EP0541448A1 - Verfahren zum kontinuierlichen Beizen von Stahl-Material in einer Behandlungsstrasse - Google Patents

Verfahren zum kontinuierlichen Beizen von Stahl-Material in einer Behandlungsstrasse Download PDF

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Publication number
EP0541448A1
EP0541448A1 EP92402999A EP92402999A EP0541448A1 EP 0541448 A1 EP0541448 A1 EP 0541448A1 EP 92402999 A EP92402999 A EP 92402999A EP 92402999 A EP92402999 A EP 92402999A EP 0541448 A1 EP0541448 A1 EP 0541448A1
Authority
EP
European Patent Office
Prior art keywords
pickling
solution
materials
carried out
contact
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
EP92402999A
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English (en)
French (fr)
Other versions
EP0541448B1 (de
Inventor
Didier Paul
Dominique Henriet
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.)
USINOR SA
Original Assignee
Ugine SA
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Filing date
Publication date
Application filed by Ugine SA filed Critical Ugine SA
Publication of EP0541448A1 publication Critical patent/EP0541448A1/de
Application granted granted Critical
Publication of EP0541448B1 publication Critical patent/EP0541448B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23G1/08—Iron or steel
    • C23G1/086—Iron or steel solutions containing HF

Definitions

  • the invention relates to a method for treating metallic materials, and more specifically, for pickling steel materials continuously on a processing line, which may successively comprise a blasting operation, a preparation operation, a pickling operation and an operation. passivation.
  • the pickling process can be implemented on metallic steel materials in an industrial environment, before leaving the factory, for example for descaling but also by non-professionals in metallurgy for cleaning steel elements.
  • Such a pickling process is known.
  • the treatment process used successively comprises: a shot-blasting operation, an operation of preparation by electrolytic pickling in sodium sulfate, or chemical in a bath of molten salts of composition determined, for example: NaOH 90%, NaNo3 9% NaCl 1%, then a pickling operation and a passivation operation.
  • the preparation operation conditions the layers of scale for the pickling operation which dissolves said layers.
  • the pickling baths are based on hydrofluoric acid with an oxidant which is most often nitric acid but it is advantageous to use hydrogen peroxide as an oxidant. This is followed by a passivation operation in an acid bath, the acid bath generally used being nitric acid.
  • This process has the disadvantage of being polluting, the preparation operation generating chromium compounds with the degree of oxidation + VI, (CrVI), which are particularly toxic.
  • the pickling operation making use of a mixture of nitric acid and HF also produces releases of particularly toxic oxide or nitrogen dioxide vapors, and a release of nitro compounds such as nitrites and nitrates in effluents. If the maximum authorized content of nitrates is relatively high, that relating to nitrites is much lower because nitrites lead to the formation of harmful nitrosamines.
  • the object of the invention is to eliminate nuisances such as the formation of CrVI compounds, the release of nitrous vapors or the release of nitro compounds described above, and also to reduce the processing time of the materials.
  • the subject of the invention is a method for pickling steel materials, in particular continuously on a treatment line, comprising a blasting operation, a preparation operation, then at least one pickling operation and at least one passivation operation, characterized in that the preparation operation is carried out by bringing the materials into contact with at least one solution of sulfuric acid of 2 to 10 N at a temperature above 50 ° C, the metal content being below saturation, and in that the pickling operation is carried out by bringing the materials into contact with at least one solution whose temperature is between 40 and 95 ° C, containing 1 to 10% by weight of hydrofluoric acid, and Fe2 ions + and Fe3+ in such a way that the concentration of Fe3+ ions is between 1 and 190g / l, and that the redox potential or between - 200 and + 800 mV, this potential being measured with a platinum electrode relative to an Ag / Ag Cl electrode.
  • the chemical dissolution of steel in H2SO4 does not allow the oxidation of Cr III to Cr VI, during the preparation operation. Indeed, the following reactions are observed: Fe + H2SO4 ⁇ H2 + Fe SO4 2 Cr + 3H2SO4 ⁇ 3H2 + Cr (SO4) 3
  • the absence of nitric acid in the pickling solution makes it possible to suppress any release of oxide or nitrogen dioxide as well as any salting out of nitro compounds such as nitrites and nitrates in the effluents.
  • the base metal, Fe is dissolved by oxidants, mainly Fe3+ but also HF, depending on the reactions: 2 Fe3+ + Fe ⁇ 3 Fe2+ Fe + 2HF ⁇ H2 + Fe F2
  • the redox potential or REDOX is the potential difference measured between a non-corrodable electrode (for example made of platinum) and a reference electrode (Ag / AgCl), these two electrodes being immersed in the pickling solution.
  • the measured value makes it possible to characterize the oxidizing power of the pickling solution, and to deduce from the values of the concentration of Fe3+ and of the temperature of the pickling solution, that of the concentration of Fe2+.
  • the pickling operation is carried out by bringing the materials into contact with several successive solutions, and even more preferably, with two successive solutions.
  • the pickling solution preferably has a concentration of Fe3+ ions of 30 g / l, a temperature of 50 ° C and a redox potential. between 100 and 250 mV measured with a platinum electrode compared to an Ag / AgCl electrode.
  • the passivation operation is carried out by bringing the materials into contact with at least one solution chosen from a sulfuric acid solution containing Fe3+ ions, a phosphoric acid solution, a hydrogen peroxide solution or a solution of nitric acid or iron nitrates.
  • the preparation solution has a concentration of 4N in sulfuric acid and a temperature of 80 ° C.
  • the preparation, pickling and passivation operations can be carried out in different ways, in particular by immersion, spraying or watering.
  • the steel strip is then immersed in two consecutive pickling baths, having a concentration of 2% by weight of hydrofluoric acid, of 30 g / l of Fe3+ ions, a temperature of 50 ° C and a potential of oxido- reduction of 180 mV measured with respect to a platinum electrode and a reference Ag / AgCl electrode.
  • the steel strip After pickling, the steel strip is treated for passivation in a nitric acid bath.
  • the production of Cr VI turns out to be less than 0.1 mg per tonne of product treated, and the emission of nitrous vapors (N 0 x ) is zero.

