EP0160831A2 - Process for chemically decontaminating metallic parts of nuclear reactor plants - Google Patents

Process for chemically decontaminating metallic parts of nuclear reactor plants Download PDF

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Publication number
EP0160831A2
EP0160831A2 EP85103900A EP85103900A EP0160831A2 EP 0160831 A2 EP0160831 A2 EP 0160831A2 EP 85103900 A EP85103900 A EP 85103900A EP 85103900 A EP85103900 A EP 85103900A EP 0160831 A2 EP0160831 A2 EP 0160831A2
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Prior art keywords
dicarboxylic acids
nuclear reactor
permanganic acid
treatment
acid
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German (de)
French (fr)
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EP0160831A3 (en
EP0160831B1 (en
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Horst-Otto Bertholdt
Hans Dipl.-Ing. Hirning
Rudolf Papesch
Hubert Dipl.-Ing. Stamm
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Siemens AG
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Kraftwerk Union AG
Siemens AG
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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
    • G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
    • G21F9/002—Decontamination of the surface of objects with chemical or electrochemical processes
    • G21F9/004—Decontamination of the surface of objects with chemical or electrochemical processes of metallic surfaces

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  • the invention relates to a process for the chemical decontamination of metallic components of nuclear reactor plants, in which an oxidative treatment with a permanganate solution is carried out before dicarboxylic acids are used for further treatment.
  • an alkaline permanganate solution at a temperature of about 100 ° C. is used for the oxidative treatment. It is then rinsed out with deionate before continuing with a citrate oxalate solution which is adjusted to a pH of 3.5 with ammonia and which contains an inhibitor and ethylenediaminetetraacetic acid.
  • the inhibitor is iron III formate.
  • the known method with its individual stages and the rinsing steps in between works with high chemical concentrations and is relatively time-consuming. It has also not yet been used for primary systems of nuclear reactors which would have to be practically emptied for this purpose and which would have to be refilled after the treatment.
  • the invention is therefore based on the object of reducing the dose burden on inspection and repair personnel by chemical decontamination of the primary system To enable nuclear reactors or parts thereof, which can be carried out with less effort. As an important secondary condition, it should be ensured that chemical decontamination results in only a small amount of secondary waste, which in turn must be eliminated in a radiation-safe manner.
  • permanganic acid is used for the oxidative treatment. As has been found, this can be used for the same effect with significantly lower concentrations and, moreover, it can be achieved that the subsequent treatment with dicarboxylic acids also requires much smaller amounts of acid, so that there is correspondingly less secondary waste. Above all, however, the treatment can be carried out by introducing the permanganic acid into the primary coolant of a water-cooled nuclear reactor. It is therefore no longer necessary to drain the primary coolant. Rather, the new process can be carried out in such a way that the primary coolant is cleaned by ion exchange resins and remains in the nuclear reactor for further operation.
  • the permanganic acid is advantageously produced by converting potassium permanganate. This can be done by withdrawing potassium using an ion exchanger. The conversion can take place outside the system to be treated in special containers, but also during the decontamination of entire primary circuits with the auxiliary systems available in the nuclear power plant (such as primary coolant cleaning). The permanganic acid is then in a concentration range of 20 to 400 mg / kg.
