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Progress in Chemistry 2020, Vol. 32 Issue (2/3): 219-229 DOI: 10.7536/PC190824 Previous Articles   Next Articles

Separation of Actinides: Extraction Chemistry and Application of Unsymmetric Diglycolamides

Yaoyang Liu1, Zhibin Liu1, Chuang Zhao1, Yu Zhou1, Yang Gao1,**(), Hui He1,2   

  1. 1. College of Nuclear Science and Technology, Harbin Engineering University, Harbin 150001, China
    2. China Institute of Atomic Energy, Beijing 102413, China
  • Received: Online: Published:
  • Contact: Yang Gao
  • About author:
    ** e-mail:
  • Supported by:
    Special Fund of Central University Basic Scientific Research Fee(GK2150260176)
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The high level liquid waste(HLLW) generated from PUREX reprocessing process contains more than 95% radioactivity of the spent fuel. Among HLLW, minor actinides with long half-life and high toxicity are one of the main factors that need to isolate HLLW from the biosphere for more than 100 000 years in the deep geological repositories. In order to solve the problem of HLLW more safely and reliably, “separation-transmutation” technology has been put forward, that is, the minor actinides and long-lived fission product elements are separated from HLLW by chemical methods, and then the separated elements are utilized or transmuted according to their properties. The effective separation of different kinds of elements from HLLW is the key step in the separation-transmutation technology. The diglycolamide extractants exhibit excellent extractability towards trivalent actinides and lanthanides in HLLW. In particular, the unsymmetric diglycolamides have greater advantage than the corresponding symmetric diglycolamides in relieving or avoiding the formation of the third phase in the extraction process, and at the same time maintain the good extraction performances. In this paper, the development history, synthesis method, extraction performance, coordination mechanism, flow process, and the third phase formation of unsymmetric diglycolamides are reviewed. The extraction ratio, the separation factor and the critical parameters of the third phase formation of lanthanides, actinides and other major fission elements are compared. Some suggestions are provided for the structural design, coordination mechanism research and process application of the unsymmetric diglycolamides.

Key words: high level liquid waste, actinide separation, extraction, unsymmetric diglycolamides
Fig.1 Symmetric diglycolamides structure
Fig.2 Unsymmetric diglycolamides structure
Scheme 1 (1) Synthesis of unsymmetric diglycolamides by secondary amines and acid esters;(2) Synthesis of unsymmetric diglycolamides by secondary amines and anhydrides;(3) Synthesis of unsymmetric diglycolamides by secondary amines and acyl chlorides
Fig.3 Unsymmetric diglycolamides structure
Table 1 Relationship between separation coefficient of Sr(Ⅱ)/Am(Ⅲ) and concentration of HNO3 in aqueous phase[29]
Diluent Extractant
concentration		 HNO3(M) 2 3 4 5 6 8
n-DD 0.1 DHDODGA 347 281 third phase / / /
TODGA 85 74 >157
D2DODGA 183 175 >166 >217
D3DODGA 38 172 >228 >331
0.1 DEHDODGA 144 91 >83 /
0.03 81 324 520 ~1700 >200 >20 000
Table 2 CAC and LOC of Nd(Ⅲ) and HNO3 in various unsymmetric diglycolamides extraction systems
DGA Diluent HNO3
(M)		 [DGA]
(M)		 Nd(Ⅲ) [DGA]
(M)		 HNO3
[Nd(Ⅲ)]ini
(mM)		 CAC
(mM)		 LOC
(mM)		 [HNO3]ini
(M)		 CAC
(M)		 LOC
(M)
DHDODGA n-dodecane 0.1 third phase 0.1 4 3.2 0.08
1
TODGA / / 14
2
/ 12
3
8 6.4 6 5.1 0.18
4
6 2.8
5
<1 mM <1 mM
3
D2DODGA 15 13.2 7 5.6 0.2
4
5
10 8.1
3
7 3.5
4
D3DODGA >600 32 12 9.3 0.28
5
>600 31
/
105 24
D3DBDGA Extraction of trivalent actinides in HLLW does not form any third phase 15.7 12.4 0.26
3
D3DHDGA 10.9 8.3 0.23
4
D3D2DGA 12 9.4 0.3
5
D3DEHDGA 295 225 24 11.9 9.5 0.3
1
120 41.6 19
2
40 11.5 17
3
DEHDODGA 0.1 7 0.03 9.5
3
5.3
4.1 0.1 5
0.2 11.3 / / /
0.3 / 14.3 0.2 4.9
0.4 28.9
0.5 33.3 0.5 4
DMDODGA 0.64 M
n-octanal/K.O.		 1
2
3		 0.12 / 12.77
11.7
9.98		 /
TEHDGA 1 M
DHOA/n-dodecane		 2
3		 0.2 / 72
62		 0.2 / 7.8 /
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