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WO2017178154A1 - Procédé pour le décapage électrolytique de bandes métalliques - Google Patents

Procédé pour le décapage électrolytique de bandes métalliques Download PDF

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Publication number
WO2017178154A1
WO2017178154A1 PCT/EP2017/055412 EP2017055412W WO2017178154A1 WO 2017178154 A1 WO2017178154 A1 WO 2017178154A1 EP 2017055412 W EP2017055412 W EP 2017055412W WO 2017178154 A1 WO2017178154 A1 WO 2017178154A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
acid
pickling
metal hydroxides
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.)
Ceased
Application number
PCT/EP2017/055412
Other languages
German (de)
English (en)
Inventor
Jovan Starcevic
Ulrich Krupicka
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.)
Andritz AG
Original Assignee
Andritz 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 Andritz AG filed Critical Andritz AG
Publication of WO2017178154A1 publication Critical patent/WO2017178154A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/06—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
    • C25F7/02—Regeneration of process liquids

Definitions

  • the subject of this invention is a process for the electrolytic pickling of metal strips, in particular of cold-rolled stainless steel strips.
  • the metal strip in a pickling solution with the aid of
  • Chromium goes into solution in the form of chromate (Cr 6+ ), while the other metals, such as iron and
  • Nickel in the form of hydroxides.
  • the metal content of the pickling acid is kept constant by continuously withdrawn from the pickling bath electrolyte and through
  • Na 2 S 2 O 5j Na 2 S0 3 Na 2 S 2 0 3 , Na 2 S 2 0 4 or Na 2 S 2 0 6 is added as a reducing agent.
  • Na 2 S0 4 is formed in all reactions, which can be easily recycled back into the process. There will be no
  • This regeneration is preferably performed at a pH in the range of about 2 - 3 carried out, for example by addition of H 2 S0. 4 Carrying out the reaction in the acidic range accelerates the reaction. Subsequently, the acidic solution can be neutralized by adding NaOH.
  • the resulting metal hydroxides are separated from the pickling acid by means of a filter and deposited, the
  • the aim of the invention is the recovery of these metals.
  • This object is achieved by a method in which the resulting in the regeneration metal hydroxides are dissolved in acid and the resulting metal-containing solution of a pyrohydrolytic treatment, preferably in a Sprühöstreaktor subjected. As a result, the metals are recovered in the form of metal oxides.
  • the regenerated pickling solution is from the
  • Filter cake can be cleaned or washed in acid prior to dissolution. It is also conceivable that the metal hydroxides before the
  • nitric acid or a nitric-hydrofluoric acid mixture is suitable.
  • This acid may come from a further pickling step following the electrolytic pickling.
  • the pyrohydrolytic treatment is preferably carried out in a spray roasting reactor. Such a process is for the recovery or recovery of acids
  • Fig. 1 is a schematic process diagram of
  • a metal strip 1 in this case a cold-rolled stainless steel strip, passes through a electrolytic pickling plant 2 with electrode pairs, in which the metal strip 1 with the aid of a pickling 8
  • the pickling electrolyte 8 here the sodium sulfate solution, is enriched with metals as described above.
  • the resulting Beizschlamm consists mainly of iron hydroxide in the form of goethite (FeO (OH)), nickel hydroxide and dissolved hexavalent chromium.
  • the pickling electrolyte 8 remaining on the metal strip 1 is removed.
  • the metal strip 1 passes through a Mischklarebeize 4, is removed in the remaining with the aid of nitric acid and hydrofluoric acid residual.
  • the spent pickling electrolyte 6 from the electrolytic pickling plant 2 is fed to a regeneration plant 7 in which the hexavalent chromium is converted into trivalent chromium by addition of a reducing agent.
  • Metal hydroxides 9 are separated by means of a filter from the regenerated pickling 8 and a
  • the hydroxide sludge 9 is also freed from the sulfate and chloride.
  • the purified metal hydroxides 12 are then in
  • metal-containing solution 14 is fed to the spray roasting reactor 15. There, the metal-containing solution 14 is subjected to a Pyrohydrolytolyti Customer treatment, whereby the
  • the embodiment shown in the figure represents only a preferred embodiment of the invention.
  • the invention also includes other embodiments in which, for example, the metal hydroxides are taken from a landfill.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

