Impact of uranium carbide organics treated by prolonged boiling and electrochemical oxidation upon uranium and plutonium solvent extraction
-
Chris J. Maher
,
Christine Bouyer
Abstract
The dissolution of uranium or uranium-plutonium carbide fuel in nitric acid leads to ~50% carbon evolved as carbon dioxide, the remainder remains in the solution as soluble organics. These dissolved organic molecules interfere with the solvent extraction of uranium and plutonium by complexing to the actinide ions and decreasing the efficiency of their extraction. Experiments reported here describe two series of experiments assessing the uranium carbide dissolution liquor treatment by prolonged boiling and electrochemical oxidation. Plutonium losses to aqueous and solvent raffinates are observed for untreated liquors, highlighting that mineralisation of dissolved organics is necessary to reduce the complexing effects of organic acids to an extent that permit efficient operation of a solvent extraction process both in the first solvent use (considered here) and for maintaining solvent quality during industrial solvent reuse in the highly active cycle. Solution carbon analysis and 30% TBP solvent extraction batch tests of uranium and plutonium originating from dissolved uranium carbide liquors untreated and after treatment are compared. These experiments demonstrate the reprocessing of uranium carbides by direct dissolution coupled to a mineralisation process, can achieve near quantitative uranium and high plutonium recoveries (99.9%).
Acknowledgments:
The authors would like to acknowledge financial support for this work, which was made possible by the ASGARD project (EC FPVII Euratom contract N° 2012-295825), CEA, NNL and UK’s Nuclear Decommissioning Authority (NDA).
References
1. IAEA Nuclear Energy Series Technical Report, “Status of Developments in the Back End of the Fast Reactor Fuel Cycle”, No. NF-T-4.2, (2001).Suche in Google Scholar
2. SNETP, Sustainable Nuclear Energy Technology Platform, Strategic Research Agenda; http://www.snetp.eu (2009).Suche in Google Scholar
3. Matzke, H.: Science of Advanced LMFBR Fuels (1986), North-Holland, Amsterdam.Suche in Google Scholar
4. Generation IV International Forum (GIF), Technology Roadmap Update for Generation IV Nuclear Energy Systems, (2014).Suche in Google Scholar
5. Ferris, L. M., Bradley, M. J.: Reactions of uranium carbide with nitric acid. J. Am. Chem. Soc. 87, 1710 (1965).10.1021/ja01086a016Suche in Google Scholar
6. Bokelund, H., Caceci, M., Ougier, M.: Dissolution of mixed carbide. Fuels in nitric acid. Radiochem. Acta 30, 49 (1982).10.1524/ract.1982.30.1.49Suche in Google Scholar
7. Flanary, J. R., Goode, J. H., Bradley, M. J., Ullmann, J. W., Ferris, L. M., Wall, G. C.: Hot-cell studies of aqueous dissolution processes for irradiated carbide reactor fuels. ORNL 3660 (1964).10.2172/4020314Suche in Google Scholar
8. Donaldson, D. M., Hartley, K., Lees, P., Parkinson, N.: Tran. Met. Soc. Of Aime 227, 191 (1963).Suche in Google Scholar
9. Nayak, S. K., Srinivasan, T. G., Vasudeva Rao, P. R., Mathews, C. K.: Photochemical destruction of organic compounds formed during dissolution of uranium carbide in nitric acid. Sep. Sci. Technol. 23, 1551 (1988).10.1080/01496398808075648Suche in Google Scholar
10. Zverev, D. V., Kirillov, S. N., Dvoeglazov, K. N., Shadrin, A. Yu., Logunov, M. V., Mashkin, A. N., Schmidt, O. V., Arseenkov, L. V.: Possible options for uranium-carbide SNF processing, ATALANTE 2012 International Conference on Nuclear Chemistry for Sustainable Fuel Cycles. Procedia Chem. 7, 116 (2012).10.1016/j.proche.2012.10.021Suche in Google Scholar
11. Pauson, P. L., McLean, J., Clelland, W. J.: Acid leaching of uranium and thorium carbides. Nature 197, 1200 (1963).10.1038/1971200a0Suche in Google Scholar
12. Choppin, G. R., Bukelund, H., Valkiers, S.: Oxalate complexation in dissolved carbide systems. Radiochim. Acta 33, 229 (1983).10.1524/ract.1983.33.4.229Suche in Google Scholar
13. Legand, S., Bouyer, C., Dauvois, V., Casanova, F., Lebeau D., Lamouroux, C.: Uranium carbide dissolution in nitric acid: speciation of organic compounds. J. Radioanal. Nucl. Chem. 302, 27 (2014).10.1007/s10967-014-3409-2Suche in Google Scholar
14. Chandramouli, V., Sreenivasan, N. L., Yadav, R. B.: Chemical head-end steps for aqueous reprocessing of carbide fuels. Radiochim. Acta 51, 23 (1990).10.1524/ract.1990.51.1.23Suche in Google Scholar
15. Flanary, J. R., Goode, J. H., Bradley, M. J., Ferris, L. M., Ullman, J. W.: Head end dissolution for UC processes and UC-PuC reactor fuels. Nucl. Appl. 1, 219 (1965).10.13182/NT65-A20505Suche in Google Scholar
16. Charyulu, M. M., Karekar, C. V., Rao, V. K., Natarajan, R. H.: Studies on the dissolution of carbide fuels. J. Radioanal. Nucl. Chem. 148, 229 (1894).10.1007/BF02060366Suche in Google Scholar
