EP0636712A1 - Chemisches Reinigungsverfahren von metallischen Werkstücken - Google Patents

Chemisches Reinigungsverfahren von metallischen Werkstücken Download PDF

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Publication number
EP0636712A1
EP0636712A1 EP94401729A EP94401729A EP0636712A1 EP 0636712 A1 EP0636712 A1 EP 0636712A1 EP 94401729 A EP94401729 A EP 94401729A EP 94401729 A EP94401729 A EP 94401729A EP 0636712 A1 EP0636712 A1 EP 0636712A1
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EP
European Patent Office
Prior art keywords
compounds
process according
medium
unsaturated
reaction
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EP94401729A
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English (en)
French (fr)
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EP0636712B1 (de
Inventor
Béatrice Sala
Angel Gelpi
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Areva NP SAS
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Framatome SA
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Classifications

    • 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
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • 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
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral 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
    • G21F9/001—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 present invention relates to the cleaning of metal parts on which a deposit has formed which adversely affects the characteristics of the part, containing oxides (in particular iron oxide in the form of magnetite), following an exposure to l water, in liquid and / or vapor phase at high temperature. It relates more particularly to the chemical cleaning of such parts which have been exposed to high temperature water containing iron and silicon compounds, as well as other elements such as Na, Ca, K, Al, Zn, Cu , As, Sb, Tl, Pb, C, S, Ni, Cr, Sn.
  • oxides in particular iron oxide in the form of magnetite
  • the invention finds a particularly important application in the leaching of that of the faces of the steam generator tubes of nuclear power plants which is exposed to the secondary circuit, where water containing polluting chemical elements of various origins, for example from condenser leaks, ion exchange resins used for demineralization, water treatment products, and corrosion of secondary circuit elements.
  • Deposits are formed both on the straight parts of the exchange tubes and in the interstices, in particular between the tubes and the spacers distributed along the tubes and intended to maintain them relative to each other as well as between the tubes and the tube plate.
  • the invention is however also applicable to any metal part on which a deposit has formed which is comparable to those which occur in such vapor exchangers.
  • the analyzes carried out on samples of exchanger tubes carrying deposits showed that the structure of these deposits was much more complex than imagined. They have in particular shown that, if the deposit consists mainly of magnetite, there may be locally the presence of silicates on an alveolar silicoaluminate having a solid gel structure, capable of containing carbon products insofar as this element is present in the middle.
  • the oxidized passivation layer conventionally developed during the final phase of manufacturing the exchange tubes, is destroyed under the alveolar silico-aluminate and a relatively thick, non-protective layer is substituted for it.
  • this layer has a high chromium and iron content in the usual case where the exchange tubes are made of one of the nickel-chromium alloys also containing iron and other editing elements. designated by the mark "INCONEL". It is also likely to exist, with a reduced thickness, under magnetite in the straight parts of the tubes.
  • the present invention aims to provide a method for cleaning deposits which may occur under these conditions. To this end, it offers a cleaning process chemical treatment of parts made of metallic material carrying a deposit comprising compounds with a high content of silica and of metal oxides, in particular of magnetite, according to which the metal oxides are removed on the surface by a complexation (which may be preceded by a reduction), then the siliceous compounds are dissolved by a reaction in an aqueous insertion medium with electrophilic compounds, or heteropolyacids for example, or a condensation reaction, in particular with alcohols or amines, intended to weaken the bonds, in a medium ensuring the complexation of Si (OH) 4.
  • a repassivation operation will generally be carried out which can be carried out by surface oxidation with drying and dehydroxylation.
  • One can in particular use a drying at a temperature around 300 ° C for 24 to 48 hours, in a dry oxidizing atmosphere.
  • the network of the depot thus constituted can be inserted additional species, such as AlO - 4 , which give a negative ionic character to the surface deposit.
  • This negative character can be automatically compensated for by the absorption of cations present in the aqueous phase, such as Ca2+, NH4, K+, or of cations originating from the corrosion of the metal part itself.
  • Si-O bond is one of the strongest silicon bonds there is, since it comes immediately after Si-F in the order of decreasing energies.
  • the process of cleaning a tube begins with the removal of magnetite, by any of the known methods.
