Asian Nuclear Prospects 2010

Development of Hybrid Reprocessing Technology Based on Solvent Extraction and Pyro-chemical Electrolysis
K. Mizuguchi1 , S. Kanamura1 , H. Ohmura1 , R. Fujita1, T. Omori2 and K. Utsunomiya2
Power & Industrial Research & Development Center, Toshiba Corporation, 4-1, Ukishima-cho, Kawasaki-ku, Kawasaki 210-0862, Japan, 2 Chemical System Design & Engineering Department, Toshiba Corporation
1

Abstract Toshiba has been proposing a new fuel cycle concept for a transition perio d from LW R to FR. This concept has better process economy of the LW R spent fuel reprocessing than conventional process, and proliferation resistance for FR cycle of plutoniu m with minor actin ides. Toshiba has been developing a new Advanced Hybrid process with solvent extract ion and pyro-chemical electro lysis of spent fuel reprocessing for a t ransition period fro m LW R to FR. The Advanced Hybrid Process combines the solvent extraction process of the LWR spent fuel in n itric acid to recover pure uraniu m and th e pyrochemical electrolysis in mo lten salts to recover impure plutoniu m with minor actin ides. High pure uranium is used for LWR fuel and impure p lutonium with minor actinides for metallic FR fuel. The solvent extraction test with e lectrolytic reduction test using actual LW R spent fuel and o xalate precipitation test were carried out to confirm the feasibility of the New Advanced Hybrid process. The purpose of electrolytic reduction test was to investigate the impurity of uraniu m recovery and the oxalate precip itation test was to evaluate the recovery yield of plutoniu m with minor act inides. The results suggested that the purity of recovered uranium (U) and the recovery yield of plutonium with minor act inides (Pu +MA) could ach ieve the target value in a stage (U purity : 99.97%, Pu +MA recovery yield:99.9%).

2010 Published by Elsevier Ltd

Keywords: hybrid reprocessing; pyro-chemical; solvent extraction; electrolytic reduction; LWR 1. Introducti on For next -generation Fast Reactors (FRs), it will be essential to realize a nuclear fuel cycle in which spent fuel is reprocessed and reused.

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*Corresponding author. T el.: +81-(0)44-288-8153; fax: +81-(0)44-270-1807 E-mail address: koji.mizuguchi@toshiba.co.jp

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As mentioned in the Framework for Nuclear Energy Po licy (October 2005), if Fast Reactors come online after 2050, they will coexist with Light Water Reactors (LW Rs) until at least around 2100. Toshiba has developed a reprocessing process based on hybrid reprocessing with advanced solvent extraction and pyro-chemical electro lysis that can be applied to the nuclear fuel cycle fro m the time of introduction of Fast Reactors through to their comp lete adoption, and aims to use this as the basis of a next-generation nuclear fuel cycle (Fig. 1) [1]-[2].
Fuel Fabrication

Rokkassho Reprocessing Plant

Light Water Light WaterSF Reactor Reactor Cycle

Hybrid process Fast Reactor

U,Pu,MA

U,Pu Recycle

Pyro Fuel Reprocessing Reactor Fabrication

Fast

Cycle

U,Pu,MA Recycle

Fig.1.Toshibas concept of next -generation nuclear fuel cycle.

The conventional reprocessing process shown in Fig. 2, based on the PUREX solvent extract ion method, is suitable for the recovery of uraniu m with a h igh decontamination factor. Ho wever, this process involves a high risk of nuclear proliferation because the recovery of plutoniu m with a low decontamination factor is difficult in this process.

SF PUREX

U Pu

LWR

Risk of nuclear proliferation

FP*+MA
*FP : Fission products
Fig.2.Conventional reprocessing

Waste

Toshiba has been developing a new technology, the Toshiba Hybrid Process, for spent -fuel reprocessing based on solvent extraction and pyro-chemical electrolysis, suitable for the transition fro m LWRs to FRs (Fig. 3) [1,2]. The Hybrid Process combines the solvent extraction process of LWR spent fuel in n itric acid with the recovery of h igh-purity uran iu m and the pyro-chemical process in molten salts fo r the recovery of impure plutoniu m with minor actin ides. High-purity uranium is used for LWR fuel, and impu re plutonium with minor actinides is used for metallic FR fuel. The pyro -chemical process for the FR spent fuel recycling system is based on research on an electrorefin ing process in molten salts conducted at Toshiba since 1988[10]-[13] . The new Toshiba Hybrid Process can reduce the amount of highlevel waste and secondary waste from spent-fuel reprocessing plants.

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SF Advanced Advanced Extraction Extraction

Pyro Pyro Electrolysis Electrolysis

LWR FBR

Pu+MA FP

High resistance of nuclear proliferation

Waste

Fig.3.Toshiba Hybrid Process based on advanced solvent extraction and pyroelectrolysis.