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)
  • Cosmetics (AREA)
  • Advancing Webs (AREA)
  • Controlling Rewinding, Feeding, Winding, Or Abnormalities Of Webs (AREA)
  • Control Of Velocity Or Acceleration (AREA)
  • Wire Processing (AREA)
EP92402999A 1991-11-07 1992-11-05 Verfahren zum kontinuierlichen Beizen von Stahl-Material in einer Behandlungsstrasse Expired - Lifetime EP0541448B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR919113752A FR2683551B1 (fr) 1991-11-07 1991-11-07 Procede de decapage de materiaux en acier en continu sur une ligne de traitement.
FR9113752 1991-11-07

Publications (2)

Publication Number Publication Date
EP0541448A1 true EP0541448A1 (de) 1993-05-12
EP0541448B1 EP0541448B1 (de) 1997-04-16

Family

ID=9418723

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92402999A Expired - Lifetime EP0541448B1 (de) 1991-11-07 1992-11-05 Verfahren zum kontinuierlichen Beizen von Stahl-Material in einer Behandlungsstrasse

Country Status (9)

Country Link
US (1) US5332446A (de)
EP (1) EP0541448B1 (de)
AT (1) ATE151819T1 (de)
CA (1) CA2082363A1 (de)
DE (1) DE69219072T2 (de)
DK (1) DK0541448T3 (de)
ES (1) ES2102480T3 (de)
FR (1) FR2683551B1 (de)
GR (1) GR3024040T3 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999029928A2 (en) * 1997-12-05 1999-06-17 Acciai Speciali Terni S.P.A. Process and apparatus for steel band spray pickling
WO2000015880A1 (en) * 1998-09-11 2000-03-23 Henkel Kommanditgesellschaft Auf Aktien Process for electrolytic pickling using nitric acid-free solutions

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2745301B1 (fr) * 1996-02-27 1998-04-03 Usinor Sacilor Procede de decapage d'une piece en acier et notamment d'une bande de tole en acier inoxydable
US5840173A (en) * 1996-06-19 1998-11-24 Keramchemie Gmbh Process for treating the surface of material of high-grade steel
DE19833990A1 (de) * 1998-07-29 2000-02-10 Metallgesellschaft Ag Beizmittel für Edelstähle
DE10160318A1 (de) * 2001-12-07 2003-06-18 Henkel Kgaa Verfahren zum Beizen von martensitischem oder ferritischem Edelstahl
CN114392980A (zh) * 2021-12-29 2022-04-26 沈阳梅特科航空科技有限公司 一种用于去除tbc陶瓷涂层的熔盐制备工艺和清洗工艺

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE507619A (de) *
GB2048311A (en) * 1979-04-12 1980-12-10 Sumitomo Metal Ind Chemical pickling stainless steel
FR2587369A1 (fr) * 1985-09-19 1987-03-20 Ugine Gueugnon Sa Procede de decapage acide de produits en acier inoxydable

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61117291A (ja) * 1984-11-12 1986-06-04 Nippon Steel Corp Ｃｒ系ステンレス鋼板の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE507619A (de) *
GB2048311A (en) * 1979-04-12 1980-12-10 Sumitomo Metal Ind Chemical pickling stainless steel
FR2587369A1 (fr) * 1985-09-19 1987-03-20 Ugine Gueugnon Sa Procede de decapage acide de produits en acier inoxydable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 10, no. 303 (C-378)(2359) 16 Octobre 1986 & JP-A-61 117 291 ( NIPPON STEEL CORPORATION ) 4 Juin 1986 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999029928A2 (en) * 1997-12-05 1999-06-17 Acciai Speciali Terni S.P.A. Process and apparatus for steel band spray pickling
WO1999029928A3 (en) * 1997-12-05 1999-08-26 Acciai Speciali Terni Spa Process and apparatus for steel band spray pickling
WO2000015880A1 (en) * 1998-09-11 2000-03-23 Henkel Kommanditgesellschaft Auf Aktien Process for electrolytic pickling using nitric acid-free solutions
US6565735B1 (en) 1998-09-11 2003-05-20 Henkel Kommanditgesellschaft Auf Aktien Process for electrolytic pickling using nitric acid-free solutions

Also Published As

Publication number Publication date
FR2683551A1 (fr) 1993-05-14
GR3024040T3 (en) 1997-10-31
EP0541448B1 (de) 1997-04-16
CA2082363A1 (fr) 1993-05-08
US5332446A (en) 1994-07-26
DE69219072T2 (de) 1997-07-24
FR2683551B1 (fr) 1994-09-16
ES2102480T3 (es) 1997-08-01
DE69219072D1 (de) 1997-05-22
DK0541448T3 (da) 1997-05-20
ATE151819T1 (de) 1997-05-15

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