Advertisement

Effect of nitrous acid on γ-ray radiolysis and radiolytic products of N, N-dimethylhydroxylamine

  • J. H. WangEmail author
  • P. Wang
  • Ch. Li
  • M. H. Wu
  • G. Xu
  • W. F. Zheng
  • H. He
Article
  • 34 Downloads

Abstract

N, N-dimethylhydroxylamine (DMHA) is a new salt-free reductant used in spent fuel reprocessing, this paper reports the effect of HNO2 on γ-ray radiolysis and radiolytic products of DMHA in nitric acid medium. DMHA concentration in irradiated samples decreases with the increasing dose and initial HNO2 concentration, and the radiolytic rate of DMHA is lower than 21% at 10 kGy supposed to be the maximum dose absorbed by the reagent during the U/Pu separation and the Pu purification. The main radiolytic products are H2, CH3NHOH, HCHO, and HCOOH, and their quantity increases with the dose and initial HNO2 concentration.

Keywords

N, N-dimethylhydroxylamine Nitrous acid Radiation damage Radiolytic product Chromatography Spent nuclear fuel 

Notes

Acknowledgements

The authors wish to extend warm acknowledgement for the financial assistance of National Natural Science Foundation of China (No. 20771074).

References

  1. 1.
    Shi R (2018) Dream of China commercial spent fuel reprocessing plant. Energy 10:61–63Google Scholar
  2. 2.
    Tkac P, Mattesson B (2008) Complexation of uranium(VI) with acetohydroxamic acid. J Radioanal Nucl Chem 277:31–36CrossRefGoogle Scholar
  3. 3.
    Natarajan R (2017) Reprocessing of spent nuclear fuel in India: present challenges and future programme. Prog Nucl Energy 101:118–132CrossRefGoogle Scholar
  4. 4.
    Jiang ShJ, Ren FY (1995) Nuclear fuel reprocessing technology. Atomic Energy Publisher, BeijingGoogle Scholar
  5. 5.
    Schlea CS, Caverly MR, Henry HE (1963) Uranium (IV) nitrate as a reducing agent for plutonium(IV) in the Purex process. DP-808:1–20Google Scholar
  6. 6.
    Biddle P, Miles JH (1968) Rate of reaction of nitrous acid with hydrazine and with sulphamic acid. J Inorg Nucl Chem 30:1291–1297CrossRefGoogle Scholar
  7. 7.
    Taylor RJ, Koltunov VS, Valery I (2002) Studies of U(IV) oxidation kinetics in nitric acid and TBP phases. J Nucl Sci Technol 3:355–358CrossRefGoogle Scholar
  8. 8.
    Sood DD, Patil SK (1996) Chemistry of nuclear fuel reprocessing: current status. J Radioanal Nucl Chem 203:547–573CrossRefGoogle Scholar
  9. 9.
    Perrott JR, Stedman G (1977) The kinetics of nitrite scavenging by hydrazine and hydrazoic acids at high acid acidities. J Inorg Nucl Chem 39:325–327CrossRefGoogle Scholar
  10. 10.
    Ochsenfeld W, Petrich G (1983) Neptunium decontamination in a uranium purification cycle of a spent fuel reprocessing plant. Separ Sci Technol 18:1685–1698CrossRefGoogle Scholar
  11. 11.
    Ye GA (2004) Review on the study and application of organic salt-free reagent in Purex process. At Energ Sci Technol 38:152–158Google Scholar
  12. 12.
    Koltunov VS, Pastushchak VG, Koltunov GV (2006) Kinetics of Pu(IV) reduction with tert-Butylhydrazine. Radiochemistry 48:348–351CrossRefGoogle Scholar
  13. 13.
    Koltunov VS, Marchenko VI, Zhuravleva GI (2001) Kinetics of redox reactions of U, Pu and Np in TBP solutions VII. Kinetices of reduction of Pu(IV) and Np(VI) with butanal oxime in undiluted TBP. Radiochemistry 43:334–337CrossRefGoogle Scholar
  14. 14.
    Taylor RJ, Mason Ch, Cooke R, Boxall C (2002) The reduction of Pu(IV) by formohydroxamic acid in nitric acid. J Nucl Sci Technol 39:278–281CrossRefGoogle Scholar
  15. 15.
    Koltunov VS, Baranov SM, Zharova TP (1995) Organic derivatives of hydrazine and hydroxylamine in future technology of spent nuclear fuel reprocessing. In: International confenrence on evaluation of nuclear fuel cycle systems, France, pp 577–582Google Scholar
  16. 16.
    Koltunov VS, Baranov SM, Zharova TP (1993) Kinetics of the reactions of Np and Pu ions with hydroxylamine derivatives (II)—reaction of Np(VI) with N, N-dimethylhydroxylamine. Radiokhimiya 35:49–53Google Scholar
  17. 17.