  • the second step consists in eliminating the remaining deposits, containing mainly siliceous compounds, by treatment with chemical compounds favoring the delocalization of the electrons of the Si-O-metal bonds and their weakening.
  • These compounds will be used in the aqueous phase, with a content of insertion compounds and a treatment temperature chosen as a function of the compounds. In general, it is advantageous to work at the highest temperature compatible with the physical or chemical stability of the compounds.
  • heteropolyacids and their salts in particular alkaline molybdates.
  • the silica is thus maintained in the +6 coordination state and its repolymerization is avoided.
  • boric acid can be added.
  • F ⁇ ions can be added to promote the dissolution of silica.
  • This approach which amounts to an esterification, uses the fact that the silicon compounds having silanol Si-OH functions more acid than the alcohols-R-OH (R being a carbon radical, usually alkyl) give strong hydrogen bonds which cause condensations within the layer, in an acidic or basic medium, that is to say in the presence of H+ or OH ⁇ ions. This is particularly the case for many organo-silicic compounds.
  • a representative reaction is of the kind: where R and R2 denote carbon radicals, generally alkyl such as R.
  • the silica passes in particular to the state of polysiloxane.
  • the compounds finally obtained are fluid, even at low temperature, insofar as the deposition elements do not have an excessive number of carbon atoms and do not lead to too long chains.
  • the silica-based layer has been destroyed, it is generally necessary to repassivate the base metal. This can be done conventionally by oxidation with drying and dehydroxylation.
  • the drying-oxidation can be carried out at 290-300 ° C for 24 to 48 hours with the sweeping of a dry oxidizing gas, for example consisting of dry air or air enriched with oxygen.
  • the treated specimens consisted of an "Inconel" section carrying various layers; in particular, most of them have a layer of approximately 100 ⁇ m of magnetite and, in certain areas, a siliceous coating surmounted by a layer of magnetite.
  • these compounds can be used in the form of an aqueous ammonia solution with or without ammonium fluoride having an insertion role.
  • solutions containing 1 mol per liter of ammonia, 20 to 300 g / l of phenol from 0 to 100 g / l of NH4F ammonium fluoride for tests on Inconel test tubes previously coated with aluminosilicate gel and on samples from a steam generator in a French nuclear power plant containing deposits of magnetite and alumino-silicate.
  • the temperatures used varied from 80 to 150 ° C so as to obtain the best dissolution without corroding the base metal.
  • one test consisted in placing the solution and the test tube, already freed from magnetite, in a reactor containing a magnetic stirrer. The reactor was heated to 100 ° C and the vapors released were condensed in a column and returned to the reactor. After six hours, the test piece was rinsed in a 1 M solution of NH3 hot for 15 to 20 minutes, then rinsed in ethanol with ultrasonic stirring and finally dried with compressed air.
  • a 20% ethanol solution, 10 g per liter of boric acid and 100 g per liter of molybdate were prepared. of ammonium in distilled water. The solution was further placed in a reactor and maintained at 80 ° C for seven hours. The test piece was then rinsed in ethanol with the application of ultrasound, then dried with compressed air. Observation by electron microscopy further revealed that the silica layer had been destroyed.
  • the first phase of the process is intended to remove the magnetite present on the tubes and the spacer plates.
  • the secondary circuit of the steam generator is filled with water whose temperature is increased, for example by circulation of high temperature water in the primary circuit.
  • the reagents EDTA
  • the water loaded with reagents is circulated, at a rate which will often be around 150 m3 per hour for a typical steam generator of a nuclear power plant, to drive the magnetite of the spacer plates. It is also advantageous to inject a nitrogen flow intended to activate the effect of the solution in the interstices between the tubes and the spacer plates.
  • the second step elimination of siliceous compounds, can follow immediately after the first insofar as the products used for insertion or condensation, chosen from those mentioned above, are compatible with the products used during the first phase.
  • the secondary circuit of the steam generator is drained, then refilled and reheated.
  • the insertion or condensation components intended to remove the siliceous deposit by solubilization, are injected.
  • the solution is circulated with nitrogen injection to promote solubilization in the interstices. After destruction of the layer and passage of the silicates in solution, the generator is drained.
  • Passivation can be carried out by filling with water, warming up and injecting oxygen bubbles to bring the oxidation potential measured at the saturated calomel electrode, above 350 mV. Finally, the steam generator can be drained and dried before storage.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silicon Compounds (AREA)
EP94401729A 1993-07-29 1994-07-27 Chemisches Reinigungsverfahren von metallischen Werkstücken Expired - Lifetime EP0636712B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9309360A FR2708628B1 (fr) 1993-07-29 1993-07-29 Procédé de nettoyage chimique de pièces en matériau métallique.
FR9309360 1993-07-29

