EP0188975A1 - Process for the acid pickling of steels, in particular stainless steels - Google Patents

Process for the acid pickling of steels, in particular stainless steels Download PDF

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Publication number
EP0188975A1
EP0188975A1 EP85420013A EP85420013A EP0188975A1 EP 0188975 A1 EP0188975 A1 EP 0188975A1 EP 85420013 A EP85420013 A EP 85420013A EP 85420013 A EP85420013 A EP 85420013A EP 0188975 A1 EP0188975 A1 EP 0188975A1
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Prior art keywords
solution
pickling
steels
process according
injection
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German (de)
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EP0188975B1 (en
EP0188975B8 (en
EP0188975B2 (en
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S.A. Ugine
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Ugine Aciers de Chatillon et Guegnon
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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
    • C23G1/02—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 present invention relates to a new method for carrying out the pickling of steel parts, and it relates more particularly, although not exclusively, to pickling by acid of stainless steels.
  • the object of the present invention is to avoid these drawbacks by eliminating the use of nitric acid as a pickling oxidant.
  • the method according to the invention for pickling steel parts, and in particular stainless steel consists in applying to the pieces to be pickled, a treating liquid solution, and it is characterized in that this treating liquid solution is an acid solution hydrofluoric HF.
  • the solution has a hydrofluoric acid concentration of between 5 and 50 g per liter, for a pH of between 0 and 3.
  • the pickling solution necessarily contains ferric inos Fe 3+ .
  • the pickling solution has a concentration of ferric ion Fe 3+ greater than 1 g / l and less than 150 g / l.
  • the treating solution is applied at a temperature between 10 and 70 ° C, for a residence time between 30 seconds and 5 minutes.
  • the pickling bath is subjected to an oxygenation operation.
  • the hydrofluoric acid treatment solution is placed at a REDOX potential of between -200 and +800 mV, potential measured between a platinum electrode and an Ag / Ag Cl reference electrode.
  • REDOX potential is the difference in potential measured between a non-corrodable electrode (for example platinum) and a reference electrode (for example Ag / Ag Cl or calomel saturated these two electrodes being immersed in the bath to be studied. The value thus measured makes it possible to characterize the oxidizing power of the chemical solution.
  • the new process consists in replacing the oxidant HN 0 3 by the oxidant Fe 3+ introduced in the form of fluorinated complexex.
  • Hydrofluoric acid HF is also the other necessary constituent of the stripper mixture.
  • the flow of air injected is obviously largely in excess of the stoichiometry; but the air injection also contributes to a certain agitation which is positive from the point of view of stripping action.
  • This process can be used, not only to pickle stainless steels, but also most mild steels, in particular silicon steels (which are currently often pickled with hydrochloric acid or sulfuric acid, acids requiring very important regeneration or treatment facilities).

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Process for pickling, for example after hot-rolling operations. The pickling is performed by means of a hydrofluoric acid solution in conditions which now allow only a small amount of hydrogen to be discharged to the atmosphere. Application: elimination of pollution by effluents and especially by nitric acid.

Description

La présente invention concerne un procédé nouveau pour effectuer le décapage de pièces en acier, et elle concerne plus particulièrement, quoique non exclusivement, le décapage par voie acide des aciers inoxydables.The present invention relates to a new method for carrying out the pickling of steel parts, and it relates more particularly, although not exclusively, to pickling by acid of stainless steels.

On sait qu'au cours de la fabrication des produits sidé- rurgiques, notamment des brames ou lingots d'acier, soumis à des opérations de laminage à chaud, ou des demi-produits subissant des traitements thermiques tels que, par exemple, des recuits, les pièces se recouvrent d'une couche de calamines oxydées. Aussi faut-il , compte tenu de la nécessité d'obtenir une belle qualité de surface sur produits finis, enlever la totalité de ces couches d'oxydées . L'enlèvement est assuré par une opération de décapage. .Selon les procédés connus à ce jour, l'opération ultime pour effectuer le décapage consiste à appliquer sur les pièces d'acier, des mélanges composés d'acide nitrique HN O3 à environ 150 g par litre et d'acide fluorhydrique HF à une concentration comprise entre 10 et 30 g par litre. Les températures de traitement sont souvent dans la gamme de 40 à 60° C.It is known that during the manufacture of steel products, in particular steel slabs or ingots, subjected to hot rolling operations, or semi-finished products undergoing heat treatments such as, for example, annealing. , the pieces are covered with a layer of oxidized calamines. Also, given the need to obtain a good surface quality on finished products, remove all of these oxide layers. The removal is ensured by a pickling operation. .According to the methods known to date, the ultimate operation for stripping consists in applying to the steel parts, mixtures composed of nitric acid HN O 3 at approximately 150 g per liter and hydrofluoric acid HF at a concentration of between 1 0 and 30 g per liter. Processing temperatures are often in the range of 40 to 60 ° C.

