EP1831435B1 - Procede d'exploitation continue de bains de zinc ou de bains d'alliage de zinc, acides ou alcalins - Google Patents

Procede d'exploitation continue de bains de zinc ou de bains d'alliage de zinc, acides ou alcalins Download PDF

Info

Publication number
EP1831435B1
EP1831435B1 EP05808579A EP05808579A EP1831435B1 EP 1831435 B1 EP1831435 B1 EP 1831435B1 EP 05808579 A EP05808579 A EP 05808579A EP 05808579 A EP05808579 A EP 05808579A EP 1831435 B1 EP1831435 B1 EP 1831435B1
Authority
EP
European Patent Office
Prior art keywords
zinc
phase
bath
separation
zinc alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP05808579A
Other languages
German (de)
English (en)
Other versions
EP1831435A2 (fr
Inventor
Roland Vogel
Birgit Sonntag
Jens Heydecke
Jens Geisler
Ellen Habig
Andreas Noack
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=36051511&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1831435(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Publication of EP1831435A2 publication Critical patent/EP1831435A2/fr
Application granted granted Critical
Publication of EP1831435B1 publication Critical patent/EP1831435B1/fr
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the invention relates to a method for the deposition of functional layers of acidic or alkaline zinc or zinc alloy baths, the organic additives selected from brighteners, wetting agents and complexing agents, a soluble zinc salt and optionally other metal salts selected from Fe, Ni, Co, Sn salts in which the bath can be continuously cleaned so that the process can be operated without interruption.
  • a weakly acidic zinc bath therefore contains about 10-20 g / l of organic compounds, corresponding to a content of organically bound carbon (total organic carbon, TOC) of approx. 5-10 g / l.
  • Losses of organic active substances occurring during production due to degradation processes and removal are to be compensated for by continuous replenishment.
  • a charge throughput of 10 kAh 0.5 to 1.5 kg of organic compounds are metered in.
  • the degree of determination of the organic impurities is the determination of the cloud point. Desired is a cloud point at the highest possible temperature, since above the temperature of the cloud point no satisfactory coating more.
  • Bath dilution reduces the concentration of impurities in proportion to the degree of dilution.
  • a dilution is easy to carry out, but has the disadvantage that the amount of electrolyte removed from the bath has to be supplied to cost-intensive disposal.
  • a complete new approach of the bath can be considered in this context as a special case of Badver Mednung.
  • Activated carbon treatment by stirring 0.5-2 g / l of activated carbon into the bath followed by filtration reduces the concentration of impurities by adsorption on the coal. Disadvantage of this method is that it is laborious is, causes only a relatively small reduction and removed a large part of the gloss-forming bath additives with.
  • Alkaline Zn baths contain a factor of 5 to 10 lower proportion of organic additives as acidic baths. Accordingly, contamination by decomposition products is generally less critical. In the case of alkaline alloy baths, however, the addition of significant amounts of organic complexing agents is required to complex the alloying additive (Fe, Co, Ni, Sn). These are oxidatively degraded at the anode and the accumulated decomposition products have a negative effect on the production process.
  • the EP 1 369 505 A2 discloses a method for purifying a zinc-nickel electrolyte in a galvanic process in which a portion of the process bath used in the process is evaporated until phase separation into a lower phase, at least one middle phase and an upper phase occurs, and the lower one and the upper phase are separated. This process requires several stages and is disadvantageous in terms of its energy requirements from a cost point of view.
  • the DE 198 34 353 describes a galvanic bath for applying zinc-nickel coatings. To avoid the undesirable decomposition of additives at the anode, it is proposed to separate the anode from the alkaline electrolyte through an ion exchange membrane. However, the invention has the disadvantage that the use of such membranes is cost-intensive and maintenance-prone.
  • the invention has for its object to provide a method and an apparatus for performing this method, with or with the time and effort of the bathroom cleaning with permanent guarantee of constant good bath quality and minimal use of chemicals can be reduced.
  • the invention further relates to an apparatus for carrying out this method, comprising a container (1) for receiving a zinc or zinc alloy bath, an associated mixing device (2) with a further metering device (7) for receiving an acidic or alkaline Solution or an alkaline solid is connected, at least one separator (3) and (3 ') for receiving the removed part of the zinc or zinc alloy bath, optionally means (6) for receiving the aqueous phase from the at least one separating device (3) and (3'), a container (8) for receiving the organic phase from the separating device (3), optionally a container (8 ') for receiving the solid phase from the separating device (3'), and for the recording required lines and optionally valves, the separation of the organic or enable solid phase.
  • the at least one separating device (3) and (3 ') can have devices for stirring (4) and for temperature control (5).
  • the order in which the organic and the solid phase are separated can be freely selected. Preferably, first the organic and then the solid phase is separated off.
