EP1633499B1 - Method for ecologically treating the surface of a metallic container, combining a chemical action and a mechanical action - Google Patents

Method for ecologically treating the surface of a metallic container, combining a chemical action and a mechanical action Download PDF

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Publication number
EP1633499B1
EP1633499B1 EP04742760A EP04742760A EP1633499B1 EP 1633499 B1 EP1633499 B1 EP 1633499B1 EP 04742760 A EP04742760 A EP 04742760A EP 04742760 A EP04742760 A EP 04742760A EP 1633499 B1 EP1633499 B1 EP 1633499B1
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EP
European Patent Office
Prior art keywords
solution
treatment
container
acid
pickling
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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.)
Expired - Lifetime
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EP04742760A
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German (de)
French (fr)
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EP1633499A1 (en
Inventor
Françoise Haegeli
Dominique Henriet
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Aperam Stainless France SA
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ArcelorMittal Stainless France SA
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Priority to SI200430930T priority Critical patent/SI1633499T1/en
Publication of EP1633499A1 publication Critical patent/EP1633499A1/en
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/08—Cleaning containers, e.g. tanks
    • B08B9/0804—Cleaning containers having tubular shape, e.g. casks, barrels, drums
    • B08B9/0813—Cleaning containers having tubular shape, e.g. casks, barrels, drums by the force of jets or sprays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/08—Cleaning containers, e.g. tanks
    • B08B9/0821—Handling or manipulating containers, e.g. moving or rotating containers in cleaning devices, conveying to or from cleaning devices
    • B08B9/0826—Handling or manipulating containers, e.g. moving or rotating containers in cleaning devices, conveying to or from cleaning devices the containers being brought to the cleaning device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/08—Cleaning containers, e.g. tanks
    • B08B9/093—Cleaning containers, e.g. tanks by the force of jets or sprays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/08—Cleaning containers, e.g. tanks
    • B08B9/20—Cleaning containers, e.g. tanks by using apparatus into or on to which containers, e.g. bottles, jars, cans are brought
    • B08B9/28—Cleaning containers, e.g. tanks by using apparatus into or on to which containers, e.g. bottles, jars, cans are brought the apparatus cleaning by splash, spray, or jet application, with or without soaking
    • B08B9/34—Arrangements of conduits or nozzles
    • 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
    • C23G3/00—Apparatus for cleaning or pickling metallic material

