环己基/苄基氨基膦酸酯类萃取剂的合成及对锆铪的分离性能分析  

Extraction Performance of Aminophosphorus Extractants Containing Cyclohexyl or Benzyl Group Towards Zirconium and Hafnium in Sulfate Medium

作　　者：李松松 李艳玲[1] 廖伍平[1,2,3] LI Song-Song;LI Yan-Ling;LIAO Wu-Ping(State Key Laboratory of Rare Earth Resource Utilization,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026,China;Ganjiang Innovation Academy,Chinese Academy of Sciences,Ganzhou 341000,China)

机构地区：[1]中国科学院长春应用化学研究所,稀土资源利用国家重点实验室,长春130022 [2]中国科学技术大学应用化学与工程学院,合肥230026 [3]中国科学院赣江创新研究院,赣州341000

出　　处：《分析化学》2024年第11期1775-1784,共10页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(No.51222404)资助。

摘　　要：本研究合成了氨基膦酸酯类萃取剂二(2-乙基己基)((环己基氨基)甲基)膦酸酯(CAMP)和二(2-乙基己基)((苄胺)甲基)膦酸酯(BAMP),考察了这两种萃取剂在H_(2)SO_(4)溶液中萃取分离锆和铪的性能。系统考察了萃取振荡时间、萃取剂浓度、HSO_(4)^(-)浓度和温度等因素对锆和铪萃取的影响,发现采用CAMP和BAMP萃取锆和铪时,反应在1 min内即可达到平衡,温度在289.45~318.75 K范围内对萃取过程没有影响,萃取过程为熵驱动自发进行的反应。随着H_(2)SO_(4)浓度增加,CAMP和BAMP对锆和铪的萃取率均降低,并且CAMP对锆的萃取率受H_(2)SO_(4)浓度的影响更明显,CAMP与BAMP对锆和铪的最大分离系数(β_(Zr/Hf))分别为14.21和18.68。根据斜率分析法推测出CAMP与BAMP萃取锆和铪形成的络合物分子式为MO(HSO_(4))_(2)·2L(其中,M为Zr或Hf,L为萃取剂分子)。30%(V/V)CAMP对锆和铪的饱和负载量分别为28.2和24.1 g/L,30%(V/V)BAMP对锆和铪的饱和负载量分别为27.7和22.2 g/L,0.5 mol/L HCl可以完全反萃负载有机相中的铪。In this work,the aminophosphonate extractants bis(2-ethylhexyl)(cyclohexylamino)methyl)phosphonate(CAMP)and bis(2-ethylhexyl)(benzylamine)methyl)phosphonate(BAMP)were synthesized,and the performance of these two extractants in extracting and separating zirconium and hafnium in H_(2)SO_(4) solutions was investigated.The effects of oscillation time,extractant concentration,H2SO4 concentration,and temperature on the extraction of zirconium and hafnium were systematically investigated.It was found that the reaction of extracting zirconium and hafnium by CAMP and BAMP could reach equilibrium within 1 min,and the temperature hardly affected the extraction process in the range of 289.45-318.75 K.The extraction process was an entropy-driven spontaneous reaction.With the increase of H_(2)SO_(4) concentration,the extraction rate of zirconium and hafnium by CAMP and BAMP decreased,and the extraction rate of zirconium by CAMP was more obviously affected by the H_(2)SO_(4) concentration.The maximum separation factors(βzw/Hr)of CAMP and BAMP were 14.21 and 18.68 respectively.According to the slope analysis,it was inferred that the molecular formula of the complex formed by the extraction of zirconium and hafnium by CAMP and BAMP was MO(HSO_(4))_(2)-2L(where"M"was Zr or Hf,and"L"was the extractant molecule).The saturated loadings of 30%(VIV)CAMP for zirconium and hafnium were 28.2 g/L and 24.1 g/L,while those for 30%(V/V)BAMP were 27.7 g/L for zirconium and 22.2 g/L for hafnium.Additionally,O.5 mol/L HCl could completely strip the hafnium from the loaded organic phase.

关 键 词：Α-氨基膦酸酯 锆 铪 分离 溶剂萃取 

分 类 号：TG146.414[一般工业技术—材料科学与工程] O652.62[金属学及工艺—金属材料]