EP2248134B1 - Method for conditioning radioactive ion exchange resins - Google Patents
Method for conditioning radioactive ion exchange resins Download PDFInfo
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- EP2248134B1 EP2248134B1 EP09702004A EP09702004A EP2248134B1 EP 2248134 B1 EP2248134 B1 EP 2248134B1 EP 09702004 A EP09702004 A EP 09702004A EP 09702004 A EP09702004 A EP 09702004A EP 2248134 B1 EP2248134 B1 EP 2248134B1
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- water
- ion exchange
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- exchange resin
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- 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
-
- 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
Definitions
- the invention relates to a method for conditioning radioactive ion exchange resins.
- Ion exchange resins which are generally present as approximately spherical particles, are used, for example, in the operation of nuclear facilities to clean the coolant of the primary system, ie water. The aim of this cleaning is to avoid unwanted deposits on the surfaces of the primary circuit components, to prevent corrosion and to reduce the build-up of contamination in the primary circuit of the system.
- Both acid cation exchangers and basic anion exchangers are used in this purification, the former retaining metal cations and the latter anionic compounds, for example metal complexes. Since some of the metals are radionuclides, spent or loaded ion exchangers are radioactive waste and must be disposed of temporarily or permanently.
- Radioactively contaminated exchange resins also occur in the decontamination of nuclear facilities, for example in the primary circuit decontamination.
- metal oxide layers present on the surfaces of the primary circuit components are removed by means of decontamination solutions, the solutions being passed through ion exchangers during or after the decontamination in order to remove activity or metal cations contained therein.
- contaminated ion exchangers which are essentially organic resins with acidic or basic groups, must be conditioned. Conditioning is generally understood to mean the transfer of a radioactive waste into a storable form.
- spent ion exchange resins are usually dried and after a certain storage period or decay time, in which the radioactivity has dropped to a predetermined limit, for the purpose of storage embedded in a solid matrix, for example, cemented.
- the embedding of the ion exchange resins in a solid matrix leads to an increase in volume by more than six times the volume of the resin. Due to the large amount of waste arising for the operator of a nuclear power plant considerable costs for the intermediate or final disposal. Therefore, concepts have been developed to reduce the volume of the ion exchange resins.
- One of these concepts provides for combustion. However, this requires complex filter systems to prevent leakage of radioactivity into the environment. In addition, the combustion does not work very well due to the acidic or basic groups commonly present in the resins.
- the metals and thus the activity with the aid of acids or alkalis are completely removed from the resins, so that the resins can be reused.
- the respective acid or alkali is passed over a purely organic, ie neither acidic nor basic groups containing and therefore more easily combustible resin, which binds the metals (and the activity) adsorptive.
- the complete regeneration of the acidic or basic exchange resins fall considerable Amounts of acid / base secondary waste that needs to be disposed of.
- the object of the invention is to propose a method for conditioning contaminated ion exchange resins, with which in comparison to the direct embedding in a solid matrix, a volume reduction is connected and can be carried out with little time and material.
- a method according to claim 1 namely in that the ion exchange resin is mixed with water and with the aid of an oxidizing agent added to the water is at least partially decomposed into water-soluble fragments, wherein the resulting aqueous solution is solidified with a binder the method of reducing the volume of solid resin particles achieved in the reduction of volume consists mainly in the transition from the solid phase in which the resin is in the form of a bulky network of macromolecules to dissolved fragments of this network. Essentially, the process does not require more than one tank for carrying out the resin oxidation and possibly a second tank for the Consolidation.
- the added oxidizing agent causes the polymer network of the resin, for example, a copolymer of vinylbenzene and divinylbenzene, to be broken to form water-soluble fragments.
- the water solubility results from the acid or base groups present on the fragments (eg sulfonic acid groups or aminoethyl groups).
- the oxidation is preferably continued until all or almost all of the resin has dissolved.
- the exchange resin is treated oxidatively only until it is preferably completely in the form of water-soluble fragments.
