EP0198340A1 - Procédé de nettoyage - Google Patents

Procédé de nettoyage Download PDF

Info

Publication number
EP0198340A1
EP0198340A1 EP86104517A EP86104517A EP0198340A1 EP 0198340 A1 EP0198340 A1 EP 0198340A1 EP 86104517 A EP86104517 A EP 86104517A EP 86104517 A EP86104517 A EP 86104517A EP 0198340 A1 EP0198340 A1 EP 0198340A1
Authority
EP
European Patent Office
Prior art keywords
deposits
copper
chemically
remaining
softened
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
EP86104517A
Other languages
German (de)
English (en)
Other versions
EP0198340B1 (fr
Inventor
Hermann Emmert
Herbert Hehs
Detlev Dipl.-Ing. Coerlin
Klaus Kuhnke
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.)
Siemens AG
Original Assignee
Kraftwerk Union AG
Siemens AG
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
Priority claimed from DE19853513676 external-priority patent/DE3513676A1/de
Application filed by Kraftwerk Union AG, Siemens AG filed Critical Kraftwerk Union AG
Publication of EP0198340A1 publication Critical patent/EP0198340A1/fr
Application granted granted Critical
Publication of EP0198340B1 publication Critical patent/EP0198340B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/08—Cleaning containers, e.g. tanks
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B37/00—Component parts or details of steam boilers
    • F22B37/02—Component parts or details of steam boilers applicable to more than one kind or type of steam boiler
    • F22B37/48—Devices for removing water, salt, or sludge from boilers; Arrangements of cleaning apparatus in boilers; Combinations thereof with boilers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B37/00—Component parts or details of steam boilers
    • F22B37/02—Component parts or details of steam boilers applicable to more than one kind or type of steam boiler
    • F22B37/48—Devices for removing water, salt, or sludge from boilers; Arrangements of cleaning apparatus in boilers; Combinations thereof with boilers
    • F22B37/483—Devices for removing water, salt, or sludge from boilers; Arrangements of cleaning apparatus in boilers; Combinations thereof with boilers specially adapted for nuclear steam generators
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
    • F28G9/00—Cleaning by flushing or washing, e.g. with chemical solvents

Definitions

  • the invention relates to a method for cleaning containers, in particular steam generators, in which deposits are chemically dissolved or mechanically removed.
  • the invention has for its object to develop a simple, inexpensive, yet reliable cleaning method. Since copper compounds in particular contribute very much to corrosion and, moreover, hinder other cleaning processes, the method according to the invention is primarily intended to remove all copper compounds from the steam generator. Further cleaning should then be carried out with little effort.
  • the object is achieved in that existing copper compounds are chemically dissolved and then loose deposits and liquids are mechanically removed and then remaining incrustations are softened chemically and finally the loosened deposits and the remaining chemicals are rinsed out.
  • the copper compounds present are chemically dissolved, for example, by adding suitable ligands to an aqueous solution, thereby forming soluble complexes of the copper salts.
  • incrustations which mainly consist of iron oxide, but also contain nickel, chromium, zinc and calcium mainly as phosphates and carbonates in the steam generator.
  • the poorly soluble substances are converted into soluble salts by an acid, for example citric acid.
  • an acid for example citric acid.
  • relatively strong acid can attack metal parts of the steam generator. It is therefore necessary that all acid residues are rinsed out thoroughly in the course of the second mechanical cleaning.
  • the poorly soluble substances are converted into water-soluble complexes by adding suitable acids. This conversion is possible because all copper connections have been removed beforehand. By using only weak acids, the final mechanical cleaning can be carried out in a simplified manner.
  • ethylenediamine and (NH4) 2C03 are added to an aqueous solution to form readily soluble copper amine complexes.
  • the pH is raised to a value greater than pH 10 by adding NH 4 OH and the temperature in the steam generator is kept below 80 ° C. After an exposure time of at least 24 hours, the steam generator is rinsed with deionized water for at least 1 hour.
  • Citric acid for example, which is circulated for 24 hours, is suitable for dissolving incrustations in the steam generator.
  • Another way to remove the incrustations is to form water-soluble complexes by adding EDTA or DCTA and NH 4 0H to raise the pH to pH 10.5.
  • the steam generator is rinsed until the conductivity of the rinsing water has fallen below a predetermined value.
  • Metallic copper deposits are not chemically changed by the process for the chemical dissolution of copper compounds, since the ligands suitable for complex formation in copper compounds do not form any complexes with metallic copper. Even with acids, deposits from metallic copper that cannot be mechanically attacked cannot be removed.
  • metallic copper is removed, for example, by introducing hydrogen peroxide into the contaminated containers as the first process step. This oxidizes the metallic copper. This is followed by the remaining four steps in the cleaning process. The copper oxide formed is dissolved and removed together with existing copper compounds.
  • the advantage is achieved in particular that steam generators can be cleaned quickly and reliably with little effort and in particular copper compounds can be completely dissolved.
EP86104517A 1985-04-16 1986-04-02 Procédé de nettoyage Expired - Lifetime EP0198340B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3513676 1985-04-16
DE19853513676 DE3513676A1 (de) 1985-04-16 1985-04-16 Reinigungsverfahren
DE19853533886 DE3533886A1 (de) 1985-04-16 1985-09-23 Reinigungsverfahren
DE3533886 1985-09-23

