，以及易乳化和分相困难的缺点，有可能高效地把离子交换法和液—液萃取法难以分离的组分实行有效的分离。萃取树脂色层法，对稀土元素分离的处理量、分离速度、分离效率影响最大的是萃取树脂。制备分离速度快、分离效率高的萃取树脂，是制备高纯、单一稀土的关键。目前用于稀土分离的萃取树脂主要是聚苯乙烯—二乙烯苯共聚物荷载烷基磷酸酯萃取剂，尽管有较高选择性，但是萃取树脂合成方法复杂，价格高，树脂比表面积小；在树脂制备过程中，萃取剂有可能被引入树脂颗粒的闭孔中，导致吸附在闭孔中的稀土离子难脱附，水在非极性苯乙烯—二乙烯苯共聚物表面难湿润，吸附和脱附速率小；一个烷基磷酸酯萃取剂分子只提供几个配位原子，树脂交换容量小；树脂较低的机械强度，萃取剂随流动相流失，树脂在填充床内膨胀，背压高，容易降解，限制聚苯乙烯—二乙烯苯螯合树脂在大规模工业生产中应用。
由于无机材料是由无机元素组成的，其结构的改性和修饰难度很大，难以根据实际需要来控制其大小、形状以及物理化学特性。而有机化合物则具有优良的分子剪裁与修饰的功能，但它们却在坚固性与稳定性等方面具有明显的缺点。如何将无机和有机化合物两者互补的性能结合起来，构筑结构可塑、稳定、坚固的新型杂化材料已成为无机化学与材料科学领域中的重要研究课题。近几年来运用分子设计和分子工程思想进行无机功能材料的复合、组装、杂化以及加强功能性物质结构与性能已成为无机功能材料研究热点；其中以功能为目标进行无机—有机杂化材料的精心设计和调控已成为这一领域中的挑战性课题。
本论文运用分子设计进行组装的无机—聚胺材料，用于稀土金属离子吸附分离；吸附稀土金属离子后的无机—聚胺材料，可以用淋洗液将无机—聚胺材料吸附的稀土金属离子洗脱下来，无机—聚胺材料重新活化再生，可多次循环使用，不产生二次污染物。分子组装的无机—聚胺材料，赋予特效选择稀土金属离子的筛效应与键合能力，可极大地提高对水溶液中稀土金属离子的负载容量和分离效果。该无机—聚胺材料新型萃取树脂研制开发，促进国内稀土总回收率提高，不可再生稀土资源的有效利用，稀土资源的可持续发展具有一定的意义。
本文利用表面活性剂诱导合成法和离子印迹技术，通过正硅酸乙酯和N-(2-氨乙基)-3-氨丙基三甲氧基硅烷酸性催化水解和缩聚反应，将氨基嫁接到介孔材料的孔壁上，制备出一类有序无机—聚胺杂化材料；利用锚定剂乙烯基三氯硅烷(Cl_3SiCHCH_2)，在膨润土表面，接枝低分子量壳聚糖，制备出第二类壳聚糖聚胺—膨润土材料。利用FT—IR、TG—DTA、XRD、MIP等技术，表征了上述二类杂化材料的组成和孔结构，主要研究内容及结论如下：
1、利用CTAB诱导合成法和稀土离子印迹技术，通过TEOS和AAPS酸性催化水解和缩聚反应，通过共价键结合，使带有氨基的硅烷将氨基嫁接到介孔材料内表面孔壁上，制备出一类新颖的稀土离子印迹无机—聚胺介孔杂化材料；首次应用此类新颖介孔杂化材料分离稀土。通过正交试验设计，确定了La~(3+)印迹无机—聚胺介孔杂化材料的制备最佳工艺条件为TEOS：AAPS：CTAB：H_2O：La(NO_3)_3摩尔配比是1：0.25：0.15：230：0.1，反应溶液pH值是2，反应初期水解反应温度60℃。在此工艺条件制备的La~(3+)印迹无机—聚胺介孔杂化材料，平均粒度是11.19μm，比表面积为513.4 m~2／g、平均孔径4.62 nm；在1.0×10~(-3)mol／L La~(3+)溶液测定La~(3+)吸附量为176 mmol／g。
2、首次利用稀土离子印迹技术，以及锚定剂乙烯基三氯硅烷，通过MA和AM自由基共聚反应，将壳聚糖接枝到无机膨润土表面，组装壳聚糖聚丙酰胺—膨润土材料，经过Hofmann降解反应制备出壳聚糖聚胺—膨润土材料，应用此类新颖杂化材料分离稀土。确定组装La~(3+)印迹壳聚糖聚胺—膨润土材料合理工艺条件：乙烯基硅烷化膨润土1 g，壳聚糖0.5 g，MA 0.4 g，AM 1.6 g，LaCI_3 1 g，水3 g，K_2S_2O_8 0.02 g；反应温度70℃，反应时间4 h；Hofmann降解反应：NaOH 6 g，5％NaOCI 8.1 g反应温度-10℃，反应时间6 h。La~(3+)印迹壳聚糖聚胺—膨润土材料的粒度分布不均匀，平均粒度是66.77μm，比表面积为83.52 m~2／g、平均孔径4.53 nm；在1.0×10~(-3)mol／L La~(3+)溶液测定La~(3+)吸附量为11.6 mmol／g；接枝到膨润土表面的壳聚糖、聚胺和甲基丙烯酸等有机物达到34％。
3、采用循环伏安法，扫描电位在-0.80～0.00 V范围内(vs.SCE)，分别研究了La~(3+)、Ce~(3+)、Y~(3+)三种稀土离子与三溴偶氮胂在壳聚糖修饰碳糊电极上，形成的络合吸附波，一对灵敏的氧化还原峰，利用峰电位不同，对稀土离子定性电化学识别，利用峰电流的大小，对稀土离子定量电化学识别。并分别测定了这三种稀土离子的线性范围和方法检出限，并计算出相应的回归线性关系式。获得稀土离子测试的最佳pH值范围1.5～3.0。常见碱金属和碱土金属离子不干扰测定；该方法简便、有效用于稀土离子的电化学识别。
4、采用稀土离子电化学识别，寻找到一种快速、简单方法，来量化评价离子印迹聚合物对稀土离子的化学识别。根据固相萃取过程中的分离因数，定义了识别率(the recognition ratio)R=K_(impr int ed)／K_(nonimpr int ed)；在同一电解池中，被测稀土金属离子浓度恒定时，利用稀土金属离子的电化学识别，印迹杂化材料和空白杂化材料修饰碳糊电极分别作为工作电极，循环伏安图中的峰电流，可以计算出印迹杂化材料识别率。测定的La~(3+)印迹壳聚糖聚胺—膨润土、Ce~(3+)印迹壳聚糖聚胺—膨润土、La~(3+)印迹无机—聚胺、Ce~(3+)印迹无机—聚胺杂化材料识别率分别是1.91、2.65、2.10、1.78。