- the resulting amount of carbon dioxide is relatively low.
- Cement for example Portland cement
- Portland cement usually contains high proportions of calcium oxide, which together with silicates with the mixing water forms cement hardening hydrates during the setting process. If the water of the mixture to be solidified is acidic, the calcium oxide is dissolved and is no longer available for hydrate formation and thus for cement hardening.
- a base is added for the neutralization of acids or for raising the pH of the mixture, so that it is slightly acidic to basic at the end.
- base preferably alkaline earth oxides and hydroxides are used.
- the oxidation of the ion exchange resins can in principle be carried out with any desired oxidizing agents. Preferably, however, those are used which form no reaction products in their reaction with the resin, which hinder the setting of the cement or other binder. Oxidants that have this property are hydrogen peroxide and ozone were used. Hydrogen peroxide leaves only harmless water, and ozone is reduced to oxygen, which escapes for the most part from the mixture. Resin oxidation produces CO 2 (which mostly escapes) and water.
- Resins 1 and 2 are relatively low crosslinked polystyrene-based resins having a divinylbenzene content of about 4-6%. Resins 3 and 4 are more crosslinked and have a divinylbenzene content of about 8-12%. The experiments have shown that not all resins are equally degradable. The time required to fully dissolve higher crosslinked resins (Nos. 3 and 4) is greater. Of course, the temperature is also decisive for the duration (see Experiments Nos. 1 and 2). An acceleration of the oxidation can also be achieved by the hydrogen peroxide in higher concentration is added. During oxidation with ozone, it was introduced into the mixture in gaseous form with the aid of a glass frit.
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Konditionierung radioaktiver Ionenaustauscherharze. Ionenaustauscherharze, die in der Regel als etwa kugelförmige Partikel vorliegen, werden beispielsweise beim Betrieb kerntechnischer Anlagen dazu verwendet, das Kühlmittel des Primärsystems, also Wasser, zu reinigen. Ziel dieser Reinigung ist die Vermeidung von nicht gewünschten Ablagerungen auf den Oberflächen der Primärkreiskomponenten, die Vermeidung von Korrosionen sowie die Verminderung des Kontaminationsaufbaus im Primärkreislauf der Anlage. Bei dieser Reinigung werden sowohl saure Kationentauscher als auch basische Anionentauscher eingesetzt, wobei erstere Metallkationen und letztere anionische Verbindungen, beispielsweise Metallkomplexe, zurückhalten. Da es sich bei einem Teil der Metalle um Radionuklide handelt, sind verbrauchte bzw. beladene Ionenaustauscher radioaktiver Abfall und müssen einer Zwischen- oder Endlagerung zugeführt werden. Radioaktiv kontaminierte Austauscherharze fallen auch bei der Dekontamination kerntechnischer Anlagen, z.B. bei der Primärkreisdekontamination an. Bei einem solchen Verfahren werden an den Oberflächen der Primärkreiskomponenten vorhandene Metalloxidschichten mit Hilfe von Dekontaminationslösungen abgelöst, wobei die Lösungen während oder nach der Dekontamination über Ionentauscher geleitet werden, um darin enthaltene Aktivität bzw. Metallkationen zu entfernen.The invention relates to a method for conditioning radioactive ion exchange resins. Ion exchange resins, which are generally present as approximately spherical particles, are used, for example, in the operation of nuclear facilities to clean the coolant of the primary system, ie water. The aim of this cleaning is to avoid unwanted deposits on the surfaces of the primary circuit components, to prevent corrosion and to reduce the build-up of contamination in the primary circuit of the system. Both acid cation exchangers and basic anion exchangers are used in this purification, the former retaining metal cations and the latter anionic compounds, for example metal complexes. Since some of the metals are radionuclides, spent or loaded ion exchangers are radioactive waste and must be disposed of temporarily or permanently. Radioactively contaminated exchange resins also occur in the decontamination of nuclear facilities, for example in the primary circuit decontamination. In such a method, metal oxide layers present on the surfaces of the primary circuit components are removed by means of decontamination solutions, the solutions being passed through ion exchangers during or after the decontamination in order to remove activity or metal cations contained therein.
