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Progress in Nuclear Energy 50 (2008) 466e469

www.elsevier.com/locate/pnucene

Separation of Americium(III) and Europium(III) by thermal-swing

extraction using thermosensitive polymer gel
Kenji Takeshita a,*, Tatsuro Matsumura b, Yoshio Nakano c
a
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
b
Research Group for Actinide Separation Chemistry, Japan Atomic Energy Agency, 2-4 Shirakata Shirane, Tokai-mura, Naka-gun, Ibaragi 319-1195, Japan
c
Department of Environmental Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan

Abstract

Extraction separation of Am(III) and Eu(III) was examined by the thermal-swing extraction technique using a thermosensitive gel, poly-N-
isopropylacrylamide (NIPA) crosslinked with a TPEN derivative, N,N,N0 ,N0 -tetrakis(4-propenyl-oxy-2-pyridylmethyl)ethylenediamine
(TPPEN). The separation of Am(III) from Eu(III) was observed in the swelling state of gel (5  C) and the separation factor of Am(III) was
evaluated as about 18 at pH 5.2. The distribution ratio of Am(III) was reduced to about 1/8 by the volume phase transition from the swelling
state (5  C) to the shrinking one (40  C). These results suggest that Am(III) can be separated and recovered effectively from Eu(III) in nitrate
aqueous solution by the thermal-swing extraction technique using TPPENeNIPA gel. This technique is applicable to the MA partitioning
process, which is one of the important chemical processes in the P&T technology.
2007 Elsevier Ltd. All rights reserved.

Keywords: Extraction; Thermosensitive gel; Volume phase transition; Minor actinide; Lanthanide; Nitrogen donor

1. Introduction introducing the thermal-swing extraction technique. The concept

of Fig. 1 can be realized by a thermosensitive gel copolyme-
Solvent extraction technique is applicable to the treatment rizing a thermosensitive polymer, poly-N-isopropylacrylamide
process of nuclear wastes, such as the reprocessing of spent (NIPA), and a functional ligand. Previously, the authors synthe-
nuclear fuel and the recovery of long-lived nuclides from the sized some thermosensitive NIPA gels with a phosphoric acid
high-level liquid wastes. However, since large amounts of ester and a BTP (2,6-di(3-vinylbenzyl-1,2,4-triazol-5-yl)pyri-
chemicals are supplied to these solvent extraction processes, dine) as functional groups and tested the thermal-swing extrac-
the used ones have to be managed safely as the secondary tion of heavy metals, such as lanthanide, actinide and transient
radioactive wastes. The consumption of chemicals should be elements (Takeshita et al., 2001, 2002, 2003a). The object metals
suppressed from the viewpoint of the decrease of economical were recovered successfully by these gels, but the difference in
load as well as the environmental protection. the distribution ratios of these metals between the swelling state
The authors propose a new extraction technique called ther- and the shrinking one of gel was within five times. The further
mal-swing extraction, in which the extractability of object ma- increase in the difference of distribution ratios is required for the
terials is controlled by the conformational change of polymer establishment of practical process.
network with the volume phase transition of thermosensitive Recently, the extraction separation of trivalent minor acti-
gel, as shown in Fig. 1. Therefore, further chemicals are not nides (MAs) from lanthanides, which is one of the important
added to the extraction and recovery of object material. The chemical processes in the partitioning and transmutation
consumption of chemicals will be reduced substantially by (P&T) system of long-lived nuclides, was investigated by
a flexible podand molecule, TPEN (N,N,N0 ,N0 -tetrakis(2-
* Corresponding author. Tel./fax: 81 45 924 5255. pyridylmethyl)ethylenediamine) (Jensen et al., 2000, Morss
E-mail address: [email protected] (K. Takeshita). and Rogers, 1997; Takeshita et al., 2003b, 2004). TPEN is

0149-1970/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pnucene.2007.11.085
 K. Takeshita et al. / Progress in Nuclear Energy 50 (2008) 466e469 467

Swelling state Shrinking state formed in the tar. After 4 days, TPPEN was extracted from
(Lower than LCST) (Higher than LCST) the tar by a large amount of diethylether and TPPEN was
Temperature precipitated by the removal of diethylester by an evaporator.
L swing TPPEN was copolymerized with NIPA by the radical poly-
L merization technique using 2,20 -azobis(isobutyronitrile) (AIBN)
L

