EP2257949B1 - Method for conditioning a cleaning solution resulting from the wet chemical cleaning of a nuclear steam generator - Google Patents

Method for conditioning a cleaning solution resulting from the wet chemical cleaning of a nuclear steam generator Download PDF

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EP2257949B1
EP2257949B1 EP09725983.2A EP09725983A EP2257949B1 EP 2257949 B1 EP2257949 B1 EP 2257949B1 EP 09725983 A EP09725983 A EP 09725983A EP 2257949 B1 EP2257949 B1 EP 2257949B1
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cleaning solution
cleaning
cathode
conditioning
steam generator
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German (de)
French (fr)
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EP2257949A1 (en
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Rainer Gassen
Christian Topf
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Areva GmbH
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Areva GmbH
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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
    • G21F9/04—Treating liquids
    • 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
    • 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

Definitions

  • the invention relates to a method for conditioning a resulting in the wet-chemical cleaning of a nuclear steam generator cleaning solution.
  • the resulting cleaning solutions When wet-cleaning a nuclear steam generator, the resulting cleaning solutions must be disposed of. These are usually in dissolved form complexing agent, ammonium, amines and iron. The used cleaning solutions are burnt in many cases as hazardous waste. However, special disposal problems arise when the cleaning solutions contain radioactive metallic nuclides, for example Co60, in concentrations above an allowable limit. These spent cleaning solutions can therefore not be treated as normal waste, but must be conditioned for final disposal very complex and expensive and spent in special repository.
  • radioactive metallic nuclides for example Co60
  • the invention is therefore based on the object, a method for conditioning a resulting in the wet-chemical cleaning of a nuclear steam generator cleaning solution with which also the disposal of cleaning solutions contaminated with radioactive metal nuclides is economically possible.
  • the above object is achieved according to the invention by a method having the features of claim 1. Since the cleaning solution is treated electrolytically and radioactive metal nuclides contained in the cleaning solution are deposited on a cathode, it is possible to reduce the radioactive contamination of the cleaning solution so far that it is below a predetermined exemption limit. In this way, the disposal of the present in a large amount cleaning solution is considerably simplified, since only the radioactively contaminated cathode must be disposed of as radioactive waste in compliance with the respective radiation protection and disposal conditions.
  • the cathode is a diamond electrode and therefore consists of a material which has a hydrogen overvoltage and whose potential is set above the potential of hydrogen evolution, a particularly effective deposition of radioactive metallic nuclides is achieved.
  • the anode also consists of a material which has an oxygen overvoltage, preferably also a diamond electrode whose potential is below the Potential of the oxygen evolution is adjusted, the organic components in the cleaning solution, such as a complexing agent, can be denatured during electrolysis at the same time, so that almost all Fe precipitates as oxide or hydroxide. Due to the large surface area of the precipitated iron oxide or iron hydroxide, radioactive metal nuclides, for example Co60, which are still present in the solution are also adsorbed thereon and thus removed from the cleaning solution in this way. If the electrolysis time is long enough, the entire complexing agent (eg EDTA) can be destroyed.
  • a complexing agent eg EDTA
  • the COD or TOC value (chemical oxygen demand or total content of organic carbon) drops significantly in this treatment. In this way it is possible to reduce the contamination with both organic compounds and with radioactive nuclides so far that the solution can be disposed of with little effort. Only precipitate and cathode have to be disposed of as radioactive waste with a considerably lower volume.
  • a disposal of the cathode is not required, that is, their further use is possible if the deposited on their metals with an inorganic acid are removed.
  • the neutralized acid has to be disposed of together with a precipitate (FeO, Fe 2 O 3 , Fe (OH) 2 , Fe (OH) 3 ) which may be formed by destroying the complexing agents.
  • a two-stage electrolysis is carried out, in which the cleaning solution is acidified after a first electrolytic treatment and subsequently subjected to a second electrolytic treatment becomes.
  • the cleaning solution is electrolyzed without pretreatment.
  • the dissolved Fe is deposited and additionally precipitated when using an anode with oxygen overvoltage.
  • the cleaning solution pre-treated in this way is acidified and re-electrolyzed until the concentration of activity (Co60) is below a predetermined release limit. After that it can be neutralized and disposed of.
  • a simulated DE cleaning solution (1.3 l) with 10 g / l EDTA, 11.8 g / l morpholine, corresponding to a COD of 29.2 g / l, 106 mg / l Co and 2.1 g / l Fe was electrolyzed on diamond electrodes (cathode and anode). After 6 h at 1.0 A / m 2 , the cleaning solution (in the diagram of Fig.1 graphically represented by bars I) only 0.3% of the Fe and 31% of the Co. On the cathode (in the diagram of Fig.1 represented by bars II), 1.5% of the Fe and 51% of the Co were deposited. 98.2% of the Fe and 18% of the Co were in precipitation (in the diagram of the Fig.1 illustrated by the bars III) adsorbed. The EDTA was 96% decomposed, the COD value reduced by about 50%.
  • the cleaning solution treated in this way was filtered, the filtrate acidified (pH ⁇ 2) and re-electrolyzed in a subsequent treatment step for 8 h at 2.0 A / m 2 .
  • the filtrate acidified (pH ⁇ 2) was re-electrolyzed in a subsequent treatment step for 8 h at 2.0 A / m 2 .
  • the filtrate acidified (pH ⁇ 2) was re-electrolyzed in a subsequent treatment step for 8 h at 2.0 A / m 2 .
  • 6.3 mg / l Fe 6.0 mg / l were on the cathode (in the diagram of the Fig.2 graphically represented by bars II), so that now 0.28% and only 0.4 mg / l or 0.02% of the solution originally dissolved in the cleaning solution (bar I) were present on the cathode.
  • the final values of the EDTA content and the COD value were reached at 0.01 g / l and 0.16 g / l, respectively. Both the content of EDTA and the COD value were reduced by more than 99% by the combined treatment.
  • a simulated cleaning solution (1.3 l) containing 10 g / l EDTA, 11.8 g / l morpholine, corresponding to a COD of 29.2 g / l, 63 mg / l Co, and 1.96 g / l Fe was acidified in a first step to a pH of about 2 and electrolyzed for 8h at 2000 A / m 2 .
  • 92% of the originally dissolved Co and 89% of the originally dissolved Fe were deposited on the cathode.
  • the COD content in the solution was only 0.29 g / L and the content of EDTA in the solution was reduced to 0.25 g / L.
  • the Fe and Co deposited on the cathode are removed with an acid, eg sulfuric acid, the solution is then neutralized and evaporated. Otherwise, Fe and Co can be removed anodically after acidification. The resulting solution can then be neutralized with NH 3 and then likewise evaporated.
  • an acid eg sulfuric acid
  • Example 2 The advantage of such an acidic single-stage electrolysis according to Example 2 consists essentially in the fact that the steps required in Example 1, filtration and re-electrolysis omitted.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Description