Definitions

  • the present invention relates to a method of surface treatment of a metal container having at least one orifice, said method being more particularly intended for pickling containers made of sheets assembled by welding, crimping, riveting, gluing, etc.
  • Such containers are, for example, drums, fixed or mobile tanks, storage silos, tanks, balloons for heating sanitary water, and generally all of the hollow bodies.
  • the orifice to which reference is made may, for example, be intended to receive tubing, a filling system, heating or evacuation.
  • the area most affected by this contamination is the weld seam.
  • acid can also be sprayed with a spear.
  • the acid is sprayed cold to avoid poisoning the operator with vapors.
  • EP 766 751 etching metal elements such as coil wires by subjecting them to acid spraying in a confined atmosphere such as that of a pickling tunnel, inside which a gas containing oxygen is regularly introduced, in order to regenerate the pickling solution which loses its efficiency quite rapidly.
  • This process makes it possible to multiply the overall etching kinetics by a factor of 2.5 in the most favorable example.
  • this process remains insufficient productivity and does not manage the problem of toxic fumes generated.
  • the tunnel operation is specific to the wire.
  • BE-A-1003233 discloses an interior spray treatment plant.
  • the present invention therefore aims to provide a surface treatment method does not have the disadvantages of the prior art and in particular to treat metal containers without generating large amounts of toxic effluents, safely for operators, and with improved and high productivity.
  • a second subject of the invention consists of a device for treating the surface of a metal container having at least one orifice, which comprises a treatment chamber provided with at least one receiving tank, means for holding said container, means for projecting a treatment solution in said enclosure and inside said container, recirculation means for said solution between said vessel and said projection means, said recirculation means comprising a pump for feeding said means for projection at a pressure above 8 bar.
  • a third subject of the invention consists of a surface treatment line of a metal container having at least one orifice, comprising a device according to the invention, and further comprising a conveyor chain supplying said device with said device. metal containers.
  • the process according to the invention can be applied to any metal surface, and in particular to cast iron, steel, alloy steels, ferrous alloys, nickel and its alloys, chromium and its alloys, titanium and its alloys, zirconium and its alloys, as well as copper and its alloys.
  • the present inventors have found that the projection of a pickling solution at a pressure greater than 8 bar, and preferably greater than 10 bar, made it possible to obtain pickling times divided by at least 6, compared to immersion in bins.
  • the pickling solution at a pressure of less than 90 bar.
  • the rate of addition of the solution also makes it possible to reduce the diffusion limit layer by accelerating the renewal of the acid solution on the surface of the container.
  • the device according to the invention as represented in figure 1 comprises an enclosure 1 that can be sealed to gases and liquids vis-à-vis the outside of the device.
  • a plate (not shown) provided with a receiving tank 2 connected to a recovery system of a treatment solution.
  • the enclosure 1 also includes a lower projection nozzle 3 for the treatment of the inner part of a metal container 4, as well as a series of nozzles 5, 5 ', 5 "in the upper part of the chamber 1 and intended for the treatment of the outer part of the container 4.
  • the enclosure 1 may further comprise a system for suction and condensation of acid vapors (not shown), and a heating system of the chamber 1 with automatic regulation.
  • It comprises at least one receiving tank 2, but can contain as many as there are different treatment solutions, which can collect each solution in a specific tank and thus facilitate its recycling and / or recirculation in the tank. 'pregnant.
  • reagent addition means may be provided in this chamber 1, as well as sensors 6, 6 ', 6 "making it possible to monitor the smooth running of the surface treatment.
  • sensors 6, 6 ', 6 can be implanted at different locations of the device and in particular, in the receiving tank 2 or on the collection circuit of the solution that has just been projected under pressure, but also outside the enclosure 1 in a solution preparation tank.
  • This device is therefore intended for treating the surface of a metal container 4 comprising at least one orifice 4 '.
  • This container is introduced into the chamber 1 and arranged so that its orifice 4 'is oriented downwards.
  • the lower projection nozzle 3 is inserted through the orifice 4 ', inside the container 4, then a pickling solution is sprayed at a pressure greater than 8 bar, and at a temperature included, for example, between 40 and 70 ° C.
  • a pickling solution that can be used in the process according to the invention may comprise an acid or a mixture of mineral acids comprising a halogenated compound or a sulphate, orthophosphate or metaphosphate radical, or else an acid or a mixture of aliphatic organic acids or cyclic, such as a peroxygenic acid such as peracetic acid, or acid Perboric.
  • This solution may also include mixtures of acids of different nature, such as a mixture of halogenated acid and mineral acid, for example.
  • Peroxygenic acid can also be obtained in situ by adding hydrogen peroxide to an organic acid.
  • the use of these peroxygenated acids is particularly advantageous because the pickling solutions containing them can be removed by simple combustion without release of toxic gases.
  • the concentration of the acids is preferably between 0.1 and 7 moles per liter, and more preferably between 0.1 and 6 moles per liter, while the concentration of the metals in the solution is preferably between 0 and 10 moles per liter. , 2 and 2 moles per liter.
  • This pickling solution also comprises an oxidized compound from the metal constituting the container to be treated at its maximum valence.
  • This compound may also be associated with the pickling solution by dissolving a synthetic salt in the solution or by the action of hydrogen peroxide, ozone or persalts.
  • the composition of the solution will be adapted to the composition and composition of the oxides to be removed.
  • the redox potential will be chosen so as to be greater than the oxidation-reduction potential of the redox couple of the main constituent, in an oxidant / reducer molar ratio greater than or equal to 4, in the medium in question.
  • the temperature of the solution is preferably from 40 ° C to 80 ° C, and more preferably from 60 ° C to plus or minus 2 ° C.
  • the solution spray rate is regulated to balance the rate of emptying into the chamber.
  • the container Before or after the projection of this pickling solution, the container may be rinsed with hot aqueous solutions (60 ° C) or cold (15 ° C), for example. It can also be passivated by hydrogen peroxide diluted in an acid medium, or any other solution (persalts, etc ).
  • the implementation of the method according to the invention makes it possible to obtain a surprising gain in terms of productivity.
  • the internal pickling of a 300-liter hot water tank takes only 10 minutes, compared to 60 to 90 minutes for an immersion process.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemically Coating (AREA)
  • Chemical Treatment Of Metals (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention relates to a method for treating the surface of a metallic container comprising at least one opening, using at least one treatment solution. The inventive method is characterised in that it consists of the following steps: the container is placed in a treatment enclosure in such a way that the opening thereof is downwardly oriented, said enclosure comprising a plurality of nozzles for blasting said solution under pressure and at least one receiving vessel; at least one blasting nozzle is introduced via the opening of the container; the enclosure is rendered gas-tight and liquid-tight; a treatment solution containing at least one degreasing, stripping, passivating, shining, cleaning, rinsing or colouring reagent is blasted by means of at least one blasting nozzle, under a minimum pressure of 8 bar; the solution is collected in the receiving vessel for recycling purposes; and optionally, other treatment solutions are successively blasted by means of at least one blasting nozzle, and are successively collected after use in a receiving vessel for recycling purposes, until the desired surface state is obtained. The invention also relates to a treatment device and a treatment line.

Description

La présente invention concerne un procédé de traitement de surface d'un conteneur métallique présentant au moins un orifice, ledit procédé étant plus particulièrement destiné au décapage de conteneurs constitués de tôles assemblées par soudage, sertissage, rivetage, collage, etc....The present invention relates to a method of surface treatment of a metal container having at least one orifice, said method being more particularly intended for pickling containers made of sheets assembled by welding, crimping, riveting, gluing, etc.

