EP0327691A2 - Process for permanent disposal of radioactive waste - Google Patents
Process for permanent disposal of radioactive waste Download PDFInfo
- Publication number
- EP0327691A2 EP0327691A2 EP88119450A EP88119450A EP0327691A2 EP 0327691 A2 EP0327691 A2 EP 0327691A2 EP 88119450 A EP88119450 A EP 88119450A EP 88119450 A EP88119450 A EP 88119450A EP 0327691 A2 EP0327691 A2 EP 0327691A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- potassium permanganate
- cement
- container
- waste
- carrier material
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000002901 radioactive waste Substances 0.000 title claims abstract description 7
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 40
- 239000004568 cement Substances 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 239000012876 carrier material Substances 0.000 claims description 11
- 239000004575 stone Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000003608 radiolysis reaction Methods 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005253 cladding Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/16—Processing by fixation in stable solid media
- G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
- G21F9/165—Cement or cement-like matrix
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
- G21F9/304—Cement or cement-like matrix
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S376/00—Induced nuclear reactions: processes, systems, and elements
- Y10S376/90—Particular material or material shapes for fission reactors
- Y10S376/901—Fuel
- Y10S376/902—Fuel with external lubricating or absorbing material
Definitions
- the invention relates to a method for the storage of radioactive waste materials, in which the waste materials are solidified or pressed and then enclosed in a container.
- Radioactive waste - solidified or compressed - is enclosed in containers for storage in order to avoid radioactive contamination of the environment. It has been shown that hydrogen is generated in the waste material by chemical and radiolytic processes, which is undesirable for reasons of final storage.
- radioactive wastes for example those from the reprocessing of fuel elements, such as structural parts, Zirkaloy cladding tubes and insoluble residues from the fuel solution (feed sewage sludge) are cemented for final storage in containers.
- the waste / cement mixture is usually placed in 140 l so-called insert drums, which in turn are placed in 200 l drums. After the cement has set, these insert drums are placed in 200-liter drums and sealed with rubber seals and lids.
- the water contained in the cement matrix is broken down into hydrogen and oxygen by radiolysis.
- the oxygen reacts with the materials of the waste container and is therefore usually not found in the empty space of the 200 l drums, which contains about 70 l of free gas volume.
- the potassium permanganate is expediently used in dissolved form. To do this, to apply the potassium permanganate to the surface of the carrier material, proceed according to the procedure of claim 3.
- a particularly simple and yet effective embodiment of the method according to the invention consists in adding the potassium permanganate in solid form to the cement before it sets (claim 2) or admixing it to the carrier material (claim 4).
- Ceramic materials such as Al2O3 or chamotte, are suitable as carrier material.
- oxidizing agent used Since the oxidizing agent used is consumed in the conversion of the hydrogen, a sufficient amount thereof must be used to convert the total hydrogen produced during the storage period.
- the amount of oxidizing agent used on the other hand, in the event that it is added to the cement, must not lead to a reduction in the strength of the cement. In this regard, potassium permanganate has been found to be suitable.
- potassium permanganate 10 g to 100 g of potassium permanganate are expediently used per liter of cement stone, concrete and / or carrier material used. If you mix the cement with saturated potassium permanganate solution, then about 35 g KMnO4 / liter cement stone are reached. In total, more potassium permanganate can be contained in the wrapping material, which is filled into the annular gap volume of the 200 l drums (up to 100 g / liter) can be used. If aluminum oxide is used as a carrier material for the coating material, approximately 15-30 g of potassium permanganate per kg of aluminum oxide will be applied to it. With a uniform mixture of aluminum oxide and solid potassium permanganate, 100 g per liter of carrier material can be easily adjusted.
- the H2-reactivity of potassium permanganate was compared in parallel on two samples of the same composition with and without radiation.
- two samples were made from cement stone bodies and two samples from Al2O3 (each mixed with potassium permanganate).
- the cement stone samples and the Al2O3 samples were sealed gas-tight in the 1.65-liter vessels, evacuated and charged with a gas mixture consisting of 20% H2 and 80% Kr.
- sample 1 and 2 Portland cement 35; pH 12.5
- 1270 g of cement, 575 g of water and 15 g of KMnO4 0.095 mol
- the mass of sample 1 was 1755 g
- the mass of sample 2 was 1765 g.
- One of the parallel samples was irradiated for 5 days up to a dose of 1.5 - 2.5 x 106 rad.
- the other parallel sample was stored in the laboratory at room temperature without irradiation.
- the H2 volume in the cement stone samples would be 10 - 20 ml must have arisen as a result of the radiation.
- the H2 portion of the original gas filling in the case of cement stone samples is approximately 180 ml H2.
