DE1939442C - Process for the production of residual gas-free and activating fuel elements and fuel inserts for high-temperature reactors with little contamination and activation of the reactor cooling circuit - Google Patents
Process for the production of residual gas-free and activating fuel elements and fuel inserts for high-temperature reactors with little contamination and activation of the reactor cooling circuitInfo
- Publication number
- DE1939442C DE1939442C DE19691939442 DE1939442A DE1939442C DE 1939442 C DE1939442 C DE 1939442C DE 19691939442 DE19691939442 DE 19691939442 DE 1939442 A DE1939442 A DE 1939442A DE 1939442 C DE1939442 C DE 1939442C
- Authority
- DE
- Germany
- Prior art keywords
- fuel
- inserts
- free
- cooling circuit
- residual gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000446 fuel Substances 0.000 title claims description 28
- 238000011109 contamination Methods 0.000 title claims description 4
- 238000001816 cooling Methods 0.000 title claims description 4
- 230000003213 activating Effects 0.000 title claims description 3
- 238000000034 method Methods 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title description 3
- 230000004913 activation Effects 0.000 title 1
- 238000005260 corrosion Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000000712 assembly Effects 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005202 decontamination Methods 0.000 claims description 3
- 230000003588 decontaminative Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 229910052770 Uranium Inorganic materials 0.000 description 12
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910052776 Thorium Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- ZSLUVFAKFWKJRC-UHFFFAOYSA-N thorium Chemical compound [Th] ZSLUVFAKFWKJRC-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000000112 cooling gas Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- URYAFVKLYSEINW-UHFFFAOYSA-N Chlorfenethol Chemical compound C=1C=C(Cl)C=CC=1C(O)(C)C1=CC=C(Cl)C=C1 URYAFVKLYSEINW-UHFFFAOYSA-N 0.000 description 1
- 150000001224 Uranium Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YZUCHPMXUOSLOJ-UHFFFAOYSA-N ethyne;thorium Chemical compound [Th].[C-]#[C] YZUCHPMXUOSLOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000630 rising Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Description
9595
Es ist bekannt (Nucl. Science Abstr., 20, S. 1857 [1966], Referat 15 002). Brennelementeinsätze, die nach der mechanischen Bearbeitung an ihrer Oberfläche beschädigte Brennstoffpartikeln enthalten, mit Chlorwasserstoffgas bei 1600° C zu reinigen.It is known (Nucl. Science Abstr., 20, p. 1857 [1966], Referat 15 002). Fuel assemblies that contain damaged fuel particles on their surface after mechanical processing, with Purify hydrogen chloride gas at 1600 ° C.
Brennelemente oder Brennstrffeinsätze für Hoch temperaturreaktoren bestehen im Prinzip aus mit pyrolytischem Kohlenstoff 'beschichteten Brennstoff partikeln aus Uran- und/oder Thoriumcarbid b/v,. -oxid, die entweder gemeinsam mit einem Binder, eventuell unter Zusatz von Graphitpulver, in vorgefertigte Graphitkörper eingefüllt ouer aber mit einem geeigneten Graphitpulver unter Zusatz von Bindern gemischt und dann direkt zu einem Brennelement oder Brennstoffeinsätzen verpre3t werden.Fuel elements or fuel inserts for high In principle, temperature reactors consist of fuel coated with pyrolytic carbon particles of uranium and / or thorium carbide b / v ,. oxide, which either together with a binder, possibly with the addition of graphite powder, filled into prefabricated graphite bodies or with a suitable graphite powder mixed with the addition of binders and then directly to a fuel assembly or fuel inserts.
