Cover Image

High-temperature processing of nitride spent fuel. Theoretical foundations. Part I

Alexei M. Potapov, Mikhail V. Mazannikov, Yuriy P. Zaikov

Abstract


High-temperature processing (HTP) of nitride spent nuclear fuel (SNF) is a series of head-end operations, as a result of which the fuel cladding is removed and the main components of the fuel (uranium and plutonium) are converted into pressable UO2 and PuO2 oxides. Based on the properties of uranium nitrides and oxides, a high-temperature processing (HTP) scheme for nitride spent nuclear fuel is proposed. This scheme consists of nitriding, denitriding, cladding separation, uranium oxidation to U3O8, and subsequent reduction to UO2. Theoretical and thermodynamic justification for each HTP stage is provided.

Keywords


pyrochemical processing; spent nuclear fuel; uranium nitride; uranium oxide; nitriding; voloxidation

Full Text:

PDF

References


Shishkin AV, Shishkin VY, Salyulev AB, Kesikopulos VA, et al., Electrochemical reduction of uranium dioxide in LiCl–Li2O melt, At. Energy, 131(2) (2021) 77–82. https://dx.doi.org/10.1007/s10512-022-00850-y

Shishkin AV, Shishkin VY, Pankratov AA, Burdina AA, Zaikov YP, Electrochemical reduction of La2O3, Nd2O3, and CeO2 in LiCl-Li2O melt, Materials, 15(11) (2022) 3963. https://dx.doi.org/10.3390/ma15113963

Shishkin AV, Shishkin VY, Maslennikova AA, Salyulev AB, et al., Electrochemical reduction of Pd-Nd2O3-CeO2 mixtures in the LiCl-Li2O melt, Processes, 11(6) (2023) 1599. https://dx.doi.org/10.3390/pr11061599

Zaikov YP, Shishkin VY, Potapov AM, Dedyukhin AE, et al., Research and development of the pyrochemical processing for the mixed nitride uranium-plutonium fuel, J. Phys. Conf. Ser., 1475(1) (2020) 012027. https://dx.doi.org/10.1088/1742-6596/1475/1/012027

Goode JH. Voloxidation – removal of volatile fission products from spent LMFBR fuel (ORNL-TM-3723). Oak Ridge National Laboratory; 1973. 133 p. https://www.osti.gov/biblio/4587712

Stone JA. Voloxidation studies with UO2 reactor fuels. American Nuclear Society topical meeting on "Fuel Cycles for the Eighties" DP-MS-80-9; 1980. 15 p.

Song KW, Yang MS, Formation of columnar U3O8 grains on the oxidation of UO2 pellets in air at 900 °C, J. Nucl. Mater., 209(3) (1994) 270–273. https://dx.doi.org/10.1016/0022-3115(94)90262-3

Yoo JH, Seo C-D, Kim EH, et al., A conceptual study of pyroprocessing for recovering actinides from spent oxide fuels, Nucl. Eng. Technol., 40(7) (2008) 581–592. https://dx.doi.org/10.5516/net.2008.40.7.581

Grenthe I, Janusz Drożdżyński J, Fujino T, et al. Uranium. In: The chemistry of the actinide and transactinide elements. 3rd ed. Springer: Dordrecht; 2008. 253–698 p. https://doi.org/10.1007/1-4020-3598-5_5

Thein SM, Bereolos PJ, Thermal Stabilization of 233UO2, 233UO3, and 233U3O8. Oak Ridge National Laboratory: ORNL/TM-2000/82; 2000. 15 p.