Die Erfindung bezieht sich auf ein Verfahren zum Konditionieren einer bei der nasschemischen Reinigung eines nuklearen Dampferzeugers anfallenden Reinigungslösung.The invention relates to a method for conditioning a resulting in the wet-chemical cleaning of a nuclear steam generator cleaning solution.

Bei der nasschemischen Reinigung eines nuklearen Dampferzeugers müssen die dabei entstehenden Reinigungslösungen entsorgt werden. Darin befinden sich in der Regel in gelöster Form Komplexbildner, Ammonium, Amine und Eisen. Die verbrauchten Reinigungslösungen werden in vielen Fällen als Sondermüll verbrannt. Besondere Probleme bei der Entsorgung treten jedoch auf, wenn die Reinigungslösungen radioaktive metallische Nuklide, beispielsweise Co60, in Konzentrationen oberhalb einer zulässigen Freigrenze enthalten. Diese verbrauchten Reinigungslösungen können deshalb nicht als normaler Abfall behandelt werden, sondern müssen für eine abschließende Entsorgung sehr aufwändig und teuer konditioniert und in spezielle Endlager verbracht werden.When wet-cleaning a nuclear steam generator, the resulting cleaning solutions must be disposed of. These are usually in dissolved form complexing agent, ammonium, amines and iron. The used cleaning solutions are burnt in many cases as hazardous waste. However, special disposal problems arise when the cleaning solutions contain radioactive metallic nuclides, for example Co60, in concentrations above an allowable limit. These spent cleaning solutions can therefore not be treated as normal waste, but must be conditioned for final disposal very complex and expensive and spent in special repository.