De tels conteneurs sont, par exemple, des fûts, des citernes fixes ou mobiles, des silos de stockage, des réservoirs, des ballons pour chauffage de l'eau sanitaire, et d'une manière générale l'ensemble des corps creux. L'orifice auquel il est fait référence peut, par exemple, être destiné à recevoir des tubulures, un système de remplissage, de chauffage ou d'évacuation. A l'issue de leur dernière étape de mise en forme, il est généralement nécessaire de procéder à un traitement de leur surface interne et externe, afin de supprimer la couche d'oxydation qui peut atteindre plusieurs dizaines de micromètres d'épaisseur. Lorsque le conteneur est assemblé par soudage, la zone la plus affectée par cette contamination est le cordon de soudure.Such containers are, for example, drums, fixed or mobile tanks, storage silos, tanks, balloons for heating sanitary water, and generally all of the hollow bodies. The orifice to which reference is made may, for example, be intended to receive tubing, a filling system, heating or evacuation. At the end of their last shaping step, it is generally necessary to treat their internal and external surfaces, in order to remove the oxidation layer that can reach several tens of micrometers thick. When the container is assembled by welding, the area most affected by this contamination is the weld seam.

Afin d'obtenir un état de surface compatible avec les normes de parachèvement du produit, il est donc nécessaire de décaper, dégraisser, passiver ou procéder à un brillantage de sa surface, ce qui se fait habituellement à l'aide de solutions par immersion dans des bacs contenant le réactif de traitement comprenant des acides.In order to obtain a surface condition compatible with the product's finishing standards, it is therefore necessary to strip, degrease, passivate or brighten its surface, which is usually done using immersion solutions in bins containing the processing reagent comprising acids.

Pour des conteneurs dont le volume dépasse les dix litres, tels que des ballons d'eau chaude, on peut également pulvériser de l'acide à l'aide d'une lance. Dans ce cas, l'acide est pulvérisé à froid pour éviter d'intoxiquer l'opérateur avec des vapeurs.For containers with a volume of more than 10 liters, such as hot water flasks, acid can also be sprayed with a spear. In this case, the acid is sprayed cold to avoid poisoning the operator with vapors.

Ces procédés cumulent différents inconvénients, car ils sont à la fois dangereux à mettre en oeuvre, ils génèrent de fortes quantités d'effluents toxiques à éliminer et sont en outre peu efficaces, car la vitesse de décapage reste lente.These processes combine various disadvantages, because they are both dangerous to implement, they generate large amounts of toxic effluents to be eliminated and are also ineffective, because the pickling rate remains slow.

Ainsi, le procédé le plus connu est le procédé fluonitrique qui présente de graves inconvénients, car il implique le dégagement de vapeurs nitreuses. Ces vapeurs entraînent une forte pollution atmosphérique et aqueuse, et rendent les conditions de travail des opérateurs particulièrement dangereuses.Thus, the most known method is the fluonitric process which has serious disadvantages because it involves the release of nitrous vapors. These vapors cause a great deal of atmospheric and aqueous pollution, and make the working conditions of the operators particularly dangerous.

Il est également possible d'améliorer l'état de surface par des procédés d'abrasion tels que le meulage ou le brossage. De tels procédés présentent cependant une productivité très faible, et un prix de revient élevé.It is also possible to improve the surface condition by abrasion processes such as grinding or brushing. Such methods, however, have a very low productivity, and a high cost.

Il a été proposé, dans EP 766 751 de décaper des éléments métalliques tels que des fils en bobines en les soumettant à une pulvérisation d'acide dans une atmosphère confinée telle que celle d'un tunnel de décapage, à l'intérieur duquel on introduit régulièrement un gaz contenant de l'oxygène, afin de régénérer la solution de décapage qui perd assez rapidement son efficacité. Ce procédé permet de multiplier la cinétique globale de décapage par un facteur de 2,5 dans l'exemple le plus favorable. Cependant, ce procédé reste d'une productivité insuffisante et ne permet pas de gérer le problème des vapeurs toxiques générées. En outre, l'opération sous tunnel est spécifique du fil.It has been proposed EP 766 751 etching metal elements such as coil wires by subjecting them to acid spraying in a confined atmosphere such as that of a pickling tunnel, inside which a gas containing oxygen is regularly introduced, in order to regenerate the pickling solution which loses its efficiency quite rapidly. This process makes it possible to multiply the overall etching kinetics by a factor of 2.5 in the most favorable example. However, this process remains insufficient productivity and does not manage the problem of toxic fumes generated. In addition, the tunnel operation is specific to the wire.

BE-A-1003233 décrit une installation de traitement des corps creux par pulvérisation intérieure. BE-A-1003233 discloses an interior spray treatment plant.

La présente invention a donc pour but de mettre à disposition un procédé de traitement de surface ne présentant pas les inconvénients de l'art antérieur et permettant en particulier de traiter des conteneurs métalliques sans générer de grandes quantités d'effluents toxiques, en toute sécurité pour les opérateurs, et avec une productivité améliorée et élevée.The present invention therefore aims to provide a surface treatment method does not have the disadvantages of the prior art and in particular to treat metal containers without generating large amounts of toxic effluents, safely for operators, and with improved and high productivity.