Publications (2)

Publication Number Publication Date
EP0198340A1 true EP0198340A1 (fr) 1986-10-22
EP0198340B1 EP0198340B1 (fr) 1990-07-25

Family

ID=25831402

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86104517A Expired - Lifetime EP0198340B1 (fr) 1985-04-16 1986-04-02 Procédé de nettoyage

Country Status (6)

Country Link
US (1) US4720306A (fr)
EP (1) EP0198340B1 (fr)
BR (1) BR8601684A (fr)
CA (1) CA1272433A (fr)
DE (2) DE3533886A1 (fr)
ES (1) ES8703537A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0484042A1 (fr) * 1990-10-29 1992-05-06 Westinghouse Electric Corporation Méthode pour enlever les boues et les dépôts à l'intérieur d'un réservoir d'échangeur de chaleur
DE102008005199A1 (de) 2008-01-18 2009-07-30 Areva Np Gmbh Verfahren zur Reinigung eines Wärmetauschers

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4308209C2 (de) * 1993-03-15 1996-12-05 Siemens Ag Verfahren zum Entfernen von metallischem Blei
US5413168A (en) * 1993-08-13 1995-05-09 Westinghouse Electric Corporation Cleaning method for heat exchangers
US5468303A (en) * 1994-02-25 1995-11-21 Zt Corporation Rust, corrosion, and scale remover
EP0674024B1 (fr) * 1994-03-17 1998-12-16 Calgon Corporation Procédé de contrÔle et d'élimination d'un dépÔt solide sur une surface d'un composant d'une installation de génération de vapeur
DE19712401C1 (de) * 1997-01-07 1998-05-20 Krupp Vdm Gmbh Verfahren zum Reinigen und/oder Entfetten von metallischen Formstücken
FR2764364B1 (fr) * 1997-06-05 1999-09-03 Framatome Sa Procede de nettoyage d'un generateur de vapeur d'un reacteur nucleaire refroidi par de l'eau sous pression
DE19746888C1 (de) * 1997-10-23 1999-03-04 Siemens Ag Verfahren zur Reinigung eines Behälters
US6554006B2 (en) * 2000-12-22 2003-04-29 General Electric Company Piping deposit removal from stator water cooling systems
US6740168B2 (en) * 2001-06-20 2004-05-25 Dominion Engineering Inc. Scale conditioning agents
CA2562979C (fr) * 2004-04-01 2014-05-20 Westinghouse Electric Company, Llc Agents de conditionnement anti-tartre ameliores et procede de traitement associe
EP1598629B1 (fr) * 2004-05-19 2005-12-14 Therm-Service für Kraftwerke und Industrie GmbH Procédé de nettoyage chimique d'une installation de gaz et de vapeur
EP2396595B1 (fr) * 2007-11-30 2016-07-20 Koninklijke Philips N.V. Dispositif à vapeur muni d'une fonctionnalité de rinçage
CN113186543B (zh) * 2021-04-27 2023-03-14 上海新阳半导体材料股份有限公司 一种化学机械抛光后清洗液及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1130066A (fr) * 1954-06-01 1957-01-30 Ford Procédé de désoxydation des surfaces métalliques à base de cuivre et solution pour sa mise en oeuvre
US3000767A (en) * 1959-04-30 1961-09-19 Solvent Service Inc Method of cleaning internal ferrous metal surfaces of steam generating equipment
DE1264351B (de) * 1961-02-14 1968-03-21 Pfizer & Co C Verfahren zur Entfernung von kupferhaltigem Eisenoxydkesselstein
DE2000209A1 (de) * 1969-01-06 1970-07-23 Olin Corp Verfahren zum Reinigen von Kupferlegierungen
AU441037B2 (en) * 1970-06-05 1973-10-02 The Dow Chemical Company Inservice cleaning of cooling water systems
EP0073494A1 (fr) * 1981-09-02 1983-03-09 BROWN, BOVERI & CIE Aktiengesellschaft Méthode pour le nettoyage de conducteurs creux de machines et appareils électriques refroidis