Kulyukhin SA, Nevolin YM, Gordeev AV, Gas-phase conversion of uranium mononitride in a nitrating atmosphere, Radiochemistry, 61(1) (2019) 5–11. https://dx.doi.org/10.1134/s1066362219010028

Johnson J, Rawn C, Spencer B, Meisner R, Del Cul G, Oxidation kinetics for conversion of U3O8 to ε-UO3 with NO2, J. Nucl. Mater., 490 (2017) 211–215. https://dx.doi.org/10.1016/j.jnucmat.2017.03.048

Arai Y, Maeda A, Shiozawa K, Ohmichi T, Chemical forms of solid fission products in the irradiated uranium–plutonium mixed nitride fuel, J. Nucl. Mater., 210(1–2) (1994) 161–166. https://dx.doi.org/10.1016/0022-3115(94)90233-x

Lyubimov DY, Androsov AV, Bulatov GS, Gedgovd KN, Thermodynamic modeling of the phase composition of mixed uranium-plutonium mononitride under fast-neutron irradiation to burnup 80 GW·days/ton and temperature 900–1400 K, At. Energy, 114(4) (2013) 243–248. https://dx.doi.org/10.1007/s10512-013-9704-0

Bondarenko GG, Bulatov GS, Gedgovd KN, Lyubimov DY, Yakushkin MM, Effect of the electron decay of metallic fission products on the chemical and phase compositions of an uranium-plutonium fuel irradiated by fast neutrons, Russ. Met. (metally), 2011(11) (2011) 1074–1078. https://dx.doi.org/10.1134/s0036029511110036

Alekseev SV, Zaitsev VA. Nitridnoye toplivo dly yadernoy energii [Nitride fuel for nuclear power]. Moscow: Technosfera; 2013. 240 p. Russian.

Berthold HJ, Delliehausen C, Darstellung und röntgenographische Untersuchung höherer Urannitride, Angew. Chemie, 78(15) (1966) 750–751. https://dx.doi.org/10.1002/ange.19660781512

Kim WJ, Nam JM, Ryu HJ, et al. Analyses of interaction phases of U-Mo dispersion fuel by synchrotron X-ray diffraction. In: Transactions of the Korean Nuclear Society Autumn Meeting; 2012 Oct 25–26; Gyeongju, Korea. p. 12.

Yungman VS, Glushko VP, Medvedev VA, Gurvich LV. Thermal constants of substances. Vol. 1–8. New York: Consultants Bureau; 1999. 1200 p.

Sasa Y, Atoda T, Nonstoichiometric hexagonal close‐packed uranium sesquinitride, J. Am. Ceram. Soc., 53(2) (1970) 102–105. https://dx.doi.org/10.1111/j.1151-2916.1970.tb12020.x

Uno M, Nishi T, Takano M. Thermodynamic and thermophysical properties of the actinide nitrides. In: Comprehensive Nuclear Materials. Vol. 2. Elsevier Ltd: Amsterdam; 2012. 61–85 p. https://doi.org/10.1016/B978-0-08-097774-4.00202-1

Kotelnikov RB, Bashlykov SN, Kashtanov AI, Menshikova TS. Vysokotemperaturnoye yadernoye toplivo [High temperature nuclear fuel]. Moscow: Atomizdat; 1978. 432 p. Russian.

Stöcker HJ, Naoumidis A, Investigation of the kinetics of hydrogen peroxide decomposition on manganese dioxide, Berichte der Deutschen Botanischen Gesellschaft, 79(12) (1966) 1231–1238. https://doi.org/10.1111/j.1438-8677.1966.tb00557.x

Serizawa H, Fukuda K, Ishii Y, Funahashi S. Diffraction study on the nonstoichiometric α-U2N3+x phase. In: Proceedings of the Fifth International Symposium on Advanced Nuclear Energy Research “Neutrons as Microscopic Probes”; 1993 Mar 10–12; Mito, Japan. p. 45.

