EP2399262B1 - Method for decontaminating radioactively contaminated surfaces - Google Patents
Method for decontaminating radioactively contaminated surfaces Download PDFInfo
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- EP2399262B1 EP2399262B1 EP10709987A EP10709987A EP2399262B1 EP 2399262 B1 EP2399262 B1 EP 2399262B1 EP 10709987 A EP10709987 A EP 10709987A EP 10709987 A EP10709987 A EP 10709987A EP 2399262 B1 EP2399262 B1 EP 2399262B1
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- treatment solution
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- decontamination
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- 238000011282 treatment Methods 0.000 claims description 52
- 238000005202 decontamination Methods 0.000 claims description 38
- 230000003588 decontaminative effect Effects 0.000 claims description 35
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 2
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- GUTLYIVDDKVIGB-BJUDXGSMSA-N cobalt-58 Chemical compound [58Co] GUTLYIVDDKVIGB-BJUDXGSMSA-N 0.000 description 1
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- IIRVGTWONXBBAW-UHFFFAOYSA-M disodium;dioxido(oxo)phosphanium Chemical compound [Na+].[Na+].[O-][P+]([O-])=O IIRVGTWONXBBAW-UHFFFAOYSA-M 0.000 description 1
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- FTMKAMVLFVRZQX-UHFFFAOYSA-N octadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCP(O)(O)=O FTMKAMVLFVRZQX-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
-
- 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
-
- 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
Definitions
- the invention relates to a method for the decontamination of radioactively contaminated surfaces of nuclear installations.
- a nuclear power plant which is hereinafter referred to by way of example
- the surfaces of components of the coolant system are exposed to up to about 350 ° C hot water as a coolant in power operation, even classified as corrosion-free CrNi steels and Ni alloys in some Extent be oxidized.
- an oxide layer is formed, which contains oxygen ions and metal ions.
- metal ions in dissolved form or as a constituent of oxide particles pass from the oxide layer into the cooling water and are transported by it to the reactor pressure vessel in which fuel elements are located. Due to the nuclear reactions taking place in the fuel elements, neutron radiation is generated which converts part of the metal ions into radioactive elements. For example, the nickel of the above-mentioned materials produces radioactive cobalt-58.
- the nuclear reactions taking place in the nuclear fuel give rise to alpha-emitting transuranic substances such as Am-241, for example, which leak into the coolant as oxides due to leaks of the fuel rods that receive the nuclear fuel.
- the radioactive elements are distributed by the circulating cooling water in the primary circuit and deposit on the oxide layer of component surfaces, such as on the surfaces of the tubes of the coolant system again or be incorporated into the oxide layer.
- the radioactive elements With increasing operating time increases the amount of deposited and / or incorporated radioactive nuclides and, accordingly, the radioactive radiation in the environment of the systems and components of the primary circuit. If you want to reduce this, such as in the case of decommissioning of a nuclear power plant, essentially all the contaminated oxide layer must be removed by means of a decontamination measure.
- the removal of the oxide layer on component surfaces is carried out, for example, by bringing the component surfaces into contact with a treatment solution containing an organic acid, in the case of a coolant system this being done by filling it with said solution.
- the organic acid is one which forms water-soluble complex compounds with the metal ions present in the oxide layer.
- the alloy that makes up a component contains chromium.
- an oxide layer present on the component contains hardly soluble chromium-III oxides.
- the surfaces are treated with a strong oxidizing agent such as potassium permanganate or permanganic acid prior to the said acid treatment.
- the spent cleaning solution containing the components of the oxide layer in dissolved form is either evaporated to a residual amount or passed through ion exchangers. In the latter case, the constituents of the oxide layer present in ionic form are retained by the ion exchanger and thus removed from the cleaning solution.
- the ion exchange material loaded with the partially radioactive ionic constituents and the residual amount of the cleaning solution remaining on evaporation are respectively supplied in suitable form to an intermediate or final storage.
- Such a routine such as in the course of maintenance work on the coolant system performed decontamination treatment essentially only gamma radiation emitting nuclides such as Cr-51 and Co-60 are recorded.
- These nuclides are to a large extent, for example incorporated in an oxide layer of a component, in the form of their oxides, which are relatively easily dissolved by the active substances of conventional decontamination solutions, for example of complexing acids.
- the oxides of the transuranic elements, such as the Am-241 already mentioned above, are less soluble than the oxides formed from the metals and their radioactive nuclides.
- oxide particles that are not visible to the naked eye therefore, in comparison with the original oxide layer of the components, enriched with alpha emitters.
- the particles in question only adhere loosely to the component surface, so that they can be wiped off, for example, in the course of a wipe test with a cloth.
- the components of the coolant system to be supplied to a recycling or at least can be handled without complex protective measures.
- the in question adhering to the component surfaces particles can easily peel off and get into the human body via the respiratory tract, which can only be prevented by very complex respiratory protection measures.
- the measured at a component Radioactivity with regard to gamma and beta radiation as well as with regard to alpha radiation must therefore remain below specified limits, so that the components are no longer subject to the restrictions of radiation protection.
- a practical problem accompanying any surface decontamination is the further treatment or disposal of the spent decontamination solution containing the radioactive constituents of the detached oxide layer.
- a feasible way is to pass a spent decontamination solution through an ion exchanger to remove charged components contained therein.
- the object underlying the invention is to liberate a surface of radioactive particles with the aid of an active component present in aqueous solution, in such a way that the particles are easily removable from the solution.
- the surfactants mentioned on the one hand in particular metal oxide particles with high efficiency, especially from metallic surfaces can replace and that the particles together with the surfactant an anion exchanger or a mixed-bed ion exchanger, a combination of anion and cation exchanger adhere. If, as is to be striven for, a solution is used which, apart from at least one surfactant, contains no further chemical substances, a particularly simple disposal is ensured after the decontamination has been carried out, since there is no decomposition of the further substances, for example with the aid of UV light, or their removal with the aid of an ion exchanger, which would require an additional amount to be disposed of ion-immersion resin, is required. Further advantageous embodiments are given in the dependent claims.
- the sample material used for the following examples or experiments comes from dismantled components of the primary coolant circuit of a German pressurized water reactor. These are cut coupons made of niobium-stabilized stainless steel, material number 1.4551, which have an oxide layer on their surface, which contains radioactive elements, as usual for components of the coolant system of nuclear power plants. The coupons were pretreated using a standard decontamination procedure.
