软配体化合物2，6-（5，6-二壬基-1，2，4-三嗪-3-基）吡啶的合成、表征及基础特性研究
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摘要
次锕系元素MA(Ⅲ)是高放废液中含有的长寿命和高毒性的放射性核素,必需对其进行分离,然而由于次锕系元素与镧系元素的化学性质极为相似,其有效分离一直是分离科学与技术领域的热点和难点课题。
本文合成了一种新型软配体化合物2,6-(5,6-二壬基-1,2,4-三嗪-3-基)吡啶(Non-BTP),以FT-IR、TG-DSC、ESI-MS和1H NMR等手段对中间产物和目标产物的结构与组成进行了表征,并对2,,6-吡啶二甲酰胺腙的合成工艺条件进行了优化,获得的最佳工艺条件为：2,6-吡啶二甲腈：85%水合肼：重结晶水量=1:15:174,反应时间为30 h,反应温度为30℃,产率为85.37%。
研究了Non-BTP/30%正辛醇-70%正十二烷体系对Rb(Ⅰ)、Cs(Ⅰ)、Sr(Ⅱ)、Ba(Ⅱ)、Pd(Ⅱ)、Ru(Ⅲ)、La(Ⅲ)、Co(Ⅲ)、Fe(Ⅲ)、Ni(Ⅲ)、Y(Ⅲ)、Sm(Ⅲ)、Yb(Ⅲ)、Zr(Ⅳ)和Mo(Ⅵ)等10余种典型金属离子的萃取性能。实验结果表明：Non-BTP对过渡元素尤其是Pd(Ⅱ)有较好的萃取性能,最佳HN03浓度为3.0 M;萃取平衡时间约为30 min; Pd(Ⅱ)与Non-BTP形成1:2的配合物；Non-BTP在30%正辛醇-70%正十二烷中萃取Pd(Ⅱ)离子的过程为放热反应,并计算了相关热力学参数。
利用真空活化灌注技术,以大孔硅基Si02-P为载体,制备了新型2,6-(5,6-二壬基-1,2,4-三嗪-3-基)吡啶软配体复合材料(Non-BTP/SiO2-P),以FT-IR、SEM、TG-DSC、XRD和BET等手段对其进行了表征,明确了Non-BTP/SiO2-P的微观结构、化学组成以及复合机理。
研究了Non-BTP/SiO2-P对Rb(Ⅰ)、Cs(Ⅰ)、Sr(Ⅱ)、Ba(Ⅱ)、Pd(Ⅱ)、Ru(Ⅲ)、La(Ⅲ)、Co(Ⅲ)、Fe(Ⅲ)、Ni(Ⅲ)、Y(Ⅲ)、Sm(Ⅲ)、Yb(Ⅲ)、Zr(Ⅳ)和Mo(Ⅵ)等10余种典型金属离子的吸附性能,考察了HN03浓度和接触时间变化等因素对吸附性能的影响。通过测定不同条件下水相中的有机碳含量,表明Non-BTP/SiO2-P有较好的稳定性。Non-BTP/SiO2-P对过渡元素尤其是Pd(Ⅱ)有较好的吸附性能,对Ln(Ⅲ)基本无吸附作用,最佳HN03浓度为3.0 M,吸附平衡时间约为30 min。
The long-lived minor actinide (MA(III)) elements contained in high level liquid waste (HLLW) generated in reprocessing process of nuclear spent fuel have long-term radiological risk, it is valuable to separate them from HLLW for further transmutation.
2,6-bis(5,6-dialkyl-1,2,4-triazine-3-yl)pyridine (R-BTP) is a kind of multidentate chelating agent containing nitrogen which has better complexing ability for MA(III) than Ln(III). A novel soft ligand 2,6-bis(5,6-dinonyl-1,2,4-triazine-3-yl) pyridine (Non-BTP) was synthesized using 2,6-pyridinedicarbonitrile and ethyl decanoate as raw materials. It was characterized by FT-IR, TG-DSC, ESI-MS, and 1H NMR. An improved synthetic process of 2,6-pyridinedicarboxamide dihydrazone was proposed. The optimum conditions were described as follows:2,6-pyridine dicarbonitrile: 85%N2H4=1:15, reaction time=30 h, reaction temperature=30℃. The optimum yield of the product was 85.37%.