Publications (2)

Publication Number Publication Date
EP0636712A1 true EP0636712A1 (de) 1995-02-01
EP0636712B1 EP0636712B1 (de) 1998-10-14

Family

ID=9449767

Family Applications (1)

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EP94401729A Expired - Lifetime EP0636712B1 (de) 1993-07-29 1994-07-27 Chemisches Reinigungsverfahren von metallischen Werkstücken

Country Status (4)

Country Link
US (1) US5575863A (de)
EP (1) EP0636712B1 (de)
DE (1) DE69413899D1 (de)
FR (1) FR2708628B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0674024A3 (de) * 1994-03-17 1996-07-31 Calgon Corp Verfahren zur Kontrolle und zum Entfernen von einer Feststoffablagerung auf einer Oberfläche eines Dampferzeugungsanlagebestandteils.

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5841826A (en) * 1995-08-29 1998-11-24 Westinghouse Electric Corporation Method of using a chemical solution to dislodge and dislocate scale, sludge and other deposits from nuclear steam generators
US8195273B2 (en) * 2004-02-02 2012-06-05 Esaote S.P.A. Magnetic resonance imaging apparatus
JP4807857B2 (ja) * 2004-04-01 2011-11-02 ウエスチングハウス・エレクトリック・カンパニー・エルエルシー 改良型スケール構造改変剤及び処理方法
US7861915B2 (en) * 2004-04-16 2011-01-04 Ms2 Technologies, Llc Soldering process
TW200610122A (en) * 2004-09-14 2006-03-16 P Kay Metal Inc Soldering process
US7302917B2 (en) * 2004-09-29 2007-12-04 Framatome Anp, Inc. Chemical cleaning of a steam generator during mode 5 generator shut down
DE102004054471B3 (de) * 2004-11-11 2006-04-27 Framatome Anp Gmbh Reinigungsverfahren zur Entfernung von Magnetit enthaltenden Ablagerungen aus einem Druckbehälter eines Kraftwerks
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides
DE102008005199B4 (de) * 2008-01-18 2014-01-23 Areva Gmbh Verfahren zur Reinigung eines Wärmetauschers
US8165261B2 (en) * 2008-01-22 2012-04-24 Electric Power Research Institute, Inc. Chemical enhancement of ultrasonic fuel cleaning
KR101664951B1 (ko) * 2010-01-26 2016-10-11 도미니온 엔지니어링 인코포레이티드 증착물들을 제거하기 위한 방법 및 조성물
CN103510097B (zh) * 2012-06-26 2016-02-17 杭州冠洁工业清洗水处理科技有限公司 凝汽器低腐蚀高净度化学清洗方法
CN109323237B (zh) * 2018-09-14 2020-01-07 福建宁德核电有限公司 核级聚丙烯酸分散剂用于核电厂蒸汽发生器湿保养的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013909A (en) * 1960-03-31 1961-12-19 Guyon P Pancer Method of chemical decontamination of stainless steel nuclear facilities
JPS55109498A (en) * 1979-02-15 1980-08-22 Ichiro Kudo Silicic acid scale removing agent
JPS5892499A (ja) * 1981-11-28 1983-06-01 Nippon Nohyaku Co Ltd スケ−ル除去剤
JPS5929093A (ja) * 1982-08-10 1984-02-16 Power Reactor & Nuclear Fuel Dev Corp スケ−ルの除去方法
DE3431101A1 (de) * 1984-08-24 1986-03-06 Hubert F. 6000 Frankfurt Neuhausen Flusssaeure - enthaltende waessrige organische saeuremischungen mit eventuellem zusatz von anorganischen saeuren und korrisionsinhibitoren
JPS6250489A (ja) * 1985-08-30 1987-03-05 Kawasaki Steel Corp 方向性珪素鋼板の酸化物皮膜除去方法
US4729855A (en) * 1985-11-29 1988-03-08 Westinghouse Electric Corp. Method of decontaminating radioactive metal surfaces