L
L

L
M L as an initiator. The content of TPPEN was adjusted to 3 mol%.
L
The monomer mixture was dissolved in DMF (N,N0 -dime-
M
M M
M M thylformamide) and copolymerized at 60  C for 18 h. The
M
M M
M M TPPENeNIPA copolymer gel obtained was washed several
times by pure water. DMF and unreacted compounds were re-
Extraction of metal ion Release of metal ion
moved from the gel. After drying, the gel was crashed and
L sieved in the range of 100e150 mm.
M Object metal ion
L

Encapsulating ligand M
L

Fig. 1. Concept of thermal-swing extraction. 2.2. Extraction tests of Am(III) and Eu(III) with
TPPENeNIPA gel
a hexadentate ligand with six nitrogen donors and encapsulates
a metal ion by flexible four pyridyl groups. Am(III) was sep- The extraction tests of Am(III) and Eu(III) were carried out
arated successfully from Eu(III) in a nitrate aqueous solution at 5  C (the swelling state of gel) and 40  C (the shrinking
and the separation factor of Am(III) over Eu(III) was evaluated state) and the relation between the extraction of Am and Eu
as about 100 under the optimum conditions. TPEN is a useful and the swelling behavior of gel was examined. An aqueous
extractant of trivalent MAs. In this study, a TPEN derivative, solution with 152Eu(III) (440 Bq/cm3) and 241Am(III) (77 Bq/
TPPEN (N,N,N0 ,N0 -tetrakis-(4-propenyloxy-2-pyridylmethyl)- cm3) was prepared. Dry TPPENeNIPA gel particles (10 mg)
ethylenediamine), was introduced as a crosslinker of NIPA were added in 5 cm3 aqueous solution in a vial. The extraction
polymer chains and TPPENeNIPA copolymer gel was synthe- equilibrium was attained by shaking the vial vigorously for 1 h.
sized. The steric conformation of six nitrogen donors in TPPEN Then, the pH value of the aqueous phase was adjusted to the
may be changed by the volume phase transition of gel. The ex- desired one by adding ammonia and nitric acid. The aqueous
traction separation of Am(III) from Eu(III) was examined under solution was sampled and the radioactivity of 241Am and
the thermal-swing operation between 5  C and 40  C. 152
Eu in the aqueous solution was measured by a high-purity
germanium gamma-spectrometer system (EG&G Ortec Ltd.).
2. Experimental The lines at energies of 59.54 keV and 121.78 keV were used
for evaluating the concentrations of 241Am and 152Eu, res-
2.1. Synthesis of TPPENeNIPA gel pectively. The counts of 241Am and 152Eu more than 10,000
were measured in order to guarantee the statistical error of
TPPEN was synthesized by reacting ethylenediamine and individual measurements in the order of 1% at 1s. The distri-
2-chloromethyl-4-propenyloxypyridine at 25  C for 4 days as bution ratio, DM, and the separation factor, SFAm/Eu, were
shown in Eq. (1). defined as:

O O

N N
O NH2 1N NaOH (dropwise) N + 4 HCl (1)
4 + H2N N
H2O r.t.10d, pH=8 N N
N Cl
O
2-chloro-methy1- O
4-propenyloxy-pyridine
TPPEN

Ethylenediamine and 2-chloromethyl-4-propenyloxypyri- radio activity of M in1g of dry gel

DM M Am;Eu
dine were added in the aqueous phase by the molar ratio of radio activity of M in1mL of aqueous phase
1:4. The pH value in the aqueous solution, which was 2
decreased by the formation of HCl with the reaction of Eq.
(1), was maintained at 8.0  0.1 by a pH stat using 1 M
NaOH solution. The formation of black tar was observed.
SFAm=Eu DAm =DEu 3
By the mass analysis, it was confirmed that TPPEN was
468 K. Takeshita et al. / Progress in Nuclear Energy 50 (2008) 466e469