A cet effet, un premier objet de la présente invention est constitué par un procédé de traitement de surface d'un conteneur métallique présentant au moins un orifice, par au moins une solution de traitement, caractérisé en ce qu'il comprend les étapes consistant à :

  • placer ledit conteneur dans une enceinte de traitement de telle façon que son orifice soit orienté vers le bas, ladite enceinte comprenant une pluralité de buses de projection de ladite solution sous pression et au moins une cuve réceptrice,
  • introduire au moins une buse de projection par l'orifice dudit conteneur,
  • rendre ladite enceinte étanche aux gaz et aux liquides vis-à-vis de l'extérieur, puis
  • projeter une solution de traitement contenant au moins un réactif de dégraissage, décapage, passivation, brillantage, nettoyage, rinçage ou coloration, par au moins une buse de projection sous une pression supérieure à 8 bar, et
  • collecter ladite solution dans ladite cuve réceptrice afin de la recycler, et éventuellement,
  • projeter successivement d'autres solutions de traitements par au moins une buse de projection, et à collecter successivement lesdites autres solutions après usage dans une cuve réceptrice afin de les recycler, jusqu'à obtention de l'état de surface désiré.
For this purpose, a first object of the present invention is constituted by a method of surface treatment of a metal container having at least one orifice, with at least one treatment solution, characterized in that it comprises the steps of :
  • placing said container in a treatment chamber so that its orifice is oriented downwards, said enclosure comprising a plurality of nozzles for projecting said pressurized solution and at least one receiving tank,
  • introducing at least one projection nozzle through the orifice of said container,
  • to make said enclosure gastight and liquid-tight vis-à-vis the outside, then
  • projecting a treatment solution containing at least one degreasing, pickling, passivation, brightening, cleaning, rinsing or coloring reagent by at least one spray nozzle at a pressure greater than 8 bar, and
  • collecting said solution in said receiving tank for recycling, and optionally,
  • successively projecting other treatment solutions by at least one spray nozzle, and successively collecting said other solutions after use in a receiving tank for recycling, until the desired surface state.

Le procédé selon l'invention peut également comprendre les variantes suivantes, prises isolément ou en combinaison :

  • la solution de traitement peut être projetée sous une pression supérieure à 10 bar,
  • la solution de traitement est projetée sous une pression inférieure à 90 bar,
  • la solution de décapage peut contenir au moins un acide choisi parmi un acide halogéné, un acide organique et un acide minéral,
  • l'acide halogéné peut être l'acide fluorhydrique, l'acide minéral peut être l'acide sulfurique ou phosphorique, et l'acide organique peut être un acide peroxygéné, en particulier l'acide peracétique,
  • le conteneur ou corps creux à traiter, peut être constitué de fonte, d'acier, d'acier inoxydable, de titane, de zirconium, de cuivre, de nickel, ou de leurs alliages, et de préférence de fonte, d'acier ou d'acier inoxydable, et de façon plus particulièrement préférée d'acier inoxydable,
  • le potentiel redox de la solution de décapage est maintenu à une valeur prédéterminée, située au-dessus du potentiel normal des espèces en solution, de préférence 100 mV au-dessus, et de façon plus particulièrement préférée 150 mV au-dessus,
  • le conteneur métallique peut être obtenu par soudage de tôles,
  • le conteneur métallique peut être un ballon d'eau chaude, mais aussi une cuve de vinification, une citerne pour le transport de produits alimentaires ou chimiques, par exemple.
The process according to the invention may also comprise the following variants, taken alone or in combination:
  • the treatment solution can be projected under a pressure greater than 10 bar,
  • the treatment solution is sprayed under a pressure of less than 90 bar,
  • the pickling solution may contain at least one acid selected from a halogenated acid, an organic acid and a mineral acid,
  • the halogenated acid may be hydrofluoric acid, the mineral acid may be sulfuric or phosphoric acid, and the organic acid may be a peroxygenated acid, in particular peracetic acid,
  • the container or hollow body to be treated, may be made of cast iron, steel, stainless steel, titanium, zirconium, copper, nickel, or their alloys, and preferably of cast iron, steel or stainless steel, and more particularly preferably stainless steel,
  • the redox potential of the pickling solution is maintained at a predetermined value, located above the normal potential of the species in solution, preferably 100 mV above, and more preferably 150 mV above,
  • the metal container can be obtained by welding of sheets,
  • the metal container may be a hot water tank, but also a winemaking tank, a tank for transporting food or chemical products, for example.

Un second objet de l'invention est constitué par un dispositif de traitement de surface d'un conteneur métallique présentant au moins un orifice, qui comprend une enceinte de traitement munie d'au moins une cuve réceptrice, des moyens de maintien dudit conteneur, des moyens de projection d'une solution de traitement dans ladite enceinte et à l'intérieur dudit conteneur, des moyens de recirculation de ladite solution entre ladite cuve et lesdits moyens de projections, lesdits moyens de recirculation comprenant une pompe permettant d'alimenter lesdits moyens de projection à une pression supérieure à 8 bar.A second subject of the invention consists of a device for treating the surface of a metal container having at least one orifice, which comprises a treatment chamber provided with at least one receiving tank, means for holding said container, means for projecting a treatment solution in said enclosure and inside said container, recirculation means for said solution between said vessel and said projection means, said recirculation means comprising a pump for feeding said means for projection at a pressure above 8 bar.

