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Licensed Unlicensed Requires Authentication Published by De Gruyter (O) January 11, 2020

Interference of Zr(IV) during the extraction of trivalent Nd(III) from the aqueous waste generated from metallic fuel reprocessing

  • T. Prathibha , K. Rama Swami , S. Sriram and K. A. Venkatesan EMAIL logo
From the journal Radiochimica Acta

Abstract

A metallic alloy of uranium–zirconium and uranium–plutonium–zirconium has been proposed as a fuel for fast reactors, owing to the possibility of achieving high breeding ratio in a short span of time. About 6–10 wt.% of zirconium has been added to these actinide fuels to increase the melting temperature and thermal-mechanical stability. Aqueous reprocessing of the spent metallic fuel generates the high-level liquid waste (HLLW) that contains about 60 % of the total zirconium from the fuel. In view of this, the extraction behavior of a trivalent representative ion, Nd(III) in the presence of Zr(IV) was studied from nitric acid medium using the candidate ligands proposed for trivalent actinide separation from HLLW, such as N,N,NN′-tetraoctyldiglycolamide (TODGA), and N,N-di-octyl-2-hydroxyacetamide (DOHyA). The extraction was studied as a function of nitric acid concentration, zirconium and neodymium concentration and Nd(III) to Zr(IV) ratio. The findings of dynamic light scattering (DLS) and ATR-FTIR spectral techniques were used for understanding the complex chemistry of Zr(IV) extraction under different conditions. Poor extraction of nitric acid, smaller aggregate size, no third phase formation during the extraction of Zr(IV) and Nd(III) and other unique solvent properties favor the DOHyA molecule in n-dodecane as a solvent for partitioning of trivalent actinides from HLLW generated from metallic fuel reprocessing.

Acknowledgements

The authors would like to acknowledge the support from Dr. S Ponraju and Mrs. V Snehalatha, Health and Safety Laboratory, IGCAR during ATR-FTIR measurements and Dr. S Vijayalakshmi, Analytical Chemistry and Spectroscopy division, IGCAR for ICP-OES analysis.

References

1. IAEA Nuclear Energy Series No. NF-T-4.2: Status of Developments in the Back End of the Fast Reactor Fuel Cycle. International Atomic Energy Agency, Vienna (2011), p. 15.Search in Google Scholar

2. Pruett, D. J.: Extraction chemistry of fission products. In: W. W. Schulz, L. L. Burger, J. D. Navratil, K. P. Bender (Eds.), Science and Technology of Tributyl Phosphate. CRC Press, Boca Raton, FL (1990), Vol. III, p. 81.Search in Google Scholar

3. Lamouroux, C., Moulin, C., Tabet, J. C., Jankowski, C. K.: Characterization of zirconium complexes of interest in spent nuclear fuel reprocessing by electrospray ionization mass spectrometry. Rapid Commun. Mass Spectrom. 14(19), 1869 (2000).10.1002/1097-0231(20001015)14:19<1869::AID-RCM108>3.0.CO;2-PSearch in Google Scholar

4. Wang, L. Y., Lee, M. S.: A review on the aqueous chemistry of Zr (IV) and Hf (IV) and their separation by solvent extraction. J. Ind. Eng. Chem. 39, 1 (2016).10.1016/j.jiec.2016.06.004Search in Google Scholar

5. Lee, M. S., Lee, H. Y.: Distribution of Zr (IV) ion species in aqueous solution. J. Korean Inst. Resour. Recycl. 20(6), 56 (2011).10.7844/kirr.2011.20.6.056Search in Google Scholar

6. Singhal, A., Toth, L. M., Lin, J. S., Affholter, K.: Zirconium (IV) tetramer/octamer hydrolysis equilibrium in aqueous hydrochloric acid solution. J Am. Chem. Soc. 118(46), 11529 (1996).10.1021/ja9602399Search in Google Scholar

7. Zimmer, E., Borchardt, J.: Crud formation in the PUREX and THOREX processes. Nucl. Technol. 75(3), 332 (1986).10.13182/NT86-A33845Search in Google Scholar