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA718380A (en) * 1965-09-21 A. Lesinski Chester Scale removal, ferrous metal passivation and compositions therefor
US3148150A (en) * 1960-05-12 1964-09-08 Petrolite Corp Process for preventing, reducing and removing hard-water scale employing methylol pheol derivatives
US3664870A (en) * 1969-10-29 1972-05-23 Nalco Chemical Co Removal and separation of metallic oxide scale
US4666528A (en) * 1985-11-27 1987-05-19 Halliburton Company Method of removing iron and copper-containing scale from a metal surface
US4793865A (en) * 1987-08-19 1988-12-27 Aqua Process, Inc. Method and composition for the removal of ammonium salt and metal compound deposits
US5322636A (en) * 1992-03-30 1994-06-21 Calgon Corporation Polyether polyamino methylene phosphonate n-oxides for high pH scale control

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013909A (en) * 1960-03-31 1961-12-19 Guyon P Pancer Method of chemical decontamination of stainless steel nuclear facilities
JPS55109498A (en) * 1979-02-15 1980-08-22 Ichiro Kudo Silicic acid scale removing agent
JPS5892499A (ja) * 1981-11-28 1983-06-01 Nippon Nohyaku Co Ltd スケ−ル除去剤
JPS5929093A (ja) * 1982-08-10 1984-02-16 Power Reactor & Nuclear Fuel Dev Corp スケ−ルの除去方法
DE3431101A1 (de) * 1984-08-24 1986-03-06 Hubert F. 6000 Frankfurt Neuhausen Flusssaeure - enthaltende waessrige organische saeuremischungen mit eventuellem zusatz von anorganischen saeuren und korrisionsinhibitoren
JPS6250489A (ja) * 1985-08-30 1987-03-05 Kawasaki Steel Corp 方向性珪素鋼板の酸化物皮膜除去方法
US4729855A (en) * 1985-11-29 1988-03-08 Westinghouse Electric Corp. Method of decontaminating radioactive metal surfaces

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 242 (C - 438)<2689> 7 August 1987 (1987-08-07) *
PATENT ABSTRACTS OF JAPAN vol. 4, no. 173 (C - 32)<655> 29 November 1980 (1980-11-29) *
PATENT ABSTRACTS OF JAPAN vol. 7, no. 191 (C - 182)<1336> 20 August 1983 (1983-08-20) *
PATENT ABSTRACTS OF JAPAN vol. 8, no. 118 (C - 226)<1555> 31 May 1984 (1984-05-31) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0674024A3 (de) * 1994-03-17 1996-07-31 Calgon Corp Verfahren zur Kontrolle und zum Entfernen von einer Feststoffablagerung auf einer Oberfläche eines Dampferzeugungsanlagebestandteils.

Also Published As

Publication number Publication date
US5575863A (en) 1996-11-19
DE69413899D1 (de) 1998-11-19
EP0636712B1 (de) 1998-10-14
FR2708628B1 (fr) 1997-07-18
FR2708628A1 (fr) 1995-02-10

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