Enfin, un troisième objet de l'invention est constitué par une ligne de traitement de surface d'un conteneur métallique présentant au moins un orifice, comprenant un dispositif selon l'invention, et comprenant en outre une chaîne transporteuse venant alimenter ledit dispositif en lesdits conteneurs métalliques.Finally, a third subject of the invention consists of a surface treatment line of a metal container having at least one orifice, comprising a device according to the invention, and further comprising a conveyor chain supplying said device with said device. metal containers.

Le dispositif selon l'invention peut également comprendre les variantes suivantes, prises isolément ou en combinaison :

  • il comprend des moyens de contrôle comprenant au moins une sonde de mesure, notamment de la température, de la concentration en ions H+, ou du potentiel redox de la solution de traitement, implantés en un point quelconque du circuit de recirculation de la solution,
  • le dispositif comprend un système d'aspiration et de condensation des vapeurs d'acides.
The device according to the invention may also comprise the following variants, taken separately or in combination:
  • it comprises control means comprising at least one measuring probe, in particular the temperature, the concentration of H + ions, or the redox potential of the treatment solution, implanted at any point in the recirculation circuit of the solution,
  • the device comprises a system for sucking and condensing acid vapors.

Le procédé selon l'invention peut être appliqué à toute surface métallique, et, en particulier, à la fonte, l'acier, aux aciers alliés, aux alliages ferreux, au nickel et ses alliages, au chrome et ses alliages, au titane et ses alliages, au zirconium et ses alliages, ainsi qu'au cuivre et ses alliages.The process according to the invention can be applied to any metal surface, and in particular to cast iron, steel, alloy steels, ferrous alloys, nickel and its alloys, chromium and its alloys, titanium and its alloys, zirconium and its alloys, as well as copper and its alloys.

Il est plus particulièrement destiné au traitement des conteneurs présentant au moins un orifice et produites par tout procédé d'assemblage de tôles tel que, par exemple, le soudage, le rivetage, le collage, l'agrafage, le pointage ou bien encore, par moulage, emboutissage, extrusion, estampage, cintrage ou décolletage.It is more particularly intended for the treatment of containers having at least one orifice and produced by any method of assembling sheets such as, for example, welding, riveting, gluing, stapling, pointing or even by molding, stamping, extrusion, stamping, bending or bar turning.

Les présents inventeurs ont constaté que la projection d'une solution de décapage à une pression supérieure à 8 bar, et de préférence supérieure à 10 bar, permettait d'obtenir des temps de décapage divisés au moins par 6, par rapport à des procédés d'immersion dans des bacs.The present inventors have found that the projection of a pickling solution at a pressure greater than 8 bar, and preferably greater than 10 bar, made it possible to obtain pickling times divided by at least 6, compared to immersion in bins.

Sans vouloir être lié par une théorie, on pense que la projection de la solution de décapage permet de fissurer les calamines et d'injecter ensuite la solution dans ses fissures. Cette action mécanique est associée à une action chimique par un mécanisme de percolation - dissolution chimique.Without wishing to be bound by a theory, it is thought that the projection of the pickling solution makes it possible to crack the calamines and then to inject the solution into its cracks. This mechanical action is associated with a chemical action by a mechanism of percolation - chemical dissolution.

Cependant, pour éviter tout risque de détérioration ou de découpe du conteneur métallique, par exemple lorsque le conteneur est en acier, il est préférable de projeter la solution de décapage à une pression inférieure à 90 bar.However, to avoid any risk of deterioration or cutting of the metal container, for example when the container is steel, it is preferable to project the pickling solution at a pressure of less than 90 bar.

La vitesse d'apport de la solution permet en outre de réduire la couche limite de diffusion en accélérant le renouvellement de la solution acide à la surface du conteneur.The rate of addition of the solution also makes it possible to reduce the diffusion limit layer by accelerating the renewal of the acid solution on the surface of the container.

Par ailleurs, l'ensemble des vapeurs nocives est capté puis condensé, sans jamais sortir de l'enceinte sous forme gazeuse.Moreover, all harmful vapors are captured and condensed without ever leaving the enclosure in gaseous form.

Le dispositif selon l'invention tel qu'il est représenté en figure 1 comprend une enceinte 1 que l'on peut rendre étanche aux gaz et aux liquides vis-à-vis de l'extérieur du dispositif. Dans cette enceinte 1 est installée une platine (non représentée) munie d'une cuve réceptrice 2 connectée à un système de récupération d'une solution de traitement. L'enceinte 1 comprend également une buse de projection inférieure 3 destinée au traitement de la partie interne d'un conteneur métallique 4, ainsi qu'une série de buses 5, 5', 5" en partie supérieure de l'enceinte 1 et destinées au traitement de la partie externe du conteneur 4.The device according to the invention as represented in figure 1 comprises an enclosure 1 that can be sealed to gases and liquids vis-à-vis the outside of the device. In this chamber 1 is installed a plate (not shown) provided with a receiving tank 2 connected to a recovery system of a treatment solution. The enclosure 1 also includes a lower projection nozzle 3 for the treatment of the inner part of a metal container 4, as well as a series of nozzles 5, 5 ', 5 "in the upper part of the chamber 1 and intended for the treatment of the outer part of the container 4.

