Journal of Radioanalytical and Nuclear Chemistry, VoL 240, No.

3 (1999) 727-730

Recovery of actinides extracted by Truex solvent from high level waste using complexing agents
H. Counter-current studies R. R. Chitnis, ! P. K. Wattal, 1. A. Ramanujam, 2 P. S. Dhami, 2 V. Gopalakrishnan, 2 A. K. Bauri, 3 A. Banerji 3
l Process Engineering and Systems Development Division, 2 Fuel Reprocessing Division, J Bio-Organic Division, Bhabha Atomic Research Centre, Mumbai - 400 085, India (Received June 4, 1998)

These studies are an extension of earlier work on the recovery of actinides extracted by Truex solvent from simulated high level waste solution, with a mixture of weak acid, weak base and complexing agent used as a strippant. The effectiveness of the proposed strippant, consisting of formic acid, hydrazine hydrate and citric acid, is tested in a counter-current mode using mixer-settler in the present studies. The studies show that near quantitative recovery of americium and plutonium is feasible from acid-bearing Truex solvent with no reflux (reextraction) of activity. Use of this strippaut reduces considerably the generation of secondary waste.

Introduction

The stripping of americium extracted in a mixture of 0.2M octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and 1.2M tri-n-butyl phosphate (TBP) in n-dodecane (Truex solvent) using 0.04M nitric acid is associated with a high degree of reflux. 1 The reflux, which indicates reextraction of americium, is caused by the high nitric acid content of the loaded extractant and leads to incomplete stripping of americium. It requires two-step stripping 2 for a quantitative recovery of americium, resulting in a twofold increase in the volume of the secondary waste. Uranium depletion step incorporated in our scheme 1-3 will lower the concentration of plutonium to 200-300 gg/l in HLW and plutonium will be present in the same range in the loaded CMPO-TBP mixture. A separate step for the removal of this small amount of plutonium from loaded CMPO-TBP phase using oxalic acid will also add to the volume of secondary waste. If americium and plutonium are quantitatively recovered in a single step allowing no reflux to take place, process will be simplified and the generation of secondary waste will also be reduced. This requires use o f a strippant with which americium and plutonium exhibit very low distribution ratios in all the stages of mixer-settler, irrespective of the acid content of the loaded CMPOTBP mixture. In our earlier batch studies, 4 a mixture of formic acid, hydrazine hydrate and citric acid was shown to have very good capabilities for stripping the actinides from acid-bearing Truex solvent. Buffering action of mixture of formic acid and hydrazine hydrate lowers the acid content of the organic phase and the citric acid then

effectively strips the actinides through complex formation. With this strippant, it should be possible to recover americium and plutonium simultaneously in a counter-current mode without causing any reflux of the actinides. The feasibility of this recovery is tested in the present studies, using mixer-settler. The proposed strippant consists of common chemicals, which can be destroyed with conventional methods. The stripping run consists of an additional step of alkali carbonate wash for the CMPO-TBP phase using hydrazine carbonate. Hydrazine carbonate removes the residual actinides and fission products from the CMPO-TBP phase and makes the extractant suitable for reuse.
Experimental

Details about the procurement, synthesis and purification, of TBP, CMPO and n-dodecane were reported elsewhere. 5 Composition and preparation of the loaded CMPO-TBP mixture used in these studies are reported in earlier studies. 4 All other chemicals used were of analytical grade. Counter-current experfinents involved the use of mixer-settlers for stripping of americium and plutonium from loaded CMPO-TBP mixture and for an alkali carbonate wash of the lean extractant. The runs were carried out at an organic to aqueous phase ratio of 1:1. Loaded CMPO-TBP mixture was spiked with Am(III) and Pu(VI). 4 The concentration of plutonium and americium in the spiked CMPO-TBP mixture was -3 and -0.06 rag/l, respectively. The mixer-settlers fabricated from polyacrylic sheets were used for the experiments. The capacity of the mixer was 30 ml and that of settler was 130 ml for each stage. Peristaltic pumps were used for feeding the liquids. The mixing was accomplished by mechanical stirrer. Mixing time and

* Author for correspondence. 0236-5 731/99/USD 17. O0 9 1999 Akad6miai Kiad6, Budapest All rights reserved Elsevier Science B. ~, Amsterdam Akaddmiai Kiad6, Budapest

R. R. CH1TNIS al.: RECOVERY ACTINIDES et OF EXTRACTED TRUEX BY SOLVENT,II. settling time in each stage was 3.3 and 14.4 minutes, respectively. The equilibrium conditions were ascertained through the periodic checking of total activity in the exit organic and aqueous streams. Samples were collected from various stages at the end of the runs and analysed for actinides, fission products, etc. Total m-activity was analysed using alphaproportional counter. Americium activity was determined using NaI(T1) gamma-ray scintillation detector. Plutonium activity was calculated from the difference between the total and americium activity. Uranium and inactive ingredients in the samples were analysed by ICP-AE spectroscopy. For analysis using 1CP-AE spectroscopy, the organic samples were treated with nitric acid and perchloric acid mixture for destroying the organic material. The necessary dilution of the sample during the treatment restricted the lowest detectable limit for each element in original sample to -1 mg/1.
Results and discussion
Table I.

