EP2787509A1 - Procédé de décomposition d'une couche d'oxyde - Google Patents

Procédé de décomposition d'une couche d'oxyde Download PDF

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Publication number
EP2787509A1
EP2787509A1 EP14158346.8A EP14158346A EP2787509A1 EP 2787509 A1 EP2787509 A1 EP 2787509A1 EP 14158346 A EP14158346 A EP 14158346A EP 2787509 A1 EP2787509 A1 EP 2787509A1
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EP
European Patent Office
Prior art keywords
decontamination
acid
methanesulfonic acid
circuit
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14158346.8A
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German (de)
English (en)
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EP2787509B1 (fr
Inventor
Horst-Otto Bertholdt
Andreas Loeb
Hartmut Runge
Dieter Stanke
Alexander Ländner
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NIS Ingenieur GmbH
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NIS Ingenieur GmbH
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Publication of EP2787509A1 publication Critical patent/EP2787509A1/fr
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • 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
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • 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 process for the decomposition of an oxide layer containing chromium, iron, nickel, zinc and radionuclides, in particular for the decomposition of oxide layers deposited on the inner surfaces of systems and components of a nuclear power plant, by means of an aqueous decontamination solution containing an acid.
  • the invention relates to a method for the extensive degradation of radionuclides in the primary system and the auxiliary systems in a nuclear power plant using the existing operating medium and the power plant operating systems.
  • oxidic protective layers are formed at an operating temperature of> 180 ° C on the medium wetted inner surfaces of the systems and components.
  • Radionuclides are incorporated into the oxide matrix.
  • the aim of chemical decontamination methods is to dissolve this oxide layer in order to be able to remove those with incorporated radionuclides. This is to ensure that in the case of a revision the radiation exposure of the inspection staff kept as low as possible or in the case of dismantling of the nuclear reactor, the metallic materials of the components can be easily fed to a recycling cycle.
  • the oxide protective layers are considered to be chemically insoluble.
  • the oxide structure By means of a preceding oxidative chemical treatment of the oxide structure, it can be broken up and the sparingly soluble oxide matrix converted into readily soluble metal oxides.
  • This breakdown of the oxide matrix occurs by oxidation of the trivalent chromium into the hexavalent chromium: Fe0 .5 Ni 1.5 O 4 / NiFe 2 O 4 / Fe 3 O 4 ⁇ oxidation ⁇ CrO 4 2-, FeO, NiO, Fe 2 O 3 Equation (1)
  • the manganese ion is present in the permanganate in the oxidation state 7 and is reduced according to equation (2) in the oxidation state 4, at the same time present in the trivalent oxidation state chromium is oxidized to the oxidation state 6.
  • 2 MOL MnO 4- are required under acidic conditions according to equation (2).
  • steps I to V is in this case carried out three to six times (three to six decontamination cycles) in succession.
  • manganese oxihydrate [MnO (OH) 2 ] or manganese dioxide (MnO 2 ) is formed in all decontamination technologies used so far, as equations (2) illustrate.
  • the manganese oxyhydrate / manganese dioxide is insoluble and precipitates on the inner surface of the components / systems. With increasing manganese oxyhydrate / manganese dioxide deposition, the desired oxidation of the oxide protective layer is hindered. In addition, the converted iron and nickel oxides remain undissolved on the surface, so that the barrier layer on the surface further amplified.
  • Object of the present invention is to avoid the disadvantages of the prior art, in particular to allow a simplification of the process flow, the formation of manganese dioxide and metal oxalates to be avoided.
  • the emergence of CO 2 should be excluded. Also, the release of oxide particles should be largely avoided.