Pavliuk AO, Zagumennov VS, Kotlyarevskiy SG, Bespala EV, Thermodynamic simulation of equilibrium composition of reaction products at dehydration of a technological channel in a uranium-graphite reactor, Therm. Eng., 65(1) (2018) 51–56. https://dx.doi.org/10.1134/s0040601518010056

Matthews R, Chidester K, Hoth C, Mason R, Petty R, Fabrication and testing of uranium nitride fuel for space power reactors, J. Nucl. Mater., 151(3) (1988) 345. https://dx.doi.org/10.1016/0022-3115(88)90029-3

Rundle RE, Baenziger NC, Wilson AS, Mcdonald RA, The structures of the carbides, nitrides and oxides of uranium, J. Am. Chem. Soc., 70(1) (1948) 99–105. https://dx.doi.org/10.1021/ja01181a029

Benz R, Balog G, Baca BH, U-UO2-UN2 phase diagram, High temperature Sci., 2(2) (1970) 221–251. https://dx.doi.org/10.1021/ic0500199.s002

Novyi spravochnik khimika i tekhnologa. Osnovnye svoistva neorganicheskikh, organicheskihk y elemetoorganicheskikh soedineniy [New reference book for chemists and technicians. Main properties of inorganic, organic and elementorganic compounds]. Saint Petersburg: NPO "Mir i Sem'ya"; 2002. 1276 p. Russian.

Silva GW, Yeamans CB, Sattelberger AP, Hartmann T, et al., Reaction sequence and kinetics of uranium nitride decomposition, Inorg. Chem., 48(22) (2009) 10635–10642. https://dx.doi.org/10.1021/ic901165j

Tagawa H, Masaki N, X-ray and density studies of nonstoichiometric uranium sesquinitride, J. Inorg. Nucl. Chem., 36(5) (1974) 1099–1103. https://dx.doi.org/10.1016/0022-1902(74)80220-4

Benz R, Hutchinson WB, U + N2 Reaction layer growths, J. Nucl. Mater., 36(2) (1970) 135–146. https://dx.doi.org/10.1016/0022-3115(70)90137-6

Hoenig CL, Phase equilibria, vapor pressure, and kinetic studies in the uranium‐nitrogen system, J. Am. Ceram. Soc., 54(8) (1971) 391–398. https://dx.doi.org/10.1111/j.1151-2916.1971.tb12329.x

Trzebiatowski W, Troć R, Magnetic properties of uranium nitrides. The U2N3 phase of variable composition, Bulletin de l’académee Polonaise des sciences, Serie des sciences chimiques, 12 (1964) 10681–685. https://dx.doi.org/10.2307/2270953

Serizawa H, Fukuda K, Ishii Y, Morii Y, Katsura M, Crystallographic study on the phase transition of α-U2N3, J. Nucl. Mater., 208(1–2) (1994) 128–134. https://dx.doi.org/10.1016/0022-3115(94)90204-6

Hiroaki T, Phase relations and thermodynamic properties of the uranium-nitrogen system, J. Nucl. Mater., 51(1) (1974) 78–89. https://dx.doi.org/10.1016/0022-3115(74)90117-2

Masaki N, Tagawa H, Diffraction study of α-U2N3+x, J. Nucl. Mater., 57(2) (1975) 187–192. https://dx.doi.org/10.1016/0022-3115(75)90258-5

Evans P, Davies T, Uranium nitrides, J. Nucl. Mater., 10(1) (1963) 43–55. https://dx.doi.org/10.1016/0022-3115(63)90115-6

Katsura M, Serizawa H, Formation of a nitrogen-rich α-U2N3+x phase by the reaction of uranium with a stream of ammonia, J. Alloy. Compd., 187(2) (1992) 389–399. https://dx.doi.org/10.1016/0925-8388(92)90444-e

Bugl J, Bauer AA, Phase relations in the system uranium–nitrogen, J. Am. Ceram. Soc., 47(9) (1964) 425–429. https://dx.doi.org/10.1111/j.1151-2916.1964.tb14429.x

Tagawa H, Equilibrium nitrogen pressures and thermodynamic properties of uranium sesquinitride, J. Nucl. Mater., 41(3) (1971) 313–319. https://dx.doi.org/10.1016/0022-3115(71)90168-1

Roine A. HSC Chemistry® [Software]. Outotec: Pori; 2018. Available from: www.outotec.com/HSC, Accessed on 19.11.2025.