- the samples were processed on a laboratory scale in borosilicate glasses with a capacity of between 500 ml and 2 l. Samples were suspended in the treatment solution in borosilicate glass hanger, stainless steel 1.4551, stainless steel ANSI 316, or PTFE. The heating to the test temperature was carried out by means of electric heating plates. The temperature was adjusted with contact thermometers and kept constant. The mixing of the solution was carried out by using magnetic or mechanical stirrers.
- the measurement of alpha radiation requires a relatively high effort. In contrast, the determination of the gamma activity is much simpler and faster, and even more precise.
- the gamma-ray-based activity of the americium isotope 241 was therefore recorded as an indicator of the behavior of alpha-emitting actinides or transurans.
- Table 1 compares by way of example the development of the activity of Am-241 determined by gamma radiation detectors on one of the described samples with the activity of the isotopes Pu-240, Cm-242 and Am-241 detected with alpha radiation detectors in the untreated state (No. 1) Decontamination with conventional decontamination methods (No. 2) and with a decontamination method in which an active component according to the invention according to this invention was used in various concentrations (Nos. 3, 4, 5). For a comparison To facilitate the removal of activity, in addition to the measured values obtained in Bq / cm 2 , the percentage values relative to the starting quantity are also shown.
- the minimum temperature for the effectiveness of the active ingredient component or a surfactant thereof from the group consisting of sulfonic acid, phosphonic acid and carboxylic acid is inter alia dependent on the structure (eg length) of the non-polar part of the surfactant and is due to the so-called "Krafft temperature". Below this temperature, the interactions between non-polar parts can not be overcome; the active substance remains in solution as an aggregate. In the case of use octadecylphosphonic acid as active ingredient is the minimum temperature for an effective effect eg 75 ° C. The upper limit is usually dependent on process parameters. For example, it is not desirable for the treatment solution to boil. A common application temperature of decontamination treatments under atmospheric pressure is therefore for example 80-95 ° C or 90-95 ° C.
- the effectiveness of the proposed surfactants also depends on the nature of their polar portion.
- the various proposed drug components are comparable (they have a non-polar part through which they interact with each other, and a polar part through which the molecules of the drug are mutually localized and through which the interaction of the drug with polar, charged or ionized particles or surfaces is made possible)
- there are differences in the chemical properties between different functional groups which are responsible for a different effect also in the area of the decontamination in question here. These differences can be seen by comparing a selection of drug components that have different polar functional groups but identical non-polar parts.
- the effectiveness of the active component is determined not only by its polar, but also by its non-polar part, in particular by its length or chain length.
- the size or length of the non-polar parts influences the interactions between the surfactant molecules due to van der Waals forces, whereas larger non-polar parts produce greater interaction forces with comparable structure.
- this has the consequence that more molecules can be accommodated in the second layer of the bilayer which is not in contact with the surface. This increases The charge density in this layer, which leads to higher interactions with water and higher Coulomb repulsion forces. The mobilization of the activity is thereby favored.
- the inventive method is preferably for the decontamination of components of the coolant system of a nuclear power plant (see attached Fig. 1 ) used.
- a more or less thick oxide layer builds up on the surfaces of such components, which, as already mentioned, is radioactively contaminated.
- the oxide layer is removed as completely as possible.
- the component surfaces are then treated with a solution containing at least one anionic surfactant from the group of sulfonic acids, phosphonic acids, carboxylic acids and their salts. It is particularly noteworthy that, apart from the surfactant, no further chemical additives are required, ie it is preferably carried out with an aqueous solution containing exclusively at least one surfactant from said group.
- the second treatment stage is carried out at a temperature above room temperature, that is above about 25 ° C temperature, but operating below 100 ° C, in order to reduce evaporation and thus a loss of water. Preference is given to operating at temperatures of more than 50 ° C, with the best results being achieved at temperatures of more than 80 ° C.
- the pH of the treatment solution in the second treatment stage is in principle variable. Thus, it is conceivable to accept the pH which results from the surfactant present in the solution. If the surfactant is an acid, it will have a pH in the acidic range to adjust. The best results, especially when using a Phosphonklaivates as a surfactant are achieved in a pH range of 3 to 9.
- the concentration of the active component, ie a surfactant of the type in question in the second treatment solution is 0.1 g / l to 10 g / l. Below 0.1 g / l, a reduction in the alpha contamination of the component surface does not take place to a significant extent. Above 10 g / l, an increase in the decontamination factor is barely to be observed, so that concentrations in excess of the stated value are virtually ineffective. A very good compromise between the amount of surfactant used and the decontamination efficiency is achieved at surfactant concentrations up to 3 g / l.
- the first treatment solution is largely freed from the substances contained in it, ie a decontamination acid used for the purpose of detaching the oxide layer present on a component surface and metal ions originating from the oxide layer.
- a decontamination acid used for the purpose of detaching the oxide layer present on a component surface and metal ions originating from the oxide layer.
- the treatment solution is irradiated with UV light, whereby the acid is decomposed into carbon dioxide and water.
- the in the spent decontamination solution contained metal ions are removed by passing the solution through an ion exchanger.
- Fig. 1 is shown schematically the coolant system of a boiling water reactor. It comprises, in addition to the pressure vessel 1, in which at least in operation a plurality of fuel elements 2 are present, a conduit system 3, which is connected via nozzles 4.5 to the pressure vessel 1, and various internals such as capacitors, the internals in their entirety through the box 6 in Fig. 1 are symbolized.
- a treatment solution which contains, for example, a complex-forming organic acid.
- such an decontamination step is preceded by an oxidation step in order, as already mentioned, to oxidize chromium III present in the oxide layer located on the inner surfaces 7 of the components to form chromium VI.
- an oxidation step in order, as already mentioned, to oxidize chromium III present in the oxide layer located on the inner surfaces 7 of the components to form chromium VI.
- the entire cooling system is filled, otherwise only parts, for example only a portion of the power system, can be treated.
- the resulting treatment solution is dosed with a surfactant, preferably phosphonic acid or phosphonic acid salt, and the second treatment stage is carried out ,
Description
Die Erfindung betrifft ein Verfahren zur Dekontamination radioaktiv kontaminierter Oberflächen von Nuklearanlagen. Im Falle eines Kernkraftwerkes, auf das im folgenden exemplarisch Bezug genommen wird, werden im Leistungsbetrieb die Oberflächen von Bauteilen des Kühlmittelsystems mit bis zu etwa 350°C heißem Wasser als Kühlmittel beaufschlagt, wobei selbst als korrosionsfrei eingestufte CrNi-Stähle und Ni-Legierungen in gewissem Ausmaß oxidiert werden. Auf den Bauteiloberflächen bildet sich eine Oxidschicht, die Sauerstoffionen und Metallionen enthält.The invention relates to a method for the decontamination of radioactively contaminated surfaces of nuclear installations. In the case of a nuclear power plant, which is hereinafter referred to by way of example, the surfaces of components of the coolant system are exposed to up to about 350 ° C hot water as a coolant in power operation, even classified as corrosion-free CrNi steels and Ni alloys in some Extent be oxidized. On the component surfaces, an oxide layer is formed, which contains oxygen ions and metal ions.