"There is oil in the Middle East, there is rare earth in China". China has the most abundant rare earth resources, at present, it has been the largest producer and supplier in the world. In the 21st century, rare earths are important materials in high-tech areas, especially in photoelectric, magnetic functional materials, which have aroused worldwide attention. Sole, the high pure rare earth is a base to exploit and study on the application of rare earth materials. Because they have very similar physical and chemical properties, rare earth elements tend to occur together in Earth's crust, moreover, there are many impurity elements in rare earth mixtures obtained by decomposing rare earth minerals, making their separation extremely difficult. Thus, in the process of the separation of rare earth elements, we must consider not only the separation of rare earth elements among 17 elements, which have very similar physical and chemical properties, but also the separation of many impurity elements, which occur together with rare earth elements in Earth's crust. It is a challenging task to separate rare earths from rare earth ores. The most important separation processes today make use of combinations of liquid-liquid and solid-liquid extraction. Liquid-liquid extraction has been the favored route for a fast separation velocity and a big production capacity. Because of the limits of two or three vents in this separation method, most only can obtain the vent number the pure rare earths via a separation process. Thus, in order to obtain all rare earths, it is needed that intermediate concentration rare earths reentry into an organic phase that is in contact with an acidic solution of the extractor, and many extraction cycles are required. Liquid-liquid extraction may involve environmental drawbacks such as relics of solvents or extractants in water; furthermore, their technical and economic efficiencies are limited by the treatment of dilute effluents. The solid-liquid extraction includes ion exchange and extraction chromatography. The ion exchange process is not suitable for industrial production because of the very long periods required to accomplish significant separation. The extraction resin with the extraction carrier as the stationary phase instead of the ion exchanger, rare earths are extracted, counter-extracted and exchanged time after time while they are flowing along with the mobile phase through a packed bed, the effluent is sectionally collected, and simultaneously obtains many pure rare earths at one time. However, the extraction chromatography combines the selectivity and the flexibility of liquid-liquid extractions with the versatility, the high efficiency and the simplicity of chromatographic columns. Extraction chromatographic separation overcomes the defects of solvent extraction, which are easy emulsification, solvent pollution and difficulty in phase separation. Extraction chromatographic separation may separate effectively rare earths for their difficult separation by using ion exchange or liquid-liquid extraction. In extraction chromatographic separation, extraction resins influence clearly production capacity, separation velocity and