Nuclear Engineering and Technology

Korean Nuclear Society (한국원자력학회)
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Exothermic processes in nitric acid solutions imitating highly active raffinate

  • E.V. Belova (A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS (IPCE RAS)) ;
  • V.V. Kalistratova (A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS (IPCE RAS)) ;
  • A.S. Obedkov (A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS (IPCE RAS))
  • Received : 2023.01.01
  • Accepted : 2023.06.26
  • Published : 2023.10.25
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Abstract

The thermal stability of nitric acid solutions after contact with non-irradiated and irradiated tributyl phosphate (TBP) and its solution in Isopar-M has been studied. It has been established that exothermic processes occur during heating due to the interaction of soluble radiolysis products and the decomposition of the extractant with nitric acid. Such processes can occur at temperatures below 100 ℃, but unlike a thermal explosion that occurs in seconds, they are longer in time and are accompanied by weak heat evolution. Their intensity depends on the composition of the extractant, the concentration of HNO3, and the volume ratio of the organic and aqueous phases. The presence of extractant degradation products in raffinates does not pose a risk of a rapid evolution of gaseous products during evaporation, however, the presence of reducing agents can significantly increase the intensity of the exothermic decomposition of raffinates.

Keywords

Acknowledgement

The investigation was performed using the equipment of CKP FMI IPCE RAS and UNU KRHI IPCE RAS. This work was financially supported by Ministry of Science and Higher Education of Russian Federation. The authors are grateful to anonymous reviewers whose valuable comments helped to improve this article.