  • An advantageous development of the invention consists in that a mixture with an oxalic acid content of at most 1/3 is used as the dicarboxylic acids.
  • Dicarboxylic acids with a chain length of C 3 and hydroxidicarboxylic acids can be used as further dicarboxylic acids of the mixture.
  • the dicarboxylic acids are introduced directly into the permanganic acid solution, especially for cleaning primary circuits. This saves the usual rinsing processes and the draining and discarding or processing of the permanganate solution.
  • 1 shows the primary cooling circuit of a pressurized water reactor that is to be decontaminated, and the auxiliary power plants required for this purpose.
  • 2 shows the time course of the decontamination treatment for a first cycle.
  • the pressurized water reactor comprises a reactor pressure vessel 2, a steam generator 3 and a main coolant pump 4. This promotes this from the reactor pressure vessel 2 via the hot line 5 in the primary cooling water reaching the steam generator 3 via the cold strand 6 back into the reactor pressure vessel 2.
  • a volume control system 8 is used to treat the primary cooling water. It is connected to the cold line 6 in the area between the pump 4 and the steam generator 3 with an outlet line 10. It runs via a recuperative heat exchanger 12 and a cooler 13 to a shut-off valve 14. This is followed by control valves 15, 16 and 17 which lead to a storage tank 18. The coolant can be conveyed back from the storage tank 18 into the primary circuit 1 via a high-pressure feed pump 20. The cooled and cleaned primary coolant passes through the recuperative heat exchanger 12 before it returns to the cold line 6 via the line 21 behind the pump 4.
  • Devices for coolant treatment are located parallel to valves 15 to 17. They include an indicated with 24 coolant cleaning as well as a gasification g ühlstoffent- 25. For the ingestion of large amounts of refrigerant is provided a coolant storage 26th The devices 24 to 26, like a coolant preparation 27, are connected to an exhaust gas system 28, which receives the gaseous activity carriers that occur during the coolant treatment.
  • boron is removed from the coolant, which is used for combustion control.
  • the boron and the boron-free deionate can be fed to a boric acid and deionate feed 30, which is connected to the volume control system 8 via a line 31 sen, into which a chemical feed 32 also feeds.
  • the liquid waste produced in the coolant cleaning can be passed on to a treatment plant 35 for radioactive waste water, which is followed by the treatment of radioactive concentrates indicated at 36.
  • the temperature in the primary system is reduced to 60 60 ° C. and the dicarboxylic acid mixture is introduced directly into the permanganic acid solution.
  • dicarboxylic acids or hydroxidicarboxylic acids which are entered up to a concentration of 300 mg / kg in the primary coolant, as shown by curve part 41, and further 100 mg / kg parts of oxalic acid, as curve part 42 is intended to show .
  • dicarboxylic acids are mesoxalic acid, malonic acid and dihydroxyfumaric acid and dihydroxy tartaric acid are used.
  • the HMnP 4 and MnO 2 present in the system react with the oxalic acid and are reduced to Mn ++ ions.
  • the oxalic acid is oxidized to C0 2 , the C0 2 being removed via the degasser.
  • the contents of the primary circuit are heated to 100 ° C again. Parts of the primary coolant are then shunted over ion exchange filters that are part of the coolant cleaning 24 or coolant preparation 27, so that the facilities already present in the power plant are used.
  • the chemical concentration can be reduced to practically zero (curve 44).
  • the manganese content originating from the oxidative conversion is reduced, as indicated by the dashed curve part 45.
  • the components of the oxide layer are also filtered out. This happens after the curve 46, which represents the content of iron, chromium, nickel and possibly cobalt.
  • the withdrawal of the cations and the dicarboxylic acid via the ion exchanger is controlled in such a way that the dicarboxylic acid is present in excess, equivalent to the dissolved cations. This is crucial in order to prevent the activity from failing again.