Daran anschließend muß in jedem Fall eine Temperaturbehandlung, zuletzt unter Vakuum, bei Tem peraturen bis zu 1800° C durchgeführt werden, dimit einerseits der organische Binder verkokt und das Restgas, beispielsweise Kohlenmonoxid, Wasserstoff, entfernt wird, das das Korrosionsverhalten gegen Wasserdampf bzw. Sauerstoff negativ beeinflußt.In any case, this must be followed by a temperature treatment, last under vacuum, at temperatures up to 1800 ° C, dimit on the one hand, the organic binder cokes and the residual gas, for example carbon monoxide, hydrogen, is removed that adversely affects the corrosion behavior against water vapor or oxygen.
Diese thermische Behandlung wird bis jetzt vorwiegend in zwei Stufen durchgeführt:This thermal treatment has prevailed up to now carried out in two stages:
1. Zersetzung bzw. Verkoken des Binders und1. Decomposition or coking of the binder and
2. Entgasung der Brennelemente bei Temperaturen bis zu 1800° C im Vakuum.2. Degassing of the fuel elements at temperatures of up to 1800 ° C in a vacuum.
Das Restgas bestimmt jedoch nicht allein das Korrosionsverhalten; die Anwesenheit der Elemente Eisen, Chrom, Vanadium, Molybdän und andere führt infolge ihrer katalytischen Funktion zu einer erhöhten Korrosion im Wasserdampf entsprechend den Gleichungen:However, the residual gas does not only determine the corrosion behavior; the presence of the elements Iron, chromium, vanadium, molybdenum and others lead to a due to their catalytic function increased corrosion in water vapor according to the equations:
H2O + C = H, + CO bzw. H2O = H2 + >/2 O2; V2 O2 H 2 O + C = H, + CO or H 2 O = H 2 +> / 2 O 2 ; V 2 O 2
katalyt. Mecatalyt. Me
= CO= CO
Bei der obenerwähnten Temperaturbehandlung wird selbst bei 18000C im Vakuum nur ein Teil dieser Verunreinigungen verflüchtigt, so daß kein genügender Reinigungseffekt erzielt wird.In the above-mentioned temperature treatment, even at 1800 ° C. in a vacuum, only some of these impurities are volatilized, so that no adequate cleaning effect is achieved.
Andererseits tritt bei Temperaturen oberhalb 1700° C s<*hon eine merkliche, mit zunehmender Temperatur relativ steil ansteigende Spaltstoffdiffusion, z. B. von Uran und Thorium, durch die pyrolytisch abgeschiedenen Kohlenstoffschichten der beschichteten Teilchen in die umgebende Kohlenstoffmatrix ein. Dieses Uran bzw. Thorium — im folgenden als freies Uran bzw. Thorium bezeichnet — bestimmt dann im wesentlichen die Kühlgasaktivität des Reaktors, die so gering wie möglich sein sollte.On the other hand, at temperatures above 1700 ° C s <* hon occurs a noticeable, with increasing Temperature relatively steeply rising fissile material diffusion, z. B. uranium and thorium, by the pyrolytic deposited carbon layers of the coated particles into the surrounding carbon matrix. This uranium or thorium - hereinafter referred to as free uranium or thorium - then determines the essentially the cooling gas activity of the reactor, which should be as low as possible.
Diese Verfahrensweise hat den Nachteil, daß das in den beschädigten Brennstoffpartikeln enthaltene Uran (größenordnungsmäßig 1 %> des Gesamturans im Brennelement) zwar weitgehend, aber nicht völlig beseitigt wird.This procedure has the disadvantage that that contained in the damaged fuel particles Uranium (on the order of 1%> of the total uranium in the fuel element) to a large extent, but not entirely is eliminated.
Weiterhin wurden Verfahren ausgearbeitet, um entweder Hochtemperaturbrennelemente mit brennstofffreier Schalung herzustellen, so daß eine Oberflächenbearbeitung ohne Partikelbeschädigung möglich ist, oder aber die Elemente cu exakt zu fertigen, daß eine Bearbeitung fortfallen kann.Furthermore, procedures were worked out to either use high-temperature fuel elements with fuel-free Make formwork so that surface treatment is possible without particle damage, or to manufacture the elements cu exactly that one Processing can be omitted.
