EP0723038A1 - Verfahren und Einrichting zur Regenerierung von verbrauchten Ätzlösungen für Zirkoniumlegierungen - Google Patents

Verfahren und Einrichting zur Regenerierung von verbrauchten Ätzlösungen für Zirkoniumlegierungen Download PDF

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Publication number
EP0723038A1
EP0723038A1 EP96400097A EP96400097A EP0723038A1 EP 0723038 A1 EP0723038 A1 EP 0723038A1 EP 96400097 A EP96400097 A EP 96400097A EP 96400097 A EP96400097 A EP 96400097A EP 0723038 A1 EP0723038 A1 EP 0723038A1
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EP
European Patent Office
Prior art keywords
solution
pickling
crystallizer
water
acid
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
EP96400097A
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English (en)
French (fr)
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EP0723038B1 (de
Inventor
Bernard Furic
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Zircotube SNC
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Zircotube SNC
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    • 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
    • C23G1/36—Regeneration of waste pickling liquors
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/01—Waste acid containing iron

Definitions

  • the invention relates to a method for regenerating a used acid pickling solution used for pickling zirconium alloy elements.
  • the fuel assemblies for nuclear reactors and in particular the fuel assemblies for pressurized water nuclear reactors generally consist of a bundle of fuel rods parallel to each other and held by a framework comprising in particular longitudinal guide tubes and spacer grids. transverse.
  • the fuel rods can consist of a zirconium alloy sheath into which pellets of combustible material are introduced.
  • the frame guide tubes can also consist of zirconium tubes.
  • the chemical pickling of zirconium alloy tubes such as Zircaloy 4 is carried out using a solution of hydrofluoric acid HF containing a certain proportion of nitric acid HNO 3 serving as catalyst for the attack of zirconium by hydrofluoric acid, according to the chemical reaction Zr + 4HF ⁇ ZrF 4 + 2H 2 .
  • Zirconium alloy pickling baths containing pollutants can be treated to separate most of the water from the solution of pollutants that must be destroyed, in approved treatment centers.
  • the zirconium alloy tube production units must therefore bear significant costs relating to the separation and destruction of polluting products in approved centers as well as the purchase of new acid to reconstitute the pickling solution.
  • the transport of the used solution to the treatment center is also accompanied by risks which are those of road transport of dangerous materials.
  • US-A-5,076,884 and EP-A-0331,231 disclose methods for the regeneration of pickling solutions of metals such as zirconium and hafnium. These methods use a precipitation reagent which is a sodium compound.
  • the object of the invention is therefore to propose a method for regenerating a used pickling solution consisting mainly of hydrofluoric acid, nitric acid and water, after use for the pickling of elements. made of zirconium alloy, this process making it possible to limit operating costs production lines for zirconium alloy components, the rejection of polluting materials into the environment and the risks linked to the transport of hazardous materials.
  • the usual pickling process consists in preparing a new pickling solution, by mixing in a container 3, hydrofluoric acid, nitric acid and water in the quantity desired to obtain good pickling efficiency.
  • the pickling solution is used in a pickling unit 4 in which the zirconium alloy tubes are brought into contact with the pickling solution.
  • the chemical characteristics of the pickling solution are checked and, when the solution no longer has the characteristics required for an effective implementation of the pickling process, the used pickling solution is discharged into a storage tank 5.
  • the used pickling solutions stored in a tank were destroyed in an approved center as represented by step 6 which does not is not implemented in the context of the regeneration process according to the invention.