  • the mixing device (2) and the separating device (3) need not be spatially separated. It is possible first to mix the solution of the zinc and zinc alloy bath (1) and the solution from the metering device for receiving an acidic or alkaline solution or the basic solid (7) and then to separate the phases in the same container ,
  • the separation of the organic phase in the device (3) and the inorganic phase in the device (3 ') can be carried out in one unit.
  • the means for temperature control (5) must be heated to separate the organic phase and cooled to separate the solid phase.
  • both the organic phase and the solid phase can be separated off first.
  • a further separation unit 3 ' may expediently be used.
  • the solid phase is separated. This is preferably done by cooling the solution, whereby the solubility of the ingredients is reduced so far that they crystallize and can be separated.
  • Typical compounds which can be separated in this way from alkaline zinc and zinc alloy baths include carbonates, oxalates, sulfates and cyanides.
  • the separation of toxic cyanides, which form by the anodic decomposition of nitrogen-containing compounds, for example from the complexing agents, is a desired positive effect of the method according to the invention.
  • a preferred embodiment of the invention comprises a container (1) for receiving a zinc or zinc alloy bath, a mixing device (2) connected thereto via a pump (9) and having a metering device (7) for receiving an acidic or alkaline solution or an alkaline solid via a pump or chute (9), at least one separating device (3) and (3 ') for receiving the removed part of the zinc or zinc alloy bath, optionally a device (6) for receiving the aqueous phase the separating device (3) or (3 '), a container (8) for receiving the organic phase from the separating device (3), optionally a container (8') for receiving the solid phase from the separating device (3 ') and for the recording required lines and valves (11).
  • the at least one separating device (3) and (3 ') and the mixing device (2) can have devices for stirring (4) and for temperature control (5).
  • the separation of the organic and the solid phase can be carried out in the separation device (3) and (3 ') either simultaneously or in two steps one after the other.
  • the solid phase can be separated by means of a crystallizer.
  • a crystallizer Such systems for the separation of crystalline impurities from electroplating baths are known from the prior art and, for example, in US 5,376,256 described. Commercially, such a system is available from USFilter under the name CARBOLUX.
  • the separation of organic and aqueous phase takes place by means of gravity.
  • the device comprises a container (1) for receiving a zinc or zinc alloy bath, a mixing device (2) connected thereto via a pump (9), a separating device (3) connected to the mixing device (2) for receiving the removed one Part of the zinc or zinc alloy bath having a lower portion for separating the aqueous phase (3a) and a narrower upper portion for separating the organic phase (3b) and having an upper effluent for the organic phase (3c) and a lower effluent for the purified aqueous Phase (3d) is provided, optionally a further separation device (3 ') for separating the solid phase and a metering device (7) for receiving an acidic or alkaline solution or an alkaline solid, via a pump or chute (9) the mixing device (2) is connected, optionally a device (6) for receiving the aqueous phase from the separating device (3) or (3 ') and at least one
  • the at least one separating device (3) and (3 ') and the mixing device (2) can have devices for stirring (4) and for temperature control (5).
  • the separator (3) has means for temperature control (5), which preferably consists of a jacket which surrounds the separator (3a) and (3b) and contains as heat carrier, for example water or oil and the uniform heat distribution in the system and the preheating of removed portion of the zinc or Zinkleg réellesbad allows.
  • the temperature is adjusted so that the density of the organic phase is smaller than the density of the aqueous phase.
  • the densities of the phases are plotted as a function of the temperature. Shown are two intersecting curves, where the temperature to the right of the intersection represents the preferred temperature range.
  • the temperature is selected so that the density difference between the two phases is at least 1 - 1.5%.
  • the course of the two phases takes place by means of gravity.
  • the level difference of the process (3d-3c) is set to greater than 5 mm, preferably 0.8 to 1.5 cm at a total height of the device (3a) / (3b) of 1.50 - 2.50 m.
  • the solid constituents crystallize at the bottom of the separation vessel to receive the withdrawn portion of the zinc or zinc alloy bath (3) and can be separated there by suitable means as already described above.
  • the method according to the invention makes use of the fact that a phase separation occurs by lowering the pH or increasing the hydroxide ion concentration. If, for example, the pH of the bath is lowered to a pH ⁇ 1 by the addition of concentrated hydrochloric acid, the anionic surfactants contained in the bath are protonated so that they lose their emulsifying action. This leads to phase separation, i. in a separation of the zinc or zinc alloy bath in an aqueous phase and an organic phase, which is also referred to as oil phase hereinafter.
  • the organic or oil phase contains a majority of Badverungraphyen.
  • the oil phase may comprise up to 10% of the bath volume.
  • phase separation is achieved by addition of preferably solid sodium hydroxide, with a concentration greater than 200 g / l of sodium hydroxide being advantageous.
  • the oil phase floats either on the aqueous phase and can be transferred from there from the separator (3) in the container (8), or it forms on the bottom of the separator (3) and then from there into the Pumped container (8).
  • the aqueous phase is added to the bath to adjust the pH of the bath to the set point, bath additives lost with the oil phase are replenished, and it can be produced again with good quality.