Zur End- oder Zwischenlagerung müssen kontaminierte Ionentauscher, es handelt sich dabei im wesentlichen um organische Harze mit sauren oder basischen Gruppen, konditioniert werden. Unter einer Konditionierung ist dabei allgemein die Überführung eines radioaktiven Abfalls in eine lagerungsfähige Form zu verstehen.For final or intermediate storage, contaminated ion exchangers, which are essentially organic resins with acidic or basic groups, must be conditioned. Conditioning is generally understood to mean the transfer of a radioactive waste into a storable form.
Im Falle kerntechnischer Anlagen werden verbrauchte Ionenaustauscherharze üblicherweise getrocknet und nach einer gewissen Aufbewahrungsdauer bzw. Abklingzeit, in der die Radioaktivität auf einen vorgegebenen Grenzwert abgesunken ist, zum Zwecke der Lagerung in eine feste Matrix eingebettet, beispielsweise einzementiert. Die Einbettung der Ionenaustauscherharze in eine feste Matrix führt zu einer Volumenvermehrung um mehr als das Sechsfache des Harzvolumens. Auf Grund der großen Menge anfallenden Abfalls ergeben sich für den Betreiber eines Kernkraftwerks erhebliche Kosten für die Zwischen- oder Endlagerung. Es wurden daher Konzepte entwickelt, das Volumen der Ionenaustauscherharze zu verringern. Eines dieser Konzepte sieht eine Verbrennung vor. Dies erfordert jedoch aufwändige Filteranlagen, um einen Austritt von Radioaktivität in die Umgebung zu verhindern. Außerdem funktioniert die Verbrennung aufgrund der in den Harzen üblicherweise enthaltenen sauren oder basischen Gruppen nicht besonders gut. Als Alternative werden daher die Metalle und damit die Aktivität mit Hilfe von Säuren bzw. Laugen vollständig von den Harzen entfernt, so dass die Harze wiederverwendet werden können. Die jeweilige Säure bzw. Lauge wird über ein rein organisches, d.h. weder saure noch basische Gruppen enthaltendes und daher leichter verbrennbares Harz geleitet, welches die Metalle (und die Aktivität) adsorptiv bindet. Bei der vollständigen Regeneration der sauren oder basischen Austauscherharze fallen erhebliche Mengen an Säure/Base als Sekundärabfall an, der entsorgt werden muss.In the case of nuclear installations spent ion exchange resins are usually dried and after a certain storage period or decay time, in which the radioactivity has dropped to a predetermined limit, for the purpose of storage embedded in a solid matrix, for example, cemented. The embedding of the ion exchange resins in a solid matrix leads to an increase in volume by more than six times the volume of the resin. Due to the large amount of waste arising for the operator of a nuclear power plant considerable costs for the intermediate or final disposal. Therefore, concepts have been developed to reduce the volume of the ion exchange resins. One of these concepts provides for combustion. However, this requires complex filter systems to prevent leakage of radioactivity into the environment. In addition, the combustion does not work very well due to the acidic or basic groups commonly present in the resins. As an alternative, therefore, the metals and thus the activity with the aid of acids or alkalis are completely removed from the resins, so that the resins can be reused. The respective acid or alkali is passed over a purely organic, ie neither acidic nor basic groups containing and therefore more easily combustible resin, which binds the metals (and the activity) adsorptive. In the complete regeneration of the acidic or basic exchange resins fall considerable Amounts of acid / base secondary waste that needs to be disposed of.
Ein weiteres Konzept sieht eine vollständige Mineralisierung der Austauscherharze vor, bei der nur noch Metallsalze übrigbleiben. Bei einer solchen, beispielsweise aus
Aufgabe der Erfindung ist es, ein Verfahren zur Konditionierung kontaminierter Ionenaustauscherharze vorzuschlagen, mit dem im Vergleich zur direkten Einbettung in eine feste Matrix eine Volumenreduzierung verbunden ist und das sich mit geringem Zeit- und Materialaufwand durchführen lässt.The object of the invention is to propose a method for conditioning contaminated ion exchange resins, with which in comparison to the direct embedding in a solid matrix, a volume reduction is connected and can be carried out with little time and material.