17. Virota, M., Szenknecta, S., Chavea, T., Dacheuxa, N., Moisyb, P., Nikitenkoa, S. I.: Uranium carbide dissolution in nitric solution: Sonication vs. silent conditions. J. Nucl. Mater. 441, 421 (2013).10.1016/j.jnucmat.2013.06.021Suche in Google Scholar
18. Tomar, B. S., Saxena, M. K., Manchanda, V. K., Manohar, S. B.: Application of ozone in nuclear fuel reprocessing – studies on destruction of residual carbon in solutions of uranium carbide and uranium plutonium mixed carbide, National symposium on nuclear and radiochemistry (NUCAR2003); Mumbai (India); 10–13 Feb 2003; 169 (2003).Suche in Google Scholar
19. Palamalai, A., Rajun, S. K., Chinnusamy, A., Sampath, M., Vargese, P. K., Ravi, T. N., Raman, V. R., Balasubramanian, G. R.: Development of an electro-oxidative dissolution techniques for fast reactor carbide fuels. Radiochim. Acta 35, 29 (1991).10.1524/ract.1991.55.1.29Suche in Google Scholar
20. Sini, K., Mishra, S., Lawrence, F., Mallika, C., Kogant, S. B.: Destruction of soluble organics generated during the dissolution of sintered uranium carbide by mediated electrochemical oxidation process. Radiochim. Acta 99, 1 (2011).10.1524/ract.2011.1792Suche in Google Scholar
21. Taylor, R. J., Mason, C., Brown, T. L., Buchanan, D., Maher, C. J., Morris, D.: The decomposition of oxalic acid in nitric acid. J. Sol. Chem. 45, 325 (2016).10.1007/s10953-016-0437-2Suche in Google Scholar
22. Maslennikov, A., Fourest, B., Sladkov, V., Moisy, P.: Electrochemical behaviour of UC in acidic media: preliminary results. J. Alloys Comp. 444–445, 550 (2007).10.1016/j.jallcom.2007.03.143Suche in Google Scholar
23. Po, H. N., Swinehear, J. H., Allen, T. L.: The kinetics and mechanism of the oxidation of water by silver(II) in concentrated nitric acid solution. Inorg. Chem. 7, 244 (1968).10.1021/ic50060a015Suche in Google Scholar
24. Griffiths, T., Maher, C., Sarsfield, M.: Dissolution of unirradiated uranium carbide fuel pellets in nitric acid, Top Fuel reactor fuel performance 2015, Zurich Switzerland 13–17 September, Topfuel2015-A0256, (2015).Suche in Google Scholar
25. Griffith, W. L., Compere, A. L., Huxtable, W. P., Googin, J. M.: Reducing Emissions from Uranium Dissolving, ORNL/TM-12211, (1992).10.2172/6668398Suche in Google Scholar
26. Chiba, Z., Schumacher, B., Lewis, P., Murguia, L.: Mediated Electrochemical Oxidation as an Alternative to Incineration for Mixed Wastes, Waste Management WM95 Symposia, Tucson, AZ, March 1, (1995).Suche in Google Scholar
Supplemental Material:
The online version of this article offers supplementary material (https://doi.org/10.1515/ract-2017-2799).
©2018 Walter de Gruyter GmbH, Berlin/Boston
Artikel in diesem Heft
- Frontmatter
- Measurements of excitation functions of α-particle induced reactions on natNi: possibility of production of the medical isotopes 61Cu and 67Cu
- Impact of uranium carbide organics treated by prolonged boiling and electrochemical oxidation upon uranium and plutonium solvent extraction
- Effect of pKa on the extraction behavior of Am(III) in organo phosphorus acid and diglycolamide solvent system
- Plutonium leaching from polycrystalline and monocrystalline PuO2
- Adsorption of volatile polonium species on metals in various gas atmospheres: Part III – Adsorption of volatile polonium on stainless steel 316L
- Separation of radioisotopes of terbium from a europium target irradiated by 27 MeV α-particles
- Determination of selenium in roasted beans coffee samples consumed in Algeria by radiochemical neutron activation analysis method
- Effect of seawater intrusion on radioactive strontium (90Sr) sorption and transport at nuclear power plants
- Study of the radioactivity in environmental soil samples from Eastern Anatolia Region of Turkey
Artikel in diesem Heft
- Frontmatter
- Measurements of excitation functions of α-particle induced reactions on natNi: possibility of production of the medical isotopes 61Cu and 67Cu
- Impact of uranium carbide organics treated by prolonged boiling and electrochemical oxidation upon uranium and plutonium solvent extraction
- Effect of pKa on the extraction behavior of Am(III) in organo phosphorus acid and diglycolamide solvent system
- Plutonium leaching from polycrystalline and monocrystalline PuO2
- Adsorption of volatile polonium species on metals in various gas atmospheres: Part III – Adsorption of volatile polonium on stainless steel 316L
- Separation of radioisotopes of terbium from a europium target irradiated by 27 MeV α-particles
- Determination of selenium in roasted beans coffee samples consumed in Algeria by radiochemical neutron activation analysis method
- Effect of seawater intrusion on radioactive strontium (90Sr) sorption and transport at nuclear power plants
- Study of the radioactivity in environmental soil samples from Eastern Anatolia Region of Turkey