Using 30% n-octanol/70% n-dodecane as diluent, the extraction behavior of Rb(Ⅰ), Cs(Ⅰ), Sr(Ⅱ), Ba(Ⅱ), Pd(Ⅱ), Ru(Ⅲ), La(Ⅲ), Co(Ⅲ), Fe(Ⅲ), Ni(Ⅲ), Y(Ⅲ), Sm(Ⅲ), Yb(Ⅲ), Zr(Ⅳ) and Mo(Ⅳ) from HNO3 solution was studied. The influences of HNO3 concentration, Non-BTP content, contact time, and temperature on the extraction ability were investigated. It was found that the complex composition between Pd(Ⅱ) and Non-BTP was determined as 1:2 type. In addition, the thermodynamic parameters of Pd(Ⅱ) extrated by Non-BTP were calculated.
A novel macroporous silica-based 2,6-bis(5,6-dinonyl-1,2,4-triazine-3-yl) pyridine (Non-BTP/SiO2-P) was prepared through impregnation and immobilization of the corresponding R-BTP compound into the pores of the macroporous SiO-P support. The appearance, chemical composition, and inner structure were characterized by FT-IR, SEM, TG-DSC, XRD, and BET.
The effects of HNO3 concentration and contant time on the adsorption of Rb(Ⅰ), Cs(Ⅰ), Sr(Ⅱ), Ba(Ⅱ), Pd(Ⅱ), Ru(Ⅲ), La(Ⅲ), Co(Ⅲ), Fe(Ⅲ), Ni(Ⅲ), Y(Ⅲ), Sm(Ⅲ), Yb(Ⅲ), Zr(Ⅳ), Mo(Ⅵ), and more than 10 typical elements onto the Non-BTP/SiO2-P materials were investigated at 25℃. The Non-BTP/SiO2-P material showed excellent adsorption ability and selectivity for Pd(Ⅱ) over all of the other tested metals. The optium acidity for the Pd(Ⅱ) adsorption was 3.0 M HNO3. In addition, the uptake of Ln(Ⅲ) onto the Non-BTP/SiO2-P material was negligible, which was beneficial to separate MA(Ⅲ) from Ln(Ⅲ) using this composite in further researches.
本文合成了一种新型软配体化合物2,6-(5,6-二壬基-1,2,4-三嗪-3-基)吡啶(Non-BTP),以FT-IR、TG-DSC、ESI-MS和1H NMR等手段对中间产物和目标产物的结构与组成进行了表征,并对2,,6-吡啶二甲酰胺腙的合成工艺条件进行了优化,获得的最佳工艺条件为：2,6-吡啶二甲腈：85%水合肼：重结晶水量=1:15:174,反应时间为30 h,反应温度为30℃,产率为85.37%。
研究了Non-BTP/30%正辛醇-70%正十二烷体系对Rb(Ⅰ)、Cs(Ⅰ)、Sr(Ⅱ)、Ba(Ⅱ)、Pd(Ⅱ)、Ru(Ⅲ)、La(Ⅲ)、Co(Ⅲ)、Fe(Ⅲ)、Ni(Ⅲ)、Y(Ⅲ)、Sm(Ⅲ)、Yb(Ⅲ)、Zr(Ⅳ)和Mo(Ⅵ)等10余种典型金属离子的萃取性能。实验结果表明：Non-BTP对过渡元素尤其是Pd(Ⅱ)有较好的萃取性能,最佳HN03浓度为3.0 M;萃取平衡时间约为30 min; Pd(Ⅱ)与Non-BTP形成1:2的配合物；Non-BTP在30%正辛醇-70%正十二烷中萃取Pd(Ⅱ)离子的过程为放热反应,并计算了相关热力学参数。
利用真空活化灌注技术,以大孔硅基Si02-P为载体,制备了新型2,6-(5,6-二壬基-1,2,4-三嗪-3-基)吡啶软配体复合材料(Non-BTP/SiO2-P),以FT-IR、SEM、TG-DSC、XRD和BET等手段对其进行了表征,明确了Non-BTP/SiO2-P的微观结构、化学组成以及复合机理。
研究了Non-BTP/SiO2-P对Rb(Ⅰ)、Cs(Ⅰ)、Sr(Ⅱ)、Ba(Ⅱ)、Pd(Ⅱ)、Ru(Ⅲ)、La(Ⅲ)、Co(Ⅲ)、Fe(Ⅲ)、Ni(Ⅲ)、Y(Ⅲ)、Sm(Ⅲ)、Yb(Ⅲ)、Zr(Ⅳ)和Mo(Ⅵ)等10余种典型金属离子的吸附性能,考察了HN03浓度和接触时间变化等因素对吸附性能的影响。通过测定不同条件下水相中的有机碳含量,表明Non-BTP/SiO2-P有较好的稳定性。Non-BTP/SiO2-P对过渡元素尤其是Pd(Ⅱ)有较好的吸附性能,对Ln(Ⅲ)基本无吸附作用,最佳HN03浓度为3.0 M,吸附平衡时间约为30 min。
The long-lived minor actinide (MA(III)) elements contained in high level liquid waste (HLLW) generated in reprocessing process of nuclear spent fuel have long-term radiological risk, it is valuable to separate them from HLLW for further transmutation.
