EP0313843B2 - Verfahren zur Dekontamination von Oberflächen - Google Patents
Verfahren zur Dekontamination von Oberflächen Download PDFInfo
- Publication number
- EP0313843B2 EP0313843B2 EP88116003A EP88116003A EP0313843B2 EP 0313843 B2 EP0313843 B2 EP 0313843B2 EP 88116003 A EP88116003 A EP 88116003A EP 88116003 A EP88116003 A EP 88116003A EP 0313843 B2 EP0313843 B2 EP 0313843B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- treatment step
- decontamination
- acid
- decontamination solution
- samples
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 24
- 238000011282 treatment Methods 0.000 claims description 34
- 238000005202 decontamination Methods 0.000 claims description 32
- 230000003588 decontaminative effect Effects 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 17
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 13
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 13
- 239000002344 surface layer Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000002826 coolant Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 239000000243 solution Substances 0.000 description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001055 inconels 600 Inorganic materials 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910000669 Chrome steel Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910001293 incoloy Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910001026 inconel Inorganic materials 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- LXMQZGGLHVSEBA-UHFFFAOYSA-N chromium;trihydrate Chemical compound O.O.O.[Cr] LXMQZGGLHVSEBA-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010857 liquid radioactive waste Substances 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012549 training Methods 0.000 description 1
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
-
- 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 surfaces according to the preamble of claim 1.
- EP 0071336 A1 also describes a method for the chemical removal of deposits known in which using permanganate salt Decontamination is achieved in three steps becomes. Avoids the path taken there apparently the use of chromic acid.
- a second treatment step is then, usually after an intermediate rinse that loosened Oxide layer in an acid, refractory and complex-forming Solution resolved and removed.
- the oxidative treatment step there are a number of methods in use so z.
- Other known methods see the use of permanganic acid, Hydrogen peroxide, cerium IV salts or others Oxidizing agents before.
- the permanganic acid can preferably be prepared by adding an aqueous solution of a Alkali or alkaline earth permanganate via a cation exchanger passed and so the free acid is formed after the addition of chromic acid is used as a decontamination agent.
- chromic acid and salts of Permanganic acid suitable as a decontamination agent; however, the additional imported cation with the radioactive waste slightly higher salt loads arise. Characterizing for the effectiveness of the decontamination agent are the pH and the redox potential of the Solution. Therefore, this can be easily grasped
- the first treatment step is monitored and be controlled.
- the effect of the first treatment step used decontamination solution by pumping, stirring or by application of ultrasound significantly increase.
- Through the Chemical measures can also be the same Removal of the modified surface layers be accelerated in the second treatment step.
- the Solution in the circuit via an ion exchanger passed and rinsed the treated surface.
- Samples a) were made of ferritic chrome steel at room temperature (290 to 295 K) during 16 hours with a solution of 0.05 mol each Chromic and permanganic acid treated. After a Intermediate rinsing became a decontamination factor (Ratio of measured activity before and after treatment) determined from 2.
- Samples a) made of ferritic chrome steel, samples b) austenitic stainless steels and samples c) from INCOLOY 800 and from INCONEL 600 were each at room temperature for 16 hours in aqueous solutions with 0.01 to 0.1 mol Chromic acid and 0.001 to 0.05 mol permanganic acid treated, the ratio of chromic acid to permanganic acid was between 1:10 and 25: 1.
- the samples were then each during 6 Hours at room temperature in an aqueous Solution with 0.1 mol oxalic acid under the influence of ultrasound treated further. Finally were on all samples, depending on the oxidative treatment and from the sample material, decontamination factors measured between 10 and 1000.
- Samples a) made of ferritic chromium steel and samples c) made from INCONEL 600 were each treated for 16 hours at room temperature in a solution with 0.1 mol of chromic acid and 0.05 mol of permanganic acid. After a subsequent treatment with a water jet of 2.4 kbar (240 Pa) pressure at a treatment speed of 3.6 m 2 / hour, decontamination factors of about 30 were obtained on samples a) made of ferritic chromium steel and 600 decontamination factors of on samples c) from INCONEL measured over 100. Extensive follow-up examinations showed that these treatments did not attack the surfaces of the base materials.
