基于新颖固定化灌注型硅基超分子识别材料盐湖中铷铯锶分离新技术新方法

The separation of Rb、Cs and Sr from salt lake by the novel type of the macroporous silica-based supramolecular recognition material has not been reported. In present work, some derivatives of supramolecular recognition agents calix[4]arene-mono/bis-crowns such as Calix[4]R14,Calix[4]BisC6 and othes will be synthesized by molecular modification and characterized by elementary analysis, FT-IR,TG-DSC,ESI-MS,1H NMR and others. The novel macroporous silica-based supramolecular recognition materials, Calix[4]arene-crown/SiO2-P,Calix[4]arene-bis-crown/SiO2-P and crown ether/SiO2-P such as Calix[4]R14/SiO2-P、Calix[4]BisC6/SiO2-P and DtBuCH18C6/SiO2-P, are prepared. It is performed by impregnating and immobilizing Calix[4]arene-crown,Calix[4]arene-bis-crown or DtBuCH18C6 and modifier such as TBP or n-octanol into the pores of the macroporous SiO2-P particles supprot with a size of 40-60 μm and a mean pore of 0.6 μm utilizing vacuum sucking technique. Some novel macroporous silica-based supramolecular recognition materials such as (Calix[4]BisC6+M)/SiO2-P、(DtBuCH18C6+M)/SiO2-P and (Calix[4]BisC6+DtBuCH18C6)/SiO2-P are also synthesized. It is characterized by elementary analysis,FT-IR,TG-DSC,ESI-MS,1H NMR,XRD,BET,XPS,EDS,EXAFS and others.The adsorption behavior of some typical elements such as La, Y, Li, Na, K,Rb，Cs,Mg,Ca,Sr,Ba,Fe,U,B etc. onto the macroporous silica-based supramolecular recognition materials is investigated. It is conducted by examining the effects of contact time, pH value, the concentration of tested metals,temperature and others. In terms of the adsorption of the tested elements, the chromatographic separation of Rb、Cs and Sr from a fedd solution containing more than 15 elements is performed by Calix[4]arene-crown/SiO2-P,Calix[4]arene-bis-crown/SiO2-P and crown ether/SiO2-P packed column, respectively. Based on the static-state and dynamic-state adsorption experiments, a novel separation technique entitled SRCS (Separation of Rubidium, Cesium and Strontium from salt lake by Extraction Chromatography) process has been developed.

新型硅基超分子识别材料从盐湖卤水中分离稀散元素Rb、Cs和Sr的研究尚未见报道。本项目拟对超分子识别试剂杯沿进行修饰，合成与表征新颖单、双冠Calix[4]arene-mono/bis-crown衍生物；基于独创的固定化与真空活化灌注技术，以40-60微米大孔硅基SiO2-P为载体，制备与表征新颖大孔硅基超分子识别材料Calix[4]R14/SiO2-P、Calix[4]BisC6/SiO2-P、DtBuCH18C6/SiO2-P及其被修饰的协同 (Calix[4]BisC6+M)/SiO2-P、(DtBuCH18C6+M)/SiO2-P和 (Calix[4]BisC6+DtBuCH18C6)/SiO2-P材料等；基于吸附与色谱分离理论，研究大孔硅基超分子识别材料对Rb、Cs、Sr及10余种共存元素识别能力和选择性，建立从卤水中有效分离Rb、Cs、Sr新技术新方法，填补国际上该领域的空白。

青海柴达木盐湖含有国民经济发展所急需的许多重要资源，虽经多年探索与研究，其有效开发和综合利用一直是富有挑战性的世界性技术难题，尚未有效解决，其中新型硅基超分子识别材料从盐湖卤水中高效分离稀散元素Rb(I)、Cs(I)和Sr(II)的研究尚未见报道，以新材料新技术和新方法为手段是解决这一科学与技术难题的有效手段。本项目通过对Calix[4]arene母体结构的上缘和下缘进行修饰，基于缩合、消去、加成和环化反应等多步法合成与表征了七种大环单/双冠Calix[4]arene-mono/bis-crown衍生物；建立了制备技术路线；基于独创的真空活化灌注和真空固定化技术及分子修饰技术，基于分子间相互作用力和自修饰作用，以粒径为40-60微米、孔径为0.6微米的大孔硅基SiO2-P及高分子基XAD-7为载体，制备与表征了十余种新颖二元及三元固体大孔硅基/高分子基Calix[4]crown超分子识别材料及其被修饰的协同材料超分子识别材料等,明确了超分子识别材料复合机理，考察了其热稳定性；基于吸附与色谱分离理论，研究了大孔高分子基/硅基超分子识别材料对Rb(I)、Cs(I)、Sr(II)及十余种典型碱金属和碱土金属等共存元素的吸附能力和选择性，以吸附分配系数(Kd)评价了溶液酸度、pH、接触时间和温度等因素变化对超分子识别材料吸附性能的影响，以总有机碳(TOC)含量研究了其化学稳定性及可循环使用寿命；以Langmuir和Freundlich等温吸附模型，明确了大孔高分子基/硅基超分子识别材料的吸附机理，获得了相应化工吸附参数；明确了大孔硅基超分子识别材料在pH9条件下对Rb(I)和Cs(I)的吸附能力和高选择性；基于pH9溶液的弱碱性，明确了以高分子基为载体的超分子识别材料比硅基更具出色的稳定性和吸附性能，考察了从模拟盐湖和真实盐湖水中以新型大孔高分子基/硅基超分子识别材料色谱分离Rb(I)、Cs(I)、Sr(II)的技术可能性和可行性，获得了从pH9.0的盐湖卤水中吸附分离Rb(I)、Cs(I)、Sr(II)的技术要素和技术前景，建立了盐湖卤水中有效吸附分离稀散元素Rb(I)、Cs(I)和Sr(II)新技术和新方法。这些研究结果，为进一步从真实盐湖水中高效分离稀散元素提供了理论与实验依据，填补国际上该领域的空白。