L'un des inconvénients de ces procédés de décapage de type connu est la production d'une intense pollution, à la fois dans l'air atmosphérique (vapeurs nitreuses NOx) et sous forme liquide ( nitrates solubles ).One of the drawbacks of these known type pickling processes is the production of intense pollution, both in atmospheric air (nitrous vapors NO x ) and in liquid form (soluble nitrates).

La présente invention a pour but d'éviter ces inconvénients en supprimant l'emploi de l'acide nitrique comme oxydant de décapage.The object of the present invention is to avoid these drawbacks by eliminating the use of nitric acid as a pickling oxidant.

Le procédé selon l'invention pour décaper les pièces en acier, et notamment en acier inoxydable, consiste à appliquer sur les pièces à décaper, une solution liquide traitante, et il est caractérisé en ce que cette solution liquide traitante est une solution d'acide fluorhydrique HF.The method according to the invention for pickling steel parts, and in particular stainless steel, consists in applying to the pieces to be pickled, a treating liquid solution, and it is characterized in that this treating liquid solution is an acid solution hydrofluoric HF.

Suivant une autre caractéristique de l'invention, la solution présente une concentration en acide fluorhydrique comprise entre 5 et 50 g pnr litre, pour un pH compris entre O et 3.According to another characteristic of the invention, the solution has a hydrofluoric acid concentration of between 5 and 50 g per liter, for a pH of between 0 and 3.

Suivant une autre carac téristique de l'invention, la solution de décapage contiont nécessairement des inos ferriques Fe3+.According to another characteristic of the invention, the pickling solution necessarily contains ferric inos Fe 3+ .

Suivant une autre caractéristique de l'invention, la solution décapante a une concentration en ion ferrique Fe3+ supérieure à 1g/l et inférieure à 150 g/l.According to another characteristic of the invention, the pickling solution has a concentration of ferric ion Fe 3+ greater than 1 g / l and less than 150 g / l.

Suivant une autre caractéristique de l'invention, la solution traitante est appliquée à une température comprise entre 10 et 70° C, pour un temps de séjour compris entre 30 secondes et 5 minutes.According to another characteristic of the invention, the treating solution is applied at a temperature between 10 and 70 ° C, for a residence time between 30 seconds and 5 minutes.

Suivant une autre caractéristique de l'invention, on soumet le bain décapant à une opération d'oxygénation.According to another characteristic of the invention, the pickling bath is subjected to an oxygenation operation.

Suivant une autre caractéristique de l'invention, on place la solution traitante d'acide fluorhydrique à un potentiel REDOX compris entre -200 et +800 mV, potentiel mesuré entre une électrode de platine et une électrode de référence Ag/Ag Cl , On rappelle que le potentiel REDOX est la différence de potentiel mesurée entre une électrode non corrodable ( par exemple en platine ) et une électrode de référence ( par exemple Ag/ Ag Cl ou calomel saturé ces deux électrodes étant immergées dans le bain à étudier . La valeur ainsi mesurée permet de caractériser le pouvoir oxydant de la solution chimique.According to another characteristic of the invention, the hydrofluoric acid treatment solution is placed at a REDOX potential of between -200 and +800 mV, potential measured between a platinum electrode and an Ag / Ag Cl reference electrode. that the REDOX potential is the difference in potential measured between a non-corrodable electrode (for example platinum) and a reference electrode (for example Ag / Ag Cl or calomel saturated these two electrodes being immersed in the bath to be studied. The value thus measured makes it possible to characterize the oxidizing power of the chemical solution.

A titre d'illustration non limitative, on va maintenant donner quelques exemples permettant de mieux comprendre l'invention et les avantages qu'elle est susceptible de procurer.By way of nonlimiting illustration, we will now give a few examples allowing a better understanding of the invention and the advantages which it is likely to provide.

Exemple 1.Example 1.

Le nouveau procédé consiste à remplacer l'oxydant HN 03 par l'oxydant Fe3+ introduit sous forme de complexex fluorés. L'acide fluorhydrique HF est par ailleurs l'autre constituant nécessaire du mélange décapant.The new process consists in replacing the oxidant HN 0 3 by the oxidant Fe 3+ introduced in the form of fluorinated complexex. Hydrofluoric acid HF is also the other necessary constituent of the stripper mixture.