- Samples c) from INCONEL 600 were during 16 hours at room temperature with a solution of 0.05 mol of chromic acid and 0.002 mol of permanganic acid sprayed. After a further one Treatment with a water jet, as in the Example 4, decontamination factors were between 20 and 80 determined.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemical Treatment Of Metals (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH3846/87A CH673545A5 (ko) | 1987-10-02 | 1987-10-02 | |
CH3846/87 | 1987-10-02 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0313843A1 EP0313843A1 (de) | 1989-05-03 |
EP0313843B1 EP0313843B1 (de) | 1992-07-08 |
EP0313843B2 true EP0313843B2 (de) | 1998-05-13 |
Family
ID=4264738
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88116003A Expired - Lifetime EP0313843B2 (de) | 1987-10-02 | 1988-09-28 | Verfahren zur Dekontamination von Oberflächen |
Country Status (8)
Country | Link |
---|---|
US (1) | US5093073A (ko) |
EP (1) | EP0313843B2 (ko) |
JP (1) | JPH02503600A (ko) |
KR (1) | KR970011260B1 (ko) |
CH (1) | CH673545A5 (ko) |
DE (1) | DE3872656D1 (ko) |
ES (1) | ES2034088T5 (ko) |
WO (1) | WO1989003113A1 (ko) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4913849A (en) * | 1988-07-07 | 1990-04-03 | Aamir Husain | Process for pretreatment of chromium-rich oxide surfaces prior to decontamination |
DE4232246A1 (de) * | 1992-09-25 | 1994-03-31 | Siemens Ag | Verfahren zur Zerstörung einer organischen Substanz |
US5278743A (en) * | 1992-11-20 | 1994-01-11 | Westinghouse Electric Corp. | Alkaline-permanganate process |
FR2730641B1 (fr) * | 1995-02-20 | 1997-03-14 | Commissariat Energie Atomique | Mousse de decontamination a l'ozone, et procede de decontamination utilisant cette mousse |
US5678232A (en) * | 1995-07-31 | 1997-10-14 | Corpex Technologies, Inc. | Lead decontamination method |
US5591270A (en) * | 1995-07-31 | 1997-01-07 | Corpex Technologies, Inc. | Lead oxide removal method |
JP3939355B2 (ja) * | 1996-02-07 | 2007-07-04 | バックマン・ラボラトリーズ・インターナショナル・インコーポレーテッド | イオネンポリマーおよびドデシルアミン塩を含有する相乗的殺菌剤組成物ならびにその使用方法 |
US5814204A (en) * | 1996-10-11 | 1998-09-29 | Corpex Technologies, Inc. | Electrolytic decontamination processes |
US6183547B1 (en) * | 1998-03-05 | 2001-02-06 | The University Of Notre Dame Du Lac | Environmentally acceptable inhibitor formulations for metal surfaces |
JP2001124891A (ja) * | 1999-07-09 | 2001-05-11 | Hitachi Ltd | 原子力プラント構造物の表面処理方法および原子力プラント |
JP3977963B2 (ja) | 1999-09-09 | 2007-09-19 | 株式会社日立製作所 | 化学除染方法 |
FR2841802B1 (fr) * | 2002-07-08 | 2005-03-04 | Commissariat Energie Atomique | Composition, mousse et procede de decontamination de surfaces |
KR100724710B1 (ko) * | 2002-11-21 | 2007-06-04 | 가부시끼가이샤 도시바 | 방사화 부품의 화학적 오염제거 시스템 및 방법 |
KR20040077390A (ko) * | 2003-02-28 | 2004-09-04 | 김성진 | 핵 방사능 잡 고체, 시멘트, 농축 폐 액 드럼을 천일염수와 천일염으로 절게 하여 고온으로 소각시켜 핵 방사능독을 흔적없이 공중 완전 소각 방법과, 농축 천일염(수)폐액 드럼. |
JP3945780B2 (ja) * | 2004-07-22 | 2007-07-18 | 株式会社日立製作所 | 原子力プラント構成部材の放射性核種の付着抑制方法および成膜装置 |
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 |
DE102013108802A1 (de) * | 2013-08-14 | 2015-02-19 | Areva Gmbh | Verfahren zur Verringerung der radioaktiven Kontamination eines wasserführenden Kreislaufs eines Kernkraftwerks |
EP3033751B1 (de) * | 2013-08-14 | 2019-10-23 | Framatome GmbH | Verfahren zur verringerung der radioaktiven kontamination der oberfläche einer in einem kernreaktor eingesetzten komponente |
US9440847B2 (en) * | 2013-10-03 | 2016-09-13 | POSiFA MICROSYSTEMS, INC. | Single silicon wafer micromachined thermal conduction sensor |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3615817A (en) * | 1969-02-04 | 1971-10-26 | Atomic Energy Commission | Method of decontaminating radioactive metal surfaces |
US4217192A (en) * | 1979-06-11 | 1980-08-12 | The United States Of America As Represented By The United States Department Of Energy | Decontamination of metals using chemical etching |
EP0071336B1 (en) * | 1981-06-17 | 1986-03-26 | Central Electricity Generating Board | Process for the chemical dissolution of oxide deposits |
US4522928A (en) * | 1982-10-18 | 1985-06-11 | Exxon Research And Engineering Co. | Removal of metal comtaminants from catalysts using buffered oxalic acid |
SE435329B (sv) * | 1983-02-09 | 1984-09-17 | Studsvik Energiteknik Ab | Dekontaminering av tryckvattenreaktorer |
DE3413868A1 (de) * | 1984-04-12 | 1985-10-17 | Kraftwerk Union AG, 4330 Mülheim | Verfahren zur chemischen dekontamination von metallischen bauteilen von kernreaktoranlagen |
US4913849A (en) * | 1988-07-07 | 1990-04-03 | Aamir Husain | Process for pretreatment of chromium-rich oxide surfaces prior to decontamination |
-
1987
- 1987-10-02 CH CH3846/87A patent/CH673545A5/de not_active IP Right Cessation
-
1988
- 1988-09-28 WO PCT/EP1988/000870 patent/WO1989003113A1/de unknown
- 1988-09-28 KR KR1019890700977A patent/KR970011260B1/ko active IP Right Grant
- 1988-09-28 ES ES88116003T patent/ES2034088T5/es not_active Expired - Lifetime
- 1988-09-28 JP JP88508032A patent/JPH02503600A/ja active Pending
- 1988-09-28 DE DE8888116003T patent/DE3872656D1/de not_active Expired - Fee Related
- 1988-09-28 EP EP88116003A patent/EP0313843B2/de not_active Expired - Lifetime
- 1988-09-28 US US07/397,440 patent/US5093073A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
KR890702211A (ko) | 1989-12-23 |
US5093073A (en) | 1992-03-03 |
ES2034088T3 (es) | 1993-04-01 |
JPH02503600A (ja) | 1990-10-25 |
EP0313843B1 (de) | 1992-07-08 |
DE3872656D1 (de) | 1992-08-13 |
WO1989003113A1 (en) | 1989-04-06 |
ES2034088T5 (es) | 1998-10-01 |
KR970011260B1 (ko) | 1997-07-08 |
CH673545A5 (ko) | 1990-03-15 |
EP0313843A1 (de) | 1989-05-03 |
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