Study on the kinetics of bismuth oxide reduction by hydrogen as applied to the technology of removing hydrogen from circulation circuits with heavy liquid metal coolants
As part of the project of developing methods for removing hydrogen and tritium from the circulation circuits of reactor plants with heavy liquid-metal coolants, the kinetics of bismuth oxide reduction by hydrogen in the temperature range 425–500°C and hydrogen concentration 25–100 vol.% has been investigated. The kinetic characteristics of the reaction under study were determined by continuously measuring the concentration of water vapor (reaction product) in mixtures of hydrogen and helium that passed through a heated reaction vessel with a sample of bismuth oxide. The concentration of water vapor was measured using a thermoconductometric detector. The obtained time dependences of the bismuth oxide reduction degree (with varying reaction conditions) were processed by the method of affine time transformation. Thermodynamic analysis showed that reduction process proceeds without any intermediate products, i.e., directly with metallic bismuth. It was also found that the reduction process ran in kinetic mode. All kinetic curves were combined successfully by the affine time transformation method; therefore, it can be assumed that the reduction mechanism is the same in the entire temperature range and hydrogen concentration range studied. The limiting stage of the reaction is the adsorption of hydrogen on the surface of the bismuth oxide sample. The time dependence of the reduction degree is in good agreement with Yerofeev’s equation of «nucleation and growth model» with n = 1. The reaction activation energy is 92.8 ± 1.9 kJ/mol. The rate of the reduction reaction is directly proportional to the concentration of hydrogen in its mixture with an inert gas.
- Orlov Yu.I., Efanov A.D., Martynov P.N., Gulevsky V.A., Papovyants A.K., Levchenko Yu.D., Ulyanov V.V. Hydrodynamic problems of heavy liquid metal coolants technology in loop-type and mono-block-type reactor installations. Nuclear Engineering and Design. 2007, v. 237, pp. 1829-1837.
- Handbook on Lead-bismuth Eutectic Alloy and Lead Properties, Materials Compatibility, Thermal-hydraulics and Technologies. Vienna. Nuclear Energy Agency, 2007, 691 p.
- Ricapito I., Fazio C., Benamati G. Preliminary studies on PbO reduction in liquid Pb-Bi eutectic by flowing hydrogen. Journal of Nuclear Materials. 2002, v. 301, pp. 60-63.
- Niu F., Candalino R., Li N. Effect of oxygen on fouling behavior in lead-bismuth coolant systems. Journal of Nuclear Materials. 2007, v. 366, pp. 216-222.
- Kondo M., Okubo N., Irisava E., Komatsu A., Ishikawa N., Tanaka T. Oxidation characteristics of lead-alloy coolants in air ingress accident. Proc. of the Vth International Symposium on Innovative Nuclear Energy Systems, INES-5 (Tokyo, Japan, October 31 – November 2, 2016), pp. 386-394.
- Martynov P.N., Gulevich A.V., Orlov Yu.I., Gulevsky V.A. Water and hydrogen in heavy liquid metal coolant technology. Progress in Nuclear Energy. 2005, v. 47, pp. 604-615.
- Ivanov K.D., Niyazov S.-A.S., Chyoporov R.Yu. Selective removing of hydrogen and tritium from cover gas of nuclear facilities with heavy liquid metal coolants. Proc. of the IVth International Conference «Heavy Liquid Metal Coolants in Nuclear Technologies». Obninsk. GNTs RF-FEI Publ., 2013, v. 2, pp. 437-440 (in Russian).
- Ivanov I.I., Shelemet’ev V.M., Ulyanov V.V., Teplyakov Yu.A. Kinetics of the reduction of orthorhombic and tetragonal lead oxides to lead with hydrogen. Kinetika i Katalyz. 2015, v. 56, pp. 305-309 (in Russian).
- Ivanov I.I., Shelemet’ev V.M., Ulyanov V.V., Storozhenko A.N., Skobeev D.A. Studies on nickel effect on kinetics of lead reduction from its oxide by hydrogen. Research Journal of Pharmaceutical, Biological and Chemical Sciences. 2016, v. 7, pp. 1700-1709.
- Chernogorenko V.B., Lynchak K.A. Production of bismuth powder by the reduction of bismuth oxide with a mixture of molecular and atomic hydrogen. Soviet Powder Metallurgy and Metal Ceramics. 1973, v. 12, no. 5, pp. 360-362.
- Beres J., Bruckman K., Haber J., Janas J. Kinetics of reduction of bismuth molybdate catalysts in hydrogen. Bulltin de l’Academie Polonaise des sciences, Serie des sciences chimiques. 1972, v. 20, pp. 813-819.
- Delmon B. Kinetics of Heterogeneous Reactions. Moscow. Mir Publ., 1972, 554 p. (in Russian).
- Risold D., Hallstedt B., Gauckler L.J., Lukas H.L., Fries S.G. The bismuth-oxygen system. Journal of Phase Equilibria. 1995, v. 16, pp. 223-234.
- Oniyama E., Wahlbeck P.G. Phase equilibria in the bismuth-oxygen system. Journal of Pfysical Chemistry B. 1988, v. 102, pp. 4418-4425.
- Jacob K.T., Mansoor A.K. Gibbs energy of formation of bismuth (III) oxide. Thermochimica Acta. 2016, v. 630, pp. 90-096.
- Wicks C.E. and Block F.E. Thermodynamic Properties of 65 Elements – their Oxides, Halides, Carbides and Nitrides. Washington. U.S. Govt. Print. Off., 1963, 240 p.
- Barret, P. Reaction Kinetics in Heterogeneous Chemical Systems. Amsterdam. Elsevier, 1975, 399 p.
- Allnatt A.R., Jacobs P.W.M. Theory of nucleation in solid state reactions. Canadian Journal of Chemistry. 1968, v. 46, pp. 111-116.
- Polyvyanny I.R., Ablanova A.D., Batyrbekova S.A., Sysoyev L.N. Metallurgy of Bismuth. Alma-Ata. Nauka Publ., 1973, 193 p. (in Russian).
- T. Havlik. Hydrometallurgy. Principles and Applications. Cambridge. Woodhead Publishing Ltd., 2008, 207 p.
heavy liquid metal coolants nuclear safety hydrogen tritium hydrogen purification of HLMC hydrogen afterburner bismuth oxide reaction kinetics thermoconductometric analysis affine time transformation method equation of nucleation and growth model Yerofeev’s equation