L'enceinte 1 peut comprendre en outre un système d'aspiration et de condensation des vapeurs acides (non représenté), ainsi qu'un système de chauffage de l'enceinte 1 avec une régulation automatique.The enclosure 1 may further comprise a system for suction and condensation of acid vapors (not shown), and a heating system of the chamber 1 with automatic regulation.

Elle comprend au moins une cuve réceptrice 2, mais peut en contenir autant qu'il y a de solutions de traitement différentes, ce qui peut permettre de collecter chaque solution dans une cuve spécifique et donc de faciliter son recyclage et/ou sa recirculation dans l'enceinte.It comprises at least one receiving tank 2, but can contain as many as there are different treatment solutions, which can collect each solution in a specific tank and thus facilitate its recycling and / or recirculation in the tank. 'pregnant.

On peut prévoir par ailleurs des moyens d'addition de réactifs dans cette enceinte 1, ainsi que des capteurs 6, 6', 6" permettant de suivre le bon déroulement du traitement de surface.In addition, reagent addition means may be provided in this chamber 1, as well as sensors 6, 6 ', 6 "making it possible to monitor the smooth running of the surface treatment.

Ces capteurs 6, 6', 6" peuvent être implantés à différents endroits du dispositif et notamment, dans la cuve réceptrice 2 ou sur le circuit de collecte de la solution venant d'être projetée sous pression, mais aussi en dehors de l'enceinte 1 dans un bac de préparation de la solution.These sensors 6, 6 ', 6 "can be implanted at different locations of the device and in particular, in the receiving tank 2 or on the collection circuit of the solution that has just been projected under pressure, but also outside the enclosure 1 in a solution preparation tank.

On pourra notamment utiliser des capteurs 6, 6', 6" mesurant le potentiel redox, la concentration en H+, la température, ou tout autre capteur pouvant permettre de déterminer si la solution doit être traitée avant d'être utilisée.In particular, it will be possible to use sensors 6, 6 ', 6 "measuring the redox potential, the H + concentration, the temperature, or any other sensor that can make it possible to determine whether the solution must be treated before being used.

Ce dispositif est donc destiné au traitement de la surface d'un conteneur métallique 4 comprenant au moins un orifice 4'. Ce conteneur est introduit dans l'enceinte 1 et disposé de telle sorte que son orifice 4' soit orienté vers le bas. La buse inférieure de projection 3 est insérée par l'orifice 4', à l'intérieur du conteneur 4, puis l'on projette une solution de décapage à une pression supérieure à 8 bar, et à une température comprise, par exemple, entre 40 et 70°C.This device is therefore intended for treating the surface of a metal container 4 comprising at least one orifice 4 '. This container is introduced into the chamber 1 and arranged so that its orifice 4 'is oriented downwards. The lower projection nozzle 3 is inserted through the orifice 4 ', inside the container 4, then a pickling solution is sprayed at a pressure greater than 8 bar, and at a temperature included, for example, between 40 and 70 ° C.

Une solution de décapage utilisable dans le procédé selon l'invention peut comprendre un acide ou un mélange d'acides minéraux comprenant un composé halogéné ou un radical sulfate, orthophosphate ou métaphosphate, ou bien encore un acide ou un mélange d'acides organiques aliphatiques ou cycliques, tel qu'un acide peroxygéné comme l'acide peracétique, ou l'acide perborique. Cette solution peut également comprendre des mélanges d'acides de nature différente, comme un mélange d'acide halogéné et d'acide minéral, par exemple.A pickling solution that can be used in the process according to the invention may comprise an acid or a mixture of mineral acids comprising a halogenated compound or a sulphate, orthophosphate or metaphosphate radical, or else an acid or a mixture of aliphatic organic acids or cyclic, such as a peroxygenic acid such as peracetic acid, or acid Perboric. This solution may also include mixtures of acids of different nature, such as a mixture of halogenated acid and mineral acid, for example.

L'acide peroxygéné peut d'ailleurs être obtenu in situ par ajout de peroxyde d'hydrogène sur un acide organique. L'utilisation de ces acides peroxygénés est particulièrement avantageuse, car les solutions de décapage les contenant peuvent être éliminées par simple combustion sans dégagement de gaz toxiques.Peroxygenic acid can also be obtained in situ by adding hydrogen peroxide to an organic acid. The use of these peroxygenated acids is particularly advantageous because the pickling solutions containing them can be removed by simple combustion without release of toxic gases.