separation efficiency of rare earth. The extraction resin with a fast separation velocity and high separation efficiency is a key to separate rare earth. Conventional poly (styrene-divinylbenzene) resin with organophosphorus compounds as an extractant, seems to have favourable properties such as the high selectivity, but their very complicated methods of synthesis, high cost, small specific surface area of resins, slow sorption and desorption, small exchange capacity of resins, low mechanical strength, extractants loss with flow phase, large resin bed volumes, high back pressure and easily degradation have limited their application in industrial scale separation processes; moreover, extractants may be inducted into the closed pores of resin grains, and result in desorption difficulty of rare earth ions adsorbed into closed pores; water is difficult to wet surfaces of the nonpolar poly (styrene-divinylbenzene) resin; one organophosphorus extractant only provides several coordinating atoms; the resin swells in a packed bed.
Because characteristics of inorganic materials, it is extremely difficult to change or modify the configuration, according to the practicably need to control size, configuration, physical and chemical properties. Whereas, organic materials have excellent molecular tailorable and modificatory function, but have the defects of consistency and stability. How to combine each other properties both inorganic materials and organic materials, and to construct plasticity, stabilization, ruggedization of novel hybrid materials in configuration, has become an important challenging task in inorganic chemistry and materials science. In recent years, how to recombine, assemble, hybridize and reinforce functional properties of materials has become an investigating hotspot by using molecular design and engineering thoughts; especially, in order to obtain functional properties as an aim, how to design and control carefully inorganic-organic materials has become a challenging task in this area.
In this dissertation, using molecular design, inorganic polyamine materials are molecularly assembled for the adsorption and separation of rare earth ions. When rare earth ions are desorbed from adsorbed inorganic polyamine materials, they may regenerate adsorption capacity for recycled use, and do not produce contamination. Inorganic polyamine materials molecular assembly endows with a good selection and combination of rare earth ions, which improves the adsorption capacity and separation efficiency of rare earth ions in solution. To develop and exploit these inorganic polyamine materials-novel extraction resins, is very important to accelerate improvements in the overall yield of rare earth, to make efficient use of rare earth resources for their sustainable development in China, they can not be regenerated.
