EP1955335A2 - Procede de decontamination d'une surface presentant une couche d'oxyde d'un composant ou d'un systeme d'une centrale nucleaire - Google Patents

Procede de decontamination d'une surface presentant une couche d'oxyde d'un composant ou d'un systeme d'une centrale nucleaire

Info

Publication number
EP1955335A2
EP1955335A2 EP06818538A EP06818538A EP1955335A2 EP 1955335 A2 EP1955335 A2 EP 1955335A2 EP 06818538 A EP06818538 A EP 06818538A EP 06818538 A EP06818538 A EP 06818538A EP 1955335 A2 EP1955335 A2 EP 1955335A2
Authority
EP
European Patent Office
Prior art keywords
oxide layer
treated
water
treatment
ozone
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
EP06818538A
Other languages
German (de)
English (en)
Other versions
EP1955335B1 (fr
Inventor
Horst-Otto Bertholdt
Terezinha Claudete Maciel
Franz Strohmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Areva GmbH
Original Assignee
Areva NP GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Areva NP GmbH filed Critical Areva NP GmbH
Priority to EP08009058A priority Critical patent/EP1968075B1/fr
Priority to SI200631067T priority patent/SI1955335T1/sl
Publication of EP1955335A2 publication Critical patent/EP1955335A2/fr
Application granted granted Critical
Publication of EP1955335B1 publication Critical patent/EP1955335B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
    • G21F9/002—Decontamination of the surface of objects with chemical or electrochemical processes
    • 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