Katsura M, Sano T, The uranium-nitrogen system, J. Nucl. Sci. Technol., 4(6) (1967) 283–288. https://dx.doi.org/10.3327/jnst.4.283

Karfidov EA, Nikitina EB, Mazannikov MV, Potapov AM, Dedyukhin AE, Corrosion of EP-823 steel (16Kh12MVSFBR) under high-temperature spent nuclear fuel processing, Rasplavy (Melts), 6 (2024) 581–595. Russian. https://dx.doi.org/10.31857/S0235010624060014

Kulyukhin SA, Nevolin YM, Gordeev AV, Bessonov AA, Gas-phase volume oxidation of uranium mononitride, Radiochemistry, 61(2) (2019) 146–155. https://dx.doi.org/10.1134/s1066362219020036

Mazannikov MV, Potapov AM, Vylkov AI, Suzdaltsev AV, Zaykov YuP, inventors; Institute of High-Temperature Electrochemistry UB RAS, assignee. Sposob okislitelnoy obrabotki otrabotavshego nitridnogo yadernogo topliva. Russian Federation patent RU 2775563. 2021 Dec 21. Russian.

McEachern RJ, Sunder S, Taylor P., Doern DC, et al., The influence of nitrogen dioxide on the oxidation of UO2 in air at temperatures below 275 °C, J. Nucl. Mat., 255 (1998) 234–242. https://doi.org/10.1016/S0022-3115(98)00036-1

Nevolin YuM. Gas phase oxidation conversion of components of oxide, nitride and carbide spent nuclear fuel [dissertation]. Moscow (Russia); 2020. 18 p.

Momotov VN, Makarov AO, Volkov AY, Lakeev PV, et al., Voloxidation of mixed nitride uranium–plutonium spent nuclear fuel, Radiochemistry, 65(2) (2023) 177–184. https://dx.doi.org/10.1134/s1066362223020042

Shadrin A, Dvoeglazov K, Kascheyev V, Vidanov V, et al., Hydrometallurgical reprocessing of BREST-OD-300 mixed uranium-plutonium nuclear fuel, Procedia Chem., 21 (2016) 148–155. https://dx.doi.org/10.1016/j.proche.2016.10.021

Knunyants IL. Chemical encyclopedia. In 5 volumes. Moscow: Soviet encyclopedia; 1988, 625 p. Russian.

Dell RM, Wheeler VJ, Mciver EJ, Oxidation of uranium mononitride and uranium monocarbide, Trans. Faraday Soc., 62 (1966) 3591. https://dx.doi.org/10.1039/tf9666203591

Sole MJ, Van der Walt CM, Oxidation and deformation studies of uranium nitride by electron microscopy, Acta Met., 16(4) (1968) 501–510. https://dx.doi.org/10.1016/0001-6160(68)90124-7

Blackburn PE, Oxygen dissociation pressures over uranium oxides, J. Phys. Chem., 62(8) (1958) 897–902. https://dx.doi.org/10.1021/j150566a001

Volkovich VA, Smirnov AL. Uranium metallurgy and technology of its compounds. Part 3. Ekaterinburg; 2014. 140 p.

Gromov BV. Introduction to chemical engineering of uranium. Moscow: Atomizdat; 1978. 336 p.

Hur J, Choi I, Cho S, Jeong S, Seo C, Preparation and melting of uranium from U3O8, J. Alloy. Compd., 452(1) (2008) 23–26. https://dx.doi.org/10.1016/j.jallcom.2006.11.210




DOI: https://doi.org/10.15826/elmattech.2026.5.065

Copyright (c) 2026 Alexei M. Potapov, Mikhail V. Mazannikov, Yuriy P. Zaikov

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.