In this paper, there are two kinds of hybrid polyamine materials. Firstly, using both surfactant-mediated synthetic method and ionic imprinting technique, the amino group is grafted on the pore wall of mesoporous materials, a novel ordered hybrid inorganic-polyamine material is prepared via the acid-catalyzed hydrolysis and polycondensation of TEOS and AAPS. Secondly, using anchor reagent Cl_3SiCHCH_2, low molecular weight chitosan is grafted on the surface of bentonite, a novel chitosan polyamine-bentonite hybrid material is prepared via the covalent combination of polyamine ligands and bentonite. The composition and pore structures of these two kinds of hybrid materials are characterized with FT-IR, TG-DTA, XRD and MIP. The mostly investigated contents and obtained results are outlined as follows:
1. Using both CTAB surfactant-mediated synthetic method and ionic imprinting technique, the amino group is grafted on the pore wall of mesoporous materials via a covalent combination, a novel ordered hybrid inorganic-polyamine material is prepared via the acid-catalyzed hydrolysis and polycondensation of TEOS and AAPS. This novel ordered mesoporous inorganic-organic hybrid material is used to the separation of rare earth ions for the first time. The optimal technological conditions are determined by orthogonal experiments to prepare mesoporous hybrid La~(3+) imprinted inorganic-polyamine material, namely, TEOS:AAPS:CTAB: H_2O: La(NO_3)_3 mole ratio is 1: 0.25: 0.15: 230: 0.1, reaction solution pH is 2, and the hydrolysis temperature is 60℃in initial reaction stage. The mesoporous hybrid La~(3+) imprinted inorganic-polyamine material is prepared under this optimal technological conditions, its average granularity is 11.19μm, its specific surface area is 513.4 m~2/g, its average pore radius is 4.62 nm and the La~(3+) adsorption capacity is 176 mmol/g in 1.0×10~(-3) mol/L La~(3+) solution.
2. Using ionic imprinting technique and anchor reagent Cl_3SiCHCH_2, low molecular weight chitosan is grafted on the surface of bentonite, a novel hybrid chitosan polyacrylamide-bentonite material is assembled through radical copolymerization of MA and AM, Hoffmann reaction is carried out to prepare the novel hybrid chitosan polyamine-bentonite material. It is first application on the separation of rare earth ions. The optimum technological conditions are obtained to assemble La~(3+) imprinted chitosan polyamine -bentonite material, namely, 1 g dried silylated bentonite, 0.5 g chitosan, 0.4 g MA, 1.6 g AM, 1 g LaCI_3, 3 g H_2O, 0.02 g K_2S_2O_8, reaction temperature is 70℃and reaction time is 4 h; moreover, in Hoffmann reaction, 6 g NaOH, 8.1 g 5% NaOCI, reaction temperature is -10℃and reaction time is 6 h. The La~(3+) imprinted chitosan polyamine-bentonite material is assembled under this technological conditions, its granularity distribution is asymmetric, its average granularity is 66.77μm, its specific surface area is 83.52 m~2/g, its average pore radius is 4.53 nm and the La~(3+) adsorption capacity is 11.6 mmol/g in 1.0×10~(-3) mol/L La~(3+) solution. The organic compound, such as chitosan, polyamine and methacrylic acid, grafted on bentonite arrives at 34 %.
3. Cyclic voltammetry is applied to electrochemically recognize La~(3+) or Ce~(3+), Y~(3+) using carbon paste electrodes modified with chitosan. A pair of well-defined sensitive redox peaks, representing the adsorptive complexes of the rare earth ion and tribromoarsenazo, are found using scanning potentials from -0.80 to 0.00 V vs. SCE. These peak potentials and peak currents are used to determine quantitatively these rare earth ions. The linear detection range and detection limit of La~(3+) or Ce~(3+), Y~(3+) are determined, respectively; linear fit relations of RE(III) are calculated. The optimal pH range 1.5～3.0 is obtained for these rare earth ions detection. Some common metal ions such as alkali and alkaline cations do not effect determination of the rare earth ion. This simple, effective method can be used to electrochemical recognition of rare earth ions.