Definitions

  • the invention relates to a method for decontamination of an oxide layer having surface of a component or a system of a nuclear facility.
  • an oxidation layer forms on the system and component surfaces, which must be removed in order, for example, to minimize the radiation exposure of the personnel in the case of revision work.
  • the material for a system or a component comes first of all Austenitic chromium-nickel steel, for example, with 72% iron, 18% chromium and 10% nickel in question. Oxidation on the surfaces forms oxide layers with spinel-like structures of the general formula AB 2 O 4 .
  • the chromium is always present in trivalent, nickel always in divalent and iron in both the two- and trivalent form in the oxide structure.
  • Such oxide layers are chemically almost insoluble.
  • the removal or dissolution of an oxide layer in the context of a decontamination process thus always precedes an oxidation step in which the trivalent chromium is converted into hexavalent chromium.
  • the compact spinel structure is destroyed and iron, chromium and nickel oxides are formed which are readily soluble in organic and mineral acids.
  • an oxidation step is followed by treatment with an acid, in particular with a complexing acid, such as oxalic acid.
  • the aforementioned pre-oxidation of the oxide layer is conventionally carried out in acidic solution with potassium permanganate and nitric acid or in alkaline solution with potassium permanganate and sodium hydroxide.
  • the acidic range is used and permanganic acid is used instead of potassium permanganate.
  • the abovementioned processes have the disadvantage that during the oxidation treatment, manganese dioxide (MnO 2 ) forms, which deposits on the oxide layer to be treated and inhibits the passage of the oxidizing agent (permanganate ion) into the oxide layer. In conventional methods, therefore, the oxide layer can not be completely oxidized in one step.
  • manganese dioxide layers must be removed by intermediate reduction treatments. Normally, three to five such reduction treatments are required, which is associated with a correspondingly high expenditure of time.
  • Another disadvantage of the known methods is the large amount of secondary waste, which is mainly due to the removal of manganese by means of ion exchangers.
  • oxidation in the literature is described by means of ozone in aqueous acidic solution with addition of chromates, nitrates or cerium-IV salts.
  • the oxidation with ozone under the conditions mentioned requires process temperatures in the range of 40-60 °. Under these conditions, however, the solubility and thermal stability of ozone is relatively low, so that it is almost impossible to produce ozone concentrations on an oxide layer which are sufficiently high to break up the spinel structure of the oxide layer in an acceptable time.
  • the introduction of ozone in large volumes of water is technically complex. Therefore, despite its disadvantages, oxidation with permanganate or permanganic acid has become established worldwide.
  • This object is achieved in a method according to claim 1, characterized in that the oxidation of the oxide layer with a gaseous oxidizing agent, that is carried out in the gas phase.
  • a gaseous oxidizing agent that is carried out in the gas phase.
  • Such a procedure initially achieves the advantage that the oxidizing agent can be applied to the oxide layer at a considerably higher concentration than is the case with an aqueous solution with its limited solubility for the oxidizing agent.
  • the suitable for the intended purpose oxidizing agents such as ozone or nitrogen oxides are less stable in aqueous solution than in the gas phase.
  • an oxidant in aqueous solution such as the primary coolant of a light water reactor, usually finds a variety of reactants, so that a portion of the oxidizing agent is consumed on its way from the feed point to the oxide layer.
  • the required oxidation reactions in particular the conversion of chromium-III to chromium-VI, would take place too slowly. It is therefore advantageous if, during the treatment, a water film is maintained on the oxide layer and a water-soluble oxidizing agent is used. The oxidizing agent then finds in the water film covering the oxide layer or in pores of the oxide layer filled with water the aqueous conditions required for the course of the oxidative reactions. In the event that emptied a previously filled with water system and then the gas phase oxidation is carried out, the oxide layer is still moistened or moistened with water, so a water film already exists, so this may need to be maintained only during the gas phase oxidation.
  • a water film is preferably generated or maintained by means of water vapor.
  • an elevated temperature may be required for the desired oxidation reactions to take place in economically justifiable periods of time.
  • heat is supplied to the surface of a system or a component or the oxide layer present on it, which takes place, for example, with the aid of an external heating device or preferably with the aid of superheated steam or hot air.
  • the desired water film is also formed on the oxide layer at the same time.
  • ozone is used as the oxidizing agent.
  • ozone is converted to oxygen, which can be fed to the exhaust air system of a nuclear installation without further aftertreatment.
  • Ozone is also much more stable in the gas phase than in the aqueous phase. Solubility problems as in the aqueous phase, especially at higher temperatures, do not occur.
  • the ozone gas can thus be introduced in high doses to a water-wetted oxide layer, so that the oxidation of the oxide layer, in particular the oxidation of chromium III to chromium-VI proceeds faster, in particular when working at higher temperatures.
  • Ozone has an oxidation potential of 2.08 V in an acidic solution, but only 1.25 V in a basic solution.
  • acidic conditions are created in the water film wetting the oxide layer, which occurs in particular due to the metered addition of nitrogen oxides can.
  • ozone as an oxidizing agent, a pH of 1 to 2 is maintained.
  • the acidification of the water film takes place preferably with the aid of gaseous acid anhydrides. These form acids under water accumulation in the water film.
  • the acid anhydrides have an oxidizing effect, they can at the same time be used as oxidizing agents, as is the case with a preferred process variant described below.
  • the occurring oxidation reactions can be accelerated by using elevated temperatures.
  • a temperature range of 40-70 0 C has been found to be particularly advantageous. From 40 0 C, the oxidation reactions take place in the oxide layer at an acceptable rate. However, a temperature increase is only useful up to about 70 0 C, since at higher temperatures, the decomposition of ozone in the gas phase increases significantly.
  • the duration for the oxidation treatment of the oxide layer can be influenced not only by the temperature but also by the concentration of the oxidizing agent. In the case of ozone, acceptable conversion rates, optimum ratios at concentrations of 100 to 120 g / Nm 3 , are achieved within the abovementioned temperature range only from about 5 g / Nm 3 .