Diese Aufgabe wird durch ein Verfahren nach Anspruch 1 gelöst, nämlich dadurch, dass das Ionenaustauscherharz mit Wasser vermischt und mit Hilfe eines dem Wasser zugesetzten Oxidationsmittels zumindest teilweise in wasserlösliche Bruchstücke zerlegt wird, wobei die entstehende wässerige Lösung mit einem Bindemittel verfestigt wird.. Die durch das Verfahren gegenüber einer Einzementierung fester Harzpartikel erzielte Volumenreduzierung besteht hauptsächlich in dem Übergang von der festen Phase, in der das Harz in Form eines voluminösen Netzwerks von Makromolekülen vorliegt, zu gelösten Bruchstücken dieses Netzwerks. Das Verfahren erfordert im Wesentlichen nicht mehr als einen Behälter zur Durchführung der HarzOxidation und allenfalls noch einen zweiten Behälter für die
Verfestigung. Das zugesetzte Oxidationsmittel bewirkt, dass das Polymer-Netzwerk des Harzes, beispielsweise eines Copolymers aus Vinylbenzol und Divinylbenzol, aufgebrochen wird, wobei wasserlösliche Bruchstücke entstehen. Die Wasserlöslichkeit ergibt sich aus an den Bruchstücken vorhandenen Säure- oder Basengruppen (z.B. Sulfonsäuregruppen bzw. Aminoethylgruppen). Um eine möglichst große Volumenreduzierung zu erreichen, wird die Oxidation vorzugsweise so lange fortgeführt, bis das gesamte oder nahezu das gesamte Harz in Lösung gegangen ist. Das Austauscherharz wird also nur so lange oxidativ behandelt, bis es vorzugsweise vollständig in Form von wasserlöslichen Bruchstücken vorliegt. Die dabei entstehende Menge an Kohlenstoffdioxid ist vergleichsweise gering. Neben Kohlenstoffdioxid kann auch noch ein geringer Anteil an Sauerstoff vorhanden sein, der im Falle der Verwendung von Wasserstoffperoxid als Oxidationsmittel durch Autoxidation entsteht. Wird die Oxidation, nachdem das Harz vollständig in Form wasserlöslicher Bruchstücke vorliegt fortgesetzt, wird der erfindungsgemäße Vorteil in zusehends geringerem Ausmaß erreicht. Erfindungsgemäß wird daher angestrebt, dass ein möglichst großer Teil des im Austauscherharz enthaltenden Kohlenstoffs in Form löslicher Molekülbruchstücke vorliegt, also nicht zu Kohlendioxid und Wasser oxidiert wird. Erfindungsgemäß ist daher ein Oxidationsgrad von weniger als 50 %, vorzugsweise von weniger als 20 % des Kohlenstoffgehaltes des Austauscherharzes vorgesehen. Die jeweils erforderliche Menge lässt sich bei Kenntnis des Kohlenstoffgehalts des Harzes und dessen chemischer Struktur berechnen. Vielfach werden entsprechende Daten des Austauscherharzes nicht zur Verfügung stehen, so dass dann die erforderliche Menge an Oxidationsmittel durch Vorversuche empirisch bestimmbar ist. Die Verfestigung erfolgt auf einfache Weise dadurch, dass die am Ende der Oxidationsbehandlung vorliegende Mischung mit wenigstens der gleichen Masse Zement verrührt wird. Neben Zement können eventuell auch andere Bindemittel wie Wasserglas verwendet werden. Gegenüber der weiter oben erwähnten direkten Einbindung des unbehandelten Ionenaustauscherharzes in Zement, bei der sich eine Volumenzunahme im Vergleich zum ursprünglichen Harz-Schüttvolumen um den Faktor 6 ergibt, wird bei erfindungsgemäßer Vorgehensweise - je nach dem vorliegenden Wasser/Harz-Verhältnis und vom Wasser/Zementwert - ein Faktor von nur 2 bis 4 erreicht. Dieser Faktor kann noch verringert werden, wenn vor der Verfestigung ein Teil des Wassers durch Verdampfen aus der Lösung entfernt wird.This object is achieved by a method according to claim 1, namely in that the ion exchange resin is mixed with water and with the aid of an oxidizing agent added to the water is at least partially decomposed into water-soluble fragments, wherein the resulting aqueous solution is solidified with a binder the method of reducing the volume of solid resin particles achieved in the reduction of volume consists mainly in the transition from the solid phase in which the resin is in the form of a bulky network of macromolecules to dissolved fragments of this network. Essentially, the process does not require more than one tank for carrying out the resin oxidation and possibly a second tank for the