As a first step, we have developed an advanced solvent extraction process in the Toshiba Hybrid Process (Fig. 3)[1]-[2]. The solvent extraction test with electrolytic reduction tests using actual LWR spent fuel was carried out to investigate the uranium recovery purity (target purity in a stage = 99.97%). As a second step, we have developed an Advanced Aqua-Pyro Process. In this process, actinides and rare earth elements are recovered fro m an aqueous solution in the extraction process by an oxalic acid precipitation method and are applied to the pyro -chemical electrolysis process. Oxalate acid precipitation tests were carried out in o rder to evaluate the recovery y ield of Pu+MA (target y ield 99.9%). 2. Uranium extraction with electrolytic reduction We have developed an advanced solvent ext raction process in the Hybrid Reprocessing shown in Fig. 3. The key technology in this process is the method for the uraniu m extract ion with electro lytic reduction shown in Fig. 4. This technology is based on the PUREX process using tributyl phosphate (TBP) with 30% n-dodecane as an extractant. The method has a single ext raction cycle consisting of extraction and electrolytic reduction. This method can extract only uraniu m by controlling the valence of plutonium ions to the trivalent state by electrolysis. This process has high resistance to nuclear proliferation because the plutonium is kept in an aqueous solution with heavy metals.
Extractive valence

SF Dissolution Dissolution U U extrac. extrac. with with e.r. e.r. U U purification purification
Extractant

UVIO22+ U Pu3+ Pu Electro-reduction Np Control valence Np5+

UVIO22+ Pu3+ Np5+

High resistance against nuclear proliferation

Fig.4.The method for uranium extraction with electroreduction.

Figure 5 shows the scheme of the uraniu m ext raction with electro lyt ic reduction. First, uranyl ions (UO2 2+) are reduced to tetravalent uranous (U4+) ions by electrolysis, and then these uranous ions act as a reductant to reduce tetravalent plutonium ions (Pu 4+) to trivalent ions (Pu 3+). In the process, the reductant uranous ions are re-o xidized to uranyl ions 1)-3). Gram-scale actual spent fuel examinat ions were carried out using the test equipment shown in Fig.6.

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U extraction

Cathode

UVIO22+
Reductant

Pu3+

2e + 4H+ Electro-reduciton

U4+

Pu4+

Fig.5.The scheme of the uranium extraction with electro-reduction Actual spent fuel electrolysis test was carried out at the cathode potential less than -0.05V vs. Ag/AgCl by using test equipment shown in Fig. 6. The decontamination factors DFM were calculated according to the following Eq.1, where C is the concentration of elements.
Reference Cathode Anode

Actual spent fuel dissolution solution

Fig.6.Test equipment

DFM

CM feed CU TBP CU feed CM TBP

(M

Pu, Np, Am, Cm)

(1)

The results, given in Table 1, suggest that the purity of recovered uranium achieved the target value of 99.97% in 5 stages. It was confirmed that uraniu m could be recovered with high decontamination factors. Table 1 Decontamination factors
DF

Pu Pu
Np
MA

5 5
100 10 500

Am Cm

3. Advanced aqua-pyro process We first developed an aqua-pyro process [5]-[9]in which minor actinides (MAs) are recovered fro m high-level radioactive liquid waste (HLLW) generated by operation of the Rokkasho Reprocessing Plant. This process is an electrolysis technology cultivated from pyro-chemical reprocessing. Next, electrolysis technology based on this aqua-pyro process was applied to an active reprocessing process, to realize a reprocessing process that makes it d ifficu lt to separate pure plutonium, wh ile redu cing the amount of HLLW. This process introduces reprocessing for LWR fuel that ensures a high level of

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support for nuclear non-proliferat ion. Subsequently, pyro-chemical reprocessing technology based on electrolysis will be applied to reprocessing of FR fuel. This approach will allow progression of the core technology fro m the coexistence of FRs and LW Rs through to complete adoption of FRs. As a result, Toshiba will be able to offer a fuel cycle suited to both LWRs and FRs. We have developed an Advanced Aqua-Pyro Process [1]-[4] by applying the aqua-pyro process in order to connect the advanced uranium ext raction process with the pyro -electrolysis process. In this process, actinides and rare earth elements are recovered fro m the aqueous solution from the extract ion process by the oxalic acid precipitation method and are applied to the pyro -chemical process. Oxalate precipitation tests were carried out on simulated spent fuel solution. Figure 7 belo w shows photographs of the test setup. Uranium was precipitated as uranyl oxalate by the addition of oxalic acid.

Fig.7.Oxalate precipitation test using simulated spent fuel.

In the experiments at (COOH)2 /UO2 =2, the precip itation rat ios achieved the target value o f 99.9% in a temperature range of 20 to 80 C (Fig.8). It was confirmed to recover 99.9% of Actinides and rare earth elements fro m simu lated spent fuel solution.
100 99.8

) Precipitation ratio(%

99.6 99.4 99.2 99 98.8 98.6 0 20 40 60

o

(COOH)2/ UO2=2 (COOH)2/ UO2=1.5 (COOH)2/ UO2=1

80

100

Tem perature( C)
Fig.8.Correlation between precipitation ratio and temperature.

Actin ides and rare earth elements in aqueous solution are recovered as oxide form by oxalic acid precipitation and conversion to o xide in molten salt. The recovered elements can be treated by pyro chemical process (Fig. 9). These results suggest that the recovery yield of Pu+MA achieved the target value.

Fig.9.The conversion of oxalate precipitation into oxide (molten salt oxidation).

K. Mizuguchi et al / Energy Procedia 00(2010) 000-000

4. Conclusion Toshiba has proposed a new fuel cycle concept for the transition from LW Rs to FRs. We have been developing a new technology, the Toshiba Hybrid Process, based on solvent extraction and a pyro chemical process for spent-fuel reprocessing in this transition. The Toshiba Hybrid Process combines the solvent extract ion process of the LWR spent fuel in nitric acid fo r recovering high -purity uraniu m for LW R fuel and the pyro-chemical process in molten salts for recovering impure plutoniu m with minor actin ides for metallic FR fuel. Our pyro-chemical process based on electrorefining, wh ich has been under development since 1998, can be a viable FR spent-fuel recycling system for the future FR age. References
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