EP0636712B1 - Chemisches Reinigungsverfahren von metallischen Werkstücken - Google Patents

Chemisches Reinigungsverfahren von metallischen Werkstücken Download PDF

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Publication number
EP0636712B1
EP0636712B1 EP94401729A EP94401729A EP0636712B1 EP 0636712 B1 EP0636712 B1 EP 0636712B1 EP 94401729 A EP94401729 A EP 94401729A EP 94401729 A EP94401729 A EP 94401729A EP 0636712 B1 EP0636712 B1 EP 0636712B1
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EP
European Patent Office
Prior art keywords
compounds
process according
unsaturated
silica
amines
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
Application number
EP94401729A
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English (en)
French (fr)
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EP0636712A1 (de
Inventor
Béatrice Sala
Angel Gelpi
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 NP SAS
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Framatome SA
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Application filed by Framatome SA filed Critical 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 parts metal on which a deposit has formed which is harmful to characteristics of the part, containing oxides (in particular iron oxide in the form of magnetite), following exposure to water, liquid and / or vapor phase high temperature. It relates more particularly to the chemical cleaning of such parts which have been exposed to high temperature water containing iron compounds and silicon, as well as other elements such as Na, Ca, X, 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 application important in the leaching of that of the faces of the tubes nuclear power plant steam generator which is exposed to the secondary circuit, where water containing polluting chemical elements of various origins, for example from condenser leaks, resins ion exchangers used for demineralization, water treatment and corrosion products of the secondary circuit. Deposits also form well on the straight parts of the exchange tubes and in the gaps, especially between tubes and spacers distributed along the tubes and intended to maintain them relative to each other as well as between the tubes and the tubular plate.
  • the invention is however also applicable to any metal part on which a comparable deposit has formed to those involved in such heat exchangers steam.
  • the analyzes carried out on samples of tubes of an exchanger carrying deposits has shown that the structure of these deposits was much more complex than never imagined it.
  • the deposit consists mainly of magnetite
  • the oxidized layer passivation conventionally developed during the phase final manufacturing of the exchange tubes, is destroyed under the alveolar silico-aluminate and it replaces one relatively thick non-protective layer.
  • this layer has a high chromium content and iron in the usual case where the exchange tubes are made of one of the nickel-chrome alloys containing also iron and other designated editing items by the brand "INCONEL". It is likely to exist also, with a lesser thickness, under the magnetite in the straight parts of the tubes.
  • the present invention aims to provide a method of cleaning of deposits likely to intervene in these conditions. To this end, it offers a cleaning process chemical treatment of metallic material parts bearing a deposit comprising compounds with a high silica content and metal oxides, in particular magnetite, according to claim 1.
  • additional species such as AlO - / 4, which give a negative ionic character to the surface deposit.
  • This negative nature can be automatically compensated for by the absorption of cations present in the aqueous phase, such as Ca 2+ , NH 4 , K + , or of cations originating from the corrosion of the metal part itself.
  • a feature that makes deposits particularly hard to tear is that the Si-O bond is one of strongest silicon bonds, since it comes immediately after Si-F in the order of energies decreasing.
  • the tube cleaning process begins with the elimination magnetite, by any of the methods known.
  • the second step is to remove deposits remaining, mainly containing siliceous compounds, by treatment with chemical compounds promoting delocalization of the electrons of Si-O-metal bonds and their weakening.
  • These compounds will be used in the aqueous phase, with a content of insertion compounds and a temperature of treatment chosen according to the compounds. In a way generally, it is best to work at the most high compatible with the physical or chemical stability of compounds.
  • heteropolyacids and their salts in particular alkaline molybdates.
  • the silica is thus maintained in the state of coordination +6 and its repolymerization is avoided.
  • boric acid can be added to maintain a pH between 1 and 5
  • 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.
  • silica passes in particular to the state of polysiloxane.
  • the compounds finally obtained are fluid, even at low temperatures, since the elements of deposit do not have an excessive number of carbon atoms and do not lead to too long chains.
  • the silica layer is general re-passivation of the base metal. It may be done in a conventional way by oxidation with drying and dehydroxylation. Drying-oxidation can be carried out at 290-300 ° C for 24 to 48 hours with gas sweeping dry oxidant, for example consisting of dry air or air enriched with oxygen.
  • the treated specimens consisted of a "Inconel" section carrying various layers; in particular, most with a layer of about 100 ⁇ m of magnetite and, in some areas, a siliceous coating topped with a layer of magnetite.
  • these compounds can be used under form of aqueous ammonia solution with or without fluoride ammonium having an insertion role.
  • solutions were used with 1 mol per liter of ammonia, 20 to 300 g / l of phenol from 0 to 100 g / l of ammonium fluoride NH 4 F, for tests on Inconel test pieces previously coated with aluminosilicate gel and on samples from the steam generator of 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 NH 3 solution under hot conditions for 15 to 20 minutes, then rinsed in ethanol with ultrasonic stirring and finally dried with compressed air.
  • a 20% ethanol solution 10 g was prepared liter of boric acid and 100 g per liter of molybdate of ammonium in distilled water. The solution was again 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 eliminate the magnetite present on tubes and 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 m 3 per hour for a typical steam generator of a nuclear power station, 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 as far where 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 and then refilled and warmed up. Insertion or condensation components, intended to remove the siliceous deposit by solubilization, are injected. The solution is put into circulation with nitrogen injection to promote solubilization in interstices. After destruction of the layer and passage of silicates in solution, the generator is drained.
  • Passivation can be done by filling of water, warming up and injecting oxygen bubbles to bring the oxidation potential measured at the electrode to the saturated calomel, above 350 mV. Finally, the generator steam can be drained and dried before storage.