4. Keeping the rare earth ion concentrations constant, permit developing a simple, effective method to evaluate quantitatively the ionic recognition of the imprinted polymers using electrochemical recognition of rare earth ions. Based on the distribution coefficient in a solid-liquid extraction process, the recognition ratio is given by R = K_(impr int ed)/K_(nonimpr int ed) . In the sameelectrochemical cell, keeping the concentrations of rare earth ions constant, the recognition ratio R is calculated by the peak current in the cyclic voltammograms. In this study, the recognition ratios of La~(3+) imprinted chitosan polyamine-bentonite material, Ce~(3+) imprinted chitosan polyamine -bentonite material, La~(3+) imprinted inorganic-polyamine material and Ce~(3+) imprinted inorganic-polyamine material are 1.91, 2.65, 2.10 and 1.78, respectively.
由于无机材料是由无机元素组成的，其结构的改性和修饰难度很大，难以根据实际需要来控制其大小、形状以及物理化学特性。而有机化合物则具有优良的分子剪裁与修饰的功能，但它们却在坚固性与稳定性等方面具有明显的缺点。如何将无机和有机化合物两者互补的性能结合起来，构筑结构可塑、稳定、坚固的新型杂化材料已成为无机化学与材料科学领域中的重要研究课题。近几年来运用分子设计和分子工程思想进行无机功能材料的复合、组装、杂化以及加强功能性物质结构与性能已成为无机功能材料研究热点；其中以功能为目标进行无机—有机杂化材料的精心设计和调控已成为这一领域中的挑战性课题。
本论文运用分子设计进行组装的无机—聚胺材料，用于稀土金属离子吸附分离；吸附稀土金属离子后的无机—聚胺材料，可以用淋洗液将无机—聚胺材料吸附的稀土金属离子洗脱下来，无机—聚胺材料重新活化再生，可多次循环使用，不产生二次污染物。分子组装的无机—聚胺材料，赋予特效选择稀土金属离子的筛效应与键合能力，可极大地提高对水溶液中稀土金属离子的负载容量和分离效果。该无机—聚胺材料新型萃取树脂研制开发，促进国内稀土总回收率提高，不可再生稀土资源的有效利用，稀土资源的可持续发展具有一定的意义。
本文利用表面活性剂诱导合成法和离子印迹技术，通过正硅酸乙酯和N-(2-氨乙基)-3-氨丙基三甲氧基硅烷酸性催化水解和缩聚反应，将氨基嫁接到介孔材料的孔壁上，制备出一类有序无机—聚胺杂化材料；利用锚定剂乙烯基三氯硅烷(Cl_3SiCHCH_2)，在膨润土表面，接枝低分子量壳聚糖，制备出第二类壳聚糖聚胺—膨润土材料。利用FT—IR、TG—DTA、XRD、MIP等技术，表征了上述二类杂化材料的组成和孔结构，主要研究内容及结论如下：
1、利用CTAB诱导合成法和稀土离子印迹技术，通过TEOS和AAPS酸性催化水解和缩聚反应，通过共价键结合，使带有氨基的硅烷将氨基嫁接到介孔材料内表面孔壁上，制备出一类新颖的稀土离子印迹无机—聚胺介孔杂化材料；首次应用此类新颖介孔杂化材料分离稀土。通过正交试验设计，确定了La~(3+)印迹无机—聚胺介孔杂化材料的制备最佳工艺条件为TEOS：AAPS：CTAB：H_2O：La(NO_3)_3摩尔配比是1：0.25：0.15：230：0.1，反应溶液pH值是2，反应初期水解反应温度60℃。在此工艺条件制备的La~(3+)印迹无机—聚胺介孔杂化材料，平均粒度是11.19μm，比表面积为513.4 m~2／g、平均孔径4.62 nm；在1.0×10~(-3)mol／L La~(3+)溶液测定La~(3+)吸附量为176 mmol／g。
2、首次利用稀土离子印迹技术，以及锚定剂乙烯基三氯硅烷，通过MA和AM自由基共聚反应，将壳聚糖接枝到无机膨润土表面，组装壳聚糖聚丙酰胺—膨润土材料，经过Hofmann降解反应制备出壳聚糖聚胺—膨润土材料，应用此类新颖杂化材料分离稀土。确定组装La~(3+)印迹壳聚糖聚胺—膨润土材料合理工艺条件：乙烯基硅烷化膨润土1 g，壳聚糖0.5 g，MA 0.4 g，AM 1.6 g，LaCI_3 1 g，水3 g，K_2S_2O_8 0.02 g；反应温度70℃，反应时间4 h；Hofmann降解反应：NaOH 6 g，5％NaOCI 8.1 g反应温度-10℃，反应时间6 h。La~(3+)印迹壳聚糖聚胺—膨润土材料的粒度分布不均匀，平均粒度是66.77μm，比表面积为83.52 m~2／g、平均孔径4.53 nm；在1.0×10~(-3)mol／L La~(3+)溶液测定La~(3+)吸附量为11.6 mmol／g；接枝到膨润土表面的壳聚糖、聚胺和甲基丙烯酸等有机物达到34％。
3、采用循环伏安法，扫描电位在-0.80～0.00 V范围内(vs.SCE)，分别研究了La~(3+)、Ce~(3+)、Y~(3+)三种稀土离子与三溴偶氮胂在壳聚糖修饰碳糊电极上，形成的络合吸附波，一对灵敏的氧化还原峰，利用峰电位不同，对稀土离子定性电化学识别，利用峰电流的大小，对稀土离子定量电化学识别。并分别测定了这三种稀土离子的线性范围和方法检出限，并计算出相应的回归线性关系式。获得稀土离子测试的最佳pH值范围1.5～3.0。常见碱金属和碱土金属离子不干扰测定；该方法简便、有效用于稀土离子的电化学识别。
4、采用稀土离子电化学识别，寻找到一种快速、简单方法，来量化评价离子印迹聚合物对稀土离子的化学识别。根据固相萃取过程中的分离因数，定义了识别率(the recognition ratio)R=K_(impr int ed)／K_(nonimpr int ed)；在同一电解池中，被测稀土金属离子浓度恒定时，利用稀土金属离子的电化学识别，印迹杂化材料和空白杂化材料修饰碳糊电极分别作为工作电极，循环伏安图中的峰电流，可以计算出印迹杂化材料识别率。测定的La~(3+)印迹壳聚糖聚胺—膨润土、Ce~(3+)印迹壳聚糖聚胺—膨润土、La~(3+)印迹无机—聚胺、Ce~(3+)印迹无机—聚胺杂化材料识别率分别是1.91、2.65、2.10、1.78。
"There is oil in the Middle East, there is rare earth in China". China has the most abundant rare earth resources, at present, it has been the largest producer and supplier in the world. In the 21st century, rare earths are important materials in high-tech areas, especially in photoelectric, magnetic functional materials, which have aroused worldwide attention. Sole, the high pure rare earth is a base to exploit and study on the application of rare earth materials. Because they have very similar physical and chemical properties, rare earth elements tend to occur together in Earth's crust, moreover, there are many impurity elements in rare earth mixtures obtained by