Während des Reaktorbetriebs gelangen aus der Oxidschicht Metallionen in gelöster Form oder als Bestandteil von Oxidpartikeln in das Kühlwasser und werden von diesem zum Reaktordruckbehälter transportiert, in dem sich Brennelemente befinden. Aufgrund der in den Brennelementen ablaufenden Kernreaktionen entsteht Neutronenstrahlung, die einen Teil der Metallionen in radioaktive Elemente umwandelt. Beispielsweise entsteht aus dem Nickel der o.g. Werkstoffe radioaktives Cobalt-58. Bei den im Kernbrennstoff ablaufenden Kernreaktionen entstehen alphastrahlende Transurane wie beispielsweise Am-241, wobei diese über Leckagen der den Kernbrennstoff aufnehmenden Brennstäbe als Oxide in das Kühlmittel gelangen. Die radioaktiven Elemente werden durch das zirkulierende Kühlwasser im Primärkreis verteilt und lagern sich auf der Oxidschicht von Bauteiloberflächen, etwa auf den Oberflächen der Rohre des Kühlmittelsystems wieder ab oder werden in die Oxidschicht eingebaut. Mit zunehmender Betriebsdauer nimmt die Menge der abgelagerten und/oder inkorporierten radioaktiven Nuklide und dementsprechend die radioaktive Strahlung im Umfeld der Systeme und Komponenten des Primärkreises zu. Will man diese, etwa im Falle des Rückbaus eines Kernkraftwerks, reduzieren, muss mittels einer Dekontaminationsmaßnahme im Wesentlichen die gesamte kontaminierte Oxidschicht entfernt werden.During the reactor operation, metal ions in dissolved form or as a constituent of oxide particles pass from the oxide layer into the cooling water and are transported by it to the reactor pressure vessel in which fuel elements are located. Due to the nuclear reactions taking place in the fuel elements, neutron radiation is generated which converts part of the metal ions into radioactive elements. For example, the nickel of the above-mentioned materials produces radioactive cobalt-58. The nuclear reactions taking place in the nuclear fuel give rise to alpha-emitting transuranic substances such as Am-241, for example, which leak into the coolant as oxides due to leaks of the fuel rods that receive the nuclear fuel. The radioactive elements are distributed by the circulating cooling water in the primary circuit and deposit on the oxide layer of component surfaces, such as on the surfaces of the tubes of the coolant system again or be incorporated into the oxide layer. With increasing operating time increases the amount of deposited and / or incorporated radioactive nuclides and, accordingly, the radioactive radiation in the environment of the systems and components of the primary circuit. If you want to reduce this, such as in the case of decommissioning of a nuclear power plant, essentially all the contaminated oxide layer must be removed by means of a decontamination measure.
Aus der
Die Entfernung der Oxidschicht auf Komponentenoberflächen erfolgt beispielsweise dadurch, dass die Bauteiloberflächen mit einer eine organische Säure enthaltenden Behandlungslösung in Kontakt gebracht werden, wobei dies im Falle eines Kühlmittelsystems dadurch geschieht, dass dieses mit der genannten Lösung gefüllt wird. Bei der organischen Säure handelt es sich um eine solche, die mit den in der Oxidschicht vorhandenden Metallionen wasserlösliche Komplexverbindungen bildet. In manchen Fällen enthält die Legierung, aus der ein Bauteil besteht, Chrom. In einem solchen Fall enthält eine auf dem Bauteil vorhandene Oxidschicht schwer lösliche Chrom-III-Oxide. Um diese in eine lösliche Form zu überführen, werden die Oberflächen vor der genannten Säurebehandlung mit einem starken Oxidationsmittel wie Kaliumpermanganat oder Permangansäure behandelt. Die Chrom-III-Oxide werden dabei in leichter lösliche Chrom-VI-Oxide umgewandelt. Unabhängig davon, ob eine oxidative Vorbehandlung erfolgt oder nicht wird die die Bestandteile der Oxidschicht in gelöster Form enthaltende verbrauchte Reinigungslösung entweder auf eine Restmenge eingedampft oder über Ionentauscher geleitet. In letzterem Fall werden die in ionischer Form vorliegenden Bestandteile der Oxidschicht von dem Ionenaustauscher zurück gehalten und somit aus der Reinigungslösung entfernt. Das mit den teilweise radioaktiven ionischen Bestandteilen beladene Ionentauschermaterial und die beim Eindampfen zurückbleibende Restmenge der Reinigungslösung werden jeweils in geeigneter Form einem Zwischen- oder Endlager zugeführt.The removal of the oxide layer on component surfaces is carried out, for example, by bringing the component surfaces into contact with a treatment solution containing an organic acid, in the case of a coolant system this being done by filling it with said solution. The organic acid is one which forms water-soluble complex compounds with the metal ions present in the oxide layer. In some cases, the alloy that makes up a component contains chromium. In such a case, an oxide layer present on the component contains hardly soluble chromium-III oxides. To convert them to a soluble form, the surfaces are treated with a strong oxidizing agent such as potassium permanganate or permanganic acid prior to the said acid treatment. The chromium-III oxides are thereby converted into more soluble chromium-VI-oxides. Regardless of whether an oxidative pretreatment takes place or not, the spent cleaning solution containing the components of the oxide layer in dissolved form is either evaporated to a residual amount or passed through ion exchangers. In the latter case, the constituents of the oxide layer present in ionic form are retained by the ion exchanger and thus removed from the cleaning solution. The ion exchange material loaded with the partially radioactive ionic constituents and the residual amount of the cleaning solution remaining on evaporation are respectively supplied in suitable form to an intermediate or final storage.