- samples No. 1 and 2 practically completely devour the H2 volume and the hydrogen released in sample 2 by irradiation during the test period. At the same time, there is presumably a certain release of O2 by elimination from the KMnO4, the O2 elimination being increased in the irradiated sample.
- insert drums (140 l) with cemented radioactive structural parts, fuel element sleeves and feed sewage sludge were removed from the larger containers (200 l drum) and sealed in specially made measuring containers.
- the empty volume of the measuring container was approx. 47 l.
- the release of radiolysis hydrogen from the cemented waste was determined by observing the internal pressure of the container and by taking gas samples with subsequent gas chromatographic analysis of the gas components.
- the H2 release was first observed over a period of 300 days and an average release rate of approx. 77 Nml H2 / day was determined.
- the measuring container was then opened and a drip tray with approx. 2.5 kg Al2O3, which had been impregnated with approx. 40 g KMnO4 in the manner indicated in Example 1, admitted.
- the measuring container was closed again gas-tight and flushed with synthetic air before the measuring phase.
- the internal pressure after the addition of the Al2O3 sample fell continuously from about 1000 mbar to about 860 mbar within 120 days.
- gas samples were taken after 56 and 120 days.
- the analyzes showed 0.4% H2, 7.2% O2, 89.5% N2 and 0.5% CH4 for the first sample, and 2.5% H2, 1.0% O2, 91, for the second sample. 4% N2 and 1.2% CH4.
- the increased H2 content at the end of the service life is due to the fact that the potassium permanganate was almost exhausted.
- 100 g KMnOprobe in crystal form was added to a freshly mixed cement sample of approx. 1 liter with a water / cement ratio of 0.43 and mixed in evenly.
- the cylindrical sample was shaped after 24 hours, placed in a sealed vessel and kept under a hydrogen partial pressure of 500-600 mbar for 32 days. During this time the vessel was in a thermostat at 50 ° C.
- the whole container was tightly closed and was kept at 50 ° C under 500 - 600 mbar hydrogen partial pressure for 8 days.
Abstract
Description
Die Erfindung bezieht sich auf ein Verfahren zur Einlagerung von radioaktiven Abfallstoffen, bei dem die Abfallstoffe verfestigt oder verpreßt und anschließend in einem Behältnis eingeschlossen werden.The invention relates to a method for the storage of radioactive waste materials, in which the waste materials are solidified or pressed and then enclosed in a container.
Radioaktive Abfälle werden - verfestigt oder verpreßt - zur Lagerung in Behältnisse eingeschlossen, um eine radioaktive Kontamination der Umwelt zu vermeiden. Dabei hat sich gezeigt, daß im Abfallmaterial durch chemische und radiolytische Vorgänge Wasserstoff entsteht, der aus Gründen der Endlagerung unerwünscht ist.Radioactive waste - solidified or compressed - is enclosed in containers for storage in order to avoid radioactive contamination of the environment. It has been shown that hydrogen is generated in the waste material by chemical and radiolytic processes, which is undesirable for reasons of final storage.
Zur Verfestigung werden radioaktive Abfälle, beispielsweise solche aus der Wiederaufarbeitung von Brennelementen, wie Strukturteile, Zirkaloy-Hüllrohre und unlösliche Rückstände aus der Brennstofflösung (Feed-Klärschlamm) zur Endlagerung in Behältnissen einzementiert. Die Abfallstoffe/Zement-Mischung wird dabei üblicherweise in 140 l fassende sog. Einsatztrommeln, die ihrerseits in 200-l-Fässer eingebracht werden, gegeben. Diese Einsatztrommeln werden nach dem Abbinden des Zements in 200-l-Fässer eingesetzt und mit Gummidichtungen und Deckeln verschlossen.For solidification, radioactive wastes, for example those from the reprocessing of fuel elements, such as structural parts, Zirkaloy cladding tubes and insoluble residues from the fuel solution (feed sewage sludge) are cemented for final storage in containers. The waste / cement mixture is usually placed in 140 l so-called insert drums, which in turn are placed in 200 l drums. After the cement has set, these insert drums are placed in 200-liter drums and sealed with rubber seals and lids.
Wie sich gezeigt hat, wird das in der Zementmatrix enthaltene Wasser durch Radiolyse in Wasserstoff und Sauerstoff zerlegt. Der Sauerstoff reagiert mit den Materialien des Abfallgebindes und wird daher üblicherweise im Leerraum der 200-l-Fässer, der etwa 70 l freies Gasvolumen umfaßt, nicht gefunden.As has been shown, the water contained in the cement matrix is broken down into hydrogen and oxygen by radiolysis. The oxygen reacts with the materials of the waste container and is therefore usually not found in the empty space of the 200 l drums, which contains about 70 l of free gas volume.