L'objet de la présente invention est un procédé pour le décapage électrolytique de bandes métalliques (1), en particulier de bandes d'acier inoxydable. Lors du procédé de décapage (2), la bande métallique (1) est débarrassée de la calamine dans un bain de décapage (B) à l'aide du courant électrique et le bain de décapage (B) usagé enrichi en métaux est régénéré. Les métaux dissous dans l'acide de décapage (6) sont séparés du bain de décapage (B) régénéré sous forme d'hydroxydes métalliques (9). Selon l'invention, les hydroxydes métalliques (9) sont dissous dans de l'acide (11) et le bain (14) contenant des métaux résultant est soumis à un traitement pyrohydrolytique, de préférence dans un réacteur de grillage par pulvérisation (15), pour la formation d'oxydes métalliques (16).
PCT/EP2017/055412 2016-04-13 2017-03-08 Procédé pour le décapage électrolytique de bandes métalliques Ceased WO2017178154A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA50320/2016A AT517710B1 (de) 2016-04-13 2016-04-13 Verfahren zum elektrolytischen beizen von metallbändern
ATA50320/2016 2016-04-13

Publications (1)

Publication Number Publication Date
WO2017178154A1 true WO2017178154A1 (fr) 2017-10-19

Family

ID=58266594

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/055412 Ceased WO2017178154A1 (fr) 2016-04-13 2017-03-08 Procédé pour le décapage électrolytique de bandes métalliques

Country Status (2)

Country Link
AT (1) AT517710B1 (fr)
WO (1) WO2017178154A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1013800A2 (fr) * 1998-12-22 2000-06-28 Andritz-Patentverwaltungs-Gesellschaft m.b.H. Procédé de décapage d'acier inoxydable
US20030089671A1 (en) * 2001-11-07 2003-05-15 Andritz Ag Process for treating acidic and metallic waste water

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT395312B (de) * 1987-06-16 1992-11-25 Andritz Ag Maschf Verfahren zur gewinnung bzw. rueckgewinnung von saeure aus metallhaltigen loesungen dieser saeure
JPH0762279B2 (ja) * 1991-08-02 1995-07-05 日本冶金工業株式会社 ステンレス鋼の中性塩電解脱スケール方法
JPH06171951A (ja) * 1992-12-07 1994-06-21 Nippon Steel Corp Ｍｎ−Ｚｎ又はＮｉ−Ｚｎ系ソフトフェライト原料液の第２鉄還元方法
AT401183B (de) * 1995-02-15 1996-07-25 Andritz Patentverwaltung Verfahren zur regeneration von elektrolyten, insbesondere na2so4 aus abbeizen von edelstahl, insbesondere edelstahlbändern
AT411575B (de) * 2002-07-25 2004-03-25 Kcs Austria Engineering Gmbh Verfahren zur reinigung verschmutzter saurer beizabwässer mittels querstrom-mikrofiltration
AT13601U1 (de) * 2012-09-06 2014-04-15 Astec Engineering Gmbh Reinigung und Entkieselung verbrauchter Säurebeizbäder mittels kombinierter Mikrofiltrationsverfahren

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1013800A2 (fr) * 1998-12-22 2000-06-28 Andritz-Patentverwaltungs-Gesellschaft m.b.H. Procédé de décapage d'acier inoxydable
US20030089671A1 (en) * 2001-11-07 2003-05-15 Andritz Ag Process for treating acidic and metallic waste water

Also Published As

Publication number Publication date
AT517710A4 (de) 2017-04-15
AT517710B1 (de) 2017-04-15

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