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  • 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)

Claims (11)

  1. Verfahren zur chemischen Reinigung metallischer Werkstücke, die eine Eisenoxidabscheidung über einer Schicht von Verbindungen mit hohem Gehalt an Siliziumdioxid tragen, gemäß dem man die Metalloxide an der Oberfläche durch eine Komplexbildung beseitigt, der eine Reduktion vorausgehen kann, dann eine Auflösung der siliziumdioxidhaltigen Verbindungen durch eine Reaktion in wässerigem Medium zur Steigerung der Koordinationszahl des Siliziumdioxids mit elektrophilen, zu der Gruppe gehörenden Verbindungen, die die ungesättigten konjugierten Systeme und die ungesättigten N-oxidverbindungen umfaßt, oder durch eine Kondensationsreaktion in wässerigem Medium mit Alkoholen oder Aminen zwecks Schwächung der Bindungen in einem Medium vornimmt, das die Komplexbildung von Si(OH)4 sichert.
  2. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die ungesättigten Systeme phenyl-substituierte Gruppen aufweisen.
  3. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die ungesättigten Verbindungen mehrere Benzolringe aufweisen.
  4. Verfahren nach dem Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man außerdem die siliziumdioxidhaltigen Verbindungen in Lösung hält, indem man dem Medium Verbindungen zur Komplexbildung von Si(OH)4 zusetzt.
  5. Verfahren nach dem Anspruch 4, dadurch gekennzeichnet, daß diese Verbindungen unter den Molybdaten gewählt werden.
  6. Verfahren nach dem Anspruch 5, dadurch gekennzeichnet, daß diese Verbindungen Ammoniummolybdate sind.
  7. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die ungesättigten konjugierten Systeme Gruppen enthalten, die zu den organischen Verbindungen mit wenigstens einer Alkoholgruppe oder zu den Aminen oder ihren löslichen Salzen gehören.
  8. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß man ein aromatisches Amin oder ein Salz eines tertiären Amins verwendet.
  9. Verfahren nach dem Anspruch 2, dadurch gekennzeichnet, daß die phenyl-substituierten Gruppen zu den Monophenyl-, Diphenyl- und Triphenylgruppen gehören.
  10. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die Kondensation durch das Phenol, das Pyrocatechol oder das Pyrogallol vorgenommen wird.
  11. Verfahren nach irgendeinem der vorstehenden Ansprüche, gekennzeichnet durch einen Endschritt einer Repassivierung durch Oxidation und Deshydroxylation.
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 EP0636712A1 (de) 1995-02-01
EP0636712B1 true EP0636712B1 (de) 1998-10-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
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
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides

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DE69506605T2 (de) * 1994-03-17 1999-07-08 Calgon Corp., Pittsburgh, Pa. Verfahren zur Kontrolle und zum Entfernen von einer Feststoffablagerung auf einer Oberfläche eines Dampferzeugungsanlagebestandteils
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
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

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Publication number Priority date Publication date Assignee Title
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Also Published As

Publication number Publication date
US5575863A (en) 1996-11-19
DE69413899D1 (de) 1998-11-19
EP0636712A1 (de) 1995-02-01
FR2708628B1 (fr) 1997-07-18
FR2708628A1 (fr) 1995-02-10

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