Der durch Radiolyse entstehende Wasserstoff dagegen verbleibt im Gasraum. Je nach Aktivitätsinhalt eines Fasses kann im Verlauf der ersten Jahrzehnte Wasserstoff bis zur Größenordnung von 1 m³ gebildet werden, was aus Gründen der Endlagerung unerwünscht ist.By contrast, the hydrogen generated by radiolysis remains in the gas space. Depending on the activity content of a barrel, hydrogen up to the order of 1 m³ can be formed in the course of the first decades, which is undesirable for reasons of final storage.
Es ist Aufgabe der Erfindung, das eingangs bezeichnete Verfahren dahingehend zu verbessern, daß die Bildung einer Wasserstoffatmosphäre im freien Gasvolumen des Behälters verhindert wird.It is an object of the invention to improve the method described in the introduction in such a way that the formation of a hydrogen atmosphere in the free gas volume of the container is prevented.
Diese Aufgabe wird erfindungsgemäß durch die Maßnahmen gemäß dem Kennzeichen des Anspruchs 1 gelöst. Dabei wird der Wasserstoff, unabhängig von seiner Entstehung, im Umhüllungsmaterial gebunden.This object is achieved by the measures according to the characterizing part of claim 1. The hydrogen is bound in the coating material, regardless of its origin.
Für den Fall, daß die Abfälle durch Einzementieren verfestigt werden, hat sich als vorteilhaft erwiesen, das Kaliumpermanganat dem Zement in gelöster oder fester Form vor dessen Abbinden zuzugeben. Der durch Radiolyse gebildete Wasserstoff wird dann noch im Zement zu Wasser oxidiert und gelangt erst gar nicht in das Leervolumen des Behälters.In the event that the waste is solidified by cementing, it has proven to be advantageous to add the potassium permanganate to the cement in dissolved or solid form before it sets. The hydrogen formed by radiolysis is then oxidized to water in the cement and does not even get into the empty volume of the container.
Soll eine homogene Verteilung des Kaliumpermanganats im Zement, im Beton oder im Umhüllungsmaterial erzielt werden, wird das Kaliumpermanganat zweckmäßigerweise in gelöster Form eingesetzt. Dazu wird, um das Kaliumpermanganat auf der Oberfläche des Trägermaterials aufzubringen, nach der Verfahrensweise gemäß Anspruch 3 vorgegangen.If a homogeneous distribution of the potassium permanganate in the cement, in the concrete or in the cladding material is to be achieved, the potassium permanganate is expediently used in dissolved form. To do this, to apply the potassium permanganate to the surface of the carrier material, proceed according to the procedure of claim 3.
Eine besonders einfache und dennoch effektive Ausführungsform des Verfahrens gemäß der Erfindung besteht darin, daß das Kaliumpermanganat in fester Form dem Zement vor dessen Abbinden beigegeben (Anspruch 2) oder dem Trägermaterial beigemischt wird (Anspruch 4).A particularly simple and yet effective embodiment of the method according to the invention consists in adding the potassium permanganate in solid form to the cement before it sets (claim 2) or admixing it to the carrier material (claim 4).
Als Trägermaterial sind keramische Materialien, wie Al₂O₃ oder Schamotte, geeignet.Ceramic materials, such as Al₂O₃ or chamotte, are suitable as carrier material.
Da das eingesetzte Oxidationsmittel bei der Umsetzung des Wasserstoffs verbraucht wird, ist davon eine hinreichende Menge einzusetzen, um den insgesamt während der Dauer der Lagerung entstehenden Wasserstoff umzusetzen. Die eingesetzte Menge an Oxidationsmittel darf andererseits - für den Fall, daß es dem Zement beigegeben wird - nicht zu einer Verminderung der Festigkeit des Zements führen. In dieser Hinsicht hat sich Kaliumpermanganat als geeignet erwiesen.Since the oxidizing agent used is consumed in the conversion of the hydrogen, a sufficient amount thereof must be used to convert the total hydrogen produced during the storage period. The amount of oxidizing agent used, on the other hand, in the event that it is added to the cement, must not lead to a reduction in the strength of the cement. In this regard, potassium permanganate has been found to be suitable.