Acid content in aqueous and organic phases in various stages of mixer-settler Acidity** Aqueous phase, pH Organic phase, M
3.60

StageNo.*
1

2 3 4 5 6

3.94 3.96 3.96 7.35 7.48

0.00 0.00 0.00 0.00 0.00 0.00

* Stripping in first four stages and washing in last two stages. ** lnitial pH of the strippant: 4.2. Analysis using ICP-AE spectroscopic method showed that the concentration of uranium in the organic feed is reduced from 11.0 to 1.2 rag/1 after stripping. Among the fission products, the concentration of zirconium and lanthanides in the lean organic phase was below the detection limit. While molybdenum content of the feed was reduced from 462 to 26 rag/l, that of ruthenium was reduced from 42 to 12mg/l. The concentration of chromium, an inactive ingredient in the loaded extractant, was reduced from 186 to 55 mg/l. Further separation of actinides from lanthanides and other elements present in the aqueous product can be carried out using ion-exchange 6 or extraction chromatographic technique. 7,8 The lean extractant was subjected to an alkali carbonate wash to remove the traces of plutonium and uranium as well as other ingredients. Hydrazine carbonate was preferred for the wash as it can be destroyed easily. The solvent was contacted with 0.5 M hydrazine carbonate at an organic to aqueous phase ratio of 1:1, in a two-stage mixer-settler (Fig. 1). The wash left less than 0.2% of plutonium, initially present in the loaded CMPO-TBP. The gradient in the stripping profile for plutonium clearly suggests the possibility of further improvement in its removal with a provision of adequate number of stripping stages. ICP-AE spectroscopic analysis showed that concentration of uranium in washed CMPO-TBP phase was below its detection limit. Concentration of molybdenum was 4.5 rag/l. Ruthenium content was close to the detection limit o f - I mg/l. Concentration of chromium was reduced to 4.4 mg/[. (Distribution of the elements in percentages after stripping and washing steps is shown in Table 2.) For further improvement in the efficiency of the wash, it is necessary to increase the number of stages of mixer-settler.

Earlier counter-current extraction studies 2 had shown the acidity of the loaded CMPO-TBP phase to be -0.35M. Present mixer-settler studies are carried out with a CMPO-TBP mixture having the same acid content as a feed. The batch studies 4 had shown that - 9 8 % of Am(III) and - 9 7 % of Pu(Vl) can be stripped from loaded Truex solvent having nitric acid content of 0.35M in a single contact, using a mixture of 0.4M formic acid, 0.4M hydrazine hydrate and 0.1M citric acid. Loaded CMPO-TBP phase was contacted with the above strippant in a four-stage mixer-settler at an organic to aqueous phase ratio of 1:1. The results of the studies are presented in Fig. 1 along with the scheme. No crude formation was observed in any of the stages of the mixer-settler. This figure shows no reflux of either americium or plutonium activity during the stripping. Organic phase is found to be practically completely free of acid as seen in Table 1. The pH of the aqueous phase (which was initially 4.2) remains above 3 in all the stages, indicating efficient buffering by the strippant. Practically all the americium was stripped from CMPO-TBP phase within 3 stages, the removal being 88.5% in the first stage. In spite of removal of about 96% in the first stage, plutonium could not be stripped completely. About 1.5% of plutonium was left in the exiting organic phase. This may be due to incornplete reduction of Pu(VI) to Pu(III). Longer mixing time may improve the stripping of plutonium.

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R. R. CHITNISet al.: RECOVERYOF ACT1NIDESEXTRACTEDBY TRUEX SOLVENT, II.

