FR2562097A1 - Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths - Google Patents

Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths Download PDF

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Publication number
FR2562097A1
FR2562097A1 FR8404837A FR8404837A FR2562097A1 FR 2562097 A1 FR2562097 A1 FR 2562097A1 FR 8404837 A FR8404837 A FR 8404837A FR 8404837 A FR8404837 A FR 8404837A FR 2562097 A1 FR2562097 A1 FR 2562097A1
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Prior art keywords
alloys
urea
pickling
tantalum
zirconium
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Pending
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FR8404837A
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French (fr)
Inventor
Albert Krepler
Udo Lehmann
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Maschinenfabrik Andritz AG
Andritz AG
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Maschinenfabrik Andritz AG
Andritz AG
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DEGREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08Iron or steel
    • C23G1/086Iron or steel solutions containing HF
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DEGREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions

Abstract

Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, special alloys, titanium, zirconium, tantalum and the like by means of nitric acid baths which can also contain other acids, for example hydrofluoric acid, baths to which urea or an aqueous solution of urea has been added, characterised in that the addition of urea is directly metered by an NOx detector working continuously in the conduit through which the gases escape and by a controller, for example a PID controller, the addition being controlled to the minimum desired concentration of NOx in the gases which escape.

Description

La présente invention est relative à un procédé pour le décapage d'aciers alliés de cuivre, d'alliages de métaux lourds non-ferreux, d'alliages spéciaux, de titane, de zirconium, de tantale, etc. The present invention relates to a method for pickling copper-alloy steel, alloys of non-ferrous metals, special alloys, titanium, zirconium, tantalum, etc. au moyen de bains d'acide nitrique qui peuvent également contenir d'autres acides, par exemple de l'acide fluorhydrique. by means of nitric acid baths may also contain other acids, for example hydrofluoric acid.

La pollution de l'environnement par les oxydes nitriques qui s'échappent sans contrôle particulier dans l'atmosphère, dégagés lors du décapage d'aciers alliés de cuivre, d'alliages de metaux lourds non-ferreux, d'alliages spéciaux, de titane, de zirconium, de tantale, etc. Environmental pollution by the nitric oxides escaping without particular control in the atmosphere, generated during the pickling steel alloys of copper, alloys of non-ferrous metals, special alloys, titanium , zirconium, tantalum, etc. dans des acides nitriques en solution aqueuses ou des mélanges de solutions aqueuses d'acides contenant de l'acide nitrique, reste un vieux problème qui actuellement n'a pas encore été résolu de manière satisfaisante. in nitric acid in aqueous solution or mixtures of aqueous solutions of acids containing nitric acid, remains an old problem which currently has not yet been satisfactorily resolved.

La présente invention concerne un procédé selon lequel les quantités de NOX alors produites ne sont pas comme usuellement séparées des gaz qui s 'échappent après le décapage, mais dont la formation est déja diminuée a une fraction lors du décapage des métaux cités dans des solutions aqueuses d'acide nitrique. The present invention relates to a method wherein the amounts of NOx, so produced are not as usually separated from the gases which s' escape after stripping, but whose formation is already reduced to a fraction from stripping of the metals cited in aqueous solutions nitric acid.

A cette fin, il a dejà été proposé d'ajouter du peroxyde d'hydrogène aux bains de décapage; To this end, it has already been proposed to add hydrogen peroxide to the pickling bath; il s'est cependant avéré qu'une partie si importante de cette substance coûteuse est décomposée par d'autres réactions que celles recherchées de sorte que le procédé est trop onéreux. it has however been found that a significant part if this expensive substance is decomposed by reactions other than those sought so that the process is too expensive.

Aussi l'addition d'urée a déjà été retenue pour le décapage de certains aciers à alliage. Also the addition of urea has been used for stripping some steel alloy. Sans tenir compte du fait que, selon l'état de la technique, cet additif est proposé à une autre fin que celle de l'objet de la présente invention, notamment pour améliorer les qualités de décapage et pour réduire le temps de décapage, cet etat de la technique ne présente aucun enseignement pour doser l'additif d'urée en tant que fonction de la concentration NO et encore moins en ce qui concerne un Regardless of the fact that, according to the state of the art, this additive is proposed for a purpose other than that of the object of the present invention, especially to improve the stripping qualities and to reduce the pickling time, this state of the art shows no teaching for assaying urea additive as a function of nO concentration and even less with respect to a
x dosage surveillé d l'additif. x monitored dosing of the additive.