  • nitrogen oxides ie mixtures of various nitrogen oxides such as NO, NO 2 , N 2 O and N 2 O 4 are used for the oxidation.
  • NO x nitrogen oxides
  • the oxidation effect can be increased by using elevated temperatures, with such an increase from about 80 0 C is noticeable. The best efficiency is achieved when operating in a temperature range of about 110 0 C to about 180 0 C.
  • the oxidation effect can also, as in the case of ozone, be influenced by the concentration of nitrogen oxides.
  • a NO x concentration of less than 0.5 g / Nm 3 is hardly effective.
  • work is carried out at NO x concentrations of 10 to 50 g / Nm 3 .
  • an oxide layer is subjected to steam after the oxidation treatment, wherein a condensation of the water vapor takes place at the oxide layer.
  • a condensation of the water vapor takes place at the oxide layer.
  • activity adhering to or in contact with the oxide layers or component surfaces for example in particle form or in dissolved or colloidal form, passes into the condensate and is removed therefrom by the surface treatment. This effect is clearly noticeable at water vapor temperatures above 100 ° C.
  • Another advantage of this approach is the comparatively small amount of accumulating condensate.
  • Treatment was performed, removed and condensed. Together with the condensate draining from a component surface, it is passed over a cation exchanger. In this way, the condensate is released from the activity and can be disposed of easily.
  • a further treatment may be expedient in advance, especially if nitrate ions are contained which originate from the oxidative treatment of an oxide layer or an acidification of a water film with nitrogen oxides.
  • the nitrates are preferably removed from the condensate by reacting with a reducing agent, in particular with hydrazine, to form gaseous nitrogen become. It is expedient to set a molar ratio of nitrate to hydrazine of 1: 0.5 to 2: 5.
  • the attached figure shows a flow chart for a decontamination process.
  • the system 1 to be decontaminated for example the primary circuit of a pressurized water system, is first emptied.
  • a component such as a primary system pipeline
  • this is arranged in a container.
  • a decontamination circuit 2 is connected to the system 1 and the container. This is gas-tight.
  • the decontamination circuit 2 and the system are checked for leaks, for example by evacuation.
  • the entire system is therefore system 1 and
  • Decontamination circuit 2 heated.
  • a feed station 3 for hot air and / or superheated steam is arranged in the decontamination circuit 2.
  • the supply of air or steam via a supply line 4.
  • a pump 5 is further provided to fill the system 1 with the appropriate gaseous medium and this, as long as necessary, circulate throughout the plant.
  • the system With the help of hot air or hot steam, the system is brought to the intended process temperature, in the case of ozone to 50-70 0 C.
  • steam is added via the feed station 3.
  • Separating or condensing water is separated off at the system outlet 6 with the aid of a liquid separator 7 and removed from the decontamination circuit 2 with the aid of a condensate line 8.
  • the water film wetting the oxide layer to be oxidized is acidified.
  • 2 gaseous nitrogen oxides or finely atomized nitric acid are added at a feed station 9 of the decontamination cycle.
  • the nitrogen oxides dissolve in the water to form the corresponding acids, such as to form nitric or nitrous acid.
  • the metered amounts of NO x or nitric acid / nitrous acid are chosen so that a pH of about 1 to 2 is established in the water film.
  • the system 1 is supplied with ozone via a feed stadium 10 having a concentration in the range of preferably 100 to 120 g / Nm 3 continuously supplied when the pump 5 is in operation. If necessary, there is a continuous feed of NO x (or HNO 3 ) to maintain the acidic conditions in the water film and hot air or superheated steam to maintain the set temperature parallel to the ozone feed.
  • NO x or HNO 3
  • part of the gas / vapor mixture present in the decontamination cycle 2 is discharged, so that fresh ozone gas and, if appropriate, other auxiliary substances such as NOx can be metered in, the discharged quantity corresponding to the metered amount of gas.
  • the discharge takes place via a gas scrubber for
  • the ozone-free, optionally still containing water vapor oxygen-air mixture is fed to the exhaust system of the power plant.
  • the ozone concentration is measured at the system return 13 by means of measuring probes (not shown).
  • a temperature monitoring is carried out with appropriate, arranged in the area of the system 1 sensors.
  • the amount of metered NO x is a function of the amount of water vapor supplied. Per Nm 3 of water vapor is supplied at least 0.1 g of NO x, thereby ensuring a pH of the water film of ⁇ 2.
  • Ozone, NO x , hot air supply turned off and a rinse step initiated.
  • the oxide layer is acted upon by steam and ensured that the component surfaces or an oxide layer located thereon have a temperature of less than 100 0 C, so that the water vapor can condense it.
  • activity present in or on the oxide layer is removed by this treatment.
  • the respective surfaces of acid residues mainly so rinsed by nitrates.
  • the nitrate is converted to gaseous nitrogen with the aid of a reducing agent, the best results of which were achieved with hydrazine, and thus removed from the condensate solution.
  • a stoichiometric amount of hydrazine is preferably employed, i. a MoI ratio of nitrate to hydrazine of 2: 5 is set.
  • the active cations are removed by passing the solution through a cation exchanger.
  • the rinsing of an oxidatively treated oxide layer can also be done by filling the system 1 with deionized water.
  • the displaced gas is passed over the catalyst 12 while the residual ozone therein is reduced to O 2 and, as already mentioned above fed to the exhaust system of the nuclear power plant.
  • the nitrate ions present on the surface of the components to be decontaminated or of the oxide layer still present there, which have been formed by metering in nitric acid or by oxidation of NO x are taken up by the deionate and remain during the subsequent treatment to dissolve the oxide coating the decontamination solution.
  • a gas phase oxidation was carried out on a pipe section of a primary system pipeline.
  • a test setup corresponding to the attached flow chart was used.
  • the pipeline originated from a pressurized water system with more than 25 years of power operation and was provided with an inner cladding made of austenitic Fe-Cr-Ni steel (DIN 1.4551).
  • the oxide layer of Inconel 600 steam generator tubes which had been in power operation for 22 years, was pre-oxidized with ozone in the gas phase.
  • comparative experiments were carried out with permanganate as the oxidant.
  • Table 1 Decontamination of austenitic Fe / Cr / Ni steel plating (DIN 1.4551) from a primary pipeline of a pressurized water reactor