Abstract

Bei Verfahren zur chemischen Dekontamination von metallischen Bauteilen von Kernreaktoranlagen erfolgt eine oxidative Behandlung mit einer Permanganatlösung, bevor mit Dicarbonsäuren gebeizt wird. Erfindungsgemäß wird zur oxidativen Behandlung Permangansäure verwendet, die vorzugsweise durch Umwandlung von Kaliumpermanganat hergestellt wird. Bei Leichtwasserreaktoren kann die Permangansäure vorteilhaft direkt in das Primärkühlmittel eingegeben werden. Danach können in das angesäuerte Primärkühlmittel unmittelbar Dicarbonsäuren eingegeben werden, das dann durch Ionenaustauscherharze gereinigt wird und im Kernreaktor verbleibt.In processes for the chemical decontamination of metallic components in nuclear reactor plants, an oxidative treatment with a permanganate solution takes place before pickling with dicarboxylic acids. According to the invention, permanganic acid is used for the oxidative treatment, which is preferably produced by converting potassium permanganate. In light water reactors, the permanganic acid can advantageously be introduced directly into the primary coolant. Thereafter, dicarboxylic acids can be added directly to the acidified primary coolant, which is then cleaned by ion exchange resins and remains in the nuclear reactor.

Description

Die Erfindung betrifft ein Verfahren zur chemischen Dekontamination von metallischen Bauteilen von Kernreaktoranlagen, bei dem zunächst eine oxidative Behandlung mit einer Permanganatlösung erfolgt, bevor zur weiteren Behandlung Dicarbonsäuren eingesetzt werden.The invention relates to a process for the chemical decontamination of metallic components of nuclear reactor plants, in which an oxidative treatment with a permanganate solution is carried out before dicarboxylic acids are used for further treatment.

Bei dem aus der-DE-PS 26 13 351 bekannten und in der Praxis bewährten Verfahren wird zur oxidativen Behandlung eine alkalische Permanganatlösung bei einer Temperatur von etwa 1000C eingesetzt. Sie wird anschließend mit Deionat ausgespült, bevor dann mit einer Citrat-Oxalat-Lösung weitergearbeitet wird, die mit Ammoniak auf einen pH-Wert von 3,5 eingestellt wird und die einen Inhibitor sowie Äthylendiamintetraessigsäure enthält. Der Inhibitor ist Eisen-III-Formiat.In the process known from DE-PS 26 13 351 and proven in practice, an alkaline permanganate solution at a temperature of about 100 ° C. is used for the oxidative treatment. It is then rinsed out with deionate before continuing with a citrate oxalate solution which is adjusted to a pH of 3.5 with ammonia and which contains an inhibitor and ethylenediaminetetraacetic acid. The inhibitor is iron III formate.

Das bekannte Verfahren mit seinen einzelnen Stufen und den dazwischen liegenden Spülgängen arbeitet mit hohen Chemikalien-Konzentrationen und ist relativ zeitaufwendig. Es ist auch noch nicht für Primärsysteme von Kernreaktoren angewendet worden, die für diesen Zweck praktisch entleert werden müßten und nach der Behandlung wieder zu füllen wären. Deshalb geht die Erfindung von der Aufgabe aus, eine Absenkung der Dosisbelastung von Inspektions- und Reparaturpersonal durch eine chemische Dekontamination des Primärsystems von Kernreaktoren bzw. von Teilen davon zu ermöglichen, die mit geringerem Aufwand durchgeführt werden kann. Dabei soll als wichtige Nebenbedingung gewährleistet sein, daß bei der chemischen Dekontamination nur wenig Sekundärabfall entsteht, der wiederum strahlungssicher beseitigt werden muß.The known method with its individual stages and the rinsing steps in between works with high chemical concentrations and is relatively time-consuming. It has also not yet been used for primary systems of nuclear reactors which would have to be practically emptied for this purpose and which would have to be refilled after the treatment. The invention is therefore based on the object of reducing the dose burden on inspection and repair personnel by chemical decontamination of the primary system To enable nuclear reactors or parts thereof, which can be carried out with less effort. As an important secondary condition, it should be ensured that chemical decontamination results in only a small amount of secondary waste, which in turn must be eliminated in a radiation-safe manner.

Erfindungsgemäß wird zur oxidativen Behandlung Permangansäure verwendet. Damit kann man, wie gefunden wurde, für den gleichen Effekt mit wesentlich geringeren Konzentrationen auskommen und außerdem erreichen, daB auch die anschließende Behandlung mit Dicarbonsäuren mit viel kleineren Säuremengen auskommt, so daB auch entsprechend weniger Sekundärabfall entsteht. Vor allem aber kann die Behandlung so erfolgen, daß die Permangansäure in das PrimärkUhlmittel eines wassergekühlten Kernreaktors eingegeben wird. Ein Ablassen des Primärkühlmittels ist also nicht mehr erforderlich. Das neue Verfahren kann vielmehr so ausgeführt werden, daß das Primärkühimittel durch Ionenaustauscherharze gereinigt wird und für den weiteren Betrieb im Kernreaktor verbleibt.According to the invention, permanganic acid is used for the oxidative treatment. As has been found, this can be used for the same effect with significantly lower concentrations and, moreover, it can be achieved that the subsequent treatment with dicarboxylic acids also requires much smaller amounts of acid, so that there is correspondingly less secondary waste. Above all, however, the treatment can be carried out by introducing the permanganic acid into the primary coolant of a water-cooled nuclear reactor. It is therefore no longer necessary to drain the primary coolant. Rather, the new process can be carried out in such a way that the primary coolant is cleaned by ion exchange resins and remains in the nuclear reactor for further operation.