Il s'est avéré maintenant qu'un apport réguJicr d'urée CO(NH2)2 sous folle solide ou dc solution aqueuse plus pratique, par exemple en tant que solution à 50 E, montre de façon beaucoup plus économique l'effet souhait. It turned out now that réguJicr supply of urea CO (NH2) 2 in solid crazy or dc preferred aqueous solution such as a solution of 50 E shows very economically the desire effect.

Au total, la réaction principale ayant ainsi lieu peut s'exprimer par la formule suivante In total, the main reaction taking place and can be expressed by the following formula
CO(NH2)2 + N203 = 2 N2 + C02 + 2 H20 CO (NH2) 2 + N203 = 2 N2 + C02 + 2 H20
Ainsi, le procédé selon l'invention pour le décapage d'aciers alliés de cuivre, d'alliages de métaux lourds non-ferreux, d'alliages spéciaux, de titane, de zirconium, de tantale, etc. Thus, the method according to the invention for pickling of steels copper alloy, alloys of non-ferrous metals, special alloys, titanium, zirconium, tantalum, etc. au moyen de bains d'acide nitrique qui peuvent également contenir d'autres acides, par exemple de l'acide fluorhydrique, bains additionnés d'urée ou d'une solution aqueuse d'urée est caractérisé en ce que l'apport d'urée est directement dosé par un détecteur de NOx travaillant en continu dans le conduit par lequel les gaz s'échappent et par un régulateur, par exemple un régulateur PID, apport réglé à la concentration minimale désirée de NO dans les gaz qui s'échap pent. by means of nitric acid baths may also contain other acids, for example hydrofluoric acid, bathroom added urea or aqueous urea solution is characterized in that the urea input is directly measured by a NOx sensor working continuously into the conduit through which the gas escapes and a regulator, for example a PID controller, input set to the desired minimum concentration of NO in the gases which escape pent.

Il est évident qu'avec une seule molécule d'urée par unité de N203 on ntobtient pas satisfaQtion,ainsi, par exemple, avec une molécule de NO et une molécule de N02 dont la formation est empêchée car d'autres reactions secondaires ont lieu. It is obvious that a single molecule of urea per unit of N203 is not ntobtient satisfaQtion, thus, for example, a molecule with a molecule of NO and N02 whose formation is prevented since other side reactions occur. Suivant le type du métal décapé, des températures de décapage, etc., l'excès nécessaire est différent. Depending on the type of etched metal, stripping temperatures, etc., excess required is different. Cependant, il s'est avéré que 130 à 160 % de la valeur théorique suffisent dans laplupartd~s cas et pourtant le développement de NO peut cotre diminué à un quart, parfois However, it turned out that 130 to 160% of the theoretical value enough in laplupartd ~ s case and yet the development of NO can cutter decreased to a quarter, sometimes
x à 20 % de la quantité autrement développée. x -20% of the amount otherwise developed.

Etant donne qu'en présence de conditions de décp- page identiques, une causalité existe entre la concentration de NO et l'addition d'urée, il s'est avéré très efficace d'utiliser l'analyse continue du NOx des gaz qui s'échappent par un régulateur PID (proportionnel intégral différentiel) pour doser la quantité d'urée. Given that in the presence of conditions décp- identical page, a causality between the NO concentration and the addition of urea, it was found very effective to use the continuous analysis of the gas of NOx s 'escape through a PID (proportional integral differential) for metering the amount of urea. Bien entendu, il faut veiller en raison de la solubilité limitée de l'urée dans les solutions nitriques qu'une saturation d'urée soit élevée, c'est-à-dire que le seuil de solubilité du nitrate d'urée ne soit pas dépassé. Of course, care must be taken because of the limited solubility of urea in nitric solutions that saturation urea is high, that is to say, the solubility limit of urea nitrate is not exceeded.