Consolidation. The added oxidizing agent causes the polymer network of the resin, for example, a copolymer of vinylbenzene and divinylbenzene, to be broken to form water-soluble fragments. The water solubility results from the acid or base groups present on the fragments (eg sulfonic acid groups or aminoethyl groups). In order to achieve the largest possible reduction in volume, the oxidation is preferably continued until all or almost all of the resin has dissolved. Thus, the exchange resin is treated oxidatively only until it is preferably completely in the form of water-soluble fragments. The resulting amount of carbon dioxide is relatively low. In addition to carbon dioxide, a small proportion of oxygen may still be present, which arises in the case of the use of hydrogen peroxide as an oxidant by autoxidation. If the oxidation continues after the resin is completely in the form of water-soluble fragments, the advantage according to the invention is achieved to an appreciably lesser extent. According to the invention, it is therefore desirable that the largest possible part of the carbon contained in the exchange resin be present in the form of soluble molecular fragments, ie not oxidized to carbon dioxide and water. According to the invention therefore an oxidation degree of less than 50%, preferably less than 20% of the carbon content of the exchange resin is provided. The amount required in each case can be calculated with knowledge of the carbon content of the resin and its chemical structure. In many cases, corresponding data of the exchange resin will not be available, so that then the required amount of oxidizing agent can be empirically determined by preliminary experiments. The solidification takes place in a simple manner by the fact that at the end of the oxidation treatment present mixture is stirred with at least the same mass of cement. In addition to cement, other binders such as water glass may also be used. Compared with the above-mentioned direct involvement of the untreated ion exchange resin in cement, which results in a volume increase compared to the original resin bulk volume by a factor of 6, is in accordance with the invention - depending on the existing water / resin ratio and the water / cement value - reached a factor of only 2 to 4. This factor can be further reduced if part of the water is removed from the solution by evaporation before solidification.
Zement, beispielsweise Portlandzement, enthält meist hohe Anteile an Calciumoxid, das beim Abbindevorgang zusammen mit Silikaten mit dem Anmachwasser die Zementhärtung bewirkende Hydrate bildet. Wenn das Wasser der zu verfestigenden Mischung sauer ist, wird das Calciumoxid aufgelöst und steht für die Hydratbildung und damit für die Zementhärtung nicht mehr zur Verfügung. Um dies zu verhindern, wird bei einer bevorzugten Verfahrensvariante der Mischung eine Base zur Neutralisation von Säuren bzw. zur Anhebung des pH-Werts der Mischung zugesetzt, sodass diese am Ende schwach sauer bis basisch ist. Als Base werden vorzugsweise Erdalkalioxide und -hydroxide eingesetzt.Cement, for example Portland cement, usually contains high proportions of calcium oxide, which together with silicates with the mixing water forms cement hardening hydrates during the setting process. If the water of the mixture to be solidified is acidic, the calcium oxide is dissolved and is no longer available for hydrate formation and thus for cement hardening. In order to prevent this, in a preferred process variant of the mixture, a base is added for the neutralization of acids or for raising the pH of the mixture, so that it is slightly acidic to basic at the end. As base preferably alkaline earth oxides and hydroxides are used.