  • - La réaction de dissolution se fait selon le mécanisme suivant:
    Figure imgb0001
    Cet équilibre est presque totalement déplacé dans le sens 1, c'est-à-dire vers la formation de Fe2+ avec dissolution du fer métallique, dans les conditions normales du traitement .    - The dissolution reaction is carried out according to the following mechanism:
    Figure imgb0001
     This equilibrium is almost completely displaced in direction 1, that is to say towards the formation of Fe 2+ with dissolution of metallic iron, under normal conditions of treatment.
  • - La réaction:
    Figure imgb0002
    est également possible si le milieu est oxydant, ce qui est le cas; mais cette deuxième réaction n'est pas favorable si elle devient prépondérante par rapport à la réaction (1), car elle conduit à un déplacement de pH vers le moins acide, ce qui n'est pas favorable pour la suite du traitement.    - The reaction:
    Figure imgb0002
     is also possible if the medium is oxidizing, which is the case; but this second reaction is not favorable if it becomes preponderant compared to the reaction (1), because it leads to a shift in pH towards the least acidic, which is not favorable for the rest of the treatment.
  • - On oxyde ensuite Fe2+ par une aération convenable de la solution décapante . La réaction d'oxydation se fait selon la réaction:
    Figure imgb0003
    L'équilibre (3) est très déplacé dans le sens 1, si la solution est correctement aérée et le pH maintenu entre 0 et 3, ce qui est le cas du mélange décapant concerné.    - Fe 2+ is then oxidized by suitable aeration of the pickling solution. The oxidation reaction takes place according to the reaction:
    Figure imgb0003
     The equilibrium (3) is very displaced in direction 1, if the solution is properly aerated and the pH maintained between 0 and 3, which is the case of the stripper mixture concerned.
  • - Une aération convenable est obtenue:
    • ...soit naturellement (surface du liquide au contact de l'air);
    • ...soit par pompage et refoulement à l'air libre du mélange de décapage;
    • ...soit par une injection convenable d'oxygène ou d'air ou d'un autre gaz oxydant.
    - Adequate ventilation is obtained:
    • ... or naturally (surface of the liquid in contact with air);
    • ... or by pumping and discharging the pickling mixture into the open air;
    • ... or by a suitable injection of oxygen or air or another oxidizing gas.
  • - Une oxydation complémentaire de Fe2+ peut également être effectuée avec des liquides oxydants tels que le peroxyde d'hydrogène H2O2 ou le permanganate de potassium K Mn O4.- An additional oxidation of Fe 2+ can also be carried out with oxidizing liquids such as hydrogen peroxide H 2 O 2 or potassium permanganate K Mn O 4 .
  • - La réaction (3) est suivie par mesure du potentiel REDOX de la solution du décapage, potentiel mesuré entre une électrode de platine et une électrode de référence Ag/AgCl à la température de la solution décapante.- Reaction (3) is followed by measuring the REDOX potential of the pickling solution, potential measured between a platinum electrode and an Ag / AgCl reference electrode at the temperature of the pickling solution.
  • - De bons résultats ont été obtenus sur aciers inoxydables ferritiques et austénitiques, par exemple avec les bains suivants:
    • .HF = 5 à 50 g/1
    • .pH compris entre O et 3
    • .Fe3+>1 g/l
    • .potentiel REDOX mesuré par rapport à Ag/AgCl compris entre -200 et +800 mV selon l'état chimique et thermodynamique du bain
    • .température comprise antre 20 et 60° C pour des temps de séjour de l'ordre de 30 secondes à 5 minutes
    • .oxygénation et aération du bain par pompage et refoulement à l'air libre et/ou injection convenable d'oxygène ou d'air dans le bain, de façon que le débit injecté soit compris entre 1 et 150 Nm3/h sous 0,01 à 5 bars de pression pour un bac de traitement de 30 m3 et/ou injection d'un liquide oxydant tel que H2O2 ou K Mn O4.
    - Good results have been obtained on ferritic and austenitic stainless steels, for example with the following baths:
    • .HF = 5 to 50 g / 1
    • .pH between O and 3
    • .Fe 3+ > 1 g / l
    • REDOX potential measured with respect to Ag / AgCl between -200 and +800 mV depending on the chemical and thermodynamic state of the bath
    • .température understood antrum 2 0 and 60 ° C for residence times of the order of 30 seconds to 5 minutes
    • .oxygenation and aeration of the bath by pumping and discharge in the open air and / or suitable injection of oxygen or air in the bath, so that the flow injected is between 1 and 150 Nm 3 / h at 0.01 to 5 bar pressure for a 30 m 3 treatment tank and / or injection of an oxidizing liquid such as H 2 O 2 or K Mn O 4 .
  • -Le procédé ne donne évidemment pas de vapeurs nitreuses NOx et ne rejette aucun nitrate soluble puisqu'il n'utilise pas d'acide nitrique . Il s'agit donc d'un procédé particulièrement non polluant.-The process obviously does not give nitrous vapors NO x and does not reject any soluble nitrate since it does not use nitric acid. It is therefore a particularly non-polluting process.
  • -Le procédé est autorégulé par le produit de solubilité de Fe F3 et de Cr F3 ( pour une moindre part ) à la température du bain. Ces produits de solubilité limitent la charge de fer et de chrome dissous dans le bain.-The process is self-regulated by the solubility product of Fe F 3 and Cr F 3 (to a lesser extent) at bath temperature. These solubility products limit the charge of iron and chromium dissolved in the bath.
  • -Le rôle de l'acide fluorhydrique est quintuple, à savoir:
    • .maintenir un pH acide de l'ordre de O à 3;
    • .solubiliser les oxydes très difficilement solubles dans les autres acides ( H Cl ou H2 SO4) tels que Si O2, Cr2 O3, Ti O2, Al2 O3, Mo O3, Nb2O3, W O3, V2 O5, etc...
    • .complexer Fe3 et Cr3+ le plus fortement possible;
    • .boucler le bilan en charge de la solution décapante;
    • .dépassiver le métal pour permettre la dissolution (traverser la couche passive ).
    -The role of hydrofluoric acid is fivefold, namely:
    • .maintain an acidic pH of the order of 0 to 3;
    • .Solubilize the oxides which are hardly soluble in the other acids (H Cl or H 2 SO 4 ) such as Si O 2 , Cr 2 O 3 , Ti O 2 , Al 2 O 3 , Mo O 3 , Nb 2 O 3 , W O 3 , V 2 O 5 , etc ...
    • .complex F e 3 and C r 3+ as strongly as possible;
    • .close the balance in charge of the stripping solution;
    • .depassivate the metal to allow dissolution (pass through the passive layer).
  • -Le nouveau procédé peut également s'appliquer ( en modifiant ou ajustant certains paramètres de réglage ) aux aciers ordinaires au carbone, aux aciers de construction, aux aciers d'outillage, et aux aciers au silicium pour usage électrique.-The new process can also be applied (by modifying or adjusting certain adjustment parameters) to ordinary carbon steels, structural steels, tool steels, and silicon steels for electrical use.
Exemple 2,Example 2,