8. Delegard, C. H., Casella, A. J.: Literature Review-Crud Formation at the Liquid/Liquid Interface of TBP-Based Solvent-Extraction Processes. Pacific Northwest National Lab, Richland, WA (United States), No. PNNL-25888 (2016).10.2172/1430463Search in Google Scholar

9. Carmack, W. J., Porter, D. L., Chang, Y. I., Hayes, S. L., Meyer, M. K., Burkes, D. E., Lee, C. B., Mizuno, T., Delage, F., Somers, J.: Metallic fuels for advanced reactors. J. Nucl. Mater. 392(2), 139 (2009).10.1016/j.jnucmat.2009.03.007Search in Google Scholar

10. Kaity, S., Banerjee, J., Nair, M. R., Ravi, K., Dash, S., Kutty, T. R. G., Kumar, A., Singh, R. P.: Microstructural and thermophysical properties of U–6 wt.% Zr alloy for fast reactor application, J. Nucl. Mat. 427, 1 (2012).10.1016/j.jnucmat.2012.03.045Search in Google Scholar

11. Sreenivasulu, B., Suresh, A., Sivaraman, N., Joseph, M.: Studies related to the processing of U-Zr and U-Pu-Zr metallic fuels using tri-iso-amyl phosphate (TiAP) as extractant. Solvent Extr. Ion Exch. 34(5), 422 (2016).10.1080/07366299.2016.1207396Search in Google Scholar

12. Prathibha, T., Robert Selvan, B., Venkatesan, K. A.: Evaluation of long chain monoamide extractants for the reprocessing of U-Pu-Zr metallic fuel solution. J. Radioanal. Nucl. Chem. 320, 765 (2019).10.1007/s10967-019-06530-9Search in Google Scholar

13. Gonzalez-Romero, E. M.: Impact of partitioning and transmutation on the high level waste management. Nucl. Eng. Des. 241(9), 3436 (2011).10.1016/j.nucengdes.2011.03.030Search in Google Scholar

14. Ansari, S. A., Pathak, P. N., Mohapatra, P. K., Manchanda, V. K., Chemistry of diglycolamides – promising extractants for actinide partitioning. Chem. Rev. 112, 1751 (2012).10.1021/cr200002fSearch in Google Scholar PubMed

15. Wilden, A., Modolo, G., Kaufholz, P., Sadowski, F., Lange, S., Sypula, M., Magnusson, D., Müllich, U., Geist, A., Bosbach, D.: Laboratory-scale counter-current centrifugal contactor demonstration of an innovative-SANEX process using a water soluble BTP. Solvent Extr. Ion Exch. 33, 91 (2015).10.1080/07366299.2014.952532Search in Google Scholar

16. Kannan, S., Vats, B. G., Pius, I. C., Noronha, D. M., Dhami, P. S., Naik, P. W., Kumar, M.: Extraction and structural studies of an unexplored monoamide, N,N′-dioctyl,α-hydroxy acetamide with lanthanide(III) and actinide(III) ions. Dalton Trans. 43, 5252 (2014).10.1039/c3dt53529kSearch in Google Scholar PubMed

17. Prathibha, T., Kumaresan, R., Nayak, P. K., Venkatesan, K. A., Subramanian, G. G. S., Rajeswari, S., Kalaiyarasu, T., Karunakaran, R., Antony, M. P.: Modifier-free separation of trivalent actinides and lanthanides from fast reactor simulated high-level liquid waste using N,N-di-octyl-2-hydroxyacetamide. J. Radioanal. Nucl. Chem. 314, 2365 (2017).10.1007/s10967-017-5528-zSearch in Google Scholar

18. Nave, S., Modolo, G., Madic, C., Testard, F.: Aggregation properties of N,N,N′,N′-tetraoctyl-3-oxapentanediamide (TODGA) in n-dodecane. Solvent Extr. Ion Exch. 22, 527 (2004).10.1081/SEI-120039721Search in Google Scholar