Erfindungsgemäß erfolgt die Herstellung von restgasfreien und den ReaktorkUhlkieislauf wenig verunreinigenden und aktivierenden Brennelementen dadurch, daß die Abtrennung der die Korrosion beeinflussenden und Kühlkreislauf verunreinigenden Restgas und der die Korrosion katalytisch beeinflussenden Verunreinigungen und die gleichzetige Spaltstoffdekontamination durch Behandlung der Brennelemente oder Brennstoffeinsätze durch Chlorgas und/ oder Chlorwasserstoffgas bei erhöhter Temperatur in einem Arbeitsschritt erfolgt.According to the invention, the production of residual gas-free and little polluting the reactor cooling circuit takes place and activating fuel elements in that the separation of the corrosion-influencing and the residual gas contaminating the cooling circuit and the catalytically influencing corrosion Impurities and the simultaneous decontamination of fissile materials through treatment of the fuel elements or fuel inserts using chlorine gas and / or hydrogen chloride gas at elevated temperature takes place in one work step.
Die geschilderten Nachteile — unbefriedigendes Korrosionsverhalten und Kontamination der Brennelemente bzw. der Brennstoffeinsätze — werden nach dem erfindungsgemäßen Verfahren beseitigt.The disadvantages outlined - unsatisfactory corrosion behavior and contamination of the fuel elements or the fuel inserts - are eliminated by the method according to the invention.
Die mit Pyrokohlenstoff beschichteten 3rennstoffteilchen werden bei einer Behandlung mit Chlor oder Chlorwasserstoffgas selbst bei hohen Temperaturen, z.B. 19000C, nicht angegriffen, weil der dichte, porenfreie Pyrolytkohlenstoff eine Reaktion mit denThe fuel particles coated with pyrocarbon are not attacked when treated with chlorine or hydrogen chloride gas, even at high temperatures, for example 1900 0 C, because the dense, pore-free pyrolytic carbon reacts with the
in den Partikeln vorhandenen Spaltstoffverbindungen verhindert.Prevents fissile material compounds present in the particles.
Durch das erfindungsgemäße Verfahren wird ein dreifacher Eflekt erzielt.A threefold eflect is achieved by the method according to the invention.
1. Verbesserte Entfernung von Korrosionskatalysatoren, 1.Improved removal of corrosion catalysts,
2. Entfernung von korrosionsbeschleunigenden Restgasen,2. Removal of residual gases that accelerate corrosion,
3. Beseitigung von Uran oder Thorium, welches bei der Behandlungstemperatur eventuell aus den3. Removal of uranium or thorium, which at the treatment temperature may be from the
beschichteten Brennstoffteilchen herausdiffundiert, also sozusagen im status nascendi. Giaphit kann schon bei Temperaturen ab 1600° C in an sich bekannter Weise mit Haicgengas, z. B. Chlorgas, gereinigt werden. Wesentlicher Inhalt der vorliegenden Erfindung ist demgegenüber die gleichzeitige Abtrennung des Restgases und der Verunreinigungen, insbesondere durch Verflüchtigung der diecoated fuel particles diffused out, so to speak in the status nascendi. Giaphite can already be used at temperatures from 1600 ° C in a known manner with Haicgengas, z. B. chlorine gas to be cleaned. In contrast, the essential content of the present invention is the simultaneous separation of the residual gas and the impurities, in particular by volatilization of the die
5555
Korrosion katalytisch beeinflussenden Elemente und Erzielen einer Dekontamination, d. h. Herabsetzung des freien Urans im Brennelement in einer Verfahrensstufe durch chlorierende Behandlung in einer Apparatur bei erhöhter Temperatur.Corrosion catalytically influencing elements and achieving decontamination, d. H. reduction of the free uranium in the fuel element in one process stage by chlorinating treatment in one Apparatus at elevated temperature.