  • the dissolution of the oxide layer in a single treatment step by means of an aqueous in a first cycle (K1) flowing decontamination with methanesulfonic acid as acid that methanesulfonic acid throughout the decontamination implementation both as a proton supplier for adjusting the decontamination solution remains at a pH ⁇ 2.5 and as an oxide solvent in the decontamination solution that the digestion of chromium-containing oxide layers with permanganic acid takes place and that after degradation of permanganic acid the solution while maintaining the operation of the first circuit (K1) via a bypass line in a second circuit (K2) flows through an ion exchanger (IT), in which the existing in the decontamination solution 2- and 3-valent cations and the dissolved radionuclides are fixed, with simultaneous release of methanesulfonic acid.
  • K1 aqueous in a first cycle
  • I ion exchanger
  • the pH is set by metered addition of methanesulfonic acid.
  • methanesulfonic acid there is no need for further addition of methanesulfonic acid.
  • the decontamination can be carried out with power plant own systems without the help of external decontamination auxiliary systems, the activity reduction without manganese formation and other cation precipitation and without CO 2 -Anfall and without release of oxide particles take place and the metal oxides are simultaneously dissolved chemically and as cations / Anions are fixed together with the manganese and the nuclides (Co-60, Co-58, Mn-54, etc.) on ion exchange resins.
  • the process may be carried out using the cycle or a subcircuit that is present in a nuclear facility such as a nuclear power plant.
  • a nuclear facility such as a nuclear power plant.
  • proprietary as well as power plant own systems are used.
  • the chemical conversion of the sparingly soluble oxides into readily soluble oxides, the dissolution of the oxides / radionuclides and the discharge and fixing of the dissolved cations to ion exchangers take place in a single process step.
  • the permanganic acid used is completely converted to the Mn 2+ cation in the course of the preoxidation step.
  • Manganese oxyhydrate / manganese precipitation does not occur.
  • methanesulfonic acid is still available at the end of the "oxidative decontamination step" for the subsequent steps.
  • the oxides (NiO, Ni 2 O 3 , FeO,) formed in the course of the "oxidative decontamination step" are already dissolved by the methanesulfonic acid during the "HMnO 4 phase".
  • methanesulfonic acid is used for pH adjustment.
  • the amount of methanesulfonic acid required to prevent MnO (OH) 2 formation is based on the permanganate concentration. As the permanganate concentration increases, the pH must be lowered, ie a higher acid concentration has to be set ( Fig. 1 ).
  • the amount of individual cations released in the respective "HMnO 4 phase" can be calculated in each case in advance , This is possible because the amount of HMnO 4 used converts to 100% in Mn 2+ and stoichiometrically produces the amount of dichromate produced.
  • the amount of oxidized Cr-III gives the amount of Fe / Cr / Ni / Zn oxides converted and thus the Fe / Ni / Zn / Mn ions produced in the "HMnO 4 phase" ,
  • the system to be decontaminated is operated in the circuit K1 without ion exchange integration, ie without circulation K2. This should be based on principle Fig. 3 be clarified.
  • the circuit K1 is in operation.
  • the circuit K2 is switched in bypass to circuit 1 when the conversion of the HMnO 4 amount to 100% in Mn 2+ is completed.
  • Ni-II-oxide Ni (CH 3 SO 3 ) 2 + H 2 O Equation (5)
  • a process temperature of preferably 60 ° C to 120 ° C is set.
  • the decontamination is preferably carried out in a temperature range of 85 ° C to 105 ° C.
  • the divalent and trivalent cations (Mn-II, Fe-II, Fe-III, Zn-II and Ni-II) as well as the radionuclides (Co-58, Co-60, Mn-54 etc .) removed from the solution.
  • the methanesulfonic acid is released and is available to the process again. See equations (8) through (11).
  • the operation of the ion exchanger IT takes place at a process temperature of ⁇ 100 ° C.
  • the operation of the ion exchanger IT is carried out in the bypass until all dissolved cations, anions and radionuclides are fixed on the ion exchange resin.
  • the bypass circuit K2 is closed and again permanganic acid is added to the circuit K1. The method steps explained above are repeated until no further activity discharge from the system K1 to be decontaminated takes place.
  • Fig. 2 shows by way of example the courses of the cation concentrations in a four-time HMnO 4 dosage in the course of a DWR primary system decontamination.
  • step II it is customary, after the completion of the pre-oxidation, to reduce the excess permanganate with oxalic acid (step II) and then to initiate the decontamination step (step III) by adding further decontamination chemicals.
  • step II all the ingredients of the pre-oxidation step (residual permanganate, colloidal MnO (OH) 2 , chromate and nickel permanganate) and all converted metal oxides are present in the system in the conventional solution. or component surface.