Zur Bindung des insgesamt während der Endlagerung entstehenden Wasserstoffs werden zweckmäßigerweise pro Liter verwendetem Zementstein, Beton und/oder Trägermaterial 10 g bis 100 g Kaliumpermanganat eingesetzt. Vermischt man den Zement mit gesättigter Kaliumpermanganatlösung, dann werden etwa 35 g KMnO₄/Liter Zementstein erreicht. Im Umhüllungsmaterial, das in das Ringspaltvolumen der 200-l-Fässer gefüllt wird, kann insgesamt mehr Kaliumpermanganat (bis zu 100 g/Liter) eingesetzt werden. Bei Verwendung von Aluminiumoxid als Trägermaterial für das Umhüllungsmaterial wird man etwa 15 - 30 g Kaliumpermanganat pro kg Aluminiumoxid auf dieses aufbringen. Bei einer gleichmäßigen Mischung aus Aluminiumoxid und festem Kaliumpermanganat sind 100 g pro Liter Trägermaterial ohne weiteres einstellbar.To bind the total hydrogen produced during final storage, 10 g to 100 g of potassium permanganate are expediently used per liter of cement stone, concrete and / or carrier material used. If you mix the cement with saturated potassium permanganate solution, then about 35 g KMnO₄ / liter cement stone are reached. In total, more potassium permanganate can be contained in the wrapping material, which is filled into the annular gap volume of the 200 l drums (up to 100 g / liter) can be used. If aluminum oxide is used as a carrier material for the coating material, approximately 15-30 g of potassium permanganate per kg of aluminum oxide will be applied to it. With a uniform mixture of aluminum oxide and solid potassium permanganate, 100 g per liter of carrier material can be easily adjusted.
Das Verfahren gemäß der Erfindung wird im folgenden anhand von vier Ausführungsbeispielen näher erläutert.The method according to the invention is explained in more detail below using four exemplary embodiments.
Das H₂-Umsetzungsvermögen von Kaliumpermanganat wurde parallel an jeweils zwei Proben gleicher Zusammensetzung mit und ohne Bestrahlung vergleichend untersucht. Hierzu wurden zwei Proben aus Zementsteinkörper und zwei Proben aus Al₂O₃ (jeweils mit Kaliumpermanganat versetzt) hergestellt.The H₂-reactivity of potassium permanganate was compared in parallel on two samples of the same composition with and without radiation. For this purpose, two samples were made from cement stone bodies and two samples from Al₂O₃ (each mixed with potassium permanganate).
Die Zementsteinproben und die Proben aus Al₂O₃ wurden für die Versuche in 1,65-l-Gefäße gasdicht verschlossen, evakuiert und mit einem Gasgemisch, bestehend aus 20 % H₂ und 80 % Kr, beaufschlagt.The cement stone samples and the Al₂O₃ samples were sealed gas-tight in the 1.65-liter vessels, evacuated and charged with a gas mixture consisting of 20% H₂ and 80% Kr.
Zur Herstellung der Zementsteinkörper (Proben 1 und 2; Portlandzement 35; pH 12,5) wurden zum Ansatz des Zementleims 1270 g Zement, 575 g Wasser und 15 g KMnO₄ verwendet (KMnO₄ = 0,095 Mol). Die Masse der Probe 1 betrug 1755 g, die Masse der Probe 2 1765 g.To prepare the cement stone bodies (samples 1 and 2; Portland cement 35; pH 12.5), 1270 g of cement, 575 g of water and 15 g of KMnO₄ (KMnO₄ = 0.095 mol) were used to prepare the cement paste. The mass of sample 1 was 1755 g, the mass of sample 2 was 1765 g.
Zur Herstellung der Proben 3 und 4 wurde Al₂O₃-Pulver mit Kaliumpermanganatlösung beaufschlagt und das behandelte Pulver anschließend vakuumgetrocknet. Die Masse der Proben 3 und 4 betrugen je 1 kg.To prepare samples 3 and 4, Al₂O₃ powder was charged with potassium permanganate solution and the treated powder was then vacuum-dried. The masses of samples 3 and 4 were 1 kg each.
Jeweils eine der Parallelproben wurde über 5 Tage bis zu einer Dosis von 1,5 - 2,5 x 10⁶ rad bestrahlt. Die andere Parallelprobe wurde ohne Bestrahlung im Labor bei Raumtemperatur aufbewahrt.One of the parallel samples was irradiated for 5 days up to a dose of 1.5 - 2.5 x 10⁶ rad. The other parallel sample was stored in the laboratory at room temperature without irradiation.
Anschließend wurden die Druckmessungen und die Gasprobennahmen mit nachfolgender Gasanalyse an allen Proben durchgeführt. Die Ergebnisse sind in der Tabelle angegeben.The pressure measurements and gas sampling with subsequent gas analysis were then carried out on all samples. The results are shown in the table.
Legt man einen GH₂-Wert für die radiolytische Erzeugung von Wasserstoff von 0,45 µMol/g H₂O x Mrad (0,45 ml H₂/10⁸ rad g Zementstein) zugrunde, so hätte in den Zementsteinproben ein H₂-Volumen von 10 - 20 ml infolge der Bestrahlung entstanden sein müssen. Demgegenüber beträgt der H₂-Anteil an der ursprünglichen Gasfüllung im Falle der Zementsteinproben ca. 180 ml H₂.If one assumes a G H₂ value for the radiolytic generation of hydrogen of 0.45 µmol / g H₂O x Mrad (0.45 ml H₂ / 10⁸ rad g cement stone), the H₂ volume in the cement stone samples would be 10 - 20 ml must have arisen as a result of the radiation. In contrast, the H₂ portion of the original gas filling in the case of cement stone samples is approximately 180 ml H₂.