Die Oxidation der Ionenaustauscherharze kann grundsätzlich mit beliebigen Oxidationsmitteln vorgenommen werden. Vorzugsweise werden aber solche eingesetzt, die bei ihrer Reaktion mit dem Harz keine Reaktionsprodukte bilden, welche das Abbinden des Zements oder eines sonstigen Bindemittels behindern. Als Oxidationsmittel, die diese Eigenschaft haben, werden Wasserstoffperoxid und Ozon eingesetzt. Von Wasserstoffperoxid bleibt lediglich unschädliches Wasser übrig, Ozon wird zu Sauerstoff reduziert, der zum größten Teil aus der Mischung entweicht. Bei der Harzoxidation entstehen CO2 (das zum größten teil entweicht) und Wasser.The oxidation of the ion exchange resins can in principle be carried out with any desired oxidizing agents. Preferably, however, those are used which form no reaction products in their reaction with the resin, which hinder the setting of the cement or other binder. Oxidants that have this property are hydrogen peroxide and ozone were used. Hydrogen peroxide leaves only harmless water, and ozone is reduced to oxygen, which escapes for the most part from the mixture. Resin oxidation produces CO 2 (which mostly escapes) and water.
Das Verfahren wurde mit verschiedenen Harzen getestet. Dabei wurde jeweils ein vorgegebenes Harzvolumen (50 ml Schüttvolumen, kugelförmige Partikel, Durchmesser ca. ≤1mm) mit Wasser vermischt und dieser Mischung 30 prozentiges Wasserstoffperoxid (wässrige Lösung) zugegeben bzw. Ozon eingeleitet. Weitere Einzelheiten sind der folgenden Tabelle zu entnehmen:
Bei den Harzen 1 und 2 handelt es sich um relativ gering vernetztes Harz auf Polystyrolbasis mit einem Divinylbenzolanteil von etwa 4 - 6 %. Die Harze 3 und 4 sind stärker vernetzt und weisen einen Divinylbenzolanteil von etwa 8 - 12 % auf. Die Versuche haben gezeigt, dass nicht alle Harze gleichermaßen abbaubar sind. Der Zeitaufwand, um höher vernetzte Harze (Nr. 3 und 4) vollständig aufzulösen ist größer. Für die Zeitdauer ist natürlich auch die Temperatur entscheidend (siehe Versuche Nr. 1 und 2). Eine Beschleunigung der Oxidation lässt sich auch dadurch erreichen, dass das Wasserstoffperoxid in höherer Konzentration zugesetzt wird. Bei der Oxidation mit Ozon wurde dieses mit Hilfe einer Glasfritte gasförmig in die Mischung eingeleitet. Auch mit Ozon wurde eine vollständige Auflösung des Harzes 1 erreicht, wobei dafür allerdings ein Zeitraum von 60 Stunden erforderlich war. In allen Fällen wurde die Mischung nach vollständiger Auflösung der Ionenaustauscherharze mit Zement bei einem Wasser-Zement-Massenverhältnis von 0,5 verfestigt. Das Volumen des entstandenen Zementsteins betrug ca. das zwei- bis dreifache des Harz-Schüttvolumens. In allen Fällen wurde in alkalischer Lösung gearbeitet.Resins 1 and 2 are relatively low crosslinked polystyrene-based resins having a divinylbenzene content of about 4-6%. Resins 3 and 4 are more crosslinked and have a divinylbenzene content of about 8-12%. The experiments have shown that not all resins are equally degradable. The time required to fully dissolve higher crosslinked resins (Nos. 3 and 4) is greater. Of course, the temperature is also decisive for the duration (see Experiments Nos. 1 and 2). An acceleration of the oxidation can also be achieved by the hydrogen peroxide in higher concentration is added. During oxidation with ozone, it was introduced into the mixture in gaseous form with the aid of a glass frit. Even with ozone, a complete dissolution of the resin 1 was achieved, but this required a period of 60 hours. In all cases, after complete dissolution of the ion exchange resins with cement, the mixture was solidified at a water to cement mass ratio of 0.5. The volume of the resulting cement paste was about two to three times the resin bulk volume. In all cases, work was carried out in alkaline solution.