decomposing rare earth minerals, making their separation extremely difficult. Thus, in the process of the separation of rare earth elements, we must consider not only the separation of rare earth elements among 17 elements, which have very similar physical and chemical properties, but also the separation of many impurity elements, which occur together with rare earth elements in Earth's crust. It is a challenging task to separate rare earths from rare earth ores. The most important separation processes today make use of combinations of liquid-liquid and solid-liquid extraction. Liquid-liquid extraction has been the favored route for a fast separation velocity and a big production capacity. Because of the limits of two or three vents in this separation method, most only can obtain the vent number the pure rare earths via a separation process. Thus, in order to obtain all rare earths, it is needed that intermediate concentration rare earths reentry into an organic phase that is in contact with an acidic solution of the extractor, and many extraction cycles are required. Liquid-liquid extraction may involve environmental drawbacks such as relics of solvents or extractants in water; furthermore, their technical and economic efficiencies are limited by the treatment of dilute effluents. The solid-liquid extraction includes ion exchange and extraction chromatography. The ion exchange process is not suitable for industrial production because of the very long periods required to accomplish significant separation. The extraction resin with the extraction carrier as the stationary phase instead of the ion exchanger, rare earths are extracted, counter-extracted and exchanged time after time while they are flowing along with the mobile phase through a packed bed, the effluent is sectionally collected, and simultaneously obtains many pure rare earths at one time. However, the extraction chromatography combines the selectivity and the flexibility of liquid-liquid extractions with the versatility, the high efficiency and the simplicity of chromatographic columns. Extraction chromatographic separation overcomes the defects of solvent extraction, which are easy emulsification, solvent pollution and difficulty in phase separation. Extraction chromatographic separation may separate effectively rare earths for their difficult separation by using ion exchange or liquid-liquid extraction. In extraction chromatographic separation, extraction resins influence clearly production capacity, separation velocity and separation efficiency of rare earth. The extraction resin with a fast separation velocity and high separation efficiency is a key to separate rare earth. Conventional poly (styrene-divinylbenzene) resin with organophosphorus compounds as an extractant, seems to have favourable properties such as the high selectivity, but their very complicated methods of synthesis, high cost, small specific surface area of resins, slow sorption and desorption, small exchange capacity of resins, low mechanical strength, extractants loss with flow phase, large resin bed volumes, high back pressure and easily degradation have limited their application in industrial scale separation processes; moreover, extractants may be inducted into the closed pores of resin grains, and result in desorption difficulty of rare earth ions adsorbed into closed pores; water is difficult to wet surfaces of the nonpolar poly (styrene-divinylbenzene) resin; one organophosphorus extractant only provides several coordinating atoms; the resin swells in a packed bed.
