EP1968075B1 - Verfahren zur Dekontamination einer eine Oxidschicht aufweisenden Oberfläche einer Komponente oder eines Systems einer kerntechnischen Anlage - Google Patents

Verfahren zur Dekontamination einer eine Oxidschicht aufweisenden Oberfläche einer Komponente oder eines Systems einer kerntechnischen Anlage Download PDF

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Publication number
EP1968075B1
EP1968075B1 EP08009058A EP08009058A EP1968075B1 EP 1968075 B1 EP1968075 B1 EP 1968075B1 EP 08009058 A EP08009058 A EP 08009058A EP 08009058 A EP08009058 A EP 08009058A EP 1968075 B1 EP1968075 B1 EP 1968075B1
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EP
European Patent Office
Prior art keywords
oxide layer
steam
oxidation
water
treated
Prior art date
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Not-in-force
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EP08009058A
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German (de)
English (en)
French (fr)
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EP1968075A1 (de
Inventor
Horst-Otto Bertholdt
Terezinha Claudete Dr. Maciel
Franz Dr. Strohmer
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Areva GmbH
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Areva NP GmbH
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Publication date
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Priority to SI200631179T priority Critical patent/SI1968075T1/sl
Publication of EP1968075A1 publication Critical patent/EP1968075A1/de
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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
    • G21F9/28—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 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.
  • Austenitic chromium-nickel steel for example, with 72% iron, 18% chromium and 10% nickel comes into consideration as material for a system or a component.
  • 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 mentioned pre-oxidation of the oxide layer is conventionally in acidic solution with potassium permanganate and nitric acid or in alkaline solution with potassium permanganate and sodium hydroxide.
  • EP 0 160 831 B1 known process is carried out in the acidic range and used instead of potassium permanganate permanganic acid.
  • the said processes have the disadvantage that during the oxidation treatment manganese dioxide (MnO 2 ) is formed, which deposits on the oxide layer to be treated and inhibits the passage of the oxidant (permanganate ion) into the oxide layer.
  • MnO 2 manganese dioxide
  • the oxide layer can not be completely oxidized in one step. Rather, acting as a diffusion barrier 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 exchanger
  • a method for cleaning radioactively contaminated plastic material in which the contaminated plastic with a decontamination solution which consists of an aqueous nitric acid solution containing a No x - generating reagent.
  • This object is achieved in a method according to claim 1, characterized in that the oxidation of the oxide layer with gaseous nitrogen oxide (NO x ) is performed.
  • NO x gaseous nitrogen oxide
  • 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.
  • nitric oxide is 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 slowly. Therefore, it is advantageous if a water film is maintained on the oxide layer during the treatment.
  • the nitrogen oxide (NO x ) finds in the oxide film covering the water film or in water-filled pores of the oxide layer, the aqueous conditions required for the course of the oxidative reactions.
  • 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 can be achieved to be required.
  • 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 supplied 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 brought 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, especially when working at higher temperatures.
  • Ozone has an oxidation potential of 2.08 V in an acid 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 is preferably carried out 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 simultaneously be used as the oxidizing agent, as is the case in a preferred process variant described below.
  • the running oxidation reactions can be accelerated by using elevated temperatures.
  • a temperature range of 40-70 ° C has been found to be particularly advantageous. From 40 ° 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 ° 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 .
  • mixtures of various nitrogen oxides such as NO, NO 2 , N 2 O and N 2 O 4 are used for the oxidation.
  • the oxidation effect can be increased by using elevated temperatures, with such an increase from about 80 ° C is noticeable.
  • the best effectiveness is achieved when working in a temperature range of about 110 ° C to about 180 ° C.
  • the oxidation effect can also, as in the case of ozone, be influenced by the concentration of nitrogen oxides.
  • An 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 .
  • a rinse is that of the above-described Way treated oxide layer, for example, with deionized appropriate.
  • an oxide layer is subjected to steam after the oxidation treatment, wherein a condensation of the water vapor takes place at the oxide layer.
  • this treatment in or adheres to the oxide layers or component surfaces adhering activity, such as in particulate form or in dissolved or colloidal form in the condensate and is removed with this from the surfaces. 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.
  • Excess water vapor that is, which has not been condensed on the treated surfaces, is removed from the system to be cleaned or a container in which an oxidative treatment has been carried out 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. 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. In the decontamination of a component, such as a primary system pipeline, this is arranged in a container. Such a container would correspond in the flow chart to the system 1.
  • a decontamination circuit 2 is connected to the system 1 and the container. This is gas-tight. Before commissioning, the decontamination circuit 2 and the system are checked for leaks, for example by evacuation.
  • the entire system, ie system 1 and decontamination circuit 2 is heated up.
  • a feed station 3 for hot air and / or superheated steam is arranged in the decontamination circuit 2.
  • a pump 5 is further provided to fill the system 1 with the appropriate gaseous medium and this, as long as necessary, to circulate in the entire system.
  • the system With the help of hot air or superheated steam, the system is brought to the intended process temperature, in the case of ozone to 50-70 ° C.
  • steam is added via the feed station 3. Separating or condensing water is separated at the system outlet 6 by means 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 in the water film a pH of about 1 to 2 sets.
  • the system 1 is supplied with ozone at a concentration of preferably 100 to 120 g via a feed stadium 10 / Nm 3 continuously supplied with in-service pump 5. 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 possibly 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 scrubber for the separation of NO x / HNO 3 / HNO 2 and then via a catalyst 12, in which a conversion of ozone to oxygen takes place.
  • 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.
  • the oxide layer is acted upon by steam and ensured that the component surfaces or an oxide layer located thereon a Temperature of below 100 ° 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.
  • aqueous solution containing nitrate and radioactive cations there is thus an aqueous solution containing nitrate and radioactive cations.
  • 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 used, ie a molar 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.
  • an organic complexing acid preferably oxalic acid, approximately corresponding to one in EP 0 160 831 B1 described method at a temperature of for example 95 ° C added. It will circulated the decontamination solution by means of the pump 5 in the decontamination circuit 2, wherein via a shunt (not shown), a part of the solution passed through ion exchange resins and cations dissolved out of the oxide layer are bound to the exchange resins. Finally, at the end of decontamination, an oxidative decomposition of the organic acid by means of UV irradiation to carbon dioxide and water, approximately corresponding to that in the EP patent 0 753 196 B1 described method.
  • a gas phase oxidation was carried out on a pipe section of a primary system pipeline.
  • the pipeline originated from a pressurized water system with more than 25 years of service operation and was provided with an inner cladding made of austenitic Fe-Cr-Ni steel (DIN 1.4551). Accordingly, dense and difficult to dissolve was the oxide formation present on the pipe inner surface.
  • the oxide layer of Inconel 600 steam generator pipes which had been in power operation for 22 years, was preoxidized with ozone in the gas phase. Comparative tests with permanganate as the oxidizing agent were carried out in each case for the first and second laboratory tests.