  • metal ions are present partially in dissolved form (MnO 4 - , CrO 4 2- ) and as easily soluble metal oxides (NiO, FeO, MnO 2 / MnO (OH) 2 ), already in the course of the second process step of the reduction ( Step II) high cation contents in the solution.
  • the CO 2 formation and release of oxide particles described above does not occur in the present invention.
  • the oxalate compounds formed from divalent cations and the reduction chemical "oxalic acid” have limited solubility in water. Depending on the process temperature, the solubility of the divalent cations is: 50 ° C 80 ° C unit NiC 2 O 4 about 3 about 6 mg Ni-II / liter FeC 2 O 4 about 15 about 45 mg Fe-II / liter MnC 2 O 4 about 120 about 170 mg Mn-II / liter
  • the oxidic protective layers of a primary system of a pressurized-water nuclear power plant usually give a total total NOx inventory of 1,900 kg to 2,400 kg [Fe, Cr, Ni oxide].
  • the already dissolved radionuclides (Co-58, Co-60, Mn-54) are incorporated into the oxalate layer. This leads to a recontamination in the systems.
  • Each nuclear power plant [PWR, SWR, etc.] has its own specific oxide structure, oxide composition, oxide dissolving behavior, and oxide / activity inventory.
  • For the preliminary planning of a decontamination only assumptions can be made. Only in the course of carrying out the decontamination then shows whether the preliminary assumptions were correct.
  • a decontamination concept must therefore be able to adapt to the respective changes during execution.
  • NPP nuclear power plants
  • the process parameters can be quickly adapted to the respective new requirements (chemical dosing, chemical concentrations, process temperature, time of IT exchanger integration, step sequences, etc.).
  • process variations can be carried out until the desired activity output or the desired dose rate reduction has been achieved.
  • the methanesulfonic acid present in the solution remains in the solution during the performance of all the process steps.
  • the concentration is not changed. Only at the end of the Automatdekontaminations- implementation of methanesulfonic acid is bound in the course of final cleaning on ion exchange resins.
  • FIGS. 1 to 3 that are self-explanatory.
  • the decontamination according to the invention is purely in principle of Fig. 2 refer to.
  • the decontamination solution is underlaid with methanesulfonic acid to ensure a pH of ⁇ 2.5.
  • methanesulfonic acid is metered into the solution in order to convert the insoluble Fe, CrNi oxide dressing into readily soluble metal oxides, the metal oxides at the same time dissolve and form readily soluble methanesulfonates.
  • the Cr-III oxide is oxidized to Cr-VI and is present in the solution as dichromic acid.
  • the solution flows through the ion exchanger IT (circuit K 2) via a bypass in the "IT operation" step, in which the dissolved cations and radionuclides are fixed.
  • IT operation the methanesulfonic acid is released again and is available to the process again.
  • the conversion of the poorly soluble Fe, Cr, Ni structure into slightly soluble oxide forms by means of permanganic acid takes place chemically.
  • the dissolved oxide forms are dissolved with methanesulfonic acid.
  • this is done in a circulation mode (cycle K1) ( Fig. 3 ) in a methanesulfonic acid / permanganic acid solution. Circulation K1 is maintained until the permanganic acid has been completely consumed and converted to Mn 2+ .
  • the permanganic acid concentration is set in the range between 30 and 50 ppm at the beginning of the process, the conversion of permanganic acid to Mn 2+ lasts for 2 to 4 hours.
  • the conversion of the oxide structure and the dissolution of the converted oxides takes place at the same time.
  • the final products of the dissolution process are metal salts of methanesulfonic acid.
  • the "IT phase” begins.
  • the metal cations present as methanesulfonates and nuclides in the bypass (circulation K2) are passed over ion exchange resins and fixed there.
  • both circuits K1 and K2 are in operation. In the exchange process, the methanesulfonic acid is released again and is the decontamination solution available again.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Food Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP14158346.8A 2013-03-08 2014-03-07 Procédé de décomposition d'une couche d'oxyde Active EP2787509B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102013102331.2A DE102013102331B3 (de) 2013-03-08 2013-03-08 Verfahren zum Abbau einer Oxidschicht