La concentration des acides est de préférence comprise entre 0,1 et 7 moles par litre, et de façon plus particulièrement préférée comprise entre 0,1 et 6 moles par litre, tandis que la concentration des métaux dans la solution est de préférence comprise entre 0,2 et 2 moles par litre.The concentration of the acids is preferably between 0.1 and 7 moles per liter, and more preferably between 0.1 and 6 moles per liter, while the concentration of the metals in the solution is preferably between 0 and 10 moles per liter. , 2 and 2 moles per liter.

Cette solution de décapage comprend également un composé oxydé provenant du métal constituant le conteneur à traiter à sa valence maximale. Ce composé peut aussi être associé à la solution de décapage par dissolution d'un sel de synthèse dans la solution ou par action de peroxyde d'hydrogène, d'ozone ou de persels.This pickling solution also comprises an oxidized compound from the metal constituting the container to be treated at its maximum valence. This compound may also be associated with the pickling solution by dissolving a synthetic salt in the solution or by the action of hydrogen peroxide, ozone or persalts.

D'une façon générale, lorsque l'on souhaite décaper, on adaptera la composition de la solution à la composition et à la constitution des oxydes à éliminer.In general, when it is desired to strip, the composition of the solution will be adapted to the composition and composition of the oxides to be removed.

Le potentiel redox sera choisi afin d'être supérieur au potentiel d'oxydo-réduction du couple redox du constituant principal, dans un rapport molaire oxydant / réducteur supérieur ou égal à 4, dans le milieu considéré.The redox potential will be chosen so as to be greater than the oxidation-reduction potential of the redox couple of the main constituent, in an oxidant / reducer molar ratio greater than or equal to 4, in the medium in question.

La température de la solution est de préférence comprise entre 40°C et 80°C, et d'une manière plus particulièrement préférée, de l'ordre de 60°C, à plus ou moins 2°C.The temperature of the solution is preferably from 40 ° C to 80 ° C, and more preferably from 60 ° C to plus or minus 2 ° C.

Le débit de projection de solution est régulé de manière à équilibrer le débit de vidange dans l'enceinte.The solution spray rate is regulated to balance the rate of emptying into the chamber.

Avant ou après la projection de cette solution de décapage, le conteneur peut être rincé à l'aide de solutions aqueuses chaudes (60°C) ou froides (15°C), par exemple. On peut également lui faire subir une passivation par du peroxyde d'hydrogène dilué en milieu acide, ou toute autre solution (persels, etc...).Before or after the projection of this pickling solution, the container may be rinsed with hot aqueous solutions (60 ° C) or cold (15 ° C), for example. It can also be passivated by hydrogen peroxide diluted in an acid medium, or any other solution (persalts, etc ...).

La mise en oeuvre du procédé selon l'invention permet d'obtenir un gain surprenant en terme de productivité. Ainsi, le décapage interne d'un ballon d'eau chaude de 300 litres ne prend que 10 minutes, contre 60 à 90 minutes pour un procédé par immersion.The implementation of the method according to the invention makes it possible to obtain a surprising gain in terms of productivity. Thus, the internal pickling of a 300-liter hot water tank takes only 10 minutes, compared to 60 to 90 minutes for an immersion process.

Claims (14)

  1. Method for surface treating a metal container exhibiting at least one orifice, using at least one treatment solution, characterized in that it comprises the steps consisting in:
    - placing said container in a treatment chamber in such a way that its orifice is directed downwards, said chamber comprising a plurality of spray nozzles for spraying said solution under pressure and at least one collecting vessel,
    - introducing at least one spray nozzle through the orifice of said container,
    - sealing said chamber in respect of gases and liquids and with respect to the outside, then
    - spraying a treatment solution containing at least one degreasing, pickling, passivation, brightening, cleaning, rinsing or colouring reagent through at least one spray nozzle at a pressure in excess of 8 bar, and
    - collecting said solution in said collecting vessel so that it can be recycled, and possibly,
    - in succession spraying other treatment solutions through at least one spray nozzle and successively collecting said other solutions after use in a collecting vessel so that they can be recycled, until the desired surface finish is obtained.
  2. Method according to Claim 1, further characterized in that said treatment solution, containing at least one degreasing, pickling, passivation, brightening, cleaning, rinsing or coloring reagent is sprayed at a pressure in excess of 10 bar.
  3. Method according to either one of Claims 1 and 2, further characterized in that said treatment solution, containing at least one degreasing, pickling, passivation, brightening, cleaning, rinsing or coloring reagent is sprayed at a pressure lower than 90 bar.
  4. Method according to any one of Claims 1 to 3, further characterized in that said pickling solution contains at least one acid chosen from a haloacid, a mineral acid and an organic acid.
  5. Method according to Claim 4, characterized in that the haloacid is hydrofluoric acid, the mineral acid is sulfuric acid or phosphoric acid, and the organic acid is a peroxyacid.
  6. Method according to Claim 5, characterized in that the acid is peracetic acid.
  7. Method according to any one of Claims 1 to 6, characterized in that said container is made of cast iron, steel or stainless steel.
  8. Method according to any one of Claims 1 to 7, in which the redox potential of the pickling solution is maintained at a predetermined value situated below the normal potential of the species in solution.
  9. Method according to any one of Claims 1 to 8, in which said metal container is obtained by welding plates together.
  10. Method according to Claim 9, in which said metal container is a hot water tank.
  11. Device for the surface treatment of a metal container (4) exhibiting at least one orifice (4'), characterized in that it comprises a treatment chamber (1) equipped with at least one collecting vessel (2), means for holding said container (4), spray means (3, 5, 5', 5") for spraying a treatment solution into said chamber (1) and into said container (4), means for recirculating said solution between said vessel (2) and said spray means (3, 5, 5', 5"), said recirculating means comprising a pump able to supply said spray means (3, 5, 5', 5") at a pressure in excess of 8 bar.
  12. Device according to Claim 11, further comprising a system for extracting and condensing acid vapors.
  13. The device according to either one of Claims 11 and 12, further comprising monitoring means (6, 6', 6") comprising at least one measurement probe measuring, in particular, the temperature of the H+ ion concentration or the redox potential of said treatment solution, these means being installed at any point in the recirculation circuit recirculating said solution.
  14. Line for the surface treatment of a metal container (4) exhibiting at least one orifice (4'), comprising a device according to any one of Claims 11 to 13 and further comprising a conveyor supplying said device with said metal containers (4).
EP04742760A 2003-06-04 2004-05-17 Method for ecologically treating the surface of a metallic container, combining a chemical action and a mechanical action Expired - Lifetime EP1633499B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200430930T SI1633499T1 (en) 2003-06-04 2004-05-17 Method for ecologically treating the surface of a metallic container, combining a chemical action and a mechanical action