Die Permangansäure wird vorteilhaft durch Umwandlung von Kaliumpermanganat hergestellt. Dies kann durch Entzug von Kalium mittels Ionenaustauscher erfolgen. Die Umwandlung kann hierbei außerhalb des zu behandelnden Systems in besonderen Behältern, aber auch während der Dekontamination ganzer Primärkreise mit den im Kernkraftwerk vorhandenen Hilfssystemen (wie Primärkuhlmittelreinigung) erfolgen. Die Permangansäure liegt dann in einem Konzentrationsbereich von 20 bis 400 mg/kg vor.The permanganic acid is advantageously produced by converting potassium permanganate. This can be done by withdrawing potassium using an ion exchanger. The conversion can take place outside the system to be treated in special containers, but also during the decontamination of entire primary circuits with the auxiliary systems available in the nuclear power plant (such as primary coolant cleaning). The permanganic acid is then in a concentration range of 20 to 400 mg / kg.

Eine vorteilhafte Weiterbildung der Erfindung besteht darin, daß als Dicarbonsäuren ein Gemisch mit einem Oxalsäureanteil von höchstens 1/3 verwendet wird. Dabei können als weitere Dicarbonsäuren des Gemisches Dicarbonsäuren mit einer Kettenlänge von C 3 und Hydroxidicarbonsäuren verwendet werden. Die Dicarbonsäuren werden insbesondere zur Reinigung von Primärkreisen unmittelbar in die Permangansäurelösung eingegeben. Man erspart damit die bisher üblichen Spülvorgänge und das Ablassen und Verwerfen oder Aufarbeiten der Permanganatlösung.An advantageous development of the invention consists in that a mixture with an oxalic acid content of at most 1/3 is used as the dicarboxylic acids. Dicarboxylic acids with a chain length of C 3 and hydroxidicarboxylic acids can be used as further dicarboxylic acids of the mixture. The dicarboxylic acids are introduced directly into the permanganic acid solution, especially for cleaning primary circuits. This saves the usual rinsing processes and the draining and discarding or processing of the permanganate solution.

Mit dem vorstehend geschilderten Verfahren ergibt sich eine gegenüber dem Bekannten vielfach geringere Chemikalien-Konzentration. Damit ist auch die Gefahr eines unerwünschten Angriffs auf die Grundmaterialien der zu dekontaminierenden Bauteile entsprechend verringert. Die geringere Chemikalien-Konzentration führt darüber hinaus zu geringeren Mengen an Sekundärabfall. Dennoch erreicht man hohe Dekontaminationsfaktoren. Zwischen-und Endspülschritte können ganz entfallen.The process described above results in a chemical concentration that is often lower than that known. This also reduces the risk of an undesirable attack on the base materials of the components to be decontaminated. The lower concentration of chemicals also leads to lower amounts of secondary waste. Nevertheless, high decontamination factors are achieved. Intermediate and final rinsing steps can be dispensed with entirely.

Zur näheren Erläuterung der Erfindung wird im folgenden anhand der beiliegenden Zeichnung ein Ausführungsbeispiel beschrieben. Dabei zeigt die Fig. 1 den Primärkühlkreis eines Druckwasserreaktors, der dekontaminiert werden soll, und die dazu benötigten kraftwerkseigenen Hilfseinrichtungen. In Fig. 2 ist der zeitliche Verlauf der Dekontaminationsbehandlung für einen ersten Zyklus dargestellt.For a more detailed explanation of the invention, an embodiment is described below with reference to the accompanying drawings. 1 shows the primary cooling circuit of a pressurized water reactor that is to be decontaminated, and the auxiliary power plants required for this purpose. 2 shows the time course of the decontamination treatment for a first cycle.

Der Druckwasserreaktor umfaßt mit seinem Primärkreis 1 einen Reaktordruckbehälter 2, einen Dampferzeuger 3 und eine Hauptkühlmittelpumpe 4. Diese fördert das aus dem Reaktordruckbehälter 2 über den heißen Strang 5 in den Dampferzeuger 3 gelangende Primärkühlwasser über den kalten Strang 6 in den Reaktordruckbehälter 2 zurück.With its primary circuit 1, the pressurized water reactor comprises a reactor pressure vessel 2, a steam generator 3 and a main coolant pump 4. This promotes this from the reactor pressure vessel 2 via the hot line 5 in the primary cooling water reaching the steam generator 3 via the cold strand 6 back into the reactor pressure vessel 2.