Bei einer solchen, etwa im Zuge von Revisionsarbeiten am Kühlmittelsystem routinemäßig durchgeführten Dekontaminationsbehandlung werden im Wesentlichen nur Gamma-Strahlung aussendende Nuklide wie Cr-51 und Co-60 erfasst. Diese Nuklide liegen zum großen Teil, beispielsweise inkorporiert in einer Oxidschicht einer Komponente, in Form ihrer Oxide vor, wobei diese von den Wirksubstanzen herkömmlicher Dekontaminationslösungen, beispielsweise von komplexierenden Säuren relativ leicht aufgelöst werden. Die Oxide der Transurane, wie beispielsweise das weiter oben schon erwähnte Am-241, sind schwerer löslich als die aus den Metallen und deren radioaktiven Nukliden gebildeten Oxide. Am Ende einer Dekontaminationsbehandlung vorhandene und vor allem an bereits von einer Oxidschicht befreiten Bauteiloberflächen haftende Oxidpartikel, die mit dem bloßen Auge nicht sichtbar sind, sind daher im Vergleich mit der ursprünglichen Oxidschicht der Bauteile, angereichert mit Alphastrahlern. Die in Rede stehenden Partikel haften nur lose an der Komponentenoberfläche, so dass sie sich etwa im Zuge eines Wischtests mit einem Tuch teilweise abwischen lassen.Such a routine, such as in the course of maintenance work on the coolant system performed decontamination treatment essentially only gamma radiation emitting nuclides such as Cr-51 and Co-60 are recorded. These nuclides are to a large extent, for example incorporated in an oxide layer of a component, in the form of their oxides, which are relatively easily dissolved by the active substances of conventional decontamination solutions, for example of complexing acids. The oxides of the transuranic elements, such as the Am-241 already mentioned above, are less soluble than the oxides formed from the metals and their radioactive nuclides. At the end of a decontamination treatment existing and especially on already freed from an oxide layer component surfaces oxide particles that are not visible to the naked eye, therefore, in comparison with the original oxide layer of the components, enriched with alpha emitters. The particles in question only adhere loosely to the component surface, so that they can be wiped off, for example, in the course of a wipe test with a cloth.
Beispielsweise beim Rückbau einer kerntechnischen Anlage sollen die Komponenten des Kühlmittelsystems einer Wiederverwertung zugeführt werden oder jedenfalls ohne aufwändige Schutzmaßnahmen gehandhabt werden können. Die in Rede stehenden an den Bauteiloberflächen haftenden Partikel können sich leicht ablösen und über die Atemwege in den menschlichen Körper gelangen, was nur durch sehr aufwändige Atemschutzmaßnahmen verhindert werden kann. Die an einer Komponente gemessene Radioaktivität hinsichtlich der Gamma- und Betastrahlung sowie hinsichtlich der Alphastrahlung muss daher unterhalb vorgegebener Grenzwerte bleiben, damit die Bauteile nicht mehr den Beschränkungen des Strahlenschutzes unterliegen.For example, when dismantling a nuclear facility, the components of the coolant system to be supplied to a recycling or at least can be handled without complex protective measures. The in question adhering to the component surfaces particles can easily peel off and get into the human body via the respiratory tract, which can only be prevented by very complex respiratory protection measures. The measured at a component Radioactivity with regard to gamma and beta radiation as well as with regard to alpha radiation must therefore remain below specified limits, so that the components are no longer subject to the restrictions of radiation protection.
Eine praktisch jede Oberflächendekontamination begleitende Problemstellung ist die Weiterbehandlung bzw. Entsorgung der die radioaktiven Bestandteile der abgelösten Oxidschicht enthaltenden verbrauchten Dekontaminationslösung. Wie weiter oben bereits erwähnt, besteht ein gangbarer Weg darin, eine verbrauchte Dekontaminationslösung über einen Ionentauscher zu leiten, um darin enthaltende geladene Bestandteile zu entfernen.A practical problem accompanying any surface decontamination is the further treatment or disposal of the spent decontamination solution containing the radioactive constituents of the detached oxide layer. As already mentioned above, a feasible way is to pass a spent decontamination solution through an ion exchanger to remove charged components contained therein.
Davon ausgehend besteht die der Erfindung zugrunde liegende Aufgabe darin, eine Oberfläche von radioaktiven Partikeln mit Hilfe einer in wässeriger Lösung vorliegenden Wirkkomponente zu befreien, und zwar derart, dass die Partikel auf einfache Weise aus der Lösung entfernbar sind.On this basis, the object underlying the invention is to liberate a surface of radioactive particles with the aid of an active component present in aqueous solution, in such a way that the particles are easily removable from the solution.
Diese Aufgabe wird durch Anspruch 1 gelöst, unter anderem dadurch dass die Oberfläche mit einer wässerigen Lösung behandelt wird, die eine Wirkkomponente zur Entfernung von an der Oberfläche haftenden Partikeln enthält, wobei die Wirkkomponente von wenigstens einem anionischen Tensid aus der Sulfonsäuren, Phos-phonsäuren, Carbonsäuren und Salze dieser Säuren enthaltenden Gruppe gebildet ist.This object is achieved by claim 1, inter alia, by treating the surface with an aqueous solution containing an active component for removing surface-adhering particles, the active component of at least one anionic surfactant being selected from sulfonic acids, phosphonic acids, Carboxylic acids and salts of these acids containing group is formed.
Es hat sich überraschenderweise herausgestellt, dass die genannten Tenside zum einen insbesondere Metalloxid-Partikel mit hohem Wirkungsgrad vor allem von metallischen Oberflächen ablösen kann und dass die Partikel zusammen mit dem Tensid an einem Anionentauscher oder einem Mischbett-Ionentauscher, eine Kombination aus Anionen- und Kationentauscher, haften. Wenn, was anzustreben ist, eine Lösung verwendet wird, die außer wenigstens einem Tensid keine weiteren chemischen Substanzen enthält, ist nach der Durchführung der Dekontamination eine besonders einfache Entsorgung gewährleistet, da weder eine Zersetzung der weiteren Substanzen etwa mit Hilfe von UV-Licht, noch deren Entfernung mit Hilfe eines Ionentauschers, was eine zusätzliche Menge an zu entsorgendem Ionentaucherharz bedingen würde, erforderlich ist. Weitere vorteilhafte Ausgestaltungen sind in den Unteransprüchen wiedergegeben.It has surprisingly been found that the surfactants mentioned on the one hand in particular metal oxide particles with high efficiency, especially from metallic surfaces can replace and that the particles together with the surfactant an anion exchanger or a mixed-bed ion exchanger, a combination of anion and cation exchanger adhere. If, as is to be striven for, a solution is used which, apart from at least one surfactant, contains no further chemical substances, a particularly simple disposal is ensured after the decontamination has been carried out, since there is no decomposition of the further substances, for example with the aid of UV light, or their removal with the aid of an ion exchanger, which would require an additional amount to be disposed of ion-immersion resin, is required. Further advantageous embodiments are given in the dependent claims.