    Chen YX, Tang HB, Liu JP (2011) The kinetics of the reduction reaction of plutonium(IV) with N, N-dimethylhydroxylamine. J Radioanal Nucl Chem 289:41–47CrossRefGoogle Scholar
  18. 18.
    Liu JP, He H, Tang HB, Chen YX (2011) The application of N, N-dimethylhydroxylamine as reductant for the separation of plutonium from uranium. J Radioanal Nucl Chem 288:351–356CrossRefGoogle Scholar
  19. 19.
    Zhang AY, Xiao GP, Hu JX, He H (2003) Hydroxylamine derivatives in the Purex Process Part VII. The redox reactive kinetics and mechanism of dimethylhydroxylamine and vanadium(V) in nitric medium. J Radioanal Nucl Chem 256:587–592CrossRefGoogle Scholar
  20. 20.
    He H, Ye GA, Tang HB, Zheng WF, Li GL, Lin RSh (2014) An advanced purex process based on salt-free reductants. Radiochim Acta 102:127–133Google Scholar
  21. 21.
    Li GL, He H (2011) Study on mechanism for oxidation of N, N-dimethylhydroxylamine by nitrous acid. J Radioanal Nucl Chem 287:673–678CrossRefGoogle Scholar
  22. 22.
    Wang JH, Li Q, Wu MH, Xu G, Li Ch, Bao BR, Zheng WF, He H, Zhang ShD (2012) Radiolysis of N, N-dimethylhydroxylamine and its radiolytic liquid organics. J Radioanal Nucl Chem 292:249–254CrossRefGoogle Scholar
  23. 23.
    Wang JH, Li Ch, Wu MH, Xu G, Bao BR, Zheng WF, He H, Zhang ShD (2010) Gaseous products of aqueous N, N-dimethyl hydroxylamine degraded by radiation. Nucl Sci Techniq 21:233–236Google Scholar
  24. 24.
    Wang JH, Cao XJ, Li Ch, Wu MH, Bao BR, Zheng WF, He H, Zhang ShD (2015) Effect of HNO3 on the γ radiolysis and radiolytic liquid products of N, N-dimethylhydroxylamine. Acta Phys Chim Sin 31:559–565Google Scholar
  25. 25.
    Li HB, Su Zh, Cong HF, Song FL, Wang XR, He H, Liu ZhY, Lin CSh (2012) α and β irradiation stability of 30% TBP-kerosene-HNO3 systems. J Nucl Radiochem 34:281–285Google Scholar
  26. 26.
    Benedict M, Pigford TH, Levi HW (1981) Nuclear chemical engineering, 2nd edn. McGraw-Hill Book Company, New YorkGoogle Scholar
  27. 27.
    Choppin GR, Khankhasayev MK (1999) Chemical separation technologies and related methods of nuclear waste management. Kluwer Academic Publishers, DordrechtCrossRefGoogle Scholar
  28. 28.
    Ren FY (2002) The behavior of the nitrite in purex process. Chin J Nucl Sci Eng 22:356–360Google Scholar
  29. 29.
    Ren FY, Zhou ZhX (2006) Foreign nuclear fuel reprocessing. Atomic Energy Publisher, BeijingGoogle Scholar
  30. 30.
    Wang JH, Wu MH, Bao BR, Li Zh, Zhang XY, Ye GA (2007) Study on hydrogen and carbon monoxide produced by radiation degradation of N, N-dimethylhydroxylamine. J Radioanal Nucl Chem 273:371–373CrossRefGoogle Scholar
  31. 31.
    Wu JL, Qi ShCh (1993) Radiation chemistry. Atomic Energy Publisher, BeijingGoogle Scholar
  32. 32.
    Spinks JWT, Woods RJ (1976) An introduction to radiation chemistry, 2nd edn. Wiley, New YorkGoogle Scholar
  33. 33.
    Alfassi ZB (1998) N-Centered radicals. Wiley, HobokenGoogle Scholar
  34. 34.
    KozŁowska-Milner E, Broszkiewicz RK (1977) Pulse radiolysis study of aqueous nitric acid solutions. Formation mechanism, yield, and reactivtty of NO3 Radical. Radiat Phys Chem 11:253–260Google Scholar
  35. 35.
    Katsumura Y, Jiang PY, Nagaishi R, Oishi T, Ishigure K (1991) Pulse radiolysis study of aqueous nitric acid solutions: formation mechanism, yield, and reactivity of NO3 radical. Phys Chem 95:4435–4439CrossRefGoogle Scholar
  36. 36.
    Wang JH, Bao BR, Wu MH, Sun XL, Zhang XY, Ye GA (2004) Qualitative and quantitative analysis of light hydrocarbons produced by radiation degradation of N, N-dimethyl hydroxylamine. Nucl Techniq 27:301–304Google Scholar
  37. 37.
    Ingold KU, Adamic K, Bowman DF, Gillan T (1971) Kinetic applications of electron paramagnetic resonance spectroscopy. I. Self-reactions of diethyl nitroxide radicals. J Am Chem Soc 93:902–908CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.School of Environmental and Chemical EngineeringShanghai UniversityShanghaiChina
  2. 2.Radiochemistry DepartmentChina Institute of Atomic EnergyBeijingChina

Personalised recommendations