Zwar ist es grundsätzlich möglich, die Inhaltsstoffe der Reinigungslösung auf Ionentauscherharze zu laden. Dies führt jedoch zu enormen radioaktiv kontaminierten Abfallvolumina.Although it is basically possible to load the ingredients of the cleaning solution on ion exchange resins. However, this leads to enormous radioactive contaminated waste volumes.

Der Erfindung liegt deshalb die Aufgabe zugrunde, ein Verfahren zur Konditionierung einer bei der nasschemischen Reinigung eines nuklearen Dampferzeugers anfallenden Reinigungslösung anzugeben, mit dem auch die Entsorgung von Reinigungslösungen wirtschaftlich möglich ist, die mit radioaktiven metallischen Nukliden kontaminiert sind.The invention is therefore based on the object, a method for conditioning a resulting in the wet-chemical cleaning of a nuclear steam generator cleaning solution with which also the disposal of cleaning solutions contaminated with radioactive metal nuclides is economically possible.

Die genannte Aufgabe wird gemäß der Erfindung gelöst mit einem Verfahren mit den Merkmalen des Patentanspruches 1. Da die Reinigungslösung elektrolytisch behandelt und in der Reinigungslösung enthaltene radioaktive metallische Nuklide an einer Kathode abgeschieden werden, ist es möglich die radioaktive Kontamination der Reinigungslösung soweit zu reduzieren, dass sie unter einer vorgegebenen Freigrenze liegt. Auf diese Weise ist die Entsorgung der in einer großen Menge vorliegenden Reinigungslösung erheblich vereinfacht, da nur die radioaktiv kontaminierte Kathode als radioaktiver Abfall unter Beachtung der jeweiligen Strahlenschutz- und Endlagerbedingungen entsorgt werden muss.The above object is achieved according to the invention by a method having the features of claim 1. Since the cleaning solution is treated electrolytically and radioactive metal nuclides contained in the cleaning solution are deposited on a cathode, it is possible to reduce the radioactive contamination of the cleaning solution so far that it is below a predetermined exemption limit. In this way, the disposal of the present in a large amount cleaning solution is considerably simplified, since only the radioactively contaminated cathode must be disposed of as radioactive waste in compliance with the respective radiation protection and disposal conditions.

Da die Kathode eine Diamantelektrode ist und demzufolge aus einem Werkstoff besteht, der eine Wasserstoffüberspannung aufweist, und deren Potential oberhalb des Potentials der Wasserstoffentwicklung eingestellt wird, wird eine besonders wirksame Abscheidung radioaktiver metallischer Nuklide erzielt.Since the cathode is a diamond electrode and therefore consists of a material which has a hydrogen overvoltage and whose potential is set above the potential of hydrogen evolution, a particularly effective deposition of radioactive metallic nuclides is achieved.