Ceci est cependant toujours possible comme cela est apparu lors du réglage des systèmes de dosage. This is still possible as it appeared when adjusting the dosing systems.

Une forme de réalisation de l'objet de l'invention est illustrée à l'aide de l'exemple suivant. An embodiment of the object of the invention is illustrated using the following example.

Exemple : un traitement de recuit et de décapage d'une bande d'acier alliée laminée à chaud est inévitable pour produire des feuillards laminés à froid. Example: treatment of annealing and pickling of a hot rolled alloyed steel strip is inevitable to produce cold-rolled strip.

Le décapage est effectué sur une ligne de traitement continue. The etching is performed on a continuous processing line. A cette fin, un mélange d'acide d'environ 15 % en poids d'HN03 et d'environ 2,5 % en poids d'HF est préparé pour l'austénité et pour la ferrite, un mélange d'acide d'environ 15 % en poids d'HN03 et d'environ 0,5 % en poids d'HF. To this end, a mixture of about 15% by weight of HN03 and about 2.5% by weight of HF was prepared for austenite and ferrite, a mixture of acid of about 15% by weight of HN03 and about 0.5% by weight of HF.

Afin d'empêcher que les vapeurs d'acide s'échap- pent dans la pièce, les bains de décapage sont recouverts et les vapeurs sont aspirées. To prevent acid vapors pent échap- the room, pickling baths are covered and vapors are sucked. Les gaz qui s'échappent sont conduits par un absorbeur à gaz et une cheminée dans l'atmosphère. The escaping gases are driven by a gas canister and a fireplace in the atmosphere.

Afin de diminuer la pollution de l'environnement par les émissions de N0x, de l'urée est ajoutée de manière appropriée dans la cuve de décapage. In order to reduce environmental pollution by emissions N0x, urea is added appropriately in the pickling tank. I1 s'est avéré que, lors du décapage d'austénité, la teneur en NOx des vapeurs aspirées a pu être réduite de 1200 ppm de NOx par lladdi- tion d'urée de 300 à 100 ppm de N0x. I1 has been found that, during the pickling of austenite, the NOx content of the aspirated vapors could be reduced to 1200 ppm of NOx per lladdi- tion of urea is 300 to 100 ppm of N0x. Lors du décapage de ferrite, la teneur en NOx des vapeurs aspirées a pu être réduite de 3000 ppm de NOx de 150 à 100 ppm NOx grâce à l'addition d'urée. When pickling ferrite, the NOx content of the aspirated vapors could be reduced to 3000 ppm of NOx from 150 to 100 ppm NOx by the addition of urea.

Claims (1)

  1. REVENDICATION CLAIM
    Procédé pour le décapage d'aciers alliés, de cuivre, d'alliages de métaux lourds non-ferreux, d'alliages spéciaux, de titane, de zirconium, de tantale, etc. A method for etching alloy steel, copper, alloys of non-ferrous metals, special alloys, titanium, zirconium, tantalum, etc. au moyen de bains d'acide nitrique qui peuvent également contenir d'autres acides, par exemple, de l'acide fluorhydrique, bains additionnés d'utée ou d'une solution aqueuse d'urée, caractérisé en ce que l'apport d'urée est directement dosé par un détecteur de NO tra by means of nitric acid baths may also contain other acids, e.g., hydrofluoric acid, added to baths Utee or an aqueous urea solution, characterized in that the supply of urea is directly assayed with an NO detector tra
    x vaillant en continu dans le conduit par lequel les gaz s'échappent et par un régulateur, par exemple un régulateur PID, apport réglé à la concentration minimale désirée de NO dans les gaz qui s'échappent. x valiant continuously into the conduit through which the gas escapes and a regulator, for example a PID controller, input set to the desired minimum concentration of NO in the gas escaping.
    x x
FR8404837A 1984-03-28 1984-03-28 Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths Pending FR2562097A1 (en)

Priority Applications (1)

