几种新型大孔硅基软配体材料制备及其吸附特性研究
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摘要
以2,6-吡啶二甲腈和脂类衍生物等试剂为原料,合成了4种2,6-二(5,6-二烷基-1,2,4-三嗪-3-基)-吡啶(R-BTP)衍生物：2,6-二(5,6-二甲基-1,2,4-三嗪-3-基)-吡啶(Me-BTP)、2,6-二(5,6-二丙基-1,2,4-三嗪-3-基)-吡啶(Pro-BTP)、2,6-二(5,6-二戊基-1,2,4-三嗪-3-基)-吡啶(Pen-BTP)和2,6-二(5,6-二庚基-1,2,4-三嗪-3-基)-吡啶(Hep-BTP),以元素分析、FT-IR、TG-DSC、ESI-MS和1H NMR等手段进行了表征,确认为目标产物。
对中间体己偶姻合成工艺条件进行了优化,其最佳工艺条件为：在室温和氮气保护条件下,钠、酯类试剂和无水乙醚的物质的量比为2：1：6,己偶姻的收率为71.54%。
以大孔SiO2-P为载体,利用固定化真空活化灌注技术制备了三种新型的大孔硅基软配体材料Me-BTP/SiO2-P、Pro-BTP/SiO2-P和Pen-BTP/SiO2-P,以FT-IR、TG-DSC、SEM、XRD和BET等手段进行了表征,明确了大孔硅基软配体材料的复合机理及微观结构。
在0.4-5.0 M HNO3溶液中,研究了Me-BTP/SiO2-P、Pro-BTP/SiO2-P和Pen-BTP/SiO2-P吸附Na(Ⅰ)、K(Ⅰ)、Rb(Ⅰ)、Cs(Ⅰ)、Sr(Ⅱ)、Ba(Ⅱ)、Ru(Ⅲ)、Mo(Ⅵ)、La(Ⅲ)、Yb(Ⅲ)、Co(Ⅱ)、Fe(Ⅲ)、Pd(Ⅱ)、Ni(Ⅱ)、Zr(Ⅵ)、Sm(Ⅲ)和Y(Ⅲ)等17种金属离子的基础特性,考察了酸度和接触时间等因素对R-BTP/SiO2-P吸附性能的影响。结果发现,三种大孔硅基软配体材料对Pd(Ⅱ)、Fe(Ⅲ)、Co(Ⅱ)和Ni(Ⅱ)等过渡金属元素有着较好的吸附选择性,其中Pen-BTP/SiO2-P对Pd(Ⅱ)有明显的吸附能力；被实验的La(Ⅲ)、Sm(Ⅲ)、Y(Ⅲ)和Yb(Ⅲ)表现为弱吸附或基本不吸附,说明R-BTP/SiO2-P对16种稀土元素RE(Ⅲ)基本无吸附性能,这对从酸性高放废物中实现An(Ⅲ)/RE(Ⅲ)有效分离有重要意义。
2,6-(5,6-dialkyl-1,2,4-triazine-3-yl)-pyridine (R-BTP) is a kind of multidentate chelating agent of soft-ligand containing nitrogen. It seems to have better complexing ability for minor actinides (MAs). To separate MA from highly active liquid waste (HLW), four derivatives of R-BTP,2,6-bis(5,6-dimethyl-1,2,4-triazine-3-yl) pyridine (Me-BTP),2,6-bis(5,6-dipropyl-1,2,4-triazine-3-yl)pyridine (Pro-BTP),2,6-bis(5,6-dipentyl-1,2,4-triazine-3-yl)pyridine (Pen-BTP), and 2,6-bis(5,6-diheptyl-1,2,4-triazine-3-yl)pyridine (Hep-BTP) were synthesized using 2,6-pyridinedicarbonitrile and ester as raw materials. They were characterized by elementary analysis, FT-IR, TG-DSC, FT-IR, ESI-MS, and 1H NMR.
The synthesis procedure of immediate hexylacyloin was optimized. The optimum conditions were described as follows:molar ratio of Na, C2H5OC2H5, and n-C5H11COOC2H5 was 2:1:6 under protection by nitrogen gas at 25℃. The yield of hexylacyloin was 71.54%.
Three novel macroporous silica-based soft ligand materials Me-BTP/SiO2-P, Pro-BTP/SiO2-P, and Pen-BTP/SiO2-P were synthesized by impregnation and immobilization of Me-BTP, Pro-BTP, and Pen-BTP molecules into the pores of SiO2-P, respectively. All the R-BTP/SiO2-P materials were characterized by FT-IR, TG-DSC, SEM, XRD, and BET.
The effects of the HNO3 concentration in the range of 0.4-5.0 M HNO3 and contact time on the adsorption of some typical elements such as Na(Ⅰ), K(Ⅰ), Rb(Ⅰ), Cs(Ⅰ), Sr(Ⅱ), Ba(Ⅱ), Pd(Ⅱ), Ru(Ⅲ), Mo(Ⅵ), Zr(Ⅵ), Fe(Ⅲ), Co(Ⅱ), Ni(Ⅱ), La(Ⅲ), Sm(Ⅲ), Yb(Ⅲ), and Y(Ⅲ) onto Me-BTP/SiO2-P, Pro-BTP/SiO2-P, and Pen-BTP/SiO2-P were investigated at 25℃. The results showed that the macroporous silica-based soft ligand materials exhibited adsorption for Pd(Ⅱ), Fe(Ⅲ), Co(Ⅱ), and/or Ni(Ⅱ). The adsorption of Pen-BTP/SiO2-P for Pd(Ⅱ) was strong with the distribution coefficient of more than 1000 cm3/g. La(Ⅲ), Sm(Ⅲ), Yb(Ⅲ), and Y(Ⅲ) as the representative of rare earths REs(Ⅲ) showed weak or almost no adsorption onto R-BTP/SiO2-P, indicative of no adsorption for all REs(Ⅲ) because of lanthanide contraction. It is beneficial to effective separation An(Ⅲ)/RE(Ⅲ) from HLLW.