Wenn zusätzlich die Anode ebenfalls aus einem Werkstoff besteht, der eine Sauerstoffüberspannung aufweist, vorzugsweise ebenfalls eine Diamantelektrode, deren Potential unterhalb des Potentials der Sauerstoffentwicklung eingestellt wird, können bei der Elektrolyse zugleich die organischen Bestandteile in der Reinigungslösung, z.B. ein Komplexbildner, denaturiert werden, so dass nahezu das gesamte Fe als Oxid oder Hydroxid ausfällt. Auf Grund der großen Oberfläche des ausgefällten Eisenoxids oder Eisenhydroxids werden außerdem in der Lösung noch vorhandene radioaktives metallische Nuklide, beispielsweise Co60, daran adsorbiert und auch auf diese Weise aus der Reinigungslösung entfernt. Bei ausreichend langer Elektrolysezeit kann der gesamte Komplexbildner (z. B. EDTA) zerstört werden. Gleichzeitig sinkt bei dieser Behandlung der CSB- oder TOC-Wert (chemischer Sauerstoffbedarf bzw. Gesamtgehalt an organischem Kohlenstoff) deutlich ab. Auf diese Weise ist es möglich, die Kontamination sowohl mit organischen Verbindungen als auch mit radioaktiven Nukliden so weit zu reduzieren, dass die Lösung mit geringem Aufwand entsorgt werden kann. Nur noch Niederschlag und Kathode müssen dann mit erheblich geringerem Volumen als radioaktiver Abfall entsorgt werden.In addition, if the anode also consists of a material which has an oxygen overvoltage, preferably also a diamond electrode whose potential is below the Potential of the oxygen evolution is adjusted, the organic components in the cleaning solution, such as a complexing agent, can be denatured during electrolysis at the same time, so that almost all Fe precipitates as oxide or hydroxide. Due to the large surface area of the precipitated iron oxide or iron hydroxide, radioactive metal nuclides, for example Co60, which are still present in the solution are also adsorbed thereon and thus removed from the cleaning solution in this way. If the electrolysis time is long enough, the entire complexing agent (eg EDTA) can be destroyed. At the same time, the COD or TOC value (chemical oxygen demand or total content of organic carbon) drops significantly in this treatment. In this way it is possible to reduce the contamination with both organic compounds and with radioactive nuclides so far that the solution can be disposed of with little effort. Only precipitate and cathode have to be disposed of as radioactive waste with a considerably lower volume.

Eine Entsorgung der Kathode ist nicht erforderlich, d. h. deren weitere Verwendung ist möglich, wenn die auf ihr abgeschiedenen Metalle mit einer anorganischen Säure abgelöst werden. In diesem Fall muss nach Neutralisation nur noch die neutralisierte Säure gemeinsam mit einem gegebenenfalls durch Zerstören der Komplexbildner entstandenen Niederschlag (FeO, Fe2O3, Fe(OH)2, Fe(OH)3) entsorgt werden.A disposal of the cathode is not required, that is, their further use is possible if the deposited on their metals with an inorganic acid are removed. In this case, after neutralization, only the neutralized acid has to be disposed of together with a precipitate (FeO, Fe 2 O 3 , Fe (OH) 2 , Fe (OH) 3 ) which may be formed by destroying the complexing agents.

Bei hoher Konzentration an radioaktivem Co60 wird in einer vorteilhaften Ausgestaltung des Verfahrens eine zweistufige Elektrolyse durchgeführt, bei dem die Reinigungslösung nach einer ersten elektrolytischen Behandlung angesäuert wird und anschließend einer zweiten elektrolytischen Behandlung unterzogen wird. Mit anderen Worten: Zunächst wird die Reinigungslösung ohne Vorbehandlung elektrolysiert. Auf diese Weise wird das gelöste Fe abgeschieden und bei der Verwendung einer Anode mit Sauerstoffüberspannung zusätzlich ausgefällt. Nach dem Abfiltrieren wird die auf diese Weise vorbehandelte Reinigungslösung angesäuert und solange erneut elektrolysiert, bis die Konzentration an Aktivität (Co60) unter einer vorgegebenen Freigrenze ist. Danach kann sie neutralisiert und entsorgt werden.With a high concentration of radioactive Co60, in an advantageous embodiment of the method, a two-stage electrolysis is carried out, in which the cleaning solution is acidified after a first electrolytic treatment and subsequently subjected to a second electrolytic treatment becomes. In other words: First, the cleaning solution is electrolyzed without pretreatment. In this way, the dissolved Fe is deposited and additionally precipitated when using an anode with oxygen overvoltage. After filtration, the cleaning solution pre-treated in this way is acidified and re-electrolyzed until the concentration of activity (Co60) is below a predetermined release limit. After that it can be neutralized and disposed of.

Zur weiteren Erläuterung der Erfindung wird auf das nachstehenden Ausführungsbeispiele verwiesen, die zusätzlich anhand der Zeichnungen erläutert sind. Es zeigen:

  • Fig. 1 und 2 jeweils in einem Diagramm den Anteil, in dem Eisen Fe und Kobalt Co nach einstufiger bzw. zweistufiger Elektrolyse in der Reinigungslösung, auf der Elektrode und im Niederschlag vorhanden sind.
For further explanation of the invention reference is made to the following embodiments, which are additionally explained with reference to the drawings. Show it:
  • Fig. 1 and 2 in each case in a diagram the proportion in which iron Fe and cobalt Co are present after one-stage or two-stage electrolysis in the cleaning solution, on the electrode and in the precipitate.