Die Erfindung wird im Folgenden näher erläutert.The invention will be explained in more detail below.
Das verwendete Probenmaterial für die folgenden Beispiele bzw. Versuche stammt aus ausgebauten Bauteilen des Primärkühlmittelkreislaufes eines deutschen Druckwasserreaktors. Es handelt sich um geschnittene Coupons aus Niob-stabilisiertem Edelstahl, Werkstoffnummer 1.4551, die eine bei Bauteilen des Kühlmittelsystems von Kernkraftwerken übliche Oxidschicht auf ihrer Oberfläche aufweisen, die radioaktive Elemente enthält. Die Coupons wurden mit einem üblichen Dekontaminationsverfahren vorbehandelt.The sample material used for the following examples or experiments comes from dismantled components of the primary coolant circuit of a German pressurized water reactor. These are cut coupons made of niobium-stabilized stainless steel, material number 1.4551, which have an oxide layer on their surface, which contains radioactive elements, as usual for components of the coolant system of nuclear power plants. The coupons were pretreated using a standard decontamination procedure.
Die Behandlung der Proben erfolgte im Labormaßstab in Borosilikatgläsern mit einer Kapazität zwischen 500 ml und 2 1. Die Proben wurden in die Behandlungslösung eingehängt, in Hängevorrichtungen aus Borosilikatglas, Edelstahl 1.4551, Edelstahl ANSI 316, oder PTFE. Das Erhitzen auf die Versuchstemperatur erfolgte mit Hilfe von elektrischen Heizplatten. Die Temperatur wurde mit Kontaktthermometern eingestellt und konstant gehalten. Die Durchmischung der Lösung erfolgte durch Einsatz von magnetischen oder mechanischen Rührern.The samples were processed on a laboratory scale in borosilicate glasses with a capacity of between 500 ml and 2 l. Samples were suspended in the treatment solution in borosilicate glass hanger, stainless steel 1.4551, stainless steel ANSI 316, or PTFE. The heating to the test temperature was carried out by means of electric heating plates. The temperature was adjusted with contact thermometers and kept constant. The mixing of the solution was carried out by using magnetic or mechanical stirrers.
Die Messung der auf den Proben vorhandenen Radioaktivität wurde in einem radiochemischen Labor durchgeführt, akkreditiert nach DIN EN ISO/IEC 17025:2005 (Deutsches Akkreditierungssystem Prüfwesen GmbH, Deutscher Akkreditierungsrat (DAR), Akkreditierungsurkunde Nr. DAP-PL-3500.81).The measurement of the radioactivity present on the samples was carried out in a radiochemical laboratory, accredited to DIN EN ISO / IEC 17025: 2005 (German Accreditation System for Testing GmbH, German Accreditation Council (DAR), Accreditation Certificate No. DAP-PL-3500.81).
Für die bessere Lesbarkeit der Ergebnisse wurde die Anzahl von Stellen hinter dem Komma begrenzt, für Berechnungen von z.B. Dekontaminationsfaktoren wurden die kompletten nicht abgerundeten Werte verwendet.For better readability of the results, the number of digits after the decimal point has been limited, for calculations of e.g. Decontamination factors were used the complete non-rounded values.
Repräsentativität der Messung von Am-241 für das Verhalten der alpha-strahlenden Actinoiden Pu, Am, Cm:Representativeness of the Am-241 measurement for the behavior of the alpha-emitting actinides Pu, Am, Cm:
Die Messung von Alphastrahlung erfordert einen relativ hohen Aufwand. Wesentlich einfacher und schneller sowie darüber hinaus auch noch präziser ist dagegen die Bestimmung der Gamma-Aktivität. Als Indikator für das Verhalten der Alphastrahlung aussendenden Actinoide bzw. Transurane wurde daher die auf Gammastrahlung basierende Aktivität des Americium-Isotops 241 erfasst.The measurement of alpha radiation requires a relatively high effort. In contrast, the determination of the gamma activity is much simpler and faster, and even more precise. The gamma-ray-based activity of the americium isotope 241 was therefore recorded as an indicator of the behavior of alpha-emitting actinides or transurans.
Tabelle 1 vergleicht exemplarisch die Entwicklung der über Gammastrahlungsdetektoren ermittelten Aktivität von Am-241 auf einer der beschriebenen Proben mit der Aktivität der Isotopen Pu-240, Cm-242 und Am-241, erfasst mit Alphastrahlungsdetektoren im unbehandelten Zustand (Nr. 1), nach einer Dekontamination mit üblichen Dekontaminationsverfahren (Nr. 2) und mit einem Dekontaminationsverfahren, bei dem eine erfindungsgemäße Wirkkomponente gemäß dieser Erfindung in verschiedenen Konzentrationen (Nr. 3, 4, 5) verwendet wurde. Um einen Vergleich der Aktivitätsentfernung zu erleichtern sind neben den erhaltenen Messwerten in Bq/cm2 auch die prozentualen Werte bezogen auf die Ausgangsmenge wiedergegeben. Es wurden jeweils Tenside mit ein und demselben organischen Rest (CH3-(CH2)15-) verwendet und zwar bei Nr.3 Sulfonsäure, bei Nr. 4 Carboxylsäure und bei Nr. 5 Phosphonsäure. Die Versuche wurden jeweils bei einer Temperatur von 95 °C und einer Tensidkonzentration von 1g/l durchgeführt. Die Behandlungsdauer betrug jeweils etwa 15 h, wobei während der Behandlung die Lösung nicht über Ionentauscher geführt wurde.