Bei geeeigneter Auslegung der öfe.n kann sogar die zunächst notwendige Zersetzung, d. h. die Verkokung des Binden, in der gleichen Ofeneinheit uurchgeführt werden.Can .n at geeeigneter interpretation OEF e even the initially necessary decomposition, ie, the coking of the binding, are uurchgeführt in the same furnace unit.
Fünf kugelförmig gepreßte Brennelementgrünlinge von 60 mm Außendurchmesser aus Graphit und Binder-Matrix mit einem Urangehalt von IgU 235 und einem Thoriumgehalt von 5 g in Form von beschichteten Brennstoffteilchen wurden in einem Röhrenofen zunächst auf 800° C, dann auf 1700° C aufgeheizt und unter Durchleiten von Chlorgas 2 Stunden bei dieser Temperatur gehalten.Five spherically pressed green fuel assemblies with an outer diameter of 60 mm made of graphite and Binder matrix with a uranium content of IgU 235 and a thorium content of 5 g in the form of coated Fuel particles were first heated to 800 ° C and then to 1700 ° C in a tube furnace heated and held at this temperature for 2 hours while passing through chlorine gas.
Parallel dazu wurden fünf gleiche Brennelementgrünlinge nach dem gleichen Temperaturprogramm ohne Chlor im Argonstrom thermisch behandelt. Anschließend wu.de d«e Korrosionsrate (Abtragung von Kohlenstoff) in Wasserdampf bei 1000° C sowie der Gehalt an freiem Uran in der Graphitmatrix gemessen. In parallel, five identical green fuel assemblies were produced using the same temperature program Thermally treated without chlorine in an argon stream. Then the rate of corrosion (removal of Carbon) in water vapor at 1000 ° C as well as the content of free uranium in the graphite matrix.
Ergebnis, MittelwerteResult, mean values
ohne CIt behandelttreated without CIt
Oxydationsrate Oxidation rate
Urangehalt in GraphitUranium content in graphite
0,8 mgC/h · cm2 0.8 mgC / h · cm 2
70 · ΙΟ"8 Teile U
pro Gesamturan
im Element70 · ΙΟ " 8 parts U
per total uranium
in the element
1,5 mgC/h · cm2 1.5 mgC / h · cm 2
300 · 10-« Teile U
pro Gesamiuran
im Element300 x 10 «parts U
per Gesamiuran
in the element
Die Werte, die mit dem erfindungsgemäßen Verfahren erreicht werden, lassen hinsichtlich der Korrosion und der Kühlgasaktivitüt ein einwandfreies Verhalten der Brennelemente im Reaktor erwarten.The values that can be achieved with the method according to the invention are low in terms of corrosion and the cooling gas activity, expect perfect behavior of the fuel elements in the reactor.
Claims (2)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691939442 DE1939442C (en) | 1969-08-02 | Process for the production of residual gas-free and activating fuel elements and fuel inserts for high-temperature reactors with little contamination and activation of the reactor cooling circuit | |
| FR6942748A FR2056947B1 (en) | 1969-08-02 | 1969-12-10 | |
| GB3623870A GB1313931A (en) | 1969-08-02 | 1970-07-27 | Production of fuel elements and fuel inserts for high temperature reactors |
| BE754068D BE754068A (en) | 1969-08-02 | 1970-07-28 | PROCESS FOR THE PREPARATION OF COMBUSTIBLE ELEMENTS OR CHARGES OF COMBUSTIBLE MATERIAL FOR HIGH TEMPERATURE NUCLEAR REACTORS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691939442 DE1939442C (en) | 1969-08-02 | Process for the production of residual gas-free and activating fuel elements and fuel inserts for high-temperature reactors with little contamination and activation of the reactor cooling circuit |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1939442A1 DE1939442A1 (en) | 1971-03-04 |
| DE1939442B2 DE1939442B2 (en) | 1972-09-07 |
| DE1939442C true DE1939442C (en) | 1973-03-29 |
Family
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