Landscapes

  • Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Treating Waste Gases (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

L'invention concerne un procédé de décontamination d'une surface présentant une couche d'oxyde d'un composant ou d'un système d'une centrale nucléaire, selon lequel la couche d'oxyde est traitée au moyen d'un agent oxydant gazeux.
EP06818538A 2005-11-29 2006-11-15 Procede de decontamination d'une surface presentant une couche d'oxyde d'un composant ou d'un systeme d'une centrale nucleaire Not-in-force EP1955335B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP08009058A EP1968075B1 (fr) 2005-11-29 2006-11-15 Procédé de décontamination d'une surface comprenant une couche d'oxyde d'un composant ou d'un système d'une installation nucléaire
SI200631067T SI1955335T1 (sl) 2005-11-29 2006-11-15 Postopek za dekontaminacijo površine, ki ima oksidno plast, komponente ali sistema jedrske naprave

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005056727 2005-11-29
PCT/EP2006/010927 WO2007062743A2 (fr) 2005-11-29 2006-11-15 Procede de decontamination d'une surface presentant une couche d'oxyde d'un composant ou d'un systeme d'une centrale nucleaire

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP08009058A Division EP1968075B1 (fr) 2005-11-29 2006-11-15 Procédé de décontamination d'une surface comprenant une couche d'oxyde d'un composant ou d'un système d'une installation nucléaire
EP08009058.2 Division-Into 2008-05-16

Publications (2)

Publication Number Publication Date
EP1955335A2 true EP1955335A2 (fr) 2008-08-13
EP1955335B1 EP1955335B1 (fr) 2011-04-27

Family

ID=38051982

Family Applications (2)

Application Number Title Priority Date Filing Date
EP08009058A Not-in-force EP1968075B1 (fr) 2005-11-29 2006-11-15 Procédé de décontamination d'une surface comprenant une couche d'oxyde d'un composant ou d'un système d'une installation nucléaire
EP06818538A Not-in-force EP1955335B1 (fr) 2005-11-29 2006-11-15 Procede de decontamination d'une surface presentant une couche d'oxyde d'un composant ou d'un systeme d'une centrale nucleaire

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP08009058A Not-in-force EP1968075B1 (fr) 2005-11-29 2006-11-15 Procédé de décontamination d'une surface comprenant une couche d'oxyde d'un composant ou d'un système d'une installation nucléaire