Die Mindesttemperatur für die Effektivität der Wirkstoffkomponente bzw. eines diese bildenden Tensids aus der Gruppe Sulfonsäure, Phosphonsäure und Carbonsäure ist unter anderem von der Struktur (z.B. Länge) des unpolaren Teiles des Tensids abhängig und ist von der sogenannten "Krafft-Temperatur" bedingt. Unterhalb dieser Temperatur können die Wechselwirkungen zwischen unpolaren Teilen nicht überwunden werden, der Wirkstoff bleibt als Aggregat in Lösung. Im Fall der Verwendung von Octadecylphosphonsäure als Wirkstoffkomponente ist die Mindesttemperatur für eine effektive Wirkung z.B. 75°C. Die obere Grenze ist in der Regel von verfahrenstechnischen Parametern abhängig. Es ist zum Beispiel nicht erwünscht, dass die Behandlungslösung zum Kochen kommt. Eine übliche Anwendungstemperatur von Dekontaminationsbehandlungen unter atmosphärischen Druck ist deswegen beispielsweise 80-95°C oder 90-95 °C.The minimum temperature for the effectiveness of the active ingredient component or a surfactant thereof from the group consisting of sulfonic acid, phosphonic acid and carboxylic acid is inter alia dependent on the structure (eg length) of the non-polar part of the surfactant and is due to the so-called "Krafft temperature". Below this temperature, the interactions between non-polar parts can not be overcome; the active substance remains in solution as an aggregate. In the case of use octadecylphosphonic acid as active ingredient is the minimum temperature for an effective effect eg 75 ° C. The upper limit is usually dependent on process parameters. For example, it is not desirable for the treatment solution to boil. A common application temperature of decontamination treatments under atmospheric pressure is therefore for example 80-95 ° C or 90-95 ° C.
Die Wirksamkeit der vorgeschlagenen Tenside hängt auch von der Art ihres polaren Teils ab. Obwohl von einem strukturellen Standpunkt aus die verschiedenen vorgeschlagenen Wirkstoffkomponenten vergleichbar sind (sie verfügen über einen unpolaren Teil, durch den sie miteinander in Wechselwirkung treten, und einen polaren Teil, durch den die Moleküle des Wirkstoffes untereinander lokalisiert abgestoßen werden und durch den die Wechselwirkung des Wirkstoffes mit polaren, geladenen oder ionisierten Partikeln oder Oberflächen ermöglicht wird), gibt es zwischen unterschiedlichen funktionellen Gruppen Unterschiede in den chemischen Eigenschaften, die für eine unterschiedliche Wirkung auch im Bereich der hier in Rede stehenden Dekontamination verantwortlich sind. Diese Unterschiede können festgestellt werden, indem man eine Auswahl von Wirkstoffkomponenten vergleicht, die über unterschiedliche polare funktionelle Gruppen, aber über identische unpolare Teile verfügt. Bei den hierzu durchgeführten Versuchen wurden sonstige Versuchsbedingungen wie Art der abzulösenden Oxidschicht, Behandlungstemperatur, pH-Wert, Konzentration der Wirkstoffkomponente und Behandlungszeit gleich gehalten. Die Proben wurden vor der Behandlung mit 3 Zyklen eines für Kernkraftwerke üblichen Dekontaminationsverfahrens behandelt (z.B. mit einer komplexierend wirkenden organischen Säure wie Oxalsäure). In Tabelle 2, welche die Ergebnisse der Versuche wiederspiegelt, ist neben der Aktivität auch der Dekontaminationsfaktor (DF) angegeben, also der Quotient aus Anfangs- und Endaktivität, der eine Einschätzung der Dekontaminationswirksamkeit erlaubt. Aus den Ergebnissen in Tabelle 2 wird deutlich, dass eine Phosponsäure mit der Formel R-PO3H2 (mit R = CH3(CH2)15) sich unter gleichen Bedingungen für die Entfernung der alphastrahlenden Kontamination am besten eignen.
Die Effektivität der Wirkkomponente wird nicht nur durch ihren polaren, sondern auch durch ihren unpolaren Teil, insbesondere durch dessen Länge bzw. Kettenlänge bestimmt. Die Größe bzw. Länge der unpolaren Teile beeinflusst die Wechselwirkungen zwischen den Tensidmolekülen aufgrund von Van-der-Waals-Kräften, wobei bei vergleichbarer Struktur größere unpolare Teile größere Wechselwirkungskräfte hervorrufen. Dies hat im Falle der Bildung von Doppelschichten auf geladenen Oberflächen zum Beispiel die Folge, dass in der zweiten, sich mit der Oberfläche nicht in Kontakt befindenden Schicht der Doppelschicht mehr Moleküle aufgenommen werden können. Dadurch erhöht sich die Ladungsdichte in dieser Schicht, was zu höheren Wechselwirkungen mit Wasser und höheren Coulomb schen Abstoßkräften führt. Die Mobilisierung der Aktivität wird dadurch begünstigt. In den hierzu durchgeführten Versuchen wurden jeweils gleiche Bedingungen (Art der auf den Proben vorhandenen Oxidschicht, Behandlungstemperatur, pH-Wert, Konzentration der Wirkstoffkomponente und Behandlungszeit) eingehalten. Das Ergebnis dieser Versuche geht aus Tabelle 3 hervor. Diese zeigt einen Vergleich zwischen der durchschnittlichen Dekontaminationswirksamkeit verschiedener Wirkstoffkomponenten mit jeweils derselben funktionellen Gruppe (Phosphonsäuregruppe) und unterschiedlichen unpolaren Resten (C14: CH3-(CH2)13-; C16: CH3-(CH2)15-; C18: CH3-(CH2)17). Die Proben wurden vor der Behandlung mit 3 Zyklen eines für Kernkraftwerke üblichen Dekontaminationsverfahrens (siehe oben) behandelt. Neben Aktivitätsangaben wird ebenfalls der übliche Dekontaminationsfaktor (DF) angegeben, der eine Einschätzung der Dekontaminationswirksamkeit vereinfacht.
Zur Bestimmung des optimalen pH-Bereiches für die Durchführung der Dekontamination wurden vier Proben parallel behandelt, und zwar jeweils unter gleichen Versuchsbedingungen wie Temperatur, Wirkstoffkonzentration oder Expositionszeit, mit Ausnahme des pH-Werts. Dieser wurde in Versuch Nr. 1 durch Zugabe von HNO3 verringert, in Nr. 2 beim eigenen Gleichgewichts-pH des verwendeten Phosphonsäurewirkstoffes belassen, bei Nr. 3 schwach alkalisiert durch Zugabe von NaOH-Lösung und bei Nr. 4 stark alkalisiert durch Zugabe größerer Mengen NaOH. Wie Tabelle 4 zeigt, werden die besten Ergebnisse bei der Neutralisierung der Phosphonsäuregruppe (Nr. 3) erhalten. In diesem Milieu ist die Gruppe zweifach ionisiert als R-PO3 2-, im Gegensatz zum normalen Zustand (R-PO3H-). Bei saurem pH (Nr. 1) wird die Dissoziation der Säuregruppe durch die erhöhte Konzentration von H3O+-Ionen im Wasser gehemmt, der Wirkstoff kann seinen erforderlichen geladenen Zustand nicht erhalten. Im Fall einer stark alkalischen Lösung ist die Säuregruppe vollkommen dissoziiert, somit maximal geladen.