References

  1. G.F. Egorov, Radiation Chemistry of Extraction Systems, Energoatomizdat, Moscow, 1986. 
  2. B.V. Gromov, B.N. Sudarikov, V.I. Savelyeva, in: V.B. Shevchenko (Ed.), Chemical Technology of Irradiated Nuclear Fuel, Atomizdat, Moscow, 1971. 
  3. R. Taylor, Reprocessing and Recycling of Spent Nuclear Fuel, Woodhead Publishing, Elsevier, 2015. 
  4. A.P. Paiva, P. Malik, Recent advances on the chemistry of solvent extraction applied to the reprocessing of spent nuclear fuels and radioactive wastes, J. Radioanal. Nucl. Chem. 261 (2) (2004), https://doi.org/10.1023/B:JRNC.0000034890.23325.b5. 
  5. H.A.C. McKay, The PUREX Process, CRC Press Inc., United States, 1990. 
  6. Z.V. Dzhivanova, E.V. Belova, G.P. Tkhorzhnitskii, D.I. Danilin, M.I. Kadyko, B.F. Myasoedov, B.Ya Zilberman, I.V. Blazheva, N.D. Goletskii, A.A. Murzin, D.V. Ryabkov, Radiation resistance of hydrocarbon diluents of tributyl phosphate in a two-phase system and carbonate regeneration of the solvent, Radiochemistry 57 (2) (2015), https://doi.org/10.1134/S106636221502006X. 
  7. Z.V. Dzhivanova, M.I. Kadyko, YuV. Nikitina, A.V. Rodin, E.V. Belova, A study of the radiolysis products of the tri-n-butyl-phosphate-isopar-M-HNO3 system before and after regeneration with carbonates of organic bases, Protect. Met. Phys. Chem. Surface 57 (1) (2021), https://doi.org/10.1134/S207020512101007X. 
  8. A. Wright, P. Paviet-Hartmann, Review of physical and chemical properties of tributyl phosphate/diluent/nitric acid systems, Separ. Sci. Technol. 45 (12-13) (2010), https://doi.org/10.1080/01496395.2010.494087. 
  9. G.F. Egorov, O.P. Afanas'ev, B.Y. Zilberman, M.N. Makarychev-Mikhailov, Radiation-chemical behavior of TBP in hydrocarbon and chlorohydrocarbon diluents under conditions of reprocessing of spent fuel from nuclear power plants, Radiochemistry 44 (2) (2002), https://doi.org/10.1023/A:1019619212460. 
  10. V.M. Adamov, V.I. Andreev, B.N. Belyaev, R.I. Lyubtsev, G.S. Markov, M.S. Polyakov, A.Eh Ritari, A.Yu Shil'nikov, Radiolysis of extraction system on the basis of tri-n-butylphosphate solutions in hydrocarbon diluents, Radiochemistry 29 (6) (1987) 822-829. 
  11. E.V. Belova, G.F. Egorov, E.R. Nazin, G.P. Tkhorzhnitskii, Thermochemical oxidation of components of extraction solutions and threshold conditions of thermal explosion: 4. Kinetics of reaction of TBP solutions in dodecane with nitric acid, Radiochemistry 43 (1) (2001), https://doi.org/10.1023/A:1012882307907. 
  12. D.F. Paddleford, Y. Hou, Е.K. Barefield, D.W. Tedder, S.I. Abdel-Khalik, Thermal Decomposition of Nitrated Tributyl Phosphate, Final Report WSRC-RP-95-259, Savannah River Company, 1995. 
  13. YuV. Serenko, E.V. Belova, A.V. Ponomarev, N.V. Yudin, The effect of radiolysis and thermally stimulated acid hydrolysis on tributyl phosphate and its solutions in ISOPAR-M, Radiat. Phys. Chem. 195 (2022), https://doi.org/10.1016/j.radphyschem.2022.110080. 
  14. YuV. Serenko, N.V. Yudin, R.T. Gritcenko, A.V. Rodin, E.V. Belova, A.V. Ponomarev, Competitive processes of tributyl phosphate degradation in HNO3-saturated solution in Isopar-M during radiolysis and aging, Radiat. Phys. Chem. 185 (2021), https://doi.org/10.1016/j.radphyschem.2021.109495. 
  15. M.K. Tian, S.L. Tang, H.B. Tang, X.H. Ju, Theoretical study on the mechanism for the formation of nitro compounds in red oil, J. Chem. 2020 (2020), https://doi.org/10.1155/2020/2012417. 
  16. E.V. Belova, G.P. Tkhorzhnitskii, G.F. Egorov, E.R. Nazin, Thermochemical oxidation of extraction system components and the boundary parameters of a thermal explosion: 5. Gas evolution in thermolysis of two-phase systems in open vessels, Radiochemistry 44 (5) (2002), https://doi.org/10.1023/A:1021131425029. 
  17. E.R. Nazin, G.M. Zachinyaev, Fire and Explosion Safety of Technological Processes in Radiochemical Industry, STC NRS, Moscow, 2009. 
  18. A.S. Emel'yanov, E.R. Nazin, E.V. Belova, B.F. Myasoedov, Thermal stability of nitric-acid solutions containing monoethanolamine, Radiochemistry 62 (6) (2020), https://doi.org/10.1134/S1066362220060041. 
  19. A.S. Obedkov, V.V. Kalistratova, I.V. Skvortsov, E.V. Belova, Thermal stability of nitric acid solutions of reducing agents used in spent nuclear fuel reprocessing, Nucl. Eng. Technol. 54 (9) (2022), https://doi.org/10.1016/j.net.2022.03.034. 
  20. P. Velavendan, S. Ganesh, N.K. Pandey, R. Geetha, M.K. Ahmed, U. Kamachi Mudali, R. Natarajan, Studies on solubility of TBP in aqueous solutions of fuel reprocessing, J. Radioanal. Nucl. Chem. 295 (2) (2013), https://doi.org/10.1007/s10967-012-1945-1. 
  21. M. Alyapyshev, A. Paulenova, M.A. Cleveland, J.E. Bruso, P. Tkac, Hydrolysis of acetohydroxamic acid under UREX+ conditions, in: Proceeding of GLOBAL 2007: Advanced Nuclear Fuel Cycles and Systems, Boise, ID, USA, September 9-13, 2007. 
  22. R.J. Gowland, G. Stedman, Kinetic and product studies on the decomposition of hydroxylamine in nitric acid, J. Inorg. Nucl. Chem. 43 (11) (1981), https://doi.org/10.1016/0022-1902(81)80631-8. 
  23. A.V. Rodin, I.V. Skvortsov, E.V. Belova, K.N. Dvoeglazov, B.F. Myasoedov, Effect of irradiation of the extraction mixture with 30% TBP in ISOPAR-M on the lower temperature limit of flame propagation, Radiochemistry 62 (6) (2020), https://doi.org/10.1134/S106636222006003X. 
  24. Recommendations on the transport of dangerous goods, Model Regulations, V1, 19th Revised Edition, United Nations, New York and Geneva, 2015. 
  25. Guidance on the Application of the CLP Criteria, Guidance to Regulation (EC) No 1272/2008 on Classification, Labeling and Packaging (CLP) of Substances and Mixtures, Version 5.0.2017, European Chemicals Agency, Helsinki, Finland, 2017, https://doi.org/10.2823/124801.