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FR8404837A FR2562097A1 (en) 1984-03-28 1984-03-28 Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths

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Application Number Priority Date Filing Date Title
FR8404837A FR2562097A1 (en) 1984-03-28 1984-03-28 Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0267166A2 (en) * 1986-09-11 1988-05-11 Eka Nobel Aktiebolag Method of reducing the emission of nitrogen oxides from a liquid containing nitric acid
US6902627B2 (en) 2002-11-25 2005-06-07 Applied Materials, Inc. Cleaning chamber surfaces to recover metal-containing compounds
WO2005068681A2 (en) * 2003-12-19 2005-07-28 Applied Materials, Inc. Cleaning tantalum-containing deposits from process chamber components
US7762114B2 (en) 2005-09-09 2010-07-27 Applied Materials, Inc. Flow-formed chamber component having a textured surface
US7910218B2 (en) 2003-10-22 2011-03-22 Applied Materials, Inc. Cleaning and refurbishing chamber components having metal coatings
US7942969B2 (en) 2007-05-30 2011-05-17 Applied Materials, Inc. Substrate cleaning chamber and components
US7964085B1 (en) 2002-11-25 2011-06-21 Applied Materials, Inc. Electrochemical removal of tantalum-containing materials
US7981262B2 (en) 2007-01-29 2011-07-19 Applied Materials, Inc. Process kit for substrate processing chamber
US8021743B2 (en) 2004-11-24 2011-09-20 Applied Materials, Inc. Process chamber component with layered coating and method
US8617672B2 (en) 2005-07-13 2013-12-31 Applied Materials, Inc. Localized surface annealing of components for substrate processing chambers

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1567825A (en) * 1967-06-08 1969-05-16

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1567825A (en) * 1967-06-08 1969-05-16

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ENVIRONMENTAL PROGRESS, vol. 3, no. 1, février 1984, pages 40-43; H.T. KARLSSON et al.: "Control of NOx in steel pickling" *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0267166A3 (en) * 1986-09-11 1989-02-15 Eka Nobel Aktiebolag Method of reducing the emission of nitrogen oxides from a liquid containing nitric acid
EP0267166A2 (en) * 1986-09-11 1988-05-11 Eka Nobel Aktiebolag Method of reducing the emission of nitrogen oxides from a liquid containing nitric acid
US6902627B2 (en) 2002-11-25 2005-06-07 Applied Materials, Inc. Cleaning chamber surfaces to recover metal-containing compounds
US9068273B2 (en) 2002-11-25 2015-06-30 Quantum Global Technologies LLC Electrochemical removal of tantalum-containing materials
US7964085B1 (en) 2002-11-25 2011-06-21 Applied Materials, Inc. Electrochemical removal of tantalum-containing materials
US7910218B2 (en) 2003-10-22 2011-03-22 Applied Materials, Inc. Cleaning and refurbishing chamber components having metal coatings
WO2005068681A2 (en) * 2003-12-19 2005-07-28 Applied Materials, Inc. Cleaning tantalum-containing deposits from process chamber components
WO2005068681A3 (en) * 2003-12-19 2005-09-15 Applied Materials Inc Cleaning tantalum-containing deposits from process chamber components
US8021743B2 (en) 2004-11-24 2011-09-20 Applied Materials, Inc. Process chamber component with layered coating and method
US9481608B2 (en) 2005-07-13 2016-11-01 Applied Materials, Inc. Surface annealing of components for substrate processing chambers
US8617672B2 (en) 2005-07-13 2013-12-31 Applied Materials, Inc. Localized surface annealing of components for substrate processing chambers
US7762114B2 (en) 2005-09-09 2010-07-27 Applied Materials, Inc. Flow-formed chamber component having a textured surface
US7981262B2 (en) 2007-01-29 2011-07-19 Applied Materials, Inc. Process kit for substrate processing chamber
US8980045B2 (en) 2007-05-30 2015-03-17 Applied Materials, Inc. Substrate cleaning chamber and components
US7942969B2 (en) 2007-05-30 2011-05-17 Applied Materials, Inc. Substrate cleaning chamber and components

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