EP0616051B1 - Procédé de nettoyage - Google Patents

Procédé de nettoyage Download PDF

Info

Publication number
EP0616051B1
EP0616051B1 EP94103219A EP94103219A EP0616051B1 EP 0616051 B1 EP0616051 B1 EP 0616051B1 EP 94103219 A EP94103219 A EP 94103219A EP 94103219 A EP94103219 A EP 94103219A EP 0616051 B1 EP0616051 B1 EP 0616051B1
Authority
EP
European Patent Office
Prior art keywords
salt
lead
ammonium
metallic lead
aqueous solution
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
EP94103219A
Other languages
German (de)
English (en)
Other versions
EP0616051A1 (fr
Inventor
Detlef Kokemüller
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
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
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP0616051A1 publication Critical patent/EP0616051A1/fr
Application granted granted Critical
Publication of EP0616051B1 publication Critical patent/EP0616051B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline 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
    • C23G1/24—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 invention relates to a method for removing metallic lead from a component, in particular from a steam generator, with the aid of a complexing agent.
  • Such a steam generator can be part of a power plant, e.g. of a nuclear power plant.
  • EP 0 198 340 B1 and EP 0 273 182 B1 describe cleaning processes which provide for the use of complexing agents.
  • the process of EP 0 198 340 B1 provides for the use of ammonia and ethylenediamine to remove copper compounds from a container, which is in particular a steam generator. An aqueous solution of ammonia and ethylenediamine is placed in the container to be cleaned. There, ammonium complexes first form and then soluble organic ethylenediamine chelate complexes of the existing copper compounds. These complexes can then be removed mechanically in a simple manner.
  • EP 0 273 182 B1 describes a method for removing iron oxide from a container.
  • a salt solution which is made up of a complexing acid, a volatile alkalizing agent and a reducing agent.
  • the salt solution has an alkaline reducing effect.
  • the use of the salt solution forms easily soluble iron complexes that can be removed mechanically in a simple manner.
  • a method is known from US 4,540,443 with which lead-containing solder metal residues can be removed from a cooling system.
  • EDTA is used for this.
  • Such a method is also known from EP 0 470 553 A1, in which, among other things, a complexing agent and also an EDTA salt are used to remove lead-containing solder metal residues.
  • the invention had for its object to provide a method for removing metallic lead from a component, with which the lead can be removed inexpensively, effectively and quickly.
  • the object is achieved according to the invention in that the metallic lead is oxidized by blowing in oxygen, air or another oxygen-containing gas, the lead compound formed by the oxidation being complexed while lead is still being oxidized, with a salt from a complexing agent complexing acid and an alkalizing agent is used in aqueous solution, and that the resulting solution is then removed.
  • the salt used as a complexing agent is particularly suitable for converting sparingly soluble lead oxide into readily soluble complexes.
  • the method according to the invention can be used in particular in the cleaning of heat exchangers or steam generators, which can be part of a nuclear power plant.
  • metallic lead contributes to corrosion.
  • the method according to the invention can also be used elsewhere for the removal of metallic lead. For example, it can be used to remove lead from earth contaminated with heavy metals.
  • ammonium-EDTA salt and / or ammonium-PDTA salt in aqueous solution can be used as complexing agents.
  • Ammonium EDTA salt is the ammonium salt of ethylenediaminetetraacetic acid (EDTA).
  • Ammonium PDTA salt is the ammonium salt of propylenediaminetetraacetic acid (PDTA).
  • the aqueous solution of ammonium EDTA salt and / or ammonium PDTA salt has, for example, a pH value between 8 and 11. Particularly good complex formation is achieved at such a pH value.
  • air is supplied continuously as an oxidizing agent and for mixing the solution.
  • an iron (III) salt is added to support the oxidation of the metallic lead.
  • an iron III salt In the presence of an iron III salt, the oxidation takes place more quickly.
  • an aqueous solution of an iron III salt of EDTA and / or PDTA is used. It has been found that these salts accelerate the oxidation process particularly well.
  • a component with the method according to the invention for example, between 4 hours and 48 hours are required.
  • the duration depends on the amount of lead to be removed.
  • the temperature during the cleaning process is, for example, between 20 ° C. and 160 ° C.
  • a temperature of 100 ° C. is particularly suitable because the boiling process promotes thorough mixing of the cleaning solution.
  • a lower temperature can be specified, as a rule external heating is dispensed with.
  • the temperature in a steam generator to be cleaned can be, for example, 50 ° C. after the system has been switched off and before cleaning begins.