Loaded CMPO-TPB in n-dodecane (4.5 ml/min)

Lean CMPO-TPB

t_,
Aqueous product 10,000

II

'
Strippant 0.4 M formic acid + 0.4 M hydrazine hydrate + 0.1 M citric acid (4.5 ml/min)

Jt
Washings 0.5 M hydrazine carbonate (4.5 ml/min)

Feed (organic)

H : 0.35 M
1,000

o :+

Am (aqueous) Am (organic)

rn > ,< 100

Stripping 10
I I I t

Wash

3 Stage number

Fig. 1. Recovery of americium and plutonium from loaded Traex solvent

Table 2. Distribution of different elements in aqueous streams

Distribution, % Aqueous product (I)* Aqueous product (II)** 89.09 98.51 -100 - 100 ~100 - 100 >2*** 1.32 -0 -0 -0 -0 Distribution, % Aqueous product (I)* Aqueous product (1I)** ~100 -100 -100 94.37 71.43 70.43 -0 -0 -0 4.65 -26 27.20

Element U Pu Am La Ce Nd

Element Sm Eu Zr Mo Ru Cr

* Aqueous phase (I): 0.4M formic acid + 0.5M hydrazine hydrate + 0.1M citric acid. ** Aqueous phase (II): 0.5M hydrazine carbonate. *** Concentration below the detection limit,

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R. R. CH1TNISet al.: RECOVERYOF ACT1N1DESEXTRACTEDBY TRUEXSOLVENT,II.

The activities used for spiking the CMPO-TBP phase were not realistic. Americium will be present in higher concentration in the extractant loaded from actual HLW. Nevertheless, practically complete stripping of lanthanides from loaded extractant, seen in the present case (which are present in millimolar levels), suggests a high extent of recovery of americium. Curium should also show a similar behavior. Concentration of plutonium in loaded CMPO-TBP phase from actual process is expected to be only 200-300 gg/I and is much lower than that used in the present experiment (3 mg/l). The concentration of plutonium left in the organic phase after stripping may not exceed 2-3 gg/1 in realistic case. Neptunium should also be stripped quantitatively. 4 It can be inferred from these observations that total a-activity left in the lean extractant from actual process after the stripping step will be in the level of few nCi/ml. With these levels of a-activity, it will be possible to treat the aqueous stream from the alkali carbonate wash as a conventional fission product contaminated waste.

plutonium can be removed by washing with alkali carbonate like hydrazine carbonate. Reflux of americium, which occurs due to high acid content of the organic phase during counter-current stripping with dilute nitric acid as strippant, is completely avoided with this strippant. This single step stripping process reduces the generation of secondary waste volume considerably. Chemicals used in the process are common chemicals that can be finally destroyed without producing any inorganic residues.
References
1. D. S. DESHNGKAR, R. R. CHITNIS, P. K. WAITAL, T. K. THEYYUNNI, A. RAMANUJAM, P. S. DHAMI, V. GOPALAKRISHNAN,M. K. RAO, J. N. MATHUR, M. S. MURAL1, R. H. IYER, L. P. BADHEKA, A. BANERJ1, BARC Report BARC/1993/EI028, 1993. 2. D. S. DESHINGKAR, R. R. CH1TNIS, P. K. WATTAL, T. K. THEYYUNNI, M. K. T. NAIR, A. RAMANU.IAM,P. S. DHAMI, V. GOPALAKRISHNAN,M. K. RAO, J. N. MATHUR, M. S. MURALI, R. H. IYER, L. P. BADHEKA, A. BANERII, BARC Report BARCII9941EIO14, 1994. 3. R. R. CHITNIS, P. K. WATrAL, A. RAMANUJAM, P. S. DHAMI, V. GOPALAKRISHNAN,J. N. MATHUR, M. S. MURAL1, Sep. Sci. Teehnol., 33 (1998) 1877. 4. R. R. CHrlNIS, P. K. WATI'AL, A. RAMANUJAM, P. S. DHAMI, V. GOPALAKRISHNAN,A. K. BAURI, A. BANERJI, J. Radioanal. Nucl. Chem., to be published. 5. J. N. MATHUR, M. S. MURALI, P. R. NATARAJAN, k P. BADHEKA,A. BANERJI, Talanta, 39 (1992) 493. 6. K. STREET, G. T. SEABORG,J. Am. Chem. Soc., 72 (1950) 2790. 7. A. RAMANUJAM, P. V. ACHUTHAN, P. S. DHAMI, V. GOPAkAKRISHNAN,R. KANSAS, J. N. MATHUR, Solv. Extr. Ion Exeh., 13(2) (1995) 301. 8. C. S. KEDARI, S. S. PANDIT, A. RAMANUJAM,J. Radioanal. Nucl. Chem., 222 (1997) 141.

Conclusions

Extension of earlier batch studies to counter-current stripping studies indicated the feasibility of quantitative recovery of americium and plutonium from loaded CMPO-TBP mixture having an acidity of 0.35M using a strippant containing 0.4M formic acid, 0.4M hydrazine hydrate and 0.1M citric acid. Although the recovery of americium was practically complete, about 1.5% of plutonium was left in the organic phase. The residual

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