Beispiel 1example 1

Eine simulierte DE-Reinigungslösung (1,3 1) mit 10 g/l EDTA, 11,8 g/l Morpholin, entsprechend einem CSB-Wert von 29,2 g/l, 106 mg/l Co und 2,1 g/l Fe wurde an Diamantelektroden (Kathode und Anode) elektrolysiert. Nach 6 h bei 1,0 A/m2 enthielt die Reinigungslösung (im Diagramm der Fig.1 graphisch durch die Balken I wiedergegeben) nur noch 0,3 % des Fe und 31% des Co. Auf der Kathode (im Diagramm der Fig.1 durch die Balken II veranschaulicht) wurden 1,5 % des Fe und 51 % des Co abgeschieden. 98,2 % des Fe und 18% des Co waren im Niederschlag (im Diagramm der Fig.1 durch die Balken III veranschaulicht) adsorbiert. Die EDTA war zu 96 % zersetzt, der CSB-Wert um etwa 50% reduziert.A simulated DE cleaning solution (1.3 l) with 10 g / l EDTA, 11.8 g / l morpholine, corresponding to a COD of 29.2 g / l, 106 mg / l Co and 2.1 g / l Fe was electrolyzed on diamond electrodes (cathode and anode). After 6 h at 1.0 A / m 2 , the cleaning solution (in the diagram of Fig.1 graphically represented by bars I) only 0.3% of the Fe and 31% of the Co. On the cathode (in the diagram of Fig.1 represented by bars II), 1.5% of the Fe and 51% of the Co were deposited. 98.2% of the Fe and 18% of the Co were in precipitation (in the diagram of the Fig.1 illustrated by the bars III) adsorbed. The EDTA was 96% decomposed, the COD value reduced by about 50%.

Die auf diese Weise behandelte Reinigungslösung wurde filtriert, das Filtrat angesäuert (pH ≈ 2) und in einem anschließenden Behandlungsschritt 8h bei 2,0 A/m2 erneut elektrolysiert. Von den in der Lösung verbliebenen 6,3 mg/l Fe wurden 6,0 mg/l auf der Kathode (im Diagramm der Fig.2 graphisch durch die Balken II wiedergegeben) abgeschieden, so dass auf der Kathode nunmehr 0,28% und in der Lösung nur noch 0,4 mg/l oder 0,02 % vom ursprünglich in der Reinigungslösung gelösten Fe (Balken I) vorhanden waren. Vom restlichen Co (33 mg/l bzw. 31 %) wurden 32,4 mg/l bzw. 30,4% vom ursprünglich gelösten Co auf der Kathode (Balken II) abgeschieden, so dass sich nur noch 0,6 ppm oder 0,6 % vom ursprünglich gelösten Co in der Reinigungslösung befanden.The cleaning solution treated in this way was filtered, the filtrate acidified (pH ≈ 2) and re-electrolyzed in a subsequent treatment step for 8 h at 2.0 A / m 2 . Of the remaining in the solution 6.3 mg / l Fe 6.0 mg / l were on the cathode (in the diagram of the Fig.2 graphically represented by bars II), so that now 0.28% and only 0.4 mg / l or 0.02% of the solution originally dissolved in the cleaning solution (bar I) were present on the cathode. Of the remaining Co (33 mg / l or 31%), 32.4 mg / l or 30.4% of the originally dissolved Co were deposited on the cathode (bar II), so that only 0.6 ppm or 0 , 6% of the originally dissolved Co in the cleaning solution.

Bereits nach einer Behandlungsdauer von 2h im zweiten Behandlungsschritt wurden die Endwerte des EDTA-Gehaltes und des CSB-Wertes mit 0,01 g/l bzw. 0,16 g/l erreicht. Sowohl der Gehalt an EDTA als auch der CSB-Wert wurden durch die kombinierte Behandlung um über 99% reduziert.After a treatment time of 2 h in the second treatment step, the final values of the EDTA content and the COD value were reached at 0.01 g / l and 0.16 g / l, respectively. Both the content of EDTA and the COD value were reduced by more than 99% by the combined treatment.