  • the aqueous phase can be stored in a container (6) and added to the bath as needed.
  • the acidified bath is preferably adjusted to a temperature of 20-70 ° C, more preferably 20-50 ° C for accelerating the phase separation, said temperature range being merely preferred and not critical, i. the process can also be carried out at a temperature in the range of 5 to 90 ° C.
  • phase separation can also be effected by increasing the hydroxide ion concentration of the bath.
  • phase separation occurs, for example, when the sodium hydroxide content is raised to a level> 200 g / l.
  • sodium hydroxide in an amount of 1-10 kg / 10 kAh in the container (7) presented.
  • Solid sodium hydroxide can then be dissolved from the container (7) in the mixing device (2) in parts of the bath and pumped into the separation means (3) or (3 ') - there occurs a phase separation, wherein in the Usually a lower solid, mostly crystalline phase and a partially crystalline upper phase occur. The upper phase is then separated and transferred to the container (8).
  • the bath may be cooled to a temperature in the range of -5 to 30 ° C, and preferably 0-8 ° C to remove unwanted inorganic components by crystallization. This is preferably done in the second separation device (3 '), but both devices can also be realized in a single unit.
  • This crystalline precipitate can in turn be separated off in a container (8 ') and the remaining aqueous electrolyte phase can be supplied to the bath, optionally with heating.
  • the aqueous phase is transferred into the container (6).
  • the aqueous phase can be stored in a container (6) and added to the bath as needed.
  • the oil phase formed in the separator (3) is discharged via appropriate lines and collected in a separate container (8) and disposed of.
  • the crystalline phase formed in the separation device (3 ') is discharged via corresponding lines and collected and disposed of in a separate container (8').
  • the lines are provided at the separation devices (3) and (3 ') so that both a settling at the bottom of the separation vessel as well as a floating phase on the aqueous phase can be separated. Expediently, devices for physical phase differentiation are provided.
  • the method according to the invention can be automated by means of a controller with the aid of pH sensors, temperature sensors, fill level meters and the said devices for physical phase differentiation.
  • the controller registers the level in the separating devices (3) and (3 ') and automatically actuates a pump as soon as it falls below a predetermined minimum value.
  • the pump then transfers as long as a proportionate solution from the zinc or zinc alloy bath (1) until a predetermined maximum level is reached in the separation devices.
  • the controller controls the optionally provided in the separators means for stirring (4) and the temperature control (5) of the removed part of the bath.
  • the controller also ensures the metered addition of an acidic or alkaline solution or an alkaline solid from the metering device (7).
  • the control unit switches off the stirring and temperature control devices, so that a phase separation is made possible.
  • the regenerated phase is transferred to a device (6) which, for example (ie with a total bath volume of 20,000 l), can take up a solution amount of 200 l.
  • the device may also be provided with level gauges and level control devices and is connected to the bath (1).
  • bath solution (1) which has been regenerated from the device (6) is introduced into the bath (1) to correct the pH or the hydroxide ion concentration is transferred. While the process of the present invention has been described above essentially with reference to the use of an acid for phase separation, it may also be carried out using bases such as, preferably, alkali or alkaline earth hydroxides, and especially sodium hydroxide, as mentioned.
  • a significant advantage of the method according to the invention is that the production process does not have to be interrupted for cleaning or replacement of the bath. Impurities can be removed continuously or discontinuously and any required bath components can be added.
  • phase separation is achieved by the addition of an acid or base, which would have to be added to the zinc or zinc alloy bath anyway due to process control.
  • a bath sample of a weakly acid zinc bath with a TOC content of 30.2 g / l and 2.6 ml / l brightener and 35.8 ml / l additional solution was lowered to pH ⁇ 1 with 20 ml / l hydrochloric acid (37%).
  • a device according to FIG. 2 with a separation unit (3) and a container (6) for receiving the aqueous phase from the separation tank (3) used. A slow separation of two phases was observed. Within 24 h, 25 ml / l of a dark brown, viscous phase settled on the bottom of the vessel.
  • the clear supernatant solution contained, after analysis, 21.5 g / l TOC, 1.5 ml / l brightener, and 26.4 ml / l adjuvant.
  • Testing by Hull cell after adjusting the pH to the working range (pH 5) showed a predominantly shiny sheet, but with burns in the high current density range.
  • the cloud point of the bath before treatment was 50 ° C, after treatment and adjustment at 75 ° C.
  • a bath sample with a TOC content of 30.2 g / l and 2.6 ml / l brightener and 35.8 ml / l additional solution was lowered to pH ⁇ 1 with 20 ml / l hydrochloric acid (37%).
  • a device according to FIG. 3 with a separation unit (3) and a container (6) for receiving the aqueous phase from the separation tank (3) used.
  • the level difference (3c) - (3d) was 15 mm, the total height of the device (3a) + (3b) 2 m.
  • the sample was heated to 50 ° C. Within 2 h separated 55 ml / l of a dark