JP0550472

JAERI-Conf 2005-007

10.23 A Study on Adsorption onto TODGA Resin after Electrolytic Reduction in

ERIX Process for Reprocessing Spent FBR-MOX Fuel
Harutaka HOSHI1, Tsuyoshi ARM 1 , Yuezhou WEI1, Mikio KUMAGAI1,
Toshihide ASAKURA2 and Yasuji MORITA2
'insttute of Research and Innovation, Kashiwa, Chiba 277-0861, Japan,
2Japan Atomic Energy Research Institute, Tokai-mura, Ibaraki 319-1195, Japan
For reprocessing spent FBR-MOX fuel, an advanced aqueous reprocessing
process "ERIX process" has been developed. In this system, hydrazine is used as
reduction holding reagent for the valance adjustment of U by electrolytic reduction
in nitric acid solution. Therefore, hydrazine is contained in high level liquid waste
after separation of U, Pu and Np. Effect of hydrazine on adsorption of FP onto
TODGA resin was examined. When hydrazine concentration was less than 0.3 M,
effect on the distribution coefficient was negligibly small. After electrolytic
reduction, some elements exist as lower valence state. Ru and Tc are most difficult
elements to control their behavior in aqueous process. The distribution coefficient
of both Ru and Tc onto TODGA decreased after electrolytic reduction, because they
are reduced to lower valence. Hence, it is difficult for Ru or Tc to diffuse to allover
the process and separation of MA from Tc and Ru was enhanced by electrolytic
reduction.
KEYWORDS: ERIX, TODGA, extraction chromatography, Electrolytic reduction,
Reprocessing, MA

1. Introduction
For the development of nuclear fuel cycle, it is one of the most important tasks to improve
reprocessing process more economically and its efficiency. Especially, to establish the Fast Breeder
Reactor (FBR) cycle system for the future, it is strongly desirable to develop a novel reprocessing
process which uses more compact equipments and produces less radioactive wastes than the present
PUREX process. For this purpose, we have proposed a novel aqueous reprocessing system named
ERIX Process (The Electrolytic Reduction and Ion Exchange Process for Reprocessing Spent
FBR-MOX Fuel) to treat spent FBR-MOX fuels13. This process consists of (1) Pd removal by selective
adsorption using a specific anion exchanger; (2) electrolytic reduction for the valence adjustment of
the major actinides including U, Pu, Np and some fission products (FP) such as Tc and Ru; (3) anion
exchange separation for the recovery of U, Pu and Np using a new type of anion exchanger, AR-01;
and (4) selective separation of long-lived minor actinides (MA=Am, Cm) by extraction
chromatography. Separation of MA from FP is attained by using two extraction chromatography
columns. Firstly, both MA and lanthanides (Ln) are separated from other FP by TODGA column
(Group separation). Secondly, MA is isolated from Ln by R-BTP column2).
Hydrazine is used as reduction holding reagent for the valance adjustment of U by electrolytic
reduction in nitric acid solution33. Therefore, hydrazine is contained in high level liquid waste after
separation of U, Pu and Np. Moreover, some elements exist as lower valence state after electrolytic
reduction. In this work, effect of electrolytic reduction on MA-Ln group separation was studied.

2. Experimental
2.1. Materials
A radioactive technetium isotope, 99Tc (DUPONT), was used after purification as described before4).