Beispiel 2Example 2

Eine simulierte Reinigungslösung (1,3 1) mit 10 g/l EDTA, 11,8 g/l Morpholin, entsprechend einem CSB-Wert von 29,2 g/l, 63 mg/l Co und 1,96 g/l Fe wurde in einem ersten Schritt auf einen pH-Wert von ungefähr 2 angesäuert und 8h mit 2000 A/m2 elektrolysiert. Nach Beendigung der sauren Elektrolyse waren auf der Kathode 92% des ursprünglich gelösten Co und 89% des ursprünglich gelösten Fe abgeschieden. In der Lösung befanden sich noch 5mg/l Co und 0,22g/l Fe. Der CSB-Gehalt in der Lösung betrug nur noch 0,29g/l und der Gehalt an EDTA in der Lösung war auf 0,25g/l reduziert.A simulated cleaning solution (1.3 l) containing 10 g / l EDTA, 11.8 g / l morpholine, corresponding to a COD of 29.2 g / l, 63 mg / l Co, and 1.96 g / l Fe was acidified in a first step to a pH of about 2 and electrolyzed for 8h at 2000 A / m 2 . Upon completion of acid electrolysis, 92% of the originally dissolved Co and 89% of the originally dissolved Fe were deposited on the cathode. In the solution were still 5mg / l Co and 0.22g / l Fe. The COD content in the solution was only 0.29 g / L and the content of EDTA in the solution was reduced to 0.25 g / L.

Im Falle einer radioaktiven Kontamination wird das auf der Kathode abgeschiedene Fe und Co mit einer Säure, z.B. Schwefelsäure abgelöst, die Lösung anschließend neutralisiert und eingedampft. Andernfalls können Fe und Co nach vorherigem Ansäuern anodisch abgelöst werden. Die entstehende Lösung kann dann mit NH3 neutralisiert und anschließend ebenfalls eingedampft werden.In the case of radioactive contamination, the Fe and Co deposited on the cathode are removed with an acid, eg sulfuric acid, the solution is then neutralized and evaporated. Otherwise, Fe and Co can be removed anodically after acidification. The resulting solution can then be neutralized with NH 3 and then likewise evaporated.

Der Vorteil einer solchen sauren einstufigen Elektrolyse nach Beispiel 2 besteht im wesentlichen darin, dass die in Beispiel 1 erforderlichen Stufen, Filtration und erneute Elektrolyse, entfallen.The advantage of such an acidic single-stage electrolysis according to Example 2 consists essentially in the fact that the steps required in Example 1, filtration and re-electrolysis omitted.

Claims (5)

  1. Method for conditioning a cleaning solution resulting from the wet chemical cleaning of a nuclear steam generator, wherein the cleaning solution is treated electrolytically and radioactive, metallic nuclides contained in the cleaning solution are deposited on a cathode, wherein the cathode is a diamond electrode, the potential of which is adjusted above the potential of hydrogen evolution.
  2. Method according to claim 1, wherein the metals deposited on the cathode are displaced with an acid.
  3. Method according to claim 1 or 2, wherein the cleaning solution is acidified after the electrolytic treatment and is then treated electrolytically again.
  4. Method according to one of the preceding claims, wherein the anode consists of a material having an oxygen surplus, and wherein the potential of the anode is adjusted below the potential of oxygen evolution.
  5. Method according to claim 4, wherein the anode is a diamond electrode.
EP09725983.2A 2008-03-28 2009-03-20 Method for conditioning a cleaning solution resulting from the wet chemical cleaning of a nuclear steam generator Active EP2257949B1 (en)

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DE102008016020A DE102008016020A1 (en) 2008-03-28 2008-03-28 A method of conditioning a cleaning solution resulting from the wet-chemical cleaning of a nuclear steam generator
PCT/EP2009/053329 WO2009118277A1 (en) 2008-03-28 2009-03-20 Method for conditioning a cleaning solution resulting from the wet chemical cleaning of a nuclear steam generator