Furthermore the pH dependence on the extraction behavior of observed for a solution of thermosensitive polymer and a ther-
a soft metal ion, Cd(II), which is used as a substitute of Am, mosensitive polymer gel with low crosslinking degree (Seida
was carried out at 5  C and 40  C. An aqueous solution con- et al., 2003). This means that the swelling behavior of polymer
taining 8.90  104 mol/L Cd(NO3)2 was prepared. Ionic network with temperature is affected by not only the crosslink-
strength in the aqueous was adjusted to 0.01 and pH in the aque- ing points between TPPEN and NIPA but also the tangles of
ous solution was changed in the range of 2e6.5. For the mea- poly-NIPA chains. Thus, the polymer network of TPPENe
surement of pH dependence, 0.1 g of dry gel were added in NIPA gel may have comparatively high flexibility due to
the aqueous solution (5 ml) in a vial. The vial was shaken vigor- low crosslinking degree.
ously for 1 h. In the preliminary tests, it was confirmed that the
extraction equilibrium was reached within 1 h. After shaking, 3.2. Thermal-swing extraction of Cd(II)
the concentration of Cd(II) in the aqueous solution was mea-
sured by ICP-AES (Inductively Coupled Plasma Atomic Emis- Fig. 3 shows the distribution ratios of Cd(II) at 5  C and
sion Spectrometry). From these experimental results and the 40  C. Cd(II) was little extracted at 40  C. But, the extraction
mass balance of Cd(II) between the gel and the aqueous solu- of Cd(II) was improved substantially by decreasing tempera-
tion, the distribution ratio of Cd(II), defined as the concentration ture to 5  C. Then, the distribution ratio increased with
ratio of Cd in the gel and the aqueous solution, were calculated. increasing the pH value and showed about 300 at pH 5. This
value corresponds to about 30 times that at 40  C. As men-
3. Results and discussion tioned in the previous section, the volume phase transition of
TPPENeNIPA gel is caused by the hydration of NIPA and
3.1. Volume phase transition of TPPENeNIPA gel the sufficient volume change of gel is observed by the ther-
mal-swing operation between 5  C and 40  C. The results of
TPPENeNIPA gel particles (2 ml) obtained was packed in Fig. 3 may be because the extractability of TPPEN is affected
a measuring cylinder and 15 ml of pure water was added. The strongly by the conformational change of TPPEN with the vol-
volume change of gel with temperature was measured from the ume phase transition. The extraction of Cd(II) can be controlled
height change of packed bed of gel particles (Seida et al., by the thermal-swing operation. Then, the extraction capacity
2003). Fig. 2 shows the volume change of TPPENeNIPA of Cd(II) at 5  C was evaluated as about 11 mg-Cd/g-dry gel,
gel with temperature. The ordinate represents the volume of which corresponds to that of practical ionic exchange resin.
packed gel (V) normalized with that at 45  C (V0). The gel vol-
ume increased with decreasing temperature. The volume
change of gel, which occurs by the hydration of NIPA, is a pe- 3.3. Extraction separation of Am(III) and Eu(III)
culiar characteristic of thermosensitive gel called the volume
phase transition (Seida et al., 2003). On the other hand, the From the experimental results in the farmer section, it was
gel volume decreased with increasing temperature because confirmed that the TPPENeNIPA gel was applicable to the
of dehydration of NIPA and was kept constant in the temper- thermal-swing extraction. Finally, we tested the extraction
ature range above 34  C. This temperature is called LCST separation of a trivalent actinide, Am(III), and a lanthanide,
(lower critical solution temperature). The TPPENeNIPA gel 400
shows clear thermosensitivity. The strong hysteresis was found 5C
in the swelling curve of Fig. 2. The same phenomenon is
40C

4
300

3
DCd [ml/g]
Swelling ratio V/V0 [-]

200
increasing
temp.
2 30 times
decreasing
temp.
100
1

0 0
0 10 20 30 40 50 1 2 3 4 5 6 7
Temp [C] pHeq

Fig. 2. Temperature change of swelling ratio of TPPENeNIPA gel. Fig. 3. Changes of distribution ratio of Cd(II) with pH at 5  C and 40  C.
 K. Takeshita et al. / Progress in Nuclear Energy 50 (2008) 466e469 469

from Eu(III) was observed in the swelling state of gel (5  C)

2000 and the separation factor of Am(III) was evaluated as about
18 at pH 5.2. The distribution ratio of Am(III) was reduced
to about 1/8 by the volume phase transition from the swelling
1500 state (5  C) to the shrinking one (40  C). These results suggest
that Am(III) is separated and recovered effectively from Eu(-
DAm [ml/g]

III) in nitrate aqueous solution by the thermal-swing extraction

1000 technique using TPPENeNIPA gel.

500
Acknowledgements
Eu
0 This research has been performed with supports from the
5C Am Development of Innovative Nuclear Technologies Project or-
40C ganized by the Ministry of Education, Culture, Sports, Science
Fig. 4. Extraction separation of Am and Eu with TPPENeNIPA gel at 5  C and Technology of Japan.
and 40  C.

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