Country Status (16)

Country Link
US (2) US8021494B2 (fr)
EP (2) EP1968075B1 (fr)
JP (3) JP4881389B2 (fr)
KR (2) KR100960783B1 (fr)
CN (2) CN101286374B (fr)
AR (2) AR058844A1 (fr)
AT (2) ATE522907T1 (fr)
BR (2) BRPI0611248A2 (fr)
CA (2) CA2614249C (fr)
DE (1) DE502006009409D1 (fr)
ES (2) ES2371685T3 (fr)
MX (1) MX2008000630A (fr)
SI (2) SI1955335T1 (fr)
TW (2) TWI406299B (fr)
WO (1) WO2007062743A2 (fr)
ZA (2) ZA200709783B (fr)

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DE102009047524A1 (de) * 2009-12-04 2011-06-09 Areva Np Gmbh Verfahren zur Oberflächen-Dekontamination
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KR20140095266A (ko) 2013-01-24 2014-08-01 한국원자력연구원 금속 표면 고착성 방사능 오염 산화막 제거를 위한 무착화성 화학 제염제 및 이를 이용한 화학 제염방법
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CN105149278B (zh) * 2015-10-14 2017-05-24 广东核电合营有限公司 核电站化学清洗去污设备
JP6615009B2 (ja) * 2016-03-04 2019-12-04 東京エレクトロン株式会社 金属汚染防止方法及び金属汚染防止装置、並びにこれらを用いた基板処理方法及び基板処理装置
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CN108630332B (zh) * 2018-03-26 2021-06-18 中国核电工程有限公司 一种草酸盐沉淀过滤母液中草酸根的破坏装置及破坏方法
CN112233827B (zh) * 2020-09-10 2023-06-13 福建福清核电有限公司 一种核电站反应堆冷却剂系统氧化停堆前溶解氢含量控制方法
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Also Published As

Publication number Publication date
MX2008000630A (es) 2008-03-13
US8608861B2 (en) 2013-12-17
US20080190450A1 (en) 2008-08-14
JP4881389B2 (ja) 2012-02-22
CN101199026B (zh) 2012-02-22
EP1968075B1 (fr) 2011-08-31
KR100879849B1 (ko) 2009-01-22
US20090250083A1 (en) 2009-10-08
JP2010107196A (ja) 2010-05-13
TW200826119A (en) 2008-06-16
WO2007062743A2 (fr) 2007-06-07
JP2009517638A (ja) 2009-04-30
TWI406299B (zh) 2013-08-21
DE502006009409D1 (de) 2011-06-09
ZA200709783B (en) 2008-11-26
CA2614249A1 (fr) 2007-06-07
SI1968075T1 (sl) 2011-12-30
EP1968075A1 (fr) 2008-09-10
CA2633626A1 (fr) 2007-06-07
JP2011169910A (ja) 2011-09-01
EP1955335B1 (fr) 2011-04-27
TWI376698B (fr) 2012-11-11
BRPI0611248A2 (pt) 2009-07-07
KR100960783B1 (ko) 2010-06-01
ES2371685T3 (es) 2012-01-09
ATE507566T1 (de) 2011-05-15
WO2007062743A3 (fr) 2007-09-27
CA2633626C (fr) 2010-05-04
SI1955335T1 (sl) 2011-09-30
KR20080016701A (ko) 2008-02-21
ATE522907T1 (de) 2011-09-15
KR20080009767A (ko) 2008-01-29
ES2365417T3 (es) 2011-10-04
CN101286374B (zh) 2012-02-22
BRPI0621970A2 (pt) 2011-07-19
AR064520A2 (es) 2009-04-08
CA2614249C (fr) 2010-11-16
ZA200800291B (en) 2009-08-26
JP4876190B2 (ja) 2012-02-15
CN101199026A (zh) 2008-06-11
CN101286374A (zh) 2008-10-15
US8021494B2 (en) 2011-09-20
AR058844A1 (es) 2008-02-27
TW200729233A (en) 2007-08-01

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