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JAERI-Conf 2005-007
Ruthenium(III) nitrosyl nitrate solution (Strem Chemicals, Inc.) and N,N,N',N'-tetraoctyl-3oxapentane-l,5-diamide (TODGA; Kanto Chemical Co., Inc.) was used as recieved. TODGA
impregnated resin (TODGA/SiO2-P) with a mean particle size of 40-60 urn was prepared as described
before5l6). All other chemicals used were of Analytical Reagent Grade.
2.2. Electrolytic reduction
Electrolytic reduction experiments were carried out using a flow type electrolysis cell (HX-201;
Hokuto Denko Ltd.). The cathode of glassy carbon fibers filled in a cylindrical column of Vyc"or
glass (porous silica glass) works as the working electrode. The Vycor glass column works as both
cathode compartment and separator. A sample solution was introduced into the Vycor glass column by
peristaltic pump at the flow rate of 1.0 cnrVmin. The electroreduction was conducted at a constant
potential -300 mV (vs. Ag/AgCl) with a potentiostat (HA-151; Hokuto Denko Ltd). The outlet
solution from the electrolysis cell was collected using glass vials with screw cap. The concentration of
Tc was determined by ICP-AES (ICPS-1000; Shimadzu) in glove box and that of Ru was determined
by ICP-AES (SPS-5000; Seiko Instruments Inc.). Absorption spectra of Tc and Ru solution were
measured by spectrophotometer (UV-3500; Hitachi) and Intelligent diode array detector (MD-2015
Plus; JASCO), respectively.
2.3. Adsorption with TODGA impregnated resin
Distribution coefficients (Kj) between TODGA/SiO2-P and nitric acid solution were measured by
batch adsorption experiments. 0.25 g of TODGA/SiO2-P was combined with 5 cm3 of a sample
solution in a screw capped glass vial. The glass vial was packed in a vinyl film bag and was shaken
mechanically for 3 hours in a water bath at 25C. The aqueous phase was filtrated through a
membrane filter with 0.45 urn pore. The concentration of metals in the solution was determined by
ICP-AES. The distribution coefficient was calculated by:
(Co ~ CS) V
K
Kd=
(1)
Cs
W
where Co and C s denote the concentration of Tc in the aqueous phase before and after adsorption,
respectively. V indicates the volume of aqueous phase and W is the weight of the dry extraction resin.

3. Results and discussion

3.1. Adsorption of Ru
UV-vis spectra of Ru in 6 M HNO3 solution before and after the electrolysis were observed. Ru
exists as nitrosylnitrato complex in nitric acid solution and its valence is trivalent state. According to
the following equation7*, valence of Ru was assumed divalent state after the electrolytic reduction at
-300 mV (vs Ag/AgCl).
Ru 3 + + e~ -> Ru 2 +
E = 0.249 V
(2)
However, there was no apparent difference in the UV-vis spectra of Ru between before and after the
electrolysis. Adsorption of Ru onto TODGA impregnated resin was examined and the distribution
coefficient of Ru was shown in Fig. 1. IQ values of Ru were almost same in more than 1 M nitric acid
solution, while Kj values of Ru after the electrolysis were rather lower than that before electrolysis.
Therefore, it is easy to recover the adsorbed Ru by adjusting nitric acid concentration for the reduced
Ru.

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JAERI-Conf 2005-007

101

A
A

cn
A

10 7r

10 1

Before reduction
After reduction

io- 2

101

10

101

[HNO3] / M

Fig. 1 Adsorption of Ru onto TODGA resin before and after electrolytic reduction.
3.2. Adsorption of Tc
Tc is one of the most important FP elements to control in reprocessing system. Usually, in nitric
acid medium, Tc shows heptavalent state as TcO4~. Because it is difficult to observe UV-vis spectra of
Tc directly, colorimetric method was used. UV-vis spectra of Tc modified with KSCN solution were
shown in Fig. 2. As absorption peak at 495 nm was observed after the electrolysis, it is considered that
Tc(VII) was reduced to Tc(IV)8'9).
The distribution coefficients of 1) Tc(VII) in nitric acid solution, 2) Tc(VII) in nitric acid solution
with addition of N2H4, 3) reduced Tc(IV) in nitric acid solution with N2H4 existence are shown in Fig.
3. IQ of Tc(VII) decreased with increasing of nitric acid solution and that obtained with N2H4 was
lower than that without N2H4. On the other hand, after electro reduction, Tc(IV) was not adsorbed onto
TODGA resin from dilute and concentrated nitric acid solution. Adsorption behavior between Tc(IV)
and Tc(VII) was obviously different. Since reduced Tc was not adsorbed onto TODGA/SiO2-P, the
separation of Tc from MA and the other Ln would become easy.
1.2

Tc(IV)
1.0
0.8
0.6

\
v

0.4
Before electrolysis

0.2
0.0
350

After
\electrolysis

400

450

500

550

f
600

^
650

700

Wave length / nm

Fig. 2

UV-Visible spectra of Tc before and after electrolytic reduction.