Claims (9)
- Method for conditioning a radioactively contaminated ion exchange resin, in which the latter is mixed with water and at least partly broken up into water-soluble fragments with the aid of an oxidizing agent added to the water, the resulting aqueous solution being consolidated with a binder, optionally after concentration by evaporation of water.
- Method according to Claim 1, characterized in that the binder used is cement.
- Method according to Claim 2, characterized in that a base is added to the mixture before the consolidation with cement.
- Method according to Claim 3, characterized in that the base used is an alkaline earth metal oxide or hydroxide.
- Method according to any of the preceding claims, characterized by the use of hydrogen peroxide or ozone as the oxidizing agent.
- Method according to any of the preceding claims, characterized in that the oxidation treatment is carried out at a temperature higher than room temperature.
- Method according to Claim 6, characterized in that the oxidation treatment is carried out at a temperature of from 80°C to 100°C.
- Method according to any of the preceding claims, characterized in that the amount of oxidizing agent is chosen so that less than 50% of the carbon present in the exchange resin is oxidized to carbon dioxide and water.
- Method according to any of Claims 1 to 7, characterized in that the amount of oxidizing agent is chosen so that less than 20% of the carbon present in the exchange resin is oxidized to carbon dioxide and water.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102008005336A DE102008005336A1 (en) | 2008-01-17 | 2008-01-17 | Process for conditioning radioactive ion exchange resins |
PCT/EP2009/050415 WO2009090209A1 (en) | 2008-01-17 | 2009-01-15 | Method for conditioning radioactive ion exchange resins |
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EP2248134A1 EP2248134A1 (en) | 2010-11-10 |
EP2248134B1 true EP2248134B1 (en) | 2011-06-22 |
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EP09702004A Active EP2248134B1 (en) | 2008-01-17 | 2009-01-15 | Method for conditioning radioactive ion exchange resins |
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US (1) | US8372289B2 (en) |
EP (1) | EP2248134B1 (en) |
JP (1) | JP5543926B2 (en) |
KR (1) | KR101183002B1 (en) |
AT (1) | ATE514168T1 (en) |
CA (1) | CA2711555C (en) |
DE (1) | DE102008005336A1 (en) |
ES (1) | ES2367238T3 (en) |
TW (1) | TWI442414B (en) |
WO (1) | WO2009090209A1 (en) |
Cited By (1)
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DE102018131902B3 (en) * | 2018-12-12 | 2020-02-27 | Framatome Gmbh | Process for conditioning ion exchange resins and device for carrying out the process |
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JPS5958400A (en) * | 1982-09-28 | 1984-04-04 | 日本原子力事業株式会社 | Method of volume-decreasing and solidifying radioactive ion exchanging resin |
JPS5998740A (en) * | 1982-11-30 | 1984-06-07 | Mitsui Eng & Shipbuild Co Ltd | Decomposition treatment of used ion exchange resin |
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JPH0232600B2 (en) * | 1983-03-07 | 1990-07-20 | Westinghouse Electric Corp | IONKOKANJUSHISUISEIEKIKONGOBUTSUOSEMENTOCHUNIFUNYUSURUHOHO |
