UNIVERSITY OF NI FACULTY OF OCCUPATIONAL SAFETY IN NI

PROCEEDINGS
The 16th Conference of the series Man and Working Environment INTERNATIONAL CONFERENCE SAFETY OF TECHNICAL SYSTEMS IN LIVING AND WORKING ENVIRONMENT

Endorsed by: Government of the Republic of Serbia MINISTRY OF EDUCATION AND SCIENCE

Ni, 27-28 October 2011

UNIVERSITY OF NIS FACULTY OF OCCUPATIONAL SAFETY IN NI

PROCEEDINGS
The 16th Conference of the series Man and Working Environment INTERNATIONAL CONFERENCE SAFETY OF TECHNICAL SYSTEMS IN LIVING AND WORKING ENVIRONMENT PUBLISHED BY: FACULTY OF OCCUPATIONAL SAFETY IN NIS arnojevi a 10a, 18000 Ni FOR THE PUBLISHER: Prof. dr Ljiljana ivkovi , dean EDITORS OF PROCEEDINGS: Prof. Dejan Petkovi , PhD Prof. Ivan Krsti , PhD GRAPHIC DESIGN AND PREPRESS: Rodoljub Avramovi PRINTED BY: M COPS CENTER , Ni CIRCULATION: 300 copies
CIP , 331.45/.46(082) 502/504(082) 614.8.084(082) INTERNATIONAL Conference of the Series Man and Working Environment Safety of Technical Systems in Living and Working Environment (16 ; 2011 ; Ni ) Proceedings / The 16th International Conference of the Series Man and Working Environment Safety of Technical Systems in Living and Working Environment - [STS-11], Ni , 27-28 October 2011. ; [organizer Faculty of Occupational Safety in Ni ; editors Dejan Petkovi , Ivan Krsti ]. - Ni : Faculty of Occupational Safety, 2011 (Ni : M Kops Centar). - 493 str. : ilustr. ; 30 cm Slike autora i bele ke o njima. - Tira 300. - Bibliografija uz svaki rad. ISBN 978-86-6093-035-6 1. Fakultet za tite na radu (Ni ) a) b) c) COBISS.SR-ID 187155980

NICOLAY BARBIN1 DMITRY TERENTEV2 SERGEI ALEXEEV3 SERGEI ORLOV4

Ural Institute of State Fire Service of Emercom of Russia
1

THERMODYNAMIC MODELLING FOR BURNING OF RADIOACTIVE GRAPHITE

Abstract: This study deals with carbon oxidation and physicalchemical transformations of radioactive elements during the combustion graphite waste in the atomic power industry. The method of thermodynamic simulation was used. Key words: radioactive graphite, thermodynamic modelling, burning.

NMBarbin@yandex.ru 2 svireppey@mail.ru 3 3608113@mail.ru 4 3608040@mail.ru

INTRODUCTION
Graphite reactors are widely used in nuclear power. It usually burns in the heterogeneous mode. The crystal structure of a graphite is deformed by action of the Wigner effect at 473 520 K. The Wigner energy has possibilities for accumulation into a graphite to a certain value, and then it can spontaneously go out and create a condition for occurrence of a fire [1]. A radioactive black lead contains various radio nuclides, such as hyzone and 14 , and also corrosion/activation products (57 , 60 ; 54Mn; 59Ni; 63Ni; 22Na etc.), fission products (134Cs, |37 , 90Sr, l52Eu, 144 etc.) and a small amount of uranium and transformation elements (238Pu, 239 u, 241Am, 243Am etc. [2]. Radio elements are remained with a nonflammable part, or are evaporated depending on degree of their fugitiveness. Gaseous radio elements are condensed on larger particles. Taken out submicrometer particles are easily inhaled in lungs. They can also be postponed at a surface of reservoirs and at food cultures.

About 100 % of cesium is existed as the condensed CsCl at temperature 300-700 . Rise of temperature to 900-1400 is resulted to 100 % transferring of chloride of cesium in a gas phase. Phase allocations of calcium and strontium are brought in figs 2 and 3. Calcium and strontium exist as condensed SaSl2 and Sr l2 at temperature 300-1000 K. Increase of temperature to 1300 K is yielded to transferring of these chlorides in a gas phase.