Zur Behandlung des PrimärkUhlwassers dient ein Volumenregelsystem 8. Es ist an den kalten Strang 6 im Bereich zwischen der Pumpe 4 und dem Dampferzeuger 3 mit einer Auslaßleitung 10 angeschlossen. Sie verläuft über einen Rekuperativ-Wärmetauscher 12 und einen Kühler 13 zu einem Absperrventil 14. Daran schließen sich Stellventile 15, 16 und 17 an, die zu einem Speicherbehälter 18 führen. Aus dem Speicherbehälter 18 kann das Kühlmittel über eine Hochdruckeinspeisepumpe 20 in den Primärkreis 1 zurückgefördert werden. Dabei passiert das abgekühlte und gereinigte Primärkühlmittel den Rekuperativ-Wärmetauscher 12, bevor es über die Leitung 21 hinter der Pumpe 4 in den kalten Strang 6 zurück gelangt.A volume control system 8 is used to treat the primary cooling water. It is connected to the cold line 6 in the area between the pump 4 and the steam generator 3 with an outlet line 10. It runs via a recuperative heat exchanger 12 and a cooler 13 to a shut-off valve 14. This is followed by control valves 15, 16 and 17 which lead to a storage tank 18. The coolant can be conveyed back from the storage tank 18 into the primary circuit 1 via a high-pressure feed pump 20. The cooled and cleaned primary coolant passes through the recuperative heat exchanger 12 before it returns to the cold line 6 via the line 21 behind the pump 4.

Parallel zu den Ventilen 15 bis 17 liegen Einrichtungen zur Kühlmittelbehandlung. Sie umfassen eine mit 24 angedeutete Kühlmittelreinigung sowie eine gühlmittelent- gasung 25. Für die Aufnahme größerer Kühlmittelmengen ist eine Kühlmittellagerung 26 vorgesehen. Die Einrichtungen 24 bis 26 sind ebenso wie eine Kühlmittelaufbereituug 27 an ein Abgassystem 28 angeschlossen, das die bei der Kühlmittelbehandlung anfallenden gasförmigen Aktivitätsträger aufnimmt.Devices for coolant treatment are located parallel to valves 15 to 17. They include an indicated with 24 coolant cleaning as well as a gasification g ühlmittelent- 25. For the ingestion of large amounts of refrigerant is provided a coolant storage 26th The devices 24 to 26, like a coolant preparation 27, are connected to an exhaust gas system 28, which receives the gaseous activity carriers that occur during the coolant treatment.

Mit der Kühlmittelaufbereitung 27 wird dem Kühlmittel Bor entzogen, das zur Abbrandregelung verwendet wird. Das Bor und das borfreie Deionat kann einer Borsäure-und Deionateinspeisung 30 zugeführt werden, die über eine Deitung 31 an das Volumenregelsystem 8 angeschlossen ist, in die auch eine Chemikalien-Einspeisung 32 einspeist.With the coolant preparation 27, boron is removed from the coolant, which is used for combustion control. The boron and the boron-free deionate can be fed to a boric acid and deionate feed 30, which is connected to the volume control system 8 via a line 31 sen, into which a chemical feed 32 also feeds.

Die in der Kühlmittelreinigung entstehenden flüssigen Abfälle können zu einer Behandlungsanlage 35 für radioaktive Abwässer weitergeleitet werden, an die sich die bei 36 angedeutete Behandlung radioaktiver Konzentrate anschließt.The liquid waste produced in the coolant cleaning can be passed on to a treatment plant 35 for radioactive waste water, which is followed by the treatment of radioactive concentrates indicated at 36.