SE8304278L (en) | 1983-08-04 | 1985-02-05 | Studsvik Energiteknik Ab | PROCEDURE FOR TREATMENT OF USE, RADIOACTIVE, ORGANIC ION EXCHANGE MASS |
JPS61165696A (en) * | 1985-01-18 | 1986-07-26 | 三菱重工業株式会社 | Method of treating radioactive waste |
JPS63158497A (en) * | 1986-08-20 | 1988-07-01 | 富士電機株式会社 | Decomposing processing method of radioactive ion exchange resin |
DE3926252A1 (en) * | 1989-08-09 | 1991-02-14 | Ghattas Nader Khalil | METHOD AND DEVICE FOR DEGRADING CONSUMED ION EXCHANGE RESINS |
WO1992003829A1 (en) * | 1990-08-28 | 1992-03-05 | Electric Power Research Institute | Organic material oxidation process utilizing no added catalyst |
FR2678761B1 (en) * | 1991-07-03 | 1994-07-01 | Commissariat Energie Atomique | BLOCK CONTAINING CONTAMINATED ION EXCHANGE RESINS AND PROCESS FOR PREPARING THE SAME. |
DE69220250T2 (en) * | 1992-11-04 | 1998-01-15 | Asea Atom Ab | METHOD AND DEVICE FOR TREATING AND DISPOSAL OF CONSUMED ION EXCHANGE RESIN |
JP3846820B2 (en) * | 1997-08-20 | 2006-11-15 | 株式会社東芝 | Solid waste treatment method |
JP4675521B2 (en) * | 2001-08-15 | 2011-04-27 | 日揮株式会社 | Method and apparatus for treating radioactive organic waste |
JP4414214B2 (en) * | 2003-12-24 | 2010-02-10 | 行政院原子能委員會核能研究所 | Treatment method of waste ion exchange resin |
EP1564188B1 (en) | 2004-02-13 | 2006-11-29 | Institute of Nuclear Energy Research, Atomic Energy Council | A method for processing spent ion-exchange resins |
EP1786000A1 (en) * | 2005-11-09 | 2007-05-16 | AREVA NP GmbH | Process for treatment of radioactive ion exchange resins |
-
2008
- 2008-01-17 DE DE102008005336A patent/DE102008005336A1/en not_active Withdrawn
-
2009
- 2009-01-15 WO PCT/EP2009/050415 patent/WO2009090209A1/en active Application Filing
- 2009-01-15 JP JP2010542625A patent/JP5543926B2/en not_active Expired - Fee Related
- 2009-01-15 ES ES09702004T patent/ES2367238T3/en active Active
- 2009-01-15 CA CA2711555A patent/CA2711555C/en not_active Expired - Fee Related
- 2009-01-15 KR KR1020107018247A patent/KR101183002B1/en active IP Right Grant
- 2009-01-15 AT AT09702004T patent/ATE514168T1/en active
- 2009-01-15 EP EP09702004A patent/EP2248134B1/en active Active
- 2009-01-16 TW TW098101513A patent/TWI442414B/en not_active IP Right Cessation
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102018131902B3 (en) * | 2018-12-12 | 2020-02-27 | Framatome Gmbh | Process for conditioning ion exchange resins and device for carrying out the process |
WO2020120143A1 (en) | 2018-12-12 | 2020-06-18 | Framatome Gmbh | Method for conditioning ion exchange resins and apparatus for carrying out the method |
US12033766B2 (en) | 2018-12-12 | 2024-07-09 | Framatome Gmbh | Method for conditioning ion exchange resins and apparatus for carrying out the method |
Also Published As
Publication number | Publication date |
---|---|
DE102008005336A1 (en) | 2009-07-30 |
US8372289B2 (en) | 2013-02-12 |
CA2711555C (en) | 2015-04-14 |
TW200941502A (en) | 2009-10-01 |
KR101183002B1 (en) | 2012-09-18 |
ES2367238T3 (en) | 2011-10-31 |
KR20100120155A (en) | 2010-11-12 |
US20100256435A1 (en) | 2010-10-07 |
JP5543926B2 (en) | 2014-07-09 |
ATE514168T1 (en) | 2011-07-15 |
JP2011510281A (en) | 2011-03-31 |
CA2711555A1 (en) | 2009-07-23 |
TWI442414B (en) | 2014-06-21 |
WO2009090209A1 (en) | 2009-07-23 |
EP2248134A1 (en) | 2010-11-10 |
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