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  • 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)
EP08009058A 2005-11-29 2006-11-15 Verfahren zur Dekontamination einer eine Oxidschicht aufweisenden Oberfläche einer Komponente oder eines Systems einer kerntechnischen Anlage Not-in-force EP1968075B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200631179T SI1968075T1 (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
EP06818538A EP1955335B1 (de) 2005-11-29 2006-11-15 Verfahren zur dekontamination einer eine oxidschicht aufweisenden oberfläche einer komponente oder eines systems einer kerntechnischen anlage

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EP06818538A Division EP1955335B1 (de) 2005-11-29 2006-11-15 Verfahren zur dekontamination einer eine oxidschicht aufweisenden oberfläche einer komponente oder eines systems einer kerntechnischen anlage
EP06818538.8 Division 2006-11-15

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EP1968075A1 EP1968075A1 (de) 2008-09-10
EP1968075B1 true EP1968075B1 (de) 2011-08-31

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EP06818538A Not-in-force EP1955335B1 (de) 2005-11-29 2006-11-15 Verfahren zur dekontamination einer eine oxidschicht aufweisenden oberfläche einer komponente oder eines systems einer kerntechnischen anlage
EP08009058A Not-in-force EP1968075B1 (de) 2005-11-29 2006-11-15 Verfahren zur Dekontamination einer eine Oxidschicht aufweisenden Oberfläche einer Komponente oder eines Systems einer kerntechnischen Anlage