Die beiden Zementsteinproben (Proben Nr. 1 und 2) zehren während der Versuchszeit das vorgelegte H₂-Volumen und den in Probe 2 durch Bestrahlung zusätzlich freigesetzten Wasserstoff praktisch vollständig auf. Gleichzeitig kommt es vermutlich durch Abspaltung aus dem KMnO₄ zu einer gewissen O₂-Freisetzung, wobei die O₂-Abspaltung in der bestrahlten Probe verstärkt ist.The two cement block samples (samples No. 1 and 2) practically completely devour the H₂ volume and the hydrogen released in sample 2 by irradiation during the test period. At the same time, there is presumably a certain release of O₂ by elimination from the KMnO₄, the O₂ elimination being increased in the irradiated sample.
Bei den Al₂O₃-Pulverproben wird der vorgelegte Wasserstoff ebenfalls vollständig verzehrt.In the Al₂O₃ powder samples, the hydrogen is also completely consumed.
Geht man davon aus, daß das KMnO₄ bei der Umsetzung mit Wasserstoff von Mn⁷⁺ nach Mn⁴⁺ übergeht, werden pro KMnO₄-Molekül 3/2 O abgegeben. 15 g KMnO₄ entsprechen demnach 1,6 Nl O₂ oder 3,2 Nl H₂. In den Proben wurden jedoch nur maximal 0,2 Nl H₂ umgesetzt.If one assumes that the KMnO₄ changes from Mn⁷⁺ to Mn⁴⁺ when reacting with hydrogen, 3/2 O are released per KMnO₄ molecule. 15 g KMnO₄ correspond to 1.6 Nl O₂ or 3.2 Nl H₂. However, only a maximum of 0.2 Nl H₂ were implemented in the samples.
Für die Untersuchung wurden Einsatztrommeln (140 l) mit zementierten radioaktiven Strukturteilen, Brennelementhülsen und Feed-Klärschlamm aus den größeren Behältern (200-l-Faß) entnommen und in hierfür eigens angefertigten Meßbehältern verschlossen. Das Leervolumen der Meßbehälter betrug ca. 47 l.For the investigation, insert drums (140 l) with cemented radioactive structural parts, fuel element sleeves and feed sewage sludge were removed from the larger containers (200 l drum) and sealed in specially made measuring containers. The empty volume of the measuring container was approx. 47 l.
Die Freisetzung von Radiolysewasserstoff aus den zementierten Abfällen wurde durch Beobachtung des Behälterinnendrucks und durch Gasprobennahmen mit nachfolgender gaschromatographischer Analyse der Gasbestandteile ermittelt.The release of radiolysis hydrogen from the cemented waste was determined by observing the internal pressure of the container and by taking gas samples with subsequent gas chromatographic analysis of the gas components.
Beim ersten Meßbehälter wurde zunächst über einen Zeitraum von 300 Tagen die H₂-Freisetzung beobachtet und eine mittlere Freisetzungsrate von ca. 77 Nml H₂/Tag ermittelt. Der Meßbehälter wurde sodann geöffnet und eine Auffangschale mit ca. 2,5 kg Al₂O₃, das mit ca. 40 g KMnO₄ in der in Ausführungsbeispiel 1 angegebenen Weise imprägniert worden war, zugegeben. Der Meßbehälter wurde wieder gasdicht verschlossen und vor der Meßphase mit synthetischer Luft gespült.In the first measuring container, the H₂ release was first observed over a period of 300 days and an average release rate of approx. 77 Nml H₂ / day was determined. The measuring container was then opened and a drip tray with approx. 2.5 kg Al₂O₃, which had been impregnated with approx. 40 g KMnO₄ in the manner indicated in Example 1, admitted. The measuring container was closed again gas-tight and flushed with synthetic air before the measuring phase.
Beim zweiten Meßbehälter, in den kein Kaliumpermanganat gegeben worden war, wurde über eine Standzeit von ca. 100 Tagen ein annähernd konstanter Druck von ca. 1000 mbar beobachtet. Anschließend nahm der Druck mit einer konstanten Rate zu (Beobachtungszeit insgesamt 120 Tage). Dieser Druckverlauf wird darauf zurückgeführt, daß sich in der Anfangsphase die O₂-Verlustrate und die H₂-Produktionsrate infolge Radiolyse annähernd kompensieren. Danach steigt der Druck linear an, sobald der Luftsauerstoff praktisch vollständig verbraucht ist.In the second measuring container, into which no potassium permanganate had been added, an approximately constant pressure of approximately 1000 mbar was observed over a service life of approximately 100 days. Then the pressure increased at a constant rate (observation time total 120 days). This pressure curve is attributed to the fact that in the initial phase the O₂ loss rate and the H₂ production rate due to radiolysis almost compensate. Then the pressure rises linearly as soon as the atmospheric oxygen is practically completely consumed.