Zu einer Dekontamination des Primärkreises 1 ergibt sich folgender verfahrenstechnischer Ablauf mit einzelnen Schritten:

  • 1.1. Primärkreis 1 mit Hauptkühlmittelpumpe 4 in Betrieb, Temperatur~90°C p≈30 bar, Borkonzentration im Primärkühlmittel 2200 mg/kg.
  • 1.2. Ansetzen der HMnO4-Lösung im Borsäureansetzbehälter der Borsäure- und Deionateinspeisung 30.
  • 1.3. Zudosieren von HMn04 im Primärkühlmittel bis zu einer Konzentration von~ 50 mg/kg.
  • 1.4. Erhöhen der Temperatur des Primärkreises 1 auf 100°C.
  • 1.5. Oxidationsbehandlung durch Umwälzen mit Hauptkühlmittelpumpe 4, 5 Stunden.
  • 1.6. Absenken der Temperatur auf 50 - 60°C.
  • 1.7. Ansetzen der Dicarbonsäuremischung zum Beispiel im Borsäureansetzbehälter der Borsäure- und Deionateinspeisung 30.
  • 1.8. Zudosierung der Dicarbonsäuren, Entgasung 25 ist mit maximaler Leistung im Betrieb.
  • 1.9. Endkonzentration ca. 300 - 400 mg/kg für die Summe der Dicarbonsäuren.
  • 2.0. Erhöhen der Temperatur des Primärkreises 1 auf 100°C.
  • 2.1. Inbetriebnahme der Kühlmittelreinigung 24.
  • 2.2. Entfernen der gelösten Kationen (Aktivität) sowie der Dicarbonsäuren mittels Anionen/Kationentauscher.
  • 2.3. Primärkühlmittel gereinigt.
  • 2.4. Bei Bedarf Wiederholung des Vorganges 1.2. - 2.3. (2. Zyklus).
  • 2.5. Bei Bedarf Wiederholung des Vorganges 1.2. - 2.3. (3. Zyklus).
Decontamination of primary circuit 1 results in the following procedural sequence with individual steps:
  • 1.1. Primary circuit 1 with main coolant pump 4 in operation, temperature ~ 90 ° C p≈30 bar, boron concentration in the primary coolant 2200 mg / kg.
  • 1.2. Prepare the HMnO 4 solution in the boric acid preparation container of the boric acid and deionate feed 30.
  • 1.3. Dosing of HMn0 4 in the primary coolant up to a concentration of ~ 50 mg / kg.
  • 1.4. Increase the temperature of the primary circuit 1 to 100 ° C.
  • 1.5. Oxidation treatment by circulation with main coolant pump 4.5 hours.
  • 1.6. Lowering the temperature to 50 - 60 ° C.
  • 1.7. Preparation of the dicarboxylic acid mixture, for example in the boric acid preparation container of the boric acid and deionate feed 30.
  • 1.8. Dosage of the dicarboxylic acids, degassing 25 is in operation at maximum output.
  • 1.9. Final concentration approx. 300 - 400 mg / kg for the sum of the dicarboxylic acids.
  • 2.0. Increase the temperature of the primary circuit 1 to 100 ° C.
  • 2.1. Commissioning of coolant cleaning 24.
  • 2.2. Removing the dissolved cations (activity) and the dicarboxylic acids using anions / cation exchangers.
  • 2.3. Primary coolant cleaned.
  • 2.4. Repeat the process if necessary 1.2. - 2.3. (2nd cycle).
  • 2.5. Repeat the process if necessary 1.2. - 2.3. (3rd cycle).

In Fig. 2 ist für einen einzelnen Zyklus die Chemikalien-Konzentration auf der Ordinate in ppm dargestellt. Die Abszisse ist die Zeitachse mit einem Höchstwert von 20 Stunden.2 shows the chemical concentration on the ordinate in ppm for a single cycle. The abscissa is the timeline with a maximum of 20 hours.

Ausgehend von einer im Zeitpunkt T1 durch ZufUhren von Permangansäure in den Primärkreis beginnenden Permanganatkonzentration von 50 ppm erfolgt eine oxidative Behandlung, die zu einer Auflockerung des Gefüges der die Kontamination verursachenden Oxidschicht führt. Dieser Vorgang ist durch den Kurvenzug 38 angedeutet. Er zeigt eine schwach abnehmende Konzentration an MnO4- und einen mit dem gestrichelten Kurvenzug 39 angedeuteten Anstieg des MnO2-Gehalts.Starting from a permanganate concentration of 50 ppm starting at time T 1 by feeding permanganic acid into the primary circuit, an oxidative treatment takes place which leads to a loosening of the structure of the oxide layer causing the contamination. This process is indicated by the curve 38. It shows a weakly decreasing concentration of MnO 4 - and an increase in the MnO 2 content indicated by the dashed curve 39.