对中间体己偶姻合成工艺条件进行了优化,其最佳工艺条件为：在室温和氮气保护条件下,钠、酯类试剂和无水乙醚的物质的量比为2：1：6,己偶姻的收率为71.54%。
以大孔SiO2-P为载体,利用固定化真空活化灌注技术制备了三种新型的大孔硅基软配体材料Me-BTP/SiO2-P、Pro-BTP/SiO2-P和Pen-BTP/SiO2-P,以FT-IR、TG-DSC、SEM、XRD和BET等手段进行了表征,明确了大孔硅基软配体材料的复合机理及微观结构。
在0.4-5.0 M HNO3溶液中,研究了Me-BTP/SiO2-P、Pro-BTP/SiO2-P和Pen-BTP/SiO2-P吸附Na(Ⅰ)、K(Ⅰ)、Rb(Ⅰ)、Cs(Ⅰ)、Sr(Ⅱ)、Ba(Ⅱ)、Ru(Ⅲ)、Mo(Ⅵ)、La(Ⅲ)、Yb(Ⅲ)、Co(Ⅱ)、Fe(Ⅲ)、Pd(Ⅱ)、Ni(Ⅱ)、Zr(Ⅵ)、Sm(Ⅲ)和Y(Ⅲ)等17种金属离子的基础特性,考察了酸度和接触时间等因素对R-BTP/SiO2-P吸附性能的影响。结果发现,三种大孔硅基软配体材料对Pd(Ⅱ)、Fe(Ⅲ)、Co(Ⅱ)和Ni(Ⅱ)等过渡金属元素有着较好的吸附选择性,其中Pen-BTP/SiO2-P对Pd(Ⅱ)有明显的吸附能力；被实验的La(Ⅲ)、Sm(Ⅲ)、Y(Ⅲ)和Yb(Ⅲ)表现为弱吸附或基本不吸附,说明R-BTP/SiO2-P对16种稀土元素RE(Ⅲ)基本无吸附性能,这对从酸性高放废物中实现An(Ⅲ)/RE(Ⅲ)有效分离有重要意义。
2,6-(5,6-dialkyl-1,2,4-triazine-3-yl)-pyridine (R-BTP) is a kind of multidentate chelating agent of soft-ligand containing nitrogen. It seems to have better complexing ability for minor actinides (MAs). To separate MA from highly active liquid waste (HLW), four derivatives of R-BTP,2,6-bis(5,6-dimethyl-1,2,4-triazine-3-yl) pyridine (Me-BTP),2,6-bis(5,6-dipropyl-1,2,4-triazine-3-yl)pyridine (Pro-BTP),2,6-bis(5,6-dipentyl-1,2,4-triazine-3-yl)pyridine (Pen-BTP), and 2,6-bis(5,6-diheptyl-1,2,4-triazine-3-yl)pyridine (Hep-BTP) were synthesized using 2,6-pyridinedicarbonitrile and ester as raw materials. They were characterized by elementary analysis, FT-IR, TG-DSC, FT-IR, ESI-MS, and 1H NMR.
The synthesis procedure of immediate hexylacyloin was optimized. The optimum conditions were described as follows:molar ratio of Na, C2H5OC2H5, and n-C5H11COOC2H5 was 2:1:6 under protection by nitrogen gas at 25℃. The yield of hexylacyloin was 71.54%.
Three novel macroporous silica-based soft ligand materials Me-BTP/SiO2-P, Pro-BTP/SiO2-P, and Pen-BTP/SiO2-P were synthesized by impregnation and immobilization of Me-BTP, Pro-BTP, and Pen-BTP molecules into the pores of SiO2-P, respectively. All the R-BTP/SiO2-P materials were characterized by FT-IR, TG-DSC, SEM, XRD, and BET.
The effects of the HNO3 concentration in the range of 0.4-5.0 M HNO3 and contact time on the adsorption of some typical elements such as Na(Ⅰ), K(Ⅰ), Rb(Ⅰ), Cs(Ⅰ), Sr(Ⅱ), Ba(Ⅱ), Pd(Ⅱ), Ru(Ⅲ), Mo(Ⅵ), Zr(Ⅵ), Fe(Ⅲ), Co(Ⅱ), Ni(Ⅱ), La(Ⅲ), Sm(Ⅲ), Yb(Ⅲ), and Y(Ⅲ) onto Me-BTP/SiO2-P, Pro-BTP/SiO2-P, and Pen-BTP/SiO2-P were investigated at 25℃. The results showed that the macroporous silica-based soft ligand materials exhibited adsorption for Pd(Ⅱ), Fe(Ⅲ), Co(Ⅱ), and/or Ni(Ⅱ). The adsorption of Pen-BTP/SiO2-P for Pd(Ⅱ) was strong with the distribution coefficient of more than 1000 cm3/g. La(Ⅲ), Sm(Ⅲ), Yb(Ⅲ), and Y(Ⅲ) as the representative of rare earths REs(Ⅲ) showed weak or almost no adsorption onto R-BTP/SiO2-P, indicative of no adsorption for all REs(Ⅲ) because of lanthanide contraction. It is beneficial to effective separation An(Ⅲ)/RE(Ⅲ) from HLLW.
引文
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