Bei ersten Meßbehälter fiel der Innendruck nach Zugabe der Al₂O₃-Probe innerhalb von 120 Tagen kontinuierlich von ca. 1000 mbar auf etwa 860 mbar. Zusätzlich wurden nach 56 und nach 120 Tagen Gasproben entnommen. Die Analysen ergaben für die erste Probe 0,4 % H₂, 7,2 % O₂, 89,5 % N₂ und 0,5 % CH₄, und für die zweite Probe 2,5 % H₂, 1,0 % O₂, 91,4 % N₂ und 1,2 % CH₄. Der erhöhte H₂-Anteil am Ende der Standzeit ist darauf zurückzuführen, daß das Kaliumpermanganat nahezu erschöpft war.In the first measuring container, the internal pressure after the addition of the Al₂O₃ sample fell continuously from about 1000 mbar to about 860 mbar within 120 days. In addition, gas samples were taken after 56 and 120 days. The analyzes showed 0.4% H₂, 7.2% O₂, 89.5% N₂ and 0.5% CH₄ for the first sample, and 2.5% H₂, 1.0% O₂, 91, for the second sample. 4% N₂ and 1.2% CH₄. The increased H₂ content at the end of the service life is due to the fact that the potassium permanganate was almost exhausted.
Nimmt man an, daß KMnO₄ bei der Umsetzung von H₂ von Mn⁷⁺ nach Mn⁴⁺ seine Wertigkeit ändert, so liefern 40 KMnO₄ stöchiometrisch eine H₂-Umsetzungskapazität von 8,6 NlH₂. Unterstellt man, daß während der Meßzeit, in der sich das Oxidationsmittel im Meßbehälter befand, die Freisetzungsrate weiterhin 77 Nml H₂/Tag betrug, so hat das Kaliumpermanganat ein H₂-Volumen von ca. 10,0 Nl H₂ umgesetzt. Diese Bilanz zeigt, daß das zugesetzte Oxidationsmittel praktisch vollständig für die Umsetzung des radiolytisch produzierten Wasserstoffs ausgenutzt worden ist.Assuming that KMnO₄ changes its value in the implementation of H₂ from Mn⁷⁺ to Mn⁴⁺, 40 KMnO₄ stoichiometrically provide an H₂ conversion capacity of 8.6 NlH₂. It is assumed that the release rate continues during the measuring time in which the oxidizing agent was in the measuring container Was 77 Nml H₂ / day, the potassium permanganate has an H₂ volume of about 10.0 Nl H₂ implemented. This balance shows that the added oxidizing agent has been used almost completely for the conversion of the radiolytically produced hydrogen.
Einer frisch angemischten Zementprobe von ca. 1 Liter, mit einem Wasser/Zement-Verhältnis von 0,43, wurden 100 g KMnO₄ in Kristallform zugefügt und gleichmäßig untergemischt. Die zylindrische Probe wurde nach 24 h ausgeformt, in ein dichtes Gefäß eingebracht und 32 Tage unter einem Wasserstoff-Partialdruck von 500 - 600 mbar gehalten. Während dieser Zeit stand das Gefäß in einem Thermostaten bei 50°C.100 g KMnOprobe in crystal form was added to a freshly mixed cement sample of approx. 1 liter with a water / cement ratio of 0.43 and mixed in evenly. The cylindrical sample was shaped after 24 hours, placed in a sealed vessel and kept under a hydrogen partial pressure of 500-600 mbar for 32 days. During this time the vessel was in a thermostat at 50 ° C.
Nach dieser Zeit wurde die Probe zerstört und auf Kaliumpermanganat untersucht.After this time the sample was destroyed and examined for potassium permanganate.
In der Probe fand sich nur noch MnO₂; das KMnO₄ hatte sich vollständig umgesetzt.Only MnO₂ was found in the sample; the KMnO₄ had fully implemented.
Für die Umsetzung von H₂ mit KMnO₄-Kristallen ist eine Mindestfeuchte erforderlich. Deshalb wurde ein feuchter Zementsteinzylinder von ca. 1 Liter mit 600 mL Al₂O₃-Pulver umgeben, die 60 g KMnO₄ in Kristallform enthielten.A minimum moisture is required for the implementation of H₂ with KMnO₄ crystals. Therefore, a damp cement stone cylinder of about 1 liter was surrounded with 600 mL Al₂O₃ powder, which contained 60 g KMnO₄ in crystal form.