Nach 5 Stunden wird im Zeitpunkt T2 die Temperatur im Primärsystem auf ≤ 600C abgesenkt und die Dicarbonsäuremischung unmittelbar in die Permangansäurelösung eingegeben. Dabei handelt es sich um Dicarbonsäuren bzw. Hydroxidicarbonsäuren, die bis zu einer Konzentration von 300 mg/kg im Primärkuhlmittel eingegeben werden, wie durch den Kurventeil 41 gezeichnet ist, sowie um weitere 100 mg/kg-Anteile Oxalsäure, wie der Kurventeil 42 zeigen soll. Als Dicarbonsäuren werden zum Beispiel Mesoxalsäure, Malonsäure, Dihydroxyfumarsäure und Dihydroxyweinsäure verwendet. Bei der Zugabe reagiert das im System vorhandene HMnP4 und MnO2 mit der Oxalsäure und wird zu Mn++-Ionen reduziert. Die Oxalsäure wird dabei zu C02 oxidiert, wobei das C02 über den Entgaser abgeführt wird.After 5 hours, at time T 2, the temperature in the primary system is reduced to 60 60 ° C. and the dicarboxylic acid mixture is introduced directly into the permanganic acid solution. These are dicarboxylic acids or hydroxidicarboxylic acids, which are entered up to a concentration of 300 mg / kg in the primary coolant, as shown by curve part 41, and further 100 mg / kg parts of oxalic acid, as curve part 42 is intended to show . Examples of dicarboxylic acids are mesoxalic acid, malonic acid and dihydroxyfumaric acid and dihydroxy tartaric acid are used. When added, the HMnP 4 and MnO 2 present in the system react with the oxalic acid and are reduced to Mn ++ ions. The oxalic acid is oxidized to C0 2 , the C0 2 being removed via the degasser.

Nach Ablauf der HMna4-Oxalsäurereaktion wird der Inhalt des Primärkreises wieder auf 100°C erwärmt. Teile des Primärkühlmittels werden dann im Nebenschluß über Ionenaustauscherfilter gefahren, die Teil der Kühlmittelreinigung 24 bzw. Kühlmittelaufbereitung 27 sind, so daß dabei die im Kraftwerk bereits vorhandenen Einrichtungen benutzt werden. Im Lauf von 20 Stunden bis zum Zeitpunkt T3 kann dabei die Chemikalien-Konzentration auf praktisch Null abgefahren werden (Kurvenzug 44). Dabei verringert sich der aus der oxidativen Umsetzung stammende Mangangehalt, wie durch den gestrichelten Kurventeil 45 angedeutet ist. Zugleich werden aber auch die Bestandteile der Oxidschicht ausgefiltert. Dies geschieht nach dem Kurvenzug 46, der den Gehalt an Eisen, Chrom, Nickel und gegebenenfalls Kobalt darstellt. Der Entzug der Kationen und der Dicarbonsäure über die Ionenaustauscher wird hierbei so gesteuert, daß die Dicarbonsäure äquivalent zu den gelösten Kationen im Überschuß vorliegt. Dies ist entscheidend, um ein Wiederausfällen der gelösten Aktivität zu vermeiden.After the HMna 4 oxalic acid reaction has ended, the contents of the primary circuit are heated to 100 ° C again. Parts of the primary coolant are then shunted over ion exchange filters that are part of the coolant cleaning 24 or coolant preparation 27, so that the facilities already present in the power plant are used. In the course of 20 hours until time T 3 , the chemical concentration can be reduced to practically zero (curve 44). The manganese content originating from the oxidative conversion is reduced, as indicated by the dashed curve part 45. At the same time, however, the components of the oxide layer are also filtered out. This happens after the curve 46, which represents the content of iron, chromium, nickel and possibly cobalt. The withdrawal of the cations and the dicarboxylic acid via the ion exchanger is controlled in such a way that the dicarboxylic acid is present in excess, equivalent to the dissolved cations. This is crucial in order to prevent the activity from failing again.