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2465228A (en) * 1946-05-07 1949-03-22 Westinghouse Electric Corp Liquid treatment of contact surfaces for copper oxide rectifiers
US2567835A (en) * 1949-08-29 1951-09-11 Dow Chemical Co Removing copper-containing incrustations from steam generators
NL154561B (nl) * 1965-04-27 1977-09-15 Lancy Lab Werkwijze voor het verwijderen van koper(i)oxyde en koper(ii)oxyde van een voorwerp met een oppervlak van koper of een koperlegering, werkwijze voor het bereiden van een hiervoor toe te passen beitsvloeistof en de door toepassing van deze beitswerkwijze verkregen voorwerpen.
US3627687A (en) * 1968-02-09 1971-12-14 Dow Chemical Co Cleaning of ferrous metal surfaces
US3686123A (en) * 1971-04-05 1972-08-22 Kurita Industrial Co Ltd Cleaning composition
SE400575B (sv) * 1974-12-13 1978-04-03 Nordnero Ab Bad for betning av koppar och dess legeringar
US3996062A (en) * 1975-08-28 1976-12-07 Halliburton Company Method for removing scale from metallic substrates
JPS54117327A (en) * 1978-03-06 1979-09-12 Kurita Kasen Kk Removing of copper and spinnel shaped scale
US4443268A (en) * 1981-11-12 1984-04-17 The Dow Chemical Company Process for removing copper and copper oxide encrustations from ferrous surfaces
US4452643A (en) * 1983-01-12 1984-06-05 Halliburton Company Method of removing copper and copper oxide from a ferrous metal surface
US4510018A (en) * 1984-02-21 1985-04-09 The Lea Manufacturing Company Solution and process for treating copper and copper alloys
US4632705A (en) * 1984-03-20 1986-12-30 Westinghouse Electric Corp. Process for the accelerated cleaning of the restricted areas of the secondary side of a steam generator
US4578162A (en) * 1984-05-29 1986-03-25 The Dow Chemical Company Method for dissolving copper in the presence of iron
US4600443A (en) * 1984-10-01 1986-07-15 Kennecott Corporation Process for removing surface oxides from a copper-base alloy
US4586961A (en) * 1985-02-15 1986-05-06 Halliburton Company Methods and compositions for removing copper and copper oxides from surfaces

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1130066A (fr) * 1954-06-01 1957-01-30 Ford Procédé de désoxydation des surfaces métalliques à base de cuivre et solution pour sa mise en oeuvre
US3000767A (en) * 1959-04-30 1961-09-19 Solvent Service Inc Method of cleaning internal ferrous metal surfaces of steam generating equipment
DE1264351B (de) * 1961-02-14 1968-03-21 Pfizer & Co C Verfahren zur Entfernung von kupferhaltigem Eisenoxydkesselstein
DE2000209A1 (de) * 1969-01-06 1970-07-23 Olin Corp Verfahren zum Reinigen von Kupferlegierungen
AU441037B2 (en) * 1970-06-05 1973-10-02 The Dow Chemical Company Inservice cleaning of cooling water systems
EP0073494A1 (fr) * 1981-09-02 1983-03-09 BROWN, BOVERI & CIE Aktiengesellschaft Méthode pour le nettoyage de conducteurs creux de machines et appareils électriques refroidis

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0484042A1 (fr) * 1990-10-29 1992-05-06 Westinghouse Electric Corporation Méthode pour enlever les boues et les dépôts à l'intérieur d'un réservoir d'échangeur de chaleur
DE102008005199A1 (de) 2008-01-18 2009-07-30 Areva Np Gmbh Verfahren zur Reinigung eines Wärmetauschers
DE102008005199B4 (de) * 2008-01-18 2014-01-23 Areva Gmbh Verfahren zur Reinigung eines Wärmetauschers

Also Published As

Publication number Publication date
ES8703537A1 (es) 1987-02-16
BR8601684A (pt) 1986-12-16
EP0198340B1 (fr) 1990-07-25
ES553990A0 (es) 1987-02-16
DE3672872D1 (de) 1990-08-30
US4720306A (en) 1988-01-19
CA1272433A (fr) 1990-08-07
DE3533886A1 (de) 1987-03-26

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