Des résultats positifs ont été obtenus dans les conditions suivantes, pour des aciers laminés à chaud et recuits:

  • . aciers A.i.S.i. 409 et Type 410 ( références normalisées );
  • .HF = 15 à 18 g/l;
  • .pH = 1,5 à 1,8;
  • .Fe3+ = 30 g/l;
  • .potentiel REDOX: +100 à +150 mV, par rapport à Ag/Ag Cl;
  • .température : 38 à 40° C,
  • . temps de traitement : 30 secondes;
  • . injection d'air:80 Nm3/h par bain de 25 à 30 m3.
Positive results have been obtained under the following conditions, for hot-rolled and annealed steels:
  • . AiSi 409 and Type 410 steels (standard references);
  • .HF = 15 to 18 g / l;
  • . p H = 1.5 to 1.8;
  • .Fe 3+ = 30 g / l;
  • REDOX potential: +100 to +150 mV, compared to Ag / Ag Cl;
  • .temperature: 38 to 40 ° C,
  • . processing time: 30 seconds;
  • . air injection: 80 Nm 3 / h per bath of 25 to 30 m 3 .

Exemple 3.Example 3.

  • .aciers A.i.S.i. 430 ( références normalisées );.Ai.Si steels 430 (standard references);
  • .HF : 18 à 20 g/1;.HF: 18 to 20 g / 1;
  • .pH = 1,5 à 1,8;.pH = 1.5 to 1.8;
  • .Fe3+: 30 g/1;.Fe 3+ : 30 g / 1;
  • .potentiel REDOX :+100 à +250 mV par rapport à Ag/Ag Cl;REDOX potential: +100 to +250 mV compared to Ag / Ag Cl;
  • .température: 44 à 46° C;.temperature: 44 to 46 ° C;
  • .temps de traitement : 1,5 à 2 minutes;treatment time: 1.5 to 2 minutes;
  • .injection d'air : 80 Nm3/h par bain de 25 à 30 m3..injection of air: 80 Nm 3 / h per bath of 25 to 30 m 3 .
Exemple 4.Example 4.

De bons résultats ont été obtenus dans les conditions suivantes, pour des aciers laminés à chaud et recuits:

  • .aciers A.i.S.i. 304 ( références normalisées );
  • .HF : 18 à 20 g/l;
  • .pH = 1,5 à 1,8;
  • .Fe3+: 30g/l;
  • .potentiel REDOX: +100 à +250 mV par rapport à Ag/Ag Cl;
  • .température : 46 à 48° C;
  • .temps de traitement : 1,5 à 2 minutes;
  • .injection d'air: 80 Nm3/h par bain de 25 à 30 m3.
Good results have been obtained under the following conditions, for hot-rolled and annealed steels:
  • .AiSi 304 steels (standard references);
  • .HF: 18 to 20 g / l;
  • . pH = 1.5 to 1.8;
  • .Fe 3+ : 30g / l;
  • REDOX potential: +100 to +250 mV compared to Ag / Ag Cl;
  • .temperature: 46 to 48 ° C;
  • treatment time: 1.5 to 2 minutes;
  • .injection of air: 80 Nm 3 / h per bath of 25 to 30 m 3 .