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EP2787509A1 true EP2787509A1 (fr) 2014-10-08
EP2787509B1 EP2787509B1 (fr) 2015-12-23

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US (1) US9502146B2 (fr)
EP (1) EP2787509B1 (fr)
DE (1) DE102013102331B3 (fr)
ES (1) ES2566353T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019007788A1 (fr) 2017-07-06 2019-01-10 Framatome Gmbh Procédé de décontamination d'une surface métallique dans une centrale nucléaire

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2705191C2 (ru) * 2015-01-26 2019-11-05 Басф Се Удаление радионуклидов из смесей
KR102122163B1 (ko) * 2017-01-19 2020-06-12 프라마톰 게엠베하 핵 시설의 금속면을 제염하기 위한 방법
WO2018149862A1 (fr) * 2017-02-14 2018-08-23 Siempelkamp NIS Ingenieurgesellschaft mbH Procédé de décomposition d'une couche d'oxyde contenant des radionucléides
JP6505810B1 (ja) * 2017-10-27 2019-04-24 株式会社東芝 除染実施方法及び除染実施装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0071336A1 (fr) 1981-06-17 1983-02-09 Central Electricity Generating Board Procédé pour la dissolution chimique des dépôts d'oxyde
US4678552A (en) * 1986-04-22 1987-07-07 Pennwalt Corporation Selective electrolytic stripping of metal coatings from base metal substrates
EP0160831B1 (fr) 1984-04-12 1991-12-04 Siemens Aktiengesellschaft Procédé pour décontaminer chimiquement les parties métalliques des installations de réacteur nucléaire
EP0675973B1 (fr) 1992-12-24 1997-08-06 Electricite De France Procede de dissolution d'oxydes deposes sur un substrat metallique
DE102004045297A1 (de) * 2004-09-16 2006-03-23 Basf Ag Verfahren zum Behandeln von metallischen Oberflächen unter Verwendung von Formulierungen auf Basis von wasserarmer Methansulfonsäure

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AT18822B (de) 1903-01-19 1905-01-10 Skodawerke Actiengesellschaft Oberlafette für Geschütze mit Rohrrücklauf.
BE904139A (nl) 1986-01-30 1986-05-15 Lemmens Godfried Werkwijze voor de decontaminatie van radioaktief besmette materialen.
EP0355628B1 (fr) * 1988-08-24 1993-11-10 Siemens Aktiengesellschaft Procédé pour décontaminer chimiquement la surface d'un élément de construction métallique d'une installation de réacteur nucléaire
FR2648946B1 (fr) * 1989-06-27 1994-02-04 Electricite De France Procede de dissolution d'oxyde depose sur un substrat metallique et son application a la decontamination
DE4410747A1 (de) * 1994-03-28 1995-10-05 Siemens Ag Verfahren und Einrichtung zum Entsorgen einer Lösung, die eine organische Säure enthält
DE19818772C2 (de) * 1998-04-27 2000-05-31 Siemens Ag Verfahren zum Abbau der Radioaktivität eines Metallteiles
ES2365417T3 (es) * 2005-11-29 2011-10-04 Areva Np Gmbh Procedimiento para la descontaminación de una superficie de un componente o un sistema de una instalación nuclear que presenta una capa de óxido.
DE102009002681A1 (de) * 2009-02-18 2010-09-09 Areva Np Gmbh Verfahren zur Dekontamination radioaktiv kontaminierter Oberflächen
JP6009218B2 (ja) * 2011-05-24 2016-10-19 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ アルファ粒子放射体除去

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0071336A1 (fr) 1981-06-17 1983-02-09 Central Electricity Generating Board Procédé pour la dissolution chimique des dépôts d'oxyde
EP0160831B1 (fr) 1984-04-12 1991-12-04 Siemens Aktiengesellschaft Procédé pour décontaminer chimiquement les parties métalliques des installations de réacteur nucléaire
US4678552A (en) * 1986-04-22 1987-07-07 Pennwalt Corporation Selective electrolytic stripping of metal coatings from base metal substrates
EP0675973B1 (fr) 1992-12-24 1997-08-06 Electricite De France Procede de dissolution d'oxydes deposes sur un substrat metallique
DE102004045297A1 (de) * 2004-09-16 2006-03-23 Basf Ag Verfahren zum Behandeln von metallischen Oberflächen unter Verwendung von Formulierungen auf Basis von wasserarmer Methansulfonsäure

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019007788A1 (fr) 2017-07-06 2019-01-10 Framatome Gmbh Procédé de décontamination d'une surface métallique dans une centrale nucléaire

Also Published As

Publication number Publication date
EP2787509B1 (fr) 2015-12-23
DE102013102331B3 (de) 2014-07-03
ES2566353T3 (es) 2016-04-12
US20140338696A1 (en) 2014-11-20
US9502146B2 (en) 2016-11-22

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