9 Patentansprüche 2 Figuren9 claims 2 figures

Claims (9)

1. Verfahren zur chemischen Dekontamination von metallischen Bauteilen von Kernreaktoranlagen, bei dem zunächst eine oxidative Behandlung mit einer Peruanganatlösung erfolgt, bevor zur weiteren Behandlung Dicarbonsäuren eingesetzt werden, dadurch gekennzeichnet, daß zur oxidativen Behandlung Permangansäure verwendet wird.1. A process for the chemical decontamination of metallic components of nuclear reactor plants, in which an oxidative treatment with a peruanganate solution is carried out before dicarboxylic acids are used for further treatment, characterized in that permanganic acid is used for the oxidative treatment. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Permangansäure durch Umwandlung von Permanganatsalzen zum Beispiel aus Kaliumpermanganat hergestellt wird.2. The method according to claim 1, characterized in that the permanganic acid is prepared by converting permanganate salts, for example from potassium permanganate. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Umwandlung sowohl außerhalb der zu dekontaminierenden Bauteile als auch während der Behandlung im System erfolgt.3. The method according to claim 2, characterized in that the conversion takes place both outside the components to be decontaminated and during the treatment in the system. 4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Permangansäure in einm Konzentrationsbereich von 20 bis 400 mg/kg verwendet wird.4. The method according to claim 3, characterized in that the permanganic acid is used in a concentration range from 20 to 400 mg / kg. 5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß ein Gemisch aus Dicarbonsäuren mit einem Oxalsäureanteil von höchstens 1/3 verwendet wird.5. The method according to any one of claims 1 to 4, characterized in that a mixture of dicarboxylic acids with an oxalic acid content of at most 1/3 is used. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß als weitere Dicarbonsäuren des Gemisches sowohl Hydroxidicarbonsäuren als auch höherkettige Dicarbonsäuren verwendet werden.6. The method according to claim 5, characterized in that both hydroxidicarboxylic acids and higher-chain dicarboxylic acids are used as further dicarboxylic acids of the mixture. 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Dicarbonsäuren unmittelbar in die Permangansäure-Lösung eingegeben werden.7. The method according to any one of claims 1 to 6, characterized in that the dicarboxylic acids are entered directly into the permanganic acid solution. 8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Permangansäure in das Primärkühlmittel eines wassergekühlten Kernreaktors eingegeben wird.8. The method according to any one of claims 1 to 7, characterized in that the permanganic acid is introduced into the primary coolant of a water-cooled nuclear reactor. 9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Primärkühlmittel durch Ionenaustauscherharze gereinigt wird und für den weiteren Betrieb im Kernreaktor verbleibt.9. The method according to claim 8, characterized in that the primary coolant is cleaned by ion exchange resins and remains in the nuclear reactor for further operation.
EP85103900A 1984-04-12 1985-04-01 Process for chemically decontaminating metallic parts of nuclear reactor plants Expired - Lifetime EP0160831B1 (en)

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CN107170503A (en) * 2017-06-02 2017-09-15 苏州热工研究院有限公司 It is a kind of to reduce the chemical cleaning method of in-service PWR nuclear power plant collective dose

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BE1002593A3 (en) * 1988-11-09 1991-04-02 Lemmens Godfried Method for decontamination of radioactively contaminated material
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CN107170503A (en) * 2017-06-02 2017-09-15 苏州热工研究院有限公司 It is a kind of to reduce the chemical cleaning method of in-service PWR nuclear power plant collective dose
CN107170503B (en) * 2017-06-02 2019-04-02 苏州热工研究院有限公司 A kind of chemical cleaning method reducing in-service PWR nuclear power plant collective dose

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FI84118B (en) 1991-06-28
JPH0310919B2 (en) 1991-02-14
FI850780L (en) 1985-10-13
ES8702726A1 (en) 1986-12-16
JPS60235099A (en) 1985-11-21
CA1254113A (en) 1989-05-16
EP0160831B1 (en) 1991-12-04
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DE3584790D1 (en) 1992-01-16
US4756768A (en) 1988-07-12

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