Exemple 5.Example 5.

De même, des résultats intéressants ont été obtenus dans les conditions suivantes, pour des aciers laminés à froid et recuits:

  • .aciers A.i.S.i. 304 ( références normalisées );
  • .HF: 20 à 25 g/l;
  • .pH = 1 à 1,5;
  • .Fe3+: 30 g/l;
  • .potentiel REDOX : +100 à +250 mV par rapport à Ag/Ag Cl;
  • .température: 50 à 55° C;
  • .temps de traitement: 1 à 2 minutes;
  • .injection d'air: 80 Nm3/h par bain de 25 à 30 m3.
Likewise, interesting results have been obtained under the following conditions, for cold-rolled and annealed steels:
  • A .aciers .iSi 304 (standard references);
  • .HF: 20 to 25 g / l;
  • .pH = 1 to 1.5;
  • .Fe 3+ : 30 g / l;
  • REDOX potential: +100 to +250 mV compared to Ag / Ag Cl;
  • .temperature: 50 to 55 ° C;
  • processing time: 1 to 2 minutes;
  • .injection of air: 80 Nm 3 / h per bath of 25 to 30 m 3 .

D' une manière générale, le débit d'air injecté est bien évidemment largement excédentaire par rapport à la stoechiométrie; mais l'injection d'air contribue aussi à une certaine agitation qui est positive du point de vue de l'action décapante.In general, the flow of air injected is obviously largely in excess of the stoichiometry; but the air injection also contributes to a certain agitation which is positive from the point of view of stripping action.

On remarque que, dans les exemples précédents, la fonction de décapage est assurée moyennant la production d'effluents uniquement constitués par:

  • -un faible débit d'hydrogène;
  • -une faible quantité d'acide fluorhydrique FH à sa tension de vapeur ( ce qui correspond donc à un débit très faible, qu'on peut facilement récupérer pour le recycler );
  • -quelques oxydes chimiquement inertes;
  • -enfin, si l'on est à basse température: quelques fluorures de fer et de chrome (mais ceux-ci se trouvant en phase liquide ou solide, ils sont faciles à éliminer: on peut aisément en extraire l'acide fluorhydrique FH qui est ensuite recyclé ).
Note that, in the previous examples, the pickling function is ensured by producing effluents only consisting of:
  • -a low hydrogen flow rate;
  • -a small amount of hydrofluoric acid FH at its vapor pressure (which therefore corresponds to a very low flow rate, which can easily be recovered for recycling);
  • -a few chemically inert oxides;
  • -Finally, if we are at low temperature: some iron and chromium fluorides (but these being in the liquid or solid phase, they are easy to remove: we can easily extract hydrofluoric acid FH which is then recycled).

En définitive, aucun effluent polluant n'est plus rejeté par la mise en oeuvre du procédé selon l'invention.Ultimately, no polluting effluent is no longer rejected by the implementation of the method according to the invention.

Ce procédé est susceptible d'être utilisé, non seulement pour décaper des aciers inoxydables, mais également la plupart des aciers doux, notamment les aciers au silicium ( qui sont actuellement souvent décapés à l'acide chlorhydrique ou à l'acide sulfurique, acides nécessitant des installations de régénération ou de traitement très importantes ).This process can be used, not only to pickle stainless steels, but also most mild steels, in particular silicon steels (which are currently often pickled with hydrochloric acid or sulfuric acid, acids requiring very important regeneration or treatment facilities).

Claims (13)