Das erfindungsgemäße Verfahren wird vorzugsweise für die Dekontamination von Bauteilen des Kühlmittelsystems eines Kernkraftwerkes (siehe beigefügte
Die zweite Behandlungsstufe wird bei einer oberhalb Raumtemperatur, also oberhalb von etwa 25°C liegenden Temperatur durchgeführt, wobei jedoch unterhalb von 100°C gearbeitet wird, um ein Abdampfen und damit einem Wasserverlust zu verringern. Vorzugsweise wird bei Temperaturen von mehr als 50°C gearbeitet, wobei die besten Ergebnisse bei Temperaturen von mehr als 80°C erreicht werden.The second treatment stage is carried out at a temperature above room temperature, that is above about 25 ° C temperature, but operating below 100 ° C, in order to reduce evaporation and thus a loss of water. Preference is given to operating at temperatures of more than 50 ° C, with the best results being achieved at temperatures of more than 80 ° C.
Der pH-Wert der Behandlungslösung in der zweiten Behandlungsstufe ist prinzipiell variierbar. So ist es denkbar, denjenigen pH-Wert zu akzeptieren, der sich durch das in der Lösung vorhandene Tensid ergibt. Sofern es sich bei dem Tensid um eine Säure handelt, wird sich ein pH-Wert im sauren Bereich einstellen. Die besten Ergebnisse, insbesondere bei der Verwendung eines Phosphonsäurederivates als Tensid werden in einem pH-Wertbereich von 3 bis 9 erreicht.The pH of the treatment solution in the second treatment stage is in principle variable. Thus, it is conceivable to accept the pH which results from the surfactant present in the solution. If the surfactant is an acid, it will have a pH in the acidic range to adjust. The best results, especially when using a Phosphonsäurederivates as a surfactant are achieved in a pH range of 3 to 9.
Die Konzentration der Wirkkomponente, also eines Tensides der in Rede stehenden Art in der zweiten Behandlungslösung beträgt 0,1g/l bis 10g/l. Unterhalb von 0,1g/l findet eine Verringerung der Alphakontamination der Bauteiloberfläche in nennenswertem Ausmaß nicht statt. Oberhalb von 10g/l ist eine Steigerung des Dekontaminationsfaktors kaum noch zu beobachten, so dass über den genannten Wert hinaus gehende Konzentrationen praktisch wirkungslos sind. Ein sehr guter Kompromiss zwischen dem Einsatz an Tensidmenge und der Dekontaminationseffektivität wird bei Tensidkonzentrationen bis 3g/l erreicht.The concentration of the active component, ie a surfactant of the type in question in the second treatment solution is 0.1 g / l to 10 g / l. Below 0.1 g / l, a reduction in the alpha contamination of the component surface does not take place to a significant extent. Above 10 g / l, an increase in the decontamination factor is barely to be observed, so that concentrations in excess of the stated value are virtually ineffective. A very good compromise between the amount of surfactant used and the decontamination efficiency is achieved at surfactant concentrations up to 3 g / l.
Zur Durchführung der zweiten Behandlungsstufe ist es prinzipiell denkbar, die nach der ersten Behandlungslösung vorhandene verbrauchte Reinigungslösung zu entfernen und durch die zweite Behandlungslösung zu ersetzen, also beispielsweise im Falle der Dekontamination des Kühlmittelsystems eines Kernkraftwerkes dieses zu entleeren und anschließend mit der zweiten Behandlungslösung wieder zu füllen. Bei der bevorzugten Vorgehensweise wird jedoch die erste Behandlungslösung weitgehend von den in ihr enthaltenen Substanzen, also einer zum Zwecke der Ablösung der auf einer Bauteiloberfläche vorhandenen Oxidschicht dienenden Dekontaminationssäure und aus der Oxidschicht stammenden Metallionen befreit. Zur Entfernung der Dekontaminationssäure, beispielsweise Oxalsäure oder ähnliche, organische Säuren, wird die Behandlungslösung mit UV-Licht bestrahlt, wodurch die Säure zu Kohlenstoffdioxid und Wasser zersetzt wird. Die in der verbrauchten Dekontaminationslösung enthaltenen Metallionen werden dadurch entfernt, dass die Lösung über einen Ionentauscher geführt wird.To carry out the second treatment stage, it is in principle conceivable to remove the used after the first treatment solution spent cleaning solution and replaced by the second treatment solution, so for example in the case of decontamination of the coolant system of a nuclear power plant to empty this and then refill with the second treatment solution , In the preferred procedure, however, the first treatment solution is largely freed from the substances contained in it, ie a decontamination acid used for the purpose of detaching the oxide layer present on a component surface and metal ions originating from the oxide layer. To remove the decontamination acid, for example, oxalic acid or the like, organic acids, the treatment solution is irradiated with UV light, whereby the acid is decomposed into carbon dioxide and water. The in the spent decontamination solution contained metal ions are removed by passing the solution through an ion exchanger.
In der beigefügten Abbildung
Nachdem die sich im System befindliche verbrauchte Lösung auf die oben beschriebene Weise gereinigt wurde, also die darin enthaltene Dekontaminationssäure zerstört und Metallionen mit Hilfe eines Ionentauschers entfernt wurden, wird der so entstandenen Behandlungslösung ein Tensid, vorzugsweise Phosphonsäure oder Phosphonsäuresalz, dosiert und die zweite Behandlungsstufe durchgeführt.After the consumed solution in the system has been cleaned in the manner described above, ie the decontamination acid contained therein was destroyed and metal ions were removed with the aid of an ion exchanger, the resulting treatment solution is dosed with a surfactant, preferably phosphonic acid or phosphonic acid salt, and the second treatment stage is carried out ,
Claims (21)
- Method for chemically decontaminating radioactively contaminated surfaces of a metallic component of nuclear plants, wherein- in a first treatment stage, an oxide layer produced on the component due to corrosion of the component material is removed from the component surface using a first aqueous treatment solution, containing an organic decontamination acid, and- in a second treatment stage connected thereto, the surface which is at least partially free of oxide is treated using a second aqueous treatment solution, containing an active component for removing particles adhering to the surface, wherein the active component consists of at least one anionic surfactant from the group of sulphonic acids, phosphonic acids and carbonic acids and salts of thereof, wherein the second treatment solution is conducted via an ion exchanger, at the latest after the second treatment stage has finished.