RESULTS AND DISCUSSION

In this paper evaporation and condensation of radio elements are investigated at burning of radioactive black lead by the method of thermodynamic modelling. TERRA soft is applied for calculations of equilibrium states for complex heterophase systems [3]. There are thermodynamic functions of 33 condensed and 35 elementary gases and compounds are used at calculation. UO2, UOCl, UOCl2, CaCl2, BeO are the major components into the condensed phase. Their concentrations are more than 10~2 molar shares. UO2 is become the dominated component at 1300 to 1500 and its concentration is about 0.98 molar shares. The main components of a gas phase are N2 ( ~0,98 bar), O2 and CO ( ~10-1 bar) at temperature above 900 . Carbon is passed into a gas phase as CO and 2 in the relation 1:1 at temperature more than 900 K. Distribution of cesium on phases is resulted in fig 1.
Figure 1. Distribution of cesium on phases

Figure 2. Distribution of calcium on phases

At temperature 300-900 K approximately 100-90 % of beryllium exists in the form of condensed BeO.

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Safety of Technical Systems in Living and Working Environment - STS 2011, October 27-28, 2011, Ni, Serbia

In the range of temperatures from 800 to 1200 K the content of condensed BeO is decreased from 90 to 5 % and a percentage share of gaseous BeCl2 is increased from 10 to 95 % because passing of the next chemical reaction. BeO + C + Cl2 BeCl2 + CO

At 1100 the concentration of the gaseous state of UCl4 is reached to 12 % and concentration of the condensed UOCl2 is fallen to zero. The further rise of temperature to 1300 conducts to disappearance of the gas phase of UCl2 and the condensed UOCl, and uranium is been as the condensed UO2. All uranium is existed in condensed state of UO2 in a temperature band from 1300 to 1600 .

Figure 3. Distribution of strontium on phases Figure 5. Distribution of nickel on phases

Figure 4. Distribution of beryllium on phases

The further increasing of temperature to 1600 is carried on to shift of equilibrium of the reaction to the left (growth of the condensed share of BeO to 95 % and reduction of the gaseous share of BeCl2 to 5 %). The nickel distribution on phases is resulted on fig. 5. At temperature 300-700 approximately 100-97 % of nickel is been in the condensed state of NiCl. Rise of temperature to 900 K is leaded to sharp reduction the condensed phase of NiCl practically to zero and to increase the gaseous phase of NiCl2 to 100 %. In the range of temperatures 900-1400 K the all nickel is been in the gaseous state of NiCl. The further rise of temperature to 1600 K is given to reduction of the gaseous share of NiCl2 to 60 % and to lead to occurrence of the gaseous form of NiCl to 30 %. The uranium distribution on phases is shown on fig. 6. In a temperature band 300-700 K uranium has existed in the condensed phases of UO2, UOCl, UOCl2.

Figure 6. Distribution of uranium on phases

Plutonium distribution on phases is resulted on fig. 7. At 300 all plutonium is been as the condensed PuCl3. In a temperature band from 800 to 1300 there are basic chemical transformations, disappears of the condensed PuCl3, occurs of the gaseous PuCl4 (~10 %), the condensed PuOCl (~75 %) and the condensed PuO2. At the further rise of temperature to 1600 is led to the condensed PuO2 as the major form of plutonium.

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Safety of Technical Systems in Living and Working Environment - STS 2011, October 27-28, 2011, Ni, Serbia

Figure 8. Distribution of americium on phases Figure 7. Distribution of plutonium on phases

Europium distribution on phases is resulted on fig. 8. In a temperature band from 300 to 600 there is increase of the condensed EuCl2 share and reduction of the condensed EuCl3 share. In a temperature band from 600 to 900 all europium is been in the form of the condensed EuCl2. In a temperature band from 900 to 1300 there is reduction of the condensed EuCl2 content and increase of the gaseous EuCl3 content to 80 %. The further temperature increase to 1600 conducts to reduction of the quantity of gaseous EuCl3 to 30 %, the condensed EuCl2 to 10 % and increase of the content of the condensed Eu2O3 to 30 % and the condensed forms of EuOCl to 20 %, and EuO to 10 %.

REFERENCES
[1] A.K. Mikeev: Fire-Prevention Atomic Power Station Protection , Energoatomizdat (Rus. Ed.), 1990, Moscow. [2] N.M. Barbin, A.V. Peshkov, M.P. Dalkov, D.I. Terentev, S.G. Alexeev: Estimation of Behavior of Radio Nuclides at Burning of Radioactive Black Lead Proc. The II Allrussian Science and Technology Conference, Symposium and XII School of Young Scientists, 2008, p. 67. [3] G.K. Moiseyev, G.P. Vyatkin, N.M. Barbin: Application of thermodynamic modelling for studying of interaction with participation of ionic melts , SUSU, 2002, Chelyabinsk.

Figure 8. Distribution of europium on phases

Americium distribution on phases is shown on fig. 9. In the range of temperatures from 300 to 800 all americium is presented in the condensed form of AmO2. Rise of temperature to 1600 is resulted to occurrence of condensed Am2O3 (~10 %) and other americium is existed as the condensed AmO2 (~90 %).

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