  • the regeneration process according to the invention as shown inside the frame 2 is implemented by carrying out a separation treatment on the used pickling solution stored in the tank 5.
  • the solution stored in the tank 5 mainly contains water, hydrofluoric acid and nitric acid as well as zirconium fluoride ZrF 4 originating from the attack of the zirconium alloy tubes by hydrofluoric acid, catalyzed by nitric acid HNO 3 .
  • the separation operations necessary for the regeneration of the pickling solution by the process according to the invention are carried out successively in a vacuum evaporator 7 and in a vacuum-crystallizer evaporator 8.
  • the vacuum evaporators used have an evaporation chamber in which a low pressure is maintained, for example of the order of 40 mm of mercury.
  • the solution to be treated in the evaporation chamber is introduced and maintained at a moderate temperature, for example of the order of 35 ° C.
  • the heating of the solution to be treated is obtained by means of a heat pump.
  • Putting the evaporation chamber under reduced pressure makes it possible to separate at least one of the constituents of the solution whose treatment is carried out, in the form of a vapor, at a moderate temperature.
  • the vacuum evaporator 7 which can be constituted by a WTSE 1000 evaporator from the company LED ITALIA makes it possible to evaporate and condense a large part of the water contained in the used pickling solution which is introduced into the evaporator chamber of the evaporator 7, from the storage tank 5.
  • the crystallizer 8 which can be a vacuum evaporator operating according to the same principle as the vacuum evaporator 7 comprises, inside its condensation chamber, a container coated with a material resistant to concentrated acids and making it possible to collect the pollutant ZrF 4 in the form of solid crystals.
  • the crystallizer 8 preferably includes a plastic coating to allow it to resist the action of acids in concentrated form.
  • the titer of the pickling solution is adjusted at a processing unit 9 into which the mixture of concentrated acid and water supplied at the outlet of the crystallizer 8 and the evaporator 7 is introduced.
  • the solution is returned to the title, for example by reintroducing pure water or new acid into the mixture, at the level of the processing unit 9.
  • the regenerated acid reaching the storage tank 3 is freed from the polluting products formed during the pickling of the zirconium alloy tubes.
  • the regeneration treatment according to the invention makes it possible to recover hydrofluoric acid from the used pickling solution and almost all of the nitric acid from the fluonitric mixture. This avoids the use of large quantities of expensive new materials.
  • Pure water is therefore introduced into the crystallizer, which makes it possible to dissolve the ZrF 4 crystals.
  • the liquid obtained is withdrawn, so as to empty the crystallizer.
  • An acid solution of ZrF4 is obtained in which the ZrF 4 can precipitate as soon as the pH of the solution reaches a value of approximately 5. It is therefore possible to recover the ZrF 4 from the aqueous solution, by neutralizing this solution.
  • ZrF 4 zirconium fluoride obtained as a by-product in the regeneration process can be used as a base product in some manufacturing.
  • a complete or only partial recycling of the used treatment solution can be carried out and any type of installation can be provided to adjust the composition of the regenerated solution and to reintroduce the regenerated solution on the pickling line of the zirconium alloy elements.
  • the invention applies to the regeneration of any fluonitric acid solution used for the pickling of elements of zirconium alloy.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP96400097A 1995-01-24 1996-01-15 Verfahren und Vorrichtung zur Regenerierung von verbrauchten Ätzlösungen für Zirkoniumlegierungen Expired - Lifetime EP0723038B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9500783 1995-01-24
FR9500783A FR2729676B1 (fr) 1995-01-24 1995-01-24 Procede et dispositif de regeneration d'une solution usagee de decapage d'elements en alliage de zirconium