Das ganze Gebinde war dicht verschlossen und wurde 8 Tage bei 50°C unter 500 - 600 mbar Wasserstoff-Partialdruck gehalten.The whole container was tightly closed and was kept at 50 ° C under 500 - 600 mbar hydrogen partial pressure for 8 days.
Danach war das KMnO₄ vollständig zu MnO₂ umgesetzt.
Claims (6)
dadurch gekennzeichnet,
daß die Abfallstoffe zum Eliminieren des während der Lagerung entstehenden Wasserstoffs mit einem Kaliumpermanganat enthaltenden Zement wenigstens teilweise umhüllt werden oder poröses, nicht reduzierend wirkendes Trägermaterial mit Kaliumpermanganat als Umhüllungsmaterial verwendet wird, wobei das Abfallmaterial und das Umhüllungsmaterial in ein gemeinsames Behältnis gegeben wird.1. a process for the storage of radioactive waste materials, in which the waste materials are solidified or compressed and then enclosed in a container,
characterized,
that the waste materials for eliminating the hydrogen formed during storage are at least partially coated with a cement containing potassium permanganate or porous, non-reducing carrier material with potassium permanganate is used as the covering material, the waste material and the covering material being placed in a common container.
dadurch gekennzeichnet,
daß für den Fall, daß die Abfälle durch Einzementieren verfestigt werden, das Kaliumpermanganat dem Zement in gelöster oder fester Form vor dessen Abbinden beigegeben wird.2. The method according to claim 1,
characterized,
that in the event that the waste is solidified by cementing, the potassium permanganate is added to the cement in dissolved or solid form before it sets.
dadurch gekennzeichnet,
daß das Kaliumpermanganat auf das Trägermaterial in gelöster Form aufgebracht wird und das Material danach vor seiner Verwendung als Umhüllungsmaterial getrocknet wird.3. The method according to claim 1,
characterized,
that the potassium permanganate is applied to the carrier material in dissolved form and the material is then dried before being used as a coating material.
dadurch gekennzeichnet,
daß das Kaliumpermanganat dem Trägermaterial in fester Form beigemischt wird.4. The method according to claim 1,
characterized,
that the potassium permanganate is admixed to the carrier material in solid form.
dadurch gekennzeichnet,
daß als Trägermaterial Al₂O₃ verwendet wird.5. The method according to claim 1, 3 or 4,
characterized,
that Al₂O₃ is used as the carrier material.
dadurch gekennzeichnet,
daß zur Endlagerung der Abfälle pro Liter verwendetem Zementstein, Beton und/oder Trägermaterial 10 g bis 100 g Kaliumpermanganat eingesetzt werden.6. The method according to any one of the preceding claims,
characterized,
that 10 g to 100 g of potassium permanganate are used for the final storage of the waste per liter of cement stone, concrete and / or carrier material used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1017809A JPH01267499A (en) | 1988-01-30 | 1989-01-30 | Storage of radioactive waste |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3802755A DE3802755A1 (en) | 1988-01-30 | 1988-01-30 | METHOD FOR STORING RADIOACTIVE WASTE |
| DE3802755 | 1988-01-30 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0327691A2 true EP0327691A2 (en) | 1989-08-16 |
| EP0327691A3 EP0327691A3 (en) | 1989-09-06 |
| EP0327691B1 EP0327691B1 (en) | 1993-09-15 |
Family
ID=6346299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88119450A Expired - Lifetime EP0327691B1 (en) | 1988-01-30 | 1988-11-23 | Process for permanent disposal of radioactive waste |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4943394A (en) |
| EP (1) | EP0327691B1 (en) |
| JP (1) | JPH01267499A (en) |
| DE (2) | DE3802755A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9017038D0 (en) * | 1990-08-03 | 1990-09-19 | Alcan Int Ltd | Controlled hydrogen generation from composite powder material |
| JP3150445B2 (en) * | 1992-09-18 | 2001-03-26 | 株式会社日立製作所 | Radioactive waste treatment method, radioactive waste solidified material and solidified material |
| US6004522A (en) * | 1993-12-15 | 1999-12-21 | Purafil, Inc. | Solid filtration media incorporating elevated levels of permanganate and water |
| DE4343500A1 (en) * | 1993-12-20 | 1995-06-22 | Forschungszentrum Juelich Gmbh | Device for avoiding overpressures in storage containers with hydrogen-developing content |