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)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Claims (8)

  1. Procédé d'élimination du plomb métallique d'un élément constitutif d'une centrale, notamment d'un générateur de vapeur, à l'aide d'un agent complexant,
    caractérisé en ce qu'il consiste à oxyder le plomb métallique par insufflation d'oxygène , d'air ou d'un autre gaz contenant de l'oxygène, à complexer le composé de plomb se formant pendant l'oxydation alors que du plomb est oxydé en utilisant comme agent complexant un sel d'un acide complexant et d'un agent d'alcalinisation en solution aqueuse et à éliminer ensuite la solution formée.
  2. Procédé suivant la revendication 1,
    caractérisé en ce que la solution aqueuse a un pH compris entre 8 et 11.
  3. Procedé suivant l'une des revendications 1 ou 2,
    caractérisé en ce qu'il consiste à utiliser comme agent complexant un sel d'ammonium et de l'acide éthylène diamine tétracétique et/ou un sel d'ammonium et de l'acide propylène diamine tétracétique en solution aqueuse.
  4. Procédé suivant l'une des revendications 1 à 3,
    caractérisé en ce qu'il consiste d'envoyer de l'air en continu.
  5. Procédé suivant l'une des revendications 1 à 4,
    caractérisé en ce qu'il consiste, pour favoriser l'oxydation du plomb métallique, à ajouter un sel de fer III.
  6. Procédé suivant la revendication 5,
    caractérisé en ce qu'il consiste, pour favoriser l'oxydation du plomb métallique, à ajouter une solution du sel de fer III de l'acide éthylène diamine tétracétique et/ou de l'acide propylène diamine tétracétique.
  7. Procédé suivant l'une des revendications 1 à 6,
    caractérisé en ce qu'il nécessite de 4 à 48 heures.
  8. Procédé suivant l'une des revendications 1 à 7,
    caractérisé en ce que la température est comprise entre 20°C et 160°C.
EP94103219A 1993-03-15 1994-03-03 Procédé de nettoyage Expired - Lifetime EP0616051B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4308209A DE4308209C2 (de) 1993-03-15 1993-03-15 Verfahren zum Entfernen von metallischem Blei
DE4308209 1993-03-15

Publications (2)

Publication Number Publication Date
EP0616051A1 EP0616051A1 (fr) 1994-09-21
EP0616051B1 true EP0616051B1 (fr) 1997-05-21

Family

ID=6482853

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94103219A Expired - Lifetime EP0616051B1 (fr) 1993-03-15 1994-03-03 Procédé de nettoyage

Country Status (7)

Country Link
EP (1) EP0616051B1 (fr)
JP (1) JPH06322567A (fr)
BR (1) BR9401146A (fr)
CA (1) CA2118829A1 (fr)
DE (2) DE4308209C2 (fr)
ES (1) ES2102082T3 (fr)
FI (1) FI941216A (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB202218581D0 (en) * 2022-12-09 2023-01-25 Bluesky Environmental Engineering Ltd Compositions for the removal of deposits and methods of use

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB988129A (en) * 1962-11-01 1965-04-07 Bendix Corp Composition for removing finishing compounds from metal surfaces
FR1373143A (fr) * 1963-08-10 1964-09-25 Soceti Soc Civ Ile D Etudes Te Procédé et produit de décapage d'ouvrages en aciers ordinaires
NL149551B (nl) * 1964-08-04 1976-05-17 Dow Chemical Co Werkwijze voor het reinigen en passiveren van ijzerhoudende metaaloppervlakken, waarop metallisch koper is afgezet.
US3664870A (en) * 1969-10-29 1972-05-23 Nalco Chemical Co Removal and separation of metallic oxide scale
US4287002A (en) * 1979-04-09 1981-09-01 Atomic Energy Of Canada Ltd. Nuclear reactor decontamination
US4443268A (en) * 1981-11-12 1984-04-17 The Dow Chemical Company Process for removing copper and copper oxide encrustations from ferrous surfaces
US4578162A (en) * 1984-05-29 1986-03-25 The Dow Chemical Company Method for dissolving copper in the presence of iron
US4540443A (en) * 1984-06-15 1985-09-10 Union Carbide Corporation Cooling system cleaning composition
DE3533886A1 (de) * 1985-04-16 1987-03-26 Kraftwerk Union Ag Reinigungsverfahren
DE3771859D1 (de) * 1986-12-01 1991-09-05 Siemens Ag Verfahren zum reinigen eines behaelters.
US5071582A (en) * 1990-08-06 1991-12-10 Basf Corporation Coolant system cleaning solutions having silicate or siliconate-based corrosion inhibitors
DE69101606T2 (de) * 1990-08-06 1994-07-21 Basf Corp Reinigungslösungen für Kühlsysteme.
JPH04263874A (ja) * 1991-02-18 1992-09-18 Jgc Corp 重金属汚染土壌の淨化方法

Also Published As

Publication number Publication date
DE59402793D1 (de) 1997-06-26
FI941216A (fi) 1994-09-16
DE4308209A1 (de) 1994-09-22
ES2102082T3 (es) 1997-07-16
JPH06322567A (ja) 1994-11-22
CA2118829A1 (fr) 1994-09-16
BR9401146A (pt) 1994-10-25
FI941216A0 (fi) 1994-03-15
DE4308209C2 (de) 1996-12-05
EP0616051A1 (fr) 1994-09-21

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