Publications (2)

Publication Number Publication Date
EP0723038A1 true EP0723038A1 (de) 1996-07-24
EP0723038B1 EP0723038B1 (de) 2000-04-12

Family

ID=9475436

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96400097A Expired - Lifetime EP0723038B1 (de) 1995-01-24 1996-01-15 Verfahren und Vorrichtung zur Regenerierung von verbrauchten Ätzlösungen für Zirkoniumlegierungen

Country Status (5)

Country Link
US (1) US5788935A (de)
EP (1) EP0723038B1 (de)
DE (1) DE69607660T2 (de)
ES (1) ES2145390T3 (de)
FR (1) FR2729676B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7988946B2 (en) 2005-06-30 2011-08-02 Compagnie Europeenne Du Zirconium-Cezus Method for recycling zirconium tetrafluoride into zirconia
CN103241784A (zh) * 2012-02-14 2013-08-14 库特勒自动化系统(苏州)有限公司 太阳能电池刻蚀废物体系的处理方法及处理装置

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6885845B1 (en) * 1993-04-05 2005-04-26 Ambit Corp. Personal communication device connectivity arrangement
FR2874220B1 (fr) * 2004-08-10 2007-07-06 Snecma Moteurs Sa Procede de regeneration des acides d'usinage chimique, installation pour la mise en oeuvre du procede et procede d'usinage chimique associe.
FR2887868B1 (fr) * 2005-06-30 2007-08-17 Cie Europ Du Zirconium Cezus S Procede de recyclage de tetrafluorure de zirconium en zircone

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2993757A (en) * 1958-07-07 1961-07-25 Crucible Steel Co America Process for recovering acid values from mixed acid waste
US3540513A (en) * 1968-10-14 1970-11-17 Daido Chem Eng Corp Apparatus for treating a pickling waste
AT374508B (de) * 1982-07-01 1984-05-10 Ruthner Industrieanlagen Ag Verfahren zur aufarbeitung verbrauchter beizoder aetzloesungen auf der basis von salpeter-flussaeure
US4572824A (en) * 1984-11-01 1986-02-25 General Electric Company Process for recovery of zirconium and acid from spent etching solutions
EP0331231A1 (de) * 1988-02-24 1989-09-06 Metallgesellschaft Ag Verfahren zum Regenerieren von ZrF4 enthaltenden Beizlösungen
WO1991014655A1 (fr) * 1990-03-21 1991-10-03 Cogema -Companie Generale Des Matieres Nucleaires- Procede de traitement d'une solution aqueuse contenant principalement de l'acide nitrique et de l'acide fluorhydrique
US5076884A (en) * 1990-07-19 1991-12-31 Westinghouse Electric Corp. Process of precipitating zirconium or hafnium from spent pickling solutions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT335251B (de) * 1975-03-10 1977-03-10 Ruthner Industrieanlagen Ag Verfahren und vorrichtung zur wiedergewinnung von salpetersaure und flusssaure aus losungen
FI58519C (fi) * 1978-12-07 1981-02-10 Rosenlew Ab Oy W Foerfarande foer regenerering av betningssyror
DE3009265A1 (de) * 1980-03-11 1981-09-24 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum regenerieren von zrf (pfeil abwaerts)4(pfeil abwaerts) enthaltenden beizloesungen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2993757A (en) * 1958-07-07 1961-07-25 Crucible Steel Co America Process for recovering acid values from mixed acid waste
US3540513A (en) * 1968-10-14 1970-11-17 Daido Chem Eng Corp Apparatus for treating a pickling waste
AT374508B (de) * 1982-07-01 1984-05-10 Ruthner Industrieanlagen Ag Verfahren zur aufarbeitung verbrauchter beizoder aetzloesungen auf der basis von salpeter-flussaeure
US4572824A (en) * 1984-11-01 1986-02-25 General Electric Company Process for recovery of zirconium and acid from spent etching solutions
EP0331231A1 (de) * 1988-02-24 1989-09-06 Metallgesellschaft Ag Verfahren zum Regenerieren von ZrF4 enthaltenden Beizlösungen
WO1991014655A1 (fr) * 1990-03-21 1991-10-03 Cogema -Companie Generale Des Matieres Nucleaires- Procede de traitement d'une solution aqueuse contenant principalement de l'acide nitrique et de l'acide fluorhydrique
US5076884A (en) * 1990-07-19 1991-12-31 Westinghouse Electric Corp. Process of precipitating zirconium or hafnium from spent pickling solutions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7988946B2 (en) 2005-06-30 2011-08-02 Compagnie Europeenne Du Zirconium-Cezus Method for recycling zirconium tetrafluoride into zirconia
CN103241784A (zh) * 2012-02-14 2013-08-14 库特勒自动化系统(苏州)有限公司 太阳能电池刻蚀废物体系的处理方法及处理装置

Also Published As

Publication number Publication date
FR2729676B1 (fr) 1997-04-11
US5788935A (en) 1998-08-04
FR2729676A1 (fr) 1996-07-26
EP0723038B1 (de) 2000-04-12
ES2145390T3 (es) 2000-07-01
DE69607660T2 (de) 2000-12-28
DE69607660D1 (de) 2000-05-18

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