2,6-bis(5,6-dialkyl-1,2,4-triazine-3-yl)pyridine (R-BTP) is a kind of multidentate chelating agent containing nitrogen which has better complexing ability for MA(III) than Ln(III). A novel soft ligand 2,6-bis(5,6-dinonyl-1,2,4-triazine-3-yl) pyridine (Non-BTP) was synthesized using 2,6-pyridinedicarbonitrile and ethyl decanoate as raw materials. It was characterized by FT-IR, TG-DSC, ESI-MS, and 1H NMR. An improved synthetic process of 2,6-pyridinedicarboxamide dihydrazone was proposed. The optimum conditions were described as follows:2,6-pyridine dicarbonitrile: 85%N2H4=1:15, reaction time=30 h, reaction temperature=30℃. The optimum yield of the product was 85.37%.
Using 30% n-octanol/70% n-dodecane as diluent, the extraction behavior of Rb(Ⅰ), Cs(Ⅰ), Sr(Ⅱ), Ba(Ⅱ), Pd(Ⅱ), Ru(Ⅲ), La(Ⅲ), Co(Ⅲ), Fe(Ⅲ), Ni(Ⅲ), Y(Ⅲ), Sm(Ⅲ), Yb(Ⅲ), Zr(Ⅳ) and Mo(Ⅳ) from HNO3 solution was studied. The influences of HNO3 concentration, Non-BTP content, contact time, and temperature on the extraction ability were investigated. It was found that the complex composition between Pd(Ⅱ) and Non-BTP was determined as 1:2 type. In addition, the thermodynamic parameters of Pd(Ⅱ) extrated by Non-BTP were calculated.
A novel macroporous silica-based 2,6-bis(5,6-dinonyl-1,2,4-triazine-3-yl) pyridine (Non-BTP/SiO2-P) was prepared through impregnation and immobilization of the corresponding R-BTP compound into the pores of the macroporous SiO-P support. The appearance, chemical composition, and inner structure were characterized by FT-IR, SEM, TG-DSC, XRD, and BET.
The effects of HNO3 concentration and contant time on the adsorption of Rb(Ⅰ), Cs(Ⅰ), Sr(Ⅱ), Ba(Ⅱ), Pd(Ⅱ), Ru(Ⅲ), La(Ⅲ), Co(Ⅲ), Fe(Ⅲ), Ni(Ⅲ), Y(Ⅲ), Sm(Ⅲ), Yb(Ⅲ), Zr(Ⅳ), Mo(Ⅵ), and more than 10 typical elements onto the Non-BTP/SiO2-P materials were investigated at 25℃. The Non-BTP/SiO2-P material showed excellent adsorption ability and selectivity for Pd(Ⅱ) over all of the other tested metals. The optium acidity for the Pd(Ⅱ) adsorption was 3.0 M HNO3. In addition, the uptake of Ln(Ⅲ) onto the Non-BTP/SiO2-P material was negligible, which was beneficial to separate MA(Ⅲ) from Ln(Ⅲ) using this composite in further researches.
引文
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