• Title/Summary/Keyword: High temperature electrochemistry

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Interaction between UN and CdCl2 in molten LiCl-KCl eutectic. II. Experiment at 1023 K

  • Zhitkov, Alexander;Potapov, Alexei;Karimov, Kirill;Kholkina, Anna;Shishkin, Vladimir;Dedyukhin, Alexander;Zaykov, Yury
    • Nuclear Engineering and Technology
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    • v.54 no.2
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    • pp.653-660
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    • 2022
  • The interaction between UN and CdCl2 in the LiCl-KCl molten eutectic was studied at 1023 K. The chlorination was monitored by sampling and recording the redox potential of the medium. At 1023 K the chlorination of UN with cadmium chloride in the molten LiCl-KCl eutectic proceeds completely and results in the formation of uranium chlorides. The melts of the LiCl-KCl-UCl3 or LiCl-KCl-UCl4 compositions can be obtained by the end of experiment depending on the presence of metallic cadmium in the reaction zone. The higher the concentration of the chlorinating agent, the faster the reaction rate. At [CdCl2]/[UN] = 1.65 (10% excess) the reaction proceeds to completion in about 7.5 h. At [CdCl2]/[UN] = 7 the complete chlorination takes 2.5-3 h.

Interaction between UN and CdCl2 in molten LiCl-KCl eutectic. I. Experiment at 773 K

  • Zhitkov, Alexander;Potapov, Alexei;Karimov, Kirill;Shishkin, Vladimir;Dedyukhin, Alexander;Zaykov, Yury
    • Nuclear Engineering and Technology
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    • v.52 no.1
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    • pp.123-134
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    • 2020
  • The interaction between UN and CdCl2 in the LiCl-KCl molten eutectic was studied at 773 K. The reaction was controlled by sampling the melt, as well as by analysis of the resulting precipitate. The process was shown to proceed according to several parallel reactions. The summary reaction was determined to have two stages: a fast one and a slow one. The 19-53% UN → UCl3 conversion was obtained for the molar ratio of CdCl2/UN = 1.22-14.9. The rest of UN converts into the precipitate of complex composition (UNCl + U2N3 + U4N7 + UN2). The increase in the CdCl2/UN molar ratio from 1.22 to 14.9 resulted in the decrease in duration of the first "fast" stage of the process from 18 h to 1 h.

Criticality analysis of pyrochemical reprocessing apparatuses for mixed uranium-plutonium nitride spent nuclear fuel using the MCU-FR and MCNP program codes

  • P.A. Kizub ;A.I. Blokhin ;P.A. Blokhin ;E.F. Mitenkova;N.A. Mosunova ;V.A. Kovrov ;A.V. Shishkin ;Yu.P. Zaikov ;O.R. Rakhmanova
    • Nuclear Engineering and Technology
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    • v.55 no.3
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    • pp.1097-1104
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    • 2023
  • A preliminary criticality analysis for novel pyrochemical apparatuses for the reprocessing of mixed uranium-plutonium nitride spent nuclear fuel from the BREST-OD-300 reactor was performed. High-temperature processing apparatuses, "metallization" electrolyzer, refinery remelting apparatus, refining electrolyzer, and "soft" chlorination apparatus are considered in this work. Computational models of apparatuses for two neutron radiation transport codes (MCU-FR and MCNP) were developed and calculations for criticality were completed using the Monte Carlo method. The criticality analysis was performed for different loads of fissile material into the apparatuses including overloading conditions. Various emergency situations were considered, in particular, those associated with water ingress into the chamber of the refinery remelting apparatus. It was revealed that for all the considered computational models nuclear safety rules are satisfied.

Anode processes on Pt and ceramic anodes in chloride and oxide-chloride melts

  • Mullabaev, A.R.;Kovrov, V.A.;Kholkina, A.S.;Zaikov, Yu.P.
    • Nuclear Engineering and Technology
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    • v.54 no.3
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    • pp.965-974
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    • 2022
  • Platinum anodes are widely used for metal oxides reduction in LiCl-Li2O, however high-cost and low-corrosion resistance hinder their implementation. NiO-Li2O ceramics is an alternative corrosion resistant anode material. Anode processes on platinum and NiO-Li2O ceramics were studied in (80 mol.%) LiCl-(20mol.%)KCl and (80 mol.%)LiCl-(20 mol.%)KCl-Li2O melts by cyclic voltammetry, potentiostatic and galvanostatic electrolysis. Experiments performed in the LiCl-KCl melt without Li2O illustrate that a Pt anode dissolution causes the Pt2+ ions formation at 3.14 V and 550℃ and at 3.04 V and 650℃. A two-stage Pt oxidation was observed in the melts with the Li2O at 2.40 ÷ 2.43 V, which resulted in the Li2PtO3 formation. Oxygen current efficiency of the Pt anode at 2.8 V and 650℃ reached about 96%. The anode process on the NiO-Li2O electrode in the LiCl-KCl melt without Li2O proceeds at the potentials more positive than 3.1 V and results in the electrochemical decomposition of ceramic electrode to NiO and O2. Oxygen current efficiency on NiO-Li2O is close to 100%. The NiO-Li2O ceramic anode demonstrated good electrochemical characteristics during the galvanostatic electrolysis at 0.25 A/cm2 for 35 h and may be successfully used for pyrochemical treating of spent nuclear fuel.

Thermal stability of nitric acid solutions of reducing agents used in spent nuclear fuel reprocessing

  • Obedkov, A.S.;Kalistratova, V.V.;Skvortsov, I.V.;Belova, E.V.
    • Nuclear Engineering and Technology
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    • v.54 no.9
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    • pp.3580-3585
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    • 2022
  • The thermal stability of carbohydrazide, hydrazine nitrate, acetohydroxamic acid in nitric acid solutions has been studied at atmospheric pressure and above atmospheric pressure. The volumes of gaseous products of thermolysis and the maximum rate of gas evolution have been determined at atmospheric pressure. It has been shown that, despite the high rate of gas evolution and large volumes of evolved gases, the conditions for the development of autocatalytic oxidation are not created. Exothermic processes are observed in a closed vessel in the temperature range of 50-250 ℃. With an increase in the concentration of nitric acid, the temperatures of the onset of exothermic effects for all mixtures decrease, and the values of the total thermal effects of reactions increase, to the greatest extent for solutions with carbohydrazide.

Electrochemical extraction of uranium on the gallium and cadmium reactive electrodes in molten salt

  • Valeri Smolenski;Alena Novoselova
    • Nuclear Engineering and Technology
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    • v.56 no.1
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    • pp.42-47
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    • 2024
  • The electrochemical extraction of uranium in ternary low melting LiCl-KCl-CsCl eutectic on inert and reactive electrodes via different electrochemical techniques was investigated. It was established that the electrochemical reduction process of U(III) ions on the inert W electrode was irreversible and proceeded in one stage. On reactive liquid Ga and liquid Cd electrodes the reduction of uranium ions took place with the considerable depolarization with the formation of UGa2, UGa3 and UCd11 intermetallic compounds. Thermodynamic characteristics of uranium compounds and alloys were calculated. The conditions for the extraction of uranium from the electrolyte in the form of alloys on both liquid reactive electrodes via potentiostatic electrolysis were found.