- Method according to claim 1,
characterised in that,
the surfactants used are ones which feature an organic radical with 12 to 22 carbon atoms. - Method according to claim 2,
characterised by
using surfactants with an organic radical with 14 to 18 carbon atoms. - Method according to one of claims 1 to 3,
characterised in that,
the second treatment stage is carried out at a temperature of 25°C to less than 100°C. - Method according to claim 4,
characterised by
a treatment temperature of greater than 50°C. - Method according to claim 4,
characterised by
a treatment temperature of greater than 80°C. - Method according to one of claims 4 to 6,
characterised by
a treatment temperature of 95°C maximum. - Method according to one of the preceding claims,
characterised in that,
during the second treatment stage, the pH value of the second treatment solution, which results due to the presence of at least one surfactant, is maintained. - Method according to one of claims 1 to 8,
characterised in that,
the pH value resulting due to the presence of at least one surfactant in the second treatment solution is altered. - Method according to claim 9,
characterised in that,
the pH value is increased. - Method according to one of the preceding claims,
characterised in that,
a pH value of 3 to 9 is regulated in the second treatment solution. - Method according to claim 11,
characterised by
a pH value of the second treatment solution of 6-8. - Method according to one of the preceding claims,
characterised in that,
the active component is contained at a concentration of 0.1 g/L to 10 g/L in the second treatment solution. - Method according to claim 13,
characterised by
a concentration of 0.1 g/L to 3 g/L. - Method according to one of the preceding claims,
characterised in that,
no further chemical substances are added to the second treatment solution, apart from at least one surfactant and, if necessary, an alkalising medium or acidifier. - Method according to one of the preceding claims,
characterised in that,
the second treatment solution is obtained from the first treatment solution, wherein at least one or more decontamination acids serving to remove the oxide layers present on a component surface are removed from the first treatment solution. - Method according to claim 16,
characterised in that,
the first treatment solution is irradiated with UV light, so as to break down a decontamination acid into carbon dioxide and water. - Method according to claim 16 or 17,
characterised in that,
the first treatment solution is conducted via at least one ion exchanger, so as to remove the metal ions contained therein. - Method according to one of the preceding claims,
characterised in that,
the first or the second treatment solution is present in a container and a component which is to be treated is immersed in the respective solution. - Method according to one of claims 1 to 19,
characterised in that,
a component surface which is to be treated is the inner surface of a container and/or a pipeline system, wherein the container and/or the pipeline system is filled with the first or the second treatment solution. - Method according to claim 20,
characterised in that,
it is applied in the cooling system of a nuclear power plant.
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DE102009009441 | 2009-02-18 | ||
DE102009002681A DE102009002681A1 (en) | 2009-02-18 | 2009-04-28 | Method for the decontamination of radioactively contaminated surfaces |
PCT/EP2010/051957 WO2010094692A1 (en) | 2009-02-18 | 2010-02-17 | Method for decontaminating radioactively contaminated surfaces |
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EP2399262B1 true EP2399262B1 (en) | 2012-11-21 |
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EP (1) | EP2399262B1 (en) |
JP (1) | JP5584706B2 (en) |
KR (1) | KR101295017B1 (en) |
CN (1) | CN102209992B (en) |
CA (1) | CA2749642C (en) |
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IT1402751B1 (en) * | 2010-11-12 | 2013-09-18 | Ecir Eco Iniziativa E Realizzazioni S R L | METHOD FOR CONDITIONING SCORES ARISING FROM DISPOSAL OF NUCLEAR PLANTS |
CN103489495B (en) * | 2012-06-14 | 2016-10-05 | 中国辐射防护研究院 | A kind of fixative for controlling radioaerosol and preparation method |
DE102013100933B3 (en) * | 2013-01-30 | 2014-03-27 | Areva Gmbh | Process for surface decontamination of components of the coolant circuit of a nuclear reactor |
DE102013102331B3 (en) | 2013-03-08 | 2014-07-03 | Horst-Otto Bertholdt | Process for breaking down an oxide layer |
CN105393309B (en) * | 2013-08-14 | 2018-01-19 | 阿海珐有限公司 | Method for the radioactive pollution on the surface of reducing the part used in nuclear reactor |
DE102013108802A1 (en) * | 2013-08-14 | 2015-02-19 | Areva Gmbh | Method for reducing the radioactive contamination of a water-bearing circuit of a nuclear power plant |
JP2017506151A (en) * | 2014-01-22 | 2017-03-02 | ジャン−ミシェル・フジェリュー | Yield optimization method for electrolytic extraction of heavy metals in high salt concentration aqueous solution and apparatus for carrying it out |
CN105895172A (en) * | 2014-12-26 | 2016-08-24 | 姚明勤 | Quick and effective design measure for passive safety of pressurized water reactor |
WO2016124240A1 (en) * | 2015-02-05 | 2016-08-11 | Areva Gmbh | Method of decontaminating metal surfaces in a cooling system of a nuclear reactor |
TWI594265B (en) * | 2015-05-13 | 2017-08-01 | 森元信吉 | Method of treating water contaminated by radiation and sealing atomic furnace device |
KR101639651B1 (en) | 2015-06-05 | 2016-08-12 | 주식회사 큐리텍 | Automatic radioactive decontamination apparatus |
CA3003488C (en) * | 2015-11-03 | 2023-03-14 | Framatome Gmbh | Method of decontaminating metal surfaces in a heavy water cooled and moderated nuclear reactor |
MX2018003997A (en) | 2016-08-04 | 2018-05-28 | Dominion Eng Inc | Suppression of radionuclide deposition on nuclear power plant components. |
KR102061287B1 (en) * | 2018-04-17 | 2019-12-31 | 한국수력원자력 주식회사 | Dismantling and decontamination system and method of biodegradable concrete of pwr type nuclear power plant |
JP7337442B2 (en) * | 2019-02-19 | 2023-09-04 | 株式会社ディスコ | Machining fluid circulation system |
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JP2012518165A (en) | 2012-08-09 |
US8353990B2 (en) | 2013-01-15 |
US20110303238A1 (en) | 2011-12-15 |
JP5584706B2 (en) | 2014-09-03 |
CA2749642A1 (en) | 2010-08-26 |
KR101295017B1 (en) | 2013-08-09 |
CN102209992A (en) | 2011-10-05 |
DE102009002681A1 (en) | 2010-09-09 |
CN102209992B (en) | 2014-11-05 |
KR20110118726A (en) | 2011-10-31 |
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ES2397256T3 (en) | 2013-03-05 |
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