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JAERI-Conf 2005-007
20

Tc

Tc-N2H<

Aftrer Reduction

15 A

10 -

5 --

a
o ,

[HNO 3 ] / M

Fig. 3

Adsorption of Tc onto TODGA resin before and after the electrolytic reduction.

3.3. Effect of hydrazine concentration on the adsorption

On the electrolytic reduction for valence adjustment of U in the ERIX Process, hydrazine is added
as a reduction holding reagent. It is necessary for successful reduction of U to suppress nitrous acid
generation due to high concentration of nitric acid l0 ' n) . Thus, a quite amount of hydrazine is contained
in HLLW after the recovery of U, Pu and Np through an anion exchanger column. The effect of
hydrazine on the distribution coefficient of typical FP was examined. Kj values obtained as a function
of hydrazine concentration were shown in Fig. 4. Kj of Zr and Pd were almost constant in whole range
of hydrazine concentration. For Nd, Ru and Mo, Kj were almost constant in dilute nitric acid solution
(< 1 M). However, Kj were decreased rapidly in 1 M HNO3 solution, especially for Mo. Kj of Sr and
Rh apparently increased with increasing of nitric acid concentration, but these values were less than 1
crnVg and are regarded as almost no adsorption. Because there was no increase on the adsorption onto
TODGA/SiO2-P with hydrazine concentration, it is considered that there should be no effect on the
separation of MA and Ln from other FP.
10 2
Zr
A

101

A
7

Pd*

^Nd

10 r

\
Sr

OJn
Ru

J O -

10 1
\

,
1

10- 2 3
10-

10" 2

10 1

10

101

[N2HJ / M

Fig. 4

Effect of hydrazine concentration on distribution coefficient of FP.

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JAERI-Conf 2005-007
3.4. Effect of corrosion products
From a practical point of view, some corrosion products (CP) are contained in HLLW from stainless
materials. Thus, it is necessary to evaluate the effect of CP on the adsorption onto TODGA/SiO2-P.
Adsorption of typical CP onto TODGA resin from nitric acid medium was examined by batch
adsorption experiment and the results are shown in Fig. 5. Kd of Co, Mn, Ni and Fe were less than 10
cm3/g in 0.03 to 6 M nitric acid solution. No adsorption of Cr was observed.
Effect of the concentration of CP on the adsorption on Nd(III) was examined by using Fe(III) as a
representative CP. Effect of Fe(III) concentration on the distribution coefficient of Nd(III) from 3 M
nitric acid solution was shown in Fig. 6. When iron concentration was less than 0.1 M, Kj of Nd(III)
was almost constant and no effect of Fe(III) concentration was confirmed. While, Kj of Nd(III)
increased in higher concentration (> 0.1 M) of Fe(III). In this region, nitrate ion released from
Fe(NO3)3 was not negligibly small compared to the nitric acid concentration (3 M). Owing to the
increase of nitrate ion, a little higher Kj of Nd(III) were observed.
10 2

1 1 1 1

Cr(III): N.A.

IO1 r-

Co

Mn

Ni

Fe

io"
A

1 0 1 r:

e ^
-

10"

io- 2

10-'

101

10
[HNO3] / M

Fig. 5

Adsorption of CP onto TODGA resin.

IO"1

10-3

io-2

IO-1

io

[Fe(NO 3 ) 3 ]/M

Fig. 6 Effect of iron concentration on the distribution coefficient of Nd from 3 M HNO3.

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JAERI-Conf 2005-007
4. Conclusion
Effect of hydrazine concentration on adsorption of FP onto TODGA/SiO2-P was examined. When
hydrazine concentration was less than 0.3 M, effect on the distribution coefficient was negligibly small.
After electrolytic reduction, Ru and Tc existed as lower valence state and the distribution coefficient of
both Ru and Tc onto TODGA/SiO2-P decreased. Hence, it is difficult for Ru or Tc to diffuse to allover
the process and separation of MA from Tc and Ru was enhanced by electrolytic reduction. It was also
confirmed that CP (Fe, Ni, Co and Mn) were not adsorbed onto TODGA/SiO2-P and there was no
effect on the adsorption of Ln.
5. Acknowledgements
This work was financed by the Ministry of Education, Culture, Sports, Science and Technology of
Japan (MEXT) under the framework of "The Development of Innovative Nuclear Technologies".
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