Applications Claiming Priority (2)

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FR0306744A FR2855773B1 (en) 2003-06-04 2003-06-04 METHOD FOR TREATING ECOLOGICAL SURFACE OF A METAL CONTAINER, ASSOCIATING CHEMICAL ACTION AND MECHANICAL ACTION
PCT/FR2004/001212 WO2004108309A1 (en) 2003-06-04 2004-05-17 Method for ecologically treating the surface of a metallic container, combining a chemical action and a mechanical action

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EP1633499A1 EP1633499A1 (en) 2006-03-15
EP1633499B1 true EP1633499B1 (en) 2008-10-15

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AT (1) ATE411119T1 (en)
DE (1) DE602004017169D1 (en)
DK (1) DK1633499T3 (en)
ES (1) ES2313028T3 (en)
FR (1) FR2855773B1 (en)
NO (1) NO329293B1 (en)
PT (1) PT1633499E (en)
SI (1) SI1633499T1 (en)
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GB0508933D0 (en) * 2005-05-03 2005-06-08 Stainless Restoration Ltd Method and apparatus for treating internal surfaces(s) of a hollow vessel
ITTO20090514A1 (en) * 2009-07-09 2011-01-10 Biemmedue S P A METHOD AND UNIT FOR WASHING A DAMIGIANA
CN101875052B (en) * 2009-11-15 2012-05-02 内蒙古科技大学 Draught beer barrel cleaner
CN103934248A (en) * 2014-04-18 2014-07-23 江苏新美星包装机械股份有限公司 Washing device in barrel washer
PL234800B1 (en) * 2018-03-16 2020-04-30 Walczak Ryszard Rotor Zakl Mechaniki Maszyn Installation for enameling heating sheets of the rotary air and waste gases heaters
PL424914A1 (en) * 2018-03-16 2019-09-23 Walczak Ryszard Rotor Zakład Mechaniki Maszyn Installation for enameling heating sheets of the rotary air and waste gases heaters
CN108672449A (en) * 2018-06-22 2018-10-19 中核核电运行管理有限公司 Cobalt isotope transports outward container and rinses environmental control system
CN110055544B (en) * 2019-05-23 2023-06-16 宝武特冶航研科技有限公司 Vertical steel pipe pickling tank

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BE1003233A4 (en) * 1988-09-08 1992-02-04 Sarl Beugin Ind System for the treatment of a hollow body
FR2792855B3 (en) * 1999-04-27 2001-05-25 Pierre Langlois A WINE TANK CLEANING METHOD AND DEVICE
US6341612B1 (en) * 2000-03-09 2002-01-29 Steris Inc Two compartment container for neutralizing used cleaning solutions
DE10128843C1 (en) * 2001-06-15 2002-12-19 Ghc Gerling Holz & Co Handels Cleaning method for interior of pressurised gas container uses pressurised water with pre-heating for heating gas container to 70 degrees

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SI1633499T1 (en) 2009-02-28
ATE411119T1 (en) 2008-10-15
ES2313028T3 (en) 2009-03-01
FR2855773B1 (en) 2005-07-15
EP1633499A1 (en) 2006-03-15
DE602004017169D1 (en) 2008-11-27
DK1633499T3 (en) 2009-01-05
NO20055761L (en) 2006-03-06
WO2004108309A1 (en) 2004-12-16
FR2855773A1 (en) 2004-12-10
NO20055761D0 (en) 2005-12-05
NO329293B1 (en) 2010-09-27
PT1633499E (en) 2008-12-02

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