19. Jensen, M. P., Yaita, T., Chiarizia, R.: Reverse-micelle formation in the partitioning of trivalent f-element cations by biphasic systems containing a tetraalkyldiglycolamide. Langmuir 23, 4765 (2007).10.1021/la0631926Search in Google Scholar PubMed

20. Prathibha, T., Robert Selvan, B., Venkatesan, K. A., Antony, M. P.: Studies on the radiolytic degradation of N,N-dioctyl-2-hydroxyacetamide using dynamic light scattering and ATR-FTIR spectroscopy. Radiochim. Acta 107(5), 441 (2019).10.1515/ract-2018-3013Search in Google Scholar

21. Prathibha, T., Venkatesan, K. A., Antony, M. P.: Comparison in the aggregation behaviour of amide extractant systems by dynamic light scattering and ATR-FTIR spectroscopy. Colloids Surf. A-Physiochem. Eng. Asp. 538, 651 (2018).10.1016/j.colsurfa.2017.11.035Search in Google Scholar

22. Chiarizia, R., Jensen, M. P., Rickert, P. G., Kolarik, Z., Borkowski, M., Thiyagarajan, P.: Extraction of zirconium nitrate by TBP in n-octane: Influence of cation type on third phase formation according to the ‘sticky spheres’ model. Langmuir 20(25), 10798 (2004).10.1021/la0488957Search in Google Scholar PubMed

23. Déjugnat, C., Dourdain, S., Dubois, V., Berthon, L., Pellet-Rostaing, S., Dufrêche, J. F., Zemb, T.: Reverse aggregate nucleation induced by acids in liquid–liquid extraction processes. Phys. Chem. Chem. Phys. 16, 7339 (2014).10.1039/c4cp00073kSearch in Google Scholar PubMed

24. Koppel, D. E.: Analysis of macromolecular polydispersity in intensity correlation spectroscopy: the method of cumulants. J. Chem. Phys. 57(11), 4814 (1972).10.1063/1.1678153Search in Google Scholar

25. Sasaki, Y., Zhu, Z. X., Sugo, Y., Suzuki, H., Kimura, T.: Extraction capacity of diglycolamide derivatives for Ca (II), Nd (III) and Zr (IV) from nitric acid to n-dodecane containing a solvent modifier. Anal. Sci. 21(10), 1171 (2005).10.2116/analsci.21.1171Search in Google Scholar PubMed

26. Prathibha, T., Kumaresan, R., Selvan, B. R., Venkatesan, K. A., Antony, M. P., Rao, P. R. V.: N,N-dialkyl-2-hydroxyacetamides for modifier-free separation of trivalent actinides from nitric acid medium. Radiochim. Acta 104, 173 (2016).10.1515/ract-2015-2477Search in Google Scholar

27. Zhu, Z. X., Sasaki, Y., Suzuki, H., Suzuki, S., Kimura, T.: Cumulative study on solvent extraction of elements by N,N,N′,N-tetraoctyl-3-oxapentanediamide (TODGA) from nitric acid into n-dodecane. Anal. Chim. Acta 527(2), 163 (2004).10.1016/j.aca.2004.09.023Search in Google Scholar

28. Qiao, B., Demars, T., Olvera de la Cruz, M., Ellis, R. J.: How hydrogen bonds affect the growth of reverse micelles around coordinating metal ions. J. Phys. Chem. Lett. 5(8), 1440 (2014).10.1021/jz500495pSearch in Google Scholar PubMed

29. Singh, M. B., Nayak S. G., Kanthe, A. D., Patil, R. B., Gaikar, V. G.: Insight into acidity driven third phase formation of TBP in organic solutions by MD simulation. J Mol. Liq. 232, 1 (2017).10.1016/j.molliq.2017.02.053Search in Google Scholar

30. Briggs, T. R.: Emulsions with finely divided solids. Ind. Eng. Chem. 13(11), 1008 (1921).10.1021/ie50143a022Search in Google Scholar


Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/ract-2019-3220).


Received: 2019-10-24
Accepted: 2019-12-13
Published Online: 2020-01-11
Published in Print: 2020-07-28

©2020 Walter de Gruyter GmbH, Berlin/Boston

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