1-Procédé pour décaper les pièces en acier, et notamment en acier inoxydable, consistant à appliquer sur les pièces à décaper, une solution liquide traitante, caractérisé en ce que cette solution liquide traitante est une solution d'acide fluorhydrique HF.1-Process for pickling steel parts, and in particular stainless steel, consisting in applying to the pieces to be picked, a treating liquid solution, characterized in that this treating liquid solution is a solution of hydrofluoric acid HF. 2-Procédé suivant la revendication 1, caractérisé en ce que la solution présente une concentration en acide fluorhydrique comprise entre 5 et 50 g par litre, pour un pH compris entre O et 3.2-A method according to claim 1, characterized in that the solution has a concentration of hydrofluoric acid between 5 and 50 g per liter, for a pH between 0 and 3. 3-Procédé suivant l'une quelconque de revendications précédentes, caractérisé en ce que la solution décapante contient des ions ferriques Fe3+ introduits sous forme de complexes fluorés.3 - Process according to any one of the preceding claims, characterized in that the pickling solution contains ferric ions Fe 3+ introduced in the form of fluorinated complexes. 4-Procédé suivant l'une quelconque des revendications précédentes,caractérisé en ce que la solution de décapage contient une concentration en ion ferrique Fe3+ comprise entre 1 et 150 g/l.4-Process according to any one of the preceding claims, characterized in that the pickling solution contains a concentration of ferric ion Fe 3+ of between 1 and 150 g / l. 5-Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que la solution traitante est appliquée à une température comprise entre 1 et 70° C, pour un temps de séjour compris entre 30 secondes et 5 minutes.5-A method according to any one of the preceding claims, characterized in that the treating solution is applied at a temperature between 1 and 70 ° C, for a residence time between 30 seconds and 5 minutes. 6-Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'on soumet le bain décapant à une opération d'oxygénation.6-A method according to any one of the preceding claims, characterized in that the pickling bath is subjected to an oxygenation operation. 7-Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que l'oxygénation de la solution décapante est obtenue par pompage et refoulement de la solution traitante à l'air libre.7-A method according to any one of the preceding claims, characterized in that the oxygenation of the pickling solution is obtained by pumping and discharging the treating solution in the open air. 8-Procédé suivant l'une quelconque des revendications 1 à 7, caractérisé en ce que l'oxygénation de la solution décapante est obtenue par injection d'air ou d'oxygène dans la solution.8-A method according to any one of claims 1 to 7, characterized in that the oxygenation of the pickling solution is obtained by injecting air or oxygen into the solution. 9-Procédé suivant l'une quelconque des revendications précédentes, céractérisé en ce que l'injection du gaz oxydant est effectuée avec un débit, ramené aux conditions normales ( 0° C, 760 mm de mercure ), tel que le débit horaire de gaz oxydant soit compris entre 0,01 et 10 fois le volume de la solution décapante dans laquelle on l'injecte.9-Process according to any one of the preceding claims, ceracterized in that the injection of the oxidizing gas is carried out with a flow rate, reduced to normal conditions (0 ° C, 760 mm of mercury), such as the hourly gas flow rate oxidant is between 0.01 and 10 times the volume of the pickling solution into which it is injected. 10-Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que l'injection du gaz oxydant est effectuée à une pression comprise entre 0,01 et 5 bars.10-A method according to any one of the preceding claims, characterized in that the injection of the oxidizing gas is carried out at a pressure between 0.01 and 5 bars. 11-Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'on place la solution traitante à un potentiel REDOX compris entre -200 et +800 mV, potentiel mesuré entre une électrode de platine et une électrode de référence Ag/Ag C1 placées dans la solution décapante.11-Process according to any one of the preceding claims, characterized in that the treating solution is placed at a REDOX potential of between -200 and +800 mV, potential measured between a platinum electrode and an Ag / Ag reference electrode C1 placed in the pickling solution. 12-Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que l'on ajuste le potentiel REDOX à la valeur souhaitée en agissant sur le débit de gaz oxydant.12-A method according to any one of the preceding claims, characterized in that the REDOX potential is adjusted to the desired value by acting on the flow of oxidizing gas. 13-Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que, pour des aciers laminés à froid et recuits, il correspond aux données suivantes: HF: 20 à 25 g/l; pH: 1 à 1,5; Fe3+: 30 g/l; Potentiel REDOX: +100 à +250 mV, par rapport à Ag/Ag Cl; température: 50 à 55° C; temps de traitement: 1 à 2 minutes; injection d'air: 80 Nm3/h par bain de 25 à 30 m3. 13-Process according to any one of the preceding claims, characterized in that, for cold-rolled and annealed steels, it corresponds to the following data: HF: 20 to 25 g / l; pH: 1 to 1.5; Fe 3+ : 30 g / l; REDOX potential: +100 to +250 mV, compared to Ag / Ag Cl; temperature: 50 to 55 ° C; processing time: 1 to 2 minutes; air injection: 80 Nm 3 / h per bath of 25 to 30 m 3 .
EP85420013A 1985-01-22 1985-01-22 Process for the acid pickling of steels, in particular stainless steels Expired - Lifetime EP0188975B8 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT85420013T ATE121804T1 (en) 1985-01-22 1985-01-22 METHOD FOR ACID PICKLING STEEL, PARTICULARLY STAINLESS STEEL.
DE3588013T DE3588013T3 (en) 1985-01-22 1985-01-22 Process for acid pickling steel, especially stainless steel.
EP85420013A EP0188975B8 (en) 1985-01-22 1985-01-22 Process for the acid pickling of steels, in particular stainless steels

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP85420013A EP0188975B8 (en) 1985-01-22 1985-01-22 Process for the acid pickling of steels, in particular stainless steels

Publications (4)

Publication Number Publication Date
EP0188975A1 true EP0188975A1 (en) 1986-07-30
EP0188975B1 EP0188975B1 (en) 1995-04-26
EP0188975B2 EP0188975B2 (en) 2001-10-24
EP0188975B8 EP0188975B8 (en) 2002-01-09