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US (2) US8021494B2 (ko)
EP (2) EP1955335B1 (ko)
JP (3) JP4881389B2 (ko)
KR (2) KR100960783B1 (ko)
CN (2) CN101286374B (ko)
AR (2) AR058844A1 (ko)
AT (2) ATE507566T1 (ko)
BR (2) BRPI0611248A2 (ko)
CA (2) CA2633626C (ko)
DE (1) DE502006009409D1 (ko)
ES (2) ES2365417T3 (ko)
MX (1) MX2008000630A (ko)
SI (2) SI1955335T1 (ko)
TW (2) TW200729233A (ko)
WO (1) WO2007062743A2 (ko)
ZA (2) ZA200709783B (ko)

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DE102009002681A1 (de) * 2009-02-18 2010-09-09 Areva Np Gmbh Verfahren zur Dekontamination radioaktiv kontaminierter Oberflächen
DE102009047524A1 (de) * 2009-12-04 2011-06-09 Areva Np Gmbh Verfahren zur Oberflächen-Dekontamination
DE102010028457A1 (de) * 2010-04-30 2011-11-03 Areva Np Gmbh Verfahren zur Oberflächen-Dekontamination
EP2758966B1 (de) 2011-09-20 2016-03-16 Horst-Otto Bertholdt Verfahren zum abbau einer oxidschicht
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
DE102013100933B3 (de) * 2013-01-30 2014-03-27 Areva Gmbh Verfahren zur Oberflächen-Dekontamination von Bauteilen des Kühlmittelkreislaufs eines Kernreaktors
DE102013102331B3 (de) 2013-03-08 2014-07-03 Horst-Otto Bertholdt Verfahren zum Abbau einer Oxidschicht
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
KR102378652B1 (ko) 2017-02-14 2022-03-28 짐펠캄프 니스 인제니어게젤샤프트 엠베하 방사성핵종 함유 산화물 층의 분해 방법
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
CN114684843B (zh) * 2020-12-25 2023-11-03 中核四0四有限公司 一种快速氧化草酸的方法
KR102631595B1 (ko) * 2021-12-13 2024-02-02 한국원자력연구원 사산화이질소를 이용한 제염 폐액의 처리 방법

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WO2007062743A2 (de) 2007-06-07
CA2633626A1 (en) 2007-06-07
CA2614249C (en) 2010-11-16
JP2011169910A (ja) 2011-09-01
EP1955335B1 (de) 2011-04-27
DE502006009409D1 (de) 2011-06-09
AR064520A2 (es) 2009-04-08
TW200729233A (en) 2007-08-01
EP1968075A1 (de) 2008-09-10
JP4881389B2 (ja) 2012-02-22
ZA200709783B (en) 2008-11-26
JP4876190B2 (ja) 2012-02-15
US8021494B2 (en) 2011-09-20
SI1955335T1 (sl) 2011-09-30
ES2365417T3 (es) 2011-10-04
CN101199026A (zh) 2008-06-11
EP1955335A2 (de) 2008-08-13
SI1968075T1 (sl) 2011-12-30
TWI406299B (zh) 2013-08-21
KR100879849B1 (ko) 2009-01-22
ATE522907T1 (de) 2011-09-15
CA2633626C (en) 2010-05-04
TW200826119A (en) 2008-06-16
US8608861B2 (en) 2013-12-17
KR100960783B1 (ko) 2010-06-01
CN101199026B (zh) 2012-02-22
AR058844A1 (es) 2008-02-27
KR20080009767A (ko) 2008-01-29
CA2614249A1 (en) 2007-06-07
CN101286374A (zh) 2008-10-15
ZA200800291B (en) 2009-08-26
TWI376698B (ko) 2012-11-11
ES2371685T3 (es) 2012-01-09
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US20090250083A1 (en) 2009-10-08
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KR20080016701A (ko) 2008-02-21
US20080190450A1 (en) 2008-08-14
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