高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (8): 1324-1333.doi: 10.7503/cjcu20170027

• 研究论文: 无机化学 • 上一篇    下一篇

吡啶吡唑基配体C8-BPP对硝酸溶液中Am3+和Eu3+的萃取

胡晓阳1, 苏冬萍1,2, 李诗萌1, 王志鹏1, 张利荣1, 刘莹1, 宋莲君1, 陈志力1, 丁颂东1   

  1. 1. 四川大学化学学院, 成都 610064;
    2. 中国核动力研究设计院, 成都 610005
  • 收稿日期:2017-01-13 修回日期:2017-07-05 出版日期:2017-08-10 发布日期:2017-07-05
  • 通讯作者: 丁颂东,男,博士,研究员,博士生导师,主要从事核燃料循环与材料研究.E-mail:dsd68@163.com E-mail:dsd68@163.com
  • 基金资助:

    国家自然科学基金(批准号:11675115,91426302,91126016)资助.

Extraction of Am(Ⅲ) and Eu(Ⅲ) from Nitric Acid Solution with the Pyridylpyrazole Based Ligand C8-BPP

HU Xiaoyang1, SU Dongping1,2, LI Shimeng1, WANG Zhipeng1, ZHANG Lirong1, LIU Ying1, SONG Lianjun1, CHEN Zhili1, DING Songdong1   

  1. 1. College of Chemistry, Sichuan University, Chengdu 610064, China;
    2. Nuclear Power Institute of China, Chengdu 610005, China
  • Received:2017-01-13 Revised:2017-07-05 Online:2017-08-10 Published:2017-07-05
  • Supported by:

    Supported by the National Natural Science Foundation of China(Nos.11675115, 91426302, 91126016).

摘要:

合成了吡啶吡唑基配体C8-BPP[2,6-bis(5-(n-octyl)-1H-pyrazol-3-yl)pyridine],并采用红外光谱、核磁共振波谱、质谱等手段对其进行了表征.以正十二烷为稀释剂,2-溴己酸为协萃剂,研究了C8-BPP从HNO3溶液中萃取Am3+和Eu3+的行为.重点考察了萃取时间、酸度和萃取剂浓度等对分配比D和分离因子SFAm/Eu的影响.在HNO3浓度为0.2~1.0 mol/L时,C8-BPP萃取Am3+和Eu3+D值随HNO3浓度增加而减小,SFAm/Eu值先增大后减小;HNO3浓度为0.5 mol/L时,SFAm/Eu达到55.随着配体浓度的增加,C8-BPP萃取Am3+和Eu3+D值均增加,SFAm/Eu值缓慢减小,但仍在40以上.斜率分析表明,C8-BPP萃取Am3+和Eu3+均形成了1: 1型的萃合物.还采用紫外滴定、高分辨质谱、红外光谱、拉曼光谱和时间分辨荧光光谱等方法研究了C8-BPP与Eu3+的配位化学行为,并得到了配合物的组成和稳定常数.

关键词: 吡啶吡唑基配体, 溶剂萃取, 镅, 铕, 分离

Abstract:

Pyridylpyrazole based ligand 2,6-bis[5-(n-octyl)-1H-pyrazol-3-yl] pyridine(C8-BPP) was synthesized and characterized by means of mass spectrometry(MS), nuclear magnetic resonance(NMR) spectrometry, and Fourier transform infrared spectrometry(FTIR). In the presence of 2-bromohexanoic acid, using n-dodecane as diluent, the extraction behaviors of Am3+ and Eu3+ with C8-BPP were investigated. Influences of diluent, contact time, acidity and the ligand concentration on the extraction of Am3+ and Eu3+ were evaluated in HNO3 solution. The distribution ratio values of Am3+ and Eu3+ decreased with increasing HNO3 concentration from 0.2 to 1.0 mol/L, and increased with increasing ligand concentration from 0.01 to 0.1 mol/L. With the increase of acidity, the separation factors(SFAm/Eu) increased firstly and then decreased. The maximum value of SFAm/Eu can reach 55 at 0.5 mol/L HNO3. Meanwhile, SFAm/Eu values decreased slowly with increasing the ligand concentration but all the SFAm/Eu values were above 40. The extraction results also showed that C8-BPP exhibited good selective extraction ability for Am3+ over RE3+. Moreover, slope analyses indicated the formation of 1:1 complexes of C8-BPP with Am3+ and Eu3+, separately. Besides, the complexation behaviors of C8-BPP with Eu3+ were also investigated by means of UV-Vis spectrometry titration, electrospray ionization mass spectrometry(ESI-MS), FTIR, Raman spectrometry and time-resolved laser-induced fluorescence spectroscopy(TRLFS). The composition and stability constant(lgK) of the complex of C8-BPP with Eu3+ were also obtained.

Key words: Pyridylpyrazole based ligand, Solvent extraction, Americium, Europium, Separation

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