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP85420013A Expired - Lifetime EP0188975B8 (en) 1985-01-22 1985-01-22 Process for the acid pickling of steels, in particular stainless steels

Country Status (3)

Country Link
EP (1) EP0188975B8 (en)
AT (1) ATE121804T1 (en)
DE (1) DE3588013T3 (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987001739A1 (en) * 1985-09-19 1987-03-26 Ugine Gueugnon S.A. Method for the acid etching of stainless steel products
US4872919A (en) * 1988-01-28 1989-10-10 The Procter & Gamble Company Method for removing precipitated calcium citrate from juice pasteurization or sterilization equipment
DE3937438A1 (en) * 1989-02-23 1990-08-30 Krupp Stahl Ag Descaling steel by pickling - using fluoric acid soln. contg. ferric ions and electrolytically producing nascent oxygen in soln. to reoxidise ferrous ions
FR2673200A1 (en) * 1991-02-25 1992-08-28 Ugine Aciers METHOD FOR OVERDRAWING STEEL MATERIALS SUCH AS STAINLESS STEELS AND ALLIED STEELS.
EP0505606A1 (en) * 1991-03-29 1992-09-30 Itb S.R.L. Process for pickling and passivating stainless steel without using nitric acid
US5154774A (en) * 1985-09-19 1992-10-13 Ugine Aciers De Chatillon Et Gueugnon Process for acid pickling of stainless steel products
EP0582121A1 (en) * 1992-08-06 1994-02-09 Itb S.R.L. Process for stainless steel pickling and passivation without using nitric acid
EP0769574A1 (en) * 1995-10-18 1997-04-23 NOVAMAX ITB s.r.l. Process for stainless steel pickling and passivation without using nitric acid
FR2745301A1 (en) * 1996-02-27 1997-08-29 Usinor Sacilor PROCESS FOR STRIPPING A STEEL PART AND PARTICULARLY A STAINLESS STEEL SHEET STRIP
US5843240A (en) * 1995-10-18 1998-12-01 Novamax Itb S.R.L. Process for stainless steel pickling and passivation without using nitric acid
FR2772050A1 (en) * 1997-12-10 1999-06-11 Imphy Sa PROCESS FOR STRIPPING STEEL AND IN PARTICULAR STAINLESS STEEL
EP0949354A1 (en) * 1998-04-06 1999-10-13 SOLVAY (Société Anonyme) Pickling process
DE19850524C2 (en) * 1998-11-03 2002-04-04 Eilenburger Elektrolyse & Umwelttechnik Gmbh Nitrate-free recycling pickling process for stainless steels
US6554908B1 (en) 1999-05-03 2003-04-29 Henkel Kommanditgesellschaft Auf Aktien Process for pickling stainless steel in the absence of nitric acid and in the presence of chloride ions
WO2003048418A2 (en) * 2001-12-07 2003-06-12 Henkel Kommanditgesellschaft Auf Aktien Method for pickling martensitic or ferritic high-grade steel
US20080280046A1 (en) * 2007-02-12 2008-11-13 Bryden Todd R Process for treating metal surfaces
WO2010056825A3 (en) * 2008-11-14 2010-07-15 Ak Steel Properties, Inc. Process for pickling silicon steel with an acidic pickling solution containing ferric ions

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
DE102012004907A1 (en) 2012-03-02 2013-09-05 Sms Siemag Ag Pickling standard steels using iron(II)ions containing pickling solution, comprises oxidizing iron(II)ions to iron(III)ions by passing oxygen gas into pickling solution, where passed oxygen is mixed with pickling solution, and is discharged

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US2474526A (en) 1940-06-15 1949-06-28 Monsanto Chemicals Picking of stainless steels
US2564549A (en) * 1945-07-02 1951-08-14 Albert R Stargardter Pickling treatment
DE899890C (en) * 1952-03-18 1953-12-17 Deutsche Edelstahlwerke Ag Process for the regeneration of pickling baths
GB2000196A (en) 1977-06-24 1979-01-04 Tokai Electro Chemical Co Controlling stainless steel pickling solution by hydrogen peroxide and sulphuric acid addition

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Publication number Priority date Publication date Assignee Title
US2474526A (en) 1940-06-15 1949-06-28 Monsanto Chemicals Picking of stainless steels
US2564549A (en) * 1945-07-02 1951-08-14 Albert R Stargardter Pickling treatment
DE899890C (en) * 1952-03-18 1953-12-17 Deutsche Edelstahlwerke Ag Process for the regeneration of pickling baths
GB2000196A (en) 1977-06-24 1979-01-04 Tokai Electro Chemical Co Controlling stainless steel pickling solution by hydrogen peroxide and sulphuric acid addition