Because characteristics of inorganic materials, it is extremely difficult to change or modify the configuration, according to the practicably need to control size, configuration, physical and chemical properties. Whereas, organic materials have excellent molecular tailorable and modificatory function, but have the defects of consistency and stability. How to combine each other properties both inorganic materials and organic materials, and to construct plasticity, stabilization, ruggedization of novel hybrid materials in configuration, has become an important challenging task in inorganic chemistry and materials science. In recent years, how to recombine, assemble, hybridize and reinforce functional properties of materials has become an investigating hotspot by using molecular design and engineering thoughts; especially, in order to obtain functional properties as an aim, how to design and control carefully inorganic-organic materials has become a challenging task in this area.
In this dissertation, using molecular design, inorganic polyamine materials are molecularly assembled for the adsorption and separation of rare earth ions. When rare earth ions are desorbed from adsorbed inorganic polyamine materials, they may regenerate adsorption capacity for recycled use, and do not produce contamination. Inorganic polyamine materials molecular assembly endows with a good selection and combination of rare earth ions, which improves the adsorption capacity and separation efficiency of rare earth ions in solution. To develop and exploit these inorganic polyamine materials-novel extraction resins, is very important to accelerate improvements in the overall yield of rare earth, to make efficient use of rare earth resources for their sustainable development in China, they can not be regenerated.
In this paper, there are two kinds of hybrid polyamine materials. Firstly, using both surfactant-mediated synthetic method and ionic imprinting technique, the amino group is grafted on the pore wall of mesoporous materials, a novel ordered hybrid inorganic-polyamine material is prepared via the acid-catalyzed hydrolysis and polycondensation of TEOS and AAPS. Secondly, using anchor reagent Cl_3SiCHCH_2, low molecular weight chitosan is grafted on the surface of bentonite, a novel chitosan polyamine-bentonite hybrid material is prepared via the covalent combination of polyamine ligands and bentonite. The composition and pore structures of these two kinds of hybrid materials are characterized with FT-IR, TG-DTA, XRD and MIP. The mostly investigated contents and obtained results are outlined as follows:
1. Using both CTAB surfactant-mediated synthetic method and ionic imprinting technique, the amino group is grafted on the pore wall of mesoporous materials via a covalent combination, a novel ordered hybrid inorganic-polyamine material is prepared via the acid-catalyzed hydrolysis and polycondensation of TEOS and AAPS. This novel ordered mesoporous inorganic-organic hybrid material is used to the separation of rare earth ions for the first time. The optimal technological conditions are determined by orthogonal experiments to prepare mesoporous hybrid La~(3+) imprinted inorganic-polyamine material, namely, TEOS:AAPS:CTAB: H_2O: La(NO_3)_3 mole ratio is 1: 0.25: 0.15: 230: 0.1, reaction solution pH is 2, and the hydrolysis temperature is 60℃in initial reaction stage. The mesoporous hybrid La~(3+) imprinted inorganic-polyamine material is prepared under this optimal technological conditions, its average granularity is 11.19μm, its specific surface area is 513.4 m~2/g, its average pore radius is 4.62 nm and the La~(3+) adsorption capacity is 176 mmol/g in 1.0×10~(-3) mol/L La~(3+) solution.