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CN112144066B (en) * 2020-09-30 2022-03-25 西安热工研究院有限公司 Chemical cleaning agent and cleaning method for secondary loop steam system of high-temperature gas cooled reactor nuclear power unit

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5851977A (en) * 1981-09-25 1983-03-26 Hitachi Ltd Regeneration of chemical decontaminating liquid
JPS6093999A (en) * 1983-10-28 1985-05-25 日立プラント建設株式会社 Method of treating chemically decontaminated waste liquor
JPH0631858B2 (en) * 1984-09-26 1994-04-27 株式会社東芝 Method for separating metal ions in solution
JPS61194398A (en) * 1985-02-23 1986-08-28 株式会社東芝 Decontaminator for material to be treated contaminated by radioactivity
JPS61231496A (en) * 1985-04-05 1986-10-15 日立プラント建設株式会社 Method of decontaminating radioactive metallic waste
JPS6336198A (en) * 1986-07-29 1988-02-16 株式会社東芝 Method of processing radioactive waste liquor
US4861444A (en) * 1988-09-06 1989-08-29 Schoessow Glen J Process for treating radioactive material to make it safe for disposal
JPH02171695A (en) * 1988-12-26 1990-07-03 Toshiba Corp Treatment of radioactive waste liquid
US5122268A (en) * 1989-08-11 1992-06-16 Westinghouse Electric Corp. Apparatus for waste disposal of radioactive hazardous waste
JPH0438499A (en) * 1990-06-04 1992-02-07 Toshiba Corp Treatment of decontamination waste liquid
JP2713828B2 (en) * 1992-01-14 1998-02-16 動力炉・核燃料開発事業団 Method for recovering valuable metals from nuclear fuel reprocessing solution
FR2690270A1 (en) * 1992-04-21 1993-10-22 Framatome Sa Enclosure for separation and containment of radioactive products contained in liquid effluents and installation and method for the treatment of these effluents.
JPH05341098A (en) * 1992-06-11 1993-12-24 Mitsubishi Heavy Ind Ltd Processing method for secondary side chemical rinsing solution of steam generator
FR2717459B1 (en) * 1994-03-16 1996-04-12 Commissariat Energie Atomique Method and installation for destroying organic solutes, in particular complexing agents, present in an aqueous solution such as a radioactive effluent.
FR2736631B1 (en) * 1995-07-11 1997-10-10 Framatome Sa PROCESS FOR THE ELECTROLYSIS TREATMENT OF A LIQUID EFFLUENT CONTAINING DISSOLVED METALS AND APPLICATION TO THE TREATMENT OF EFFLUENTS CONTAINING CERIUM
JPH10104396A (en) * 1996-10-02 1998-04-24 Toshiba Corp Method and device for chemical decontamination
GB2319040B (en) * 1996-11-08 2000-07-12 Aea Technology Plc Radioactive effluent treatment
FR2761085B1 (en) * 1997-03-24 1999-04-16 Commissariat Energie Atomique ELECTROLYTIC PROCESS FOR RECOVERING AND RECYCLING MONEY FROM A NITRIC SOLUTION
DE19842396A1 (en) * 1998-09-16 2000-04-13 Fraunhofer Ges Forschung Electrically-conductive diamond layer forming electrode for electrochemical generation of ozone and ultra-pure water
US6149797A (en) * 1998-10-27 2000-11-21 Eastman Kodak Company Method of metal recovery using electrochemical cell
DE10005681B4 (en) * 2000-02-07 2005-06-16 Atc Dr. Mann E.K. Method and device for the decontamination of metal-containing waters
US6682646B2 (en) * 2002-03-25 2004-01-27 Electric Power Research Institute Electrochemical process for decontamination of radioactive materials
JP2004321963A (en) * 2003-04-25 2004-11-18 Kurita Water Ind Ltd Treating method of nitrate nitrogen-containing water

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EP2257949A1 (en) 2010-12-08
TW200945369A (en) 2009-11-01
JP2011515687A (en) 2011-05-19
DE102008016020A1 (en) 2009-10-01
WO2009118277A1 (en) 2009-10-01
ES2411932T3 (en) 2013-07-09
US20100252449A1 (en) 2010-10-07
JP5343121B2 (en) 2013-11-13
KR20100077014A (en) 2010-07-06

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