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5154774A (en) * 1985-09-19 1992-10-13 Ugine Aciers De Chatillon Et Gueugnon Process for acid pickling of stainless steel products
WO1987001739A1 (en) * 1985-09-19 1987-03-26 Ugine Gueugnon S.A. Method for the acid etching of stainless steel products
US4872919A (en) * 1988-01-28 1989-10-10 The Procter & Gamble Company Method for removing precipitated calcium citrate from juice pasteurization or sterilization equipment
DE3937438A1 (en) * 1989-02-23 1990-08-30 Krupp Stahl Ag Descaling steel by pickling - using fluoric acid soln. contg. ferric ions and electrolytically producing nascent oxygen in soln. to reoxidise ferrous ions
DE3937438C2 (en) * 1989-02-23 1998-01-29 Wilfried Simmer Steel pickling process
EP0501867A1 (en) * 1991-02-25 1992-09-02 Ugine S.A. Method for etching steel materials such as stainless steels and alloyed steels
US5690748A (en) * 1991-02-25 1997-11-25 Ugine Aciers De Chatillon Et Gueugnon Process for the acid pickling of stainless steel products
FR2673200A1 (en) * 1991-02-25 1992-08-28 Ugine Aciers METHOD FOR OVERDRAWING STEEL MATERIALS SUCH AS STAINLESS STEELS AND ALLIED STEELS.
EP0505606A1 (en) * 1991-03-29 1992-09-30 Itb S.R.L. Process for pickling and passivating stainless steel without using nitric acid
EP0582121A1 (en) * 1992-08-06 1994-02-09 Itb S.R.L. Process for stainless steel pickling and passivation without using nitric acid
EP0769574A1 (en) * 1995-10-18 1997-04-23 NOVAMAX ITB s.r.l. Process for stainless steel pickling and passivation without using nitric acid
US5843240A (en) * 1995-10-18 1998-12-01 Novamax Itb S.R.L. Process for stainless steel pickling and passivation without using nitric acid
US6068001A (en) * 1995-10-18 2000-05-30 Novamax Itb S.R.L. Process for stainless steel pickling and passivation without using nitric acid
FR2745301A1 (en) * 1996-02-27 1997-08-29 Usinor Sacilor PROCESS FOR STRIPPING A STEEL PART AND PARTICULARLY A STAINLESS STEEL SHEET STRIP
EP0792949A1 (en) * 1996-02-27 1997-09-03 USINOR SACILOR Société Anonyme Process for pickling a steel workpiece, in particular stainless steel sheet strip
US5992196A (en) * 1996-02-27 1999-11-30 Usinor Process for pickling a piece of steel and in particular a sheet strip of stainless steel
FR2772050A1 (en) * 1997-12-10 1999-06-11 Imphy Sa PROCESS FOR STRIPPING STEEL AND IN PARTICULAR STAINLESS STEEL
EP0922787A1 (en) * 1997-12-10 1999-06-16 Imphy S.A. Process for pickling stainless steel
EP0949354A1 (en) * 1998-04-06 1999-10-13 SOLVAY (Société Anonyme) Pickling process
US6210491B1 (en) 1998-04-06 2001-04-03 Solvay Pickling process
US6428625B1 (en) 1998-04-06 2002-08-06 Solvay (Societe Anonyme) Process for pickling a metal using hydrogen peroxide
DE19850524C2 (en) * 1998-11-03 2002-04-04 Eilenburger Elektrolyse & Umwelttechnik Gmbh Nitrate-free recycling pickling process for stainless steels
US6554908B1 (en) 1999-05-03 2003-04-29 Henkel Kommanditgesellschaft Auf Aktien Process for pickling stainless steel in the absence of nitric acid and in the presence of chloride ions
WO2003048418A2 (en) * 2001-12-07 2003-06-12 Henkel Kommanditgesellschaft Auf Aktien Method for pickling martensitic or ferritic high-grade steel
WO2003048418A3 (en) * 2001-12-07 2004-08-26 Henkel Kgaa Method for pickling martensitic or ferritic high-grade steel
US20080280046A1 (en) * 2007-02-12 2008-11-13 Bryden Todd R Process for treating metal surfaces
US9234283B2 (en) * 2007-02-12 2016-01-12 Henkel Ag & Co. Kgaa Process for treating metal surfaces
WO2010056825A3 (en) * 2008-11-14 2010-07-15 Ak Steel Properties, Inc. Process for pickling silicon steel with an acidic pickling solution containing ferric ions
US8128754B2 (en) 2008-11-14 2012-03-06 Ak Steel Properties, Inc. Ferric pickling of silicon steel

Also Published As

Publication number Publication date
DE3588013T3 (en) 2002-06-06
DE3588013D1 (en) 1995-06-01
EP0188975B1 (en) 1995-04-26
ATE121804T1 (en) 1995-05-15
EP0188975B8 (en) 2002-01-09
EP0188975B2 (en) 2001-10-24
DE3588013T2 (en) 1995-09-14

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