2. Using ionic imprinting technique and anchor reagent Cl_3SiCHCH_2, low molecular weight chitosan is grafted on the surface of bentonite, a novel hybrid chitosan polyacrylamide-bentonite material is assembled through radical copolymerization of MA and AM, Hoffmann reaction is carried out to prepare the novel hybrid chitosan polyamine-bentonite material. It is first application on the separation of rare earth ions. The optimum technological conditions are obtained to assemble La~(3+) imprinted chitosan polyamine -bentonite material, namely, 1 g dried silylated bentonite, 0.5 g chitosan, 0.4 g MA, 1.6 g AM, 1 g LaCI_3, 3 g H_2O, 0.02 g K_2S_2O_8, reaction temperature is 70℃and reaction time is 4 h; moreover, in Hoffmann reaction, 6 g NaOH, 8.1 g 5% NaOCI, reaction temperature is -10℃and reaction time is 6 h. The La~(3+) imprinted chitosan polyamine-bentonite material is assembled under this technological conditions, its granularity distribution is asymmetric, its average granularity is 66.77μm, its specific surface area is 83.52 m~2/g, its average pore radius is 4.53 nm and the La~(3+) adsorption capacity is 11.6 mmol/g in 1.0×10~(-3) mol/L La~(3+) solution. The organic compound, such as chitosan, polyamine and methacrylic acid, grafted on bentonite arrives at 34 %.
3. Cyclic voltammetry is applied to electrochemically recognize La~(3+) or Ce~(3+), Y~(3+) using carbon paste electrodes modified with chitosan. A pair of well-defined sensitive redox peaks, representing the adsorptive complexes of the rare earth ion and tribromoarsenazo, are found using scanning potentials from -0.80 to 0.00 V vs. SCE. These peak potentials and peak currents are used to determine quantitatively these rare earth ions. The linear detection range and detection limit of La~(3+) or Ce~(3+), Y~(3+) are determined, respectively; linear fit relations of RE(III) are calculated. The optimal pH range 1.5～3.0 is obtained for these rare earth ions detection. Some common metal ions such as alkali and alkaline cations do not effect determination of the rare earth ion. This simple, effective method can be used to electrochemical recognition of rare earth ions.
4. Keeping the rare earth ion concentrations constant, permit developing a simple, effective method to evaluate quantitatively the ionic recognition of the imprinted polymers using electrochemical recognition of rare earth ions. Based on the distribution coefficient in a solid-liquid extraction process, the recognition ratio is given by R = K_(impr int ed)/K_(nonimpr int ed) . In the sameelectrochemical cell, keeping the concentrations of rare earth ions constant, the recognition ratio R is calculated by the peak current in the cyclic voltammograms. In this study, the recognition ratios of La~(3+) imprinted chitosan polyamine-bentonite material, Ce~(3+) imprinted chitosan polyamine -bentonite material, La~(3+) imprinted inorganic-polyamine material and Ce~(3+) imprinted inorganic-polyamine material are 1.91, 2.65, 2.10 and 1.78, respectively.
引文
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