| US5649323A (en) * | 1995-01-17 | 1997-07-15 | Kalb; Paul D. | Composition and process for the encapsulation and stabilization of radioactive hazardous and mixed wastes |
| US5942323A (en) | 1995-01-27 | 1999-08-24 | Purafil, Inc. | Fiber filter and methods of use thereof |
| TW365009B (en) * | 1996-09-24 | 1999-07-21 | Jgc Corp | Method of disposal of metallic aluminum-containing radioactive solid waste |
| FR2799876B1 (en) * | 1999-10-15 | 2002-01-04 | Tech Et D Entpr S Generales So | PROCESS FOR PACKAGING RADIOACTIVE NON-FERROUS METAL WASTE |
| JP5178988B2 (en) | 2000-12-11 | 2013-04-10 | クリー インコーポレイテッド | Method of manufacturing self-aligned bipolar junction transistor in silicon carbide and device made thereby |
| JP4615749B2 (en) * | 2001-03-22 | 2011-01-19 | 日揮株式会社 | Radioactive waste treatment method and apparatus |
| JP4040854B2 (en) * | 2001-09-28 | 2008-01-30 | 株式会社神戸製鋼所 | Radioactive waste disposal container, disposal facility and disposal method |
| FR2939700B1 (en) * | 2008-12-11 | 2014-09-12 | Commissariat Energie Atomique | MATERIAL FOR HYDROGEN TRAPPING, PROCESS FOR PREPARATION AND USES |
| US7758836B1 (en) | 2009-04-14 | 2010-07-20 | Huggins Ronald G | System and method for removing sulfur-containing contaminants from indoor air |
| US20130014670A1 (en) * | 2010-04-01 | 2013-01-17 | Commissariat a I'Energie Atomique et Aux Energies Altematives | Use of anticorrosion agents for conditioning magnesium metal, conditioning material thus obtained and preparation process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2340907A1 (en) * | 1976-02-13 | 1977-09-09 | Belgonucleaire Sa | PROCESS FOR DRYING SOLUTIONS CONTAINING BORIC ACID |
| FR2451617A1 (en) * | 1979-03-14 | 1980-10-10 | Kraftwerk Union Ag | PROCESS FOR THE TREATMENT OF RADIO-ACTIVE SOLUTIONS |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056937A (en) * | 1976-01-08 | 1977-11-08 | Kyokado Engineering Co. Ltd. | Method of consolidating soils |
| US4049545A (en) * | 1976-07-08 | 1977-09-20 | Rocky Carvalho | Chemical waste water treatment method |
| CA1100151A (en) * | 1976-07-19 | 1981-04-28 | William L. Prior | Process and composition for forming cellular inorganic resin cements and resulting product |
| US4119560A (en) * | 1977-03-28 | 1978-10-10 | United Technologies Corporation | Method of treating radioactive waste |
| WO1980000047A1 (en) * | 1978-06-08 | 1980-01-10 | Bp Chem Int Ltd | Encapsulating wastes |
| FR2490865A1 (en) * | 1980-09-19 | 1982-03-26 | Commissariat Energie Atomique | PROCESS FOR THE TREATMENT, BEFORE BITUMING, OF SOLUTIONS OR SUSPENSIONS COMPRISING REDUCING IONS |
| DE3110491C2 (en) * | 1981-03-18 | 1985-02-14 | Rheinisch-Westfälisches Elektrizitätswerk AG, 4300 Essen | Method and system for concentrating radioactive waste water containing boric acid from a nuclear power plant |
| JPS57172299A (en) * | 1981-04-16 | 1982-10-23 | Mitsubishi Genshi Nenryo Kk | Radioactive liquid waste processing method |
| BE899598A (en) * | 1984-05-07 | 1984-08-31 | Arklow S A | Neutralisation and solidification of industrial waste - by mixing in acidic medium with silicate(s), neutralising the silicic acid formed and solidifying with e.g. portland cement |
-
1988
- 1988-01-30 DE DE3802755A patent/DE3802755A1/en not_active Withdrawn
- 1988-11-23 EP EP88119450A patent/EP0327691B1/en not_active Expired - Lifetime
- 1988-11-23 DE DE88119450T patent/DE3884180D1/en not_active Expired - Fee Related
-
1989
- 1989-01-25 US US07/301,435 patent/US4943394A/en not_active Expired - Fee Related
- 1989-01-30 JP JP1017809A patent/JPH01267499A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2340907A1 (en) * | 1976-02-13 | 1977-09-09 | Belgonucleaire Sa | PROCESS FOR DRYING SOLUTIONS CONTAINING BORIC ACID |
| FR2451617A1 (en) * | 1979-03-14 | 1980-10-10 | Kraftwerk Union Ag | PROCESS FOR THE TREATMENT OF RADIO-ACTIVE SOLUTIONS |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0327691B1 (en) | 1993-09-15 |
| US4943394A (en) | 1990-07-24 |
| EP0327691A3 (en) | 1989-09-06 |
| DE3802755A1 (en) | 1989-08-10 |
| JPH01267499A (en) | 1989-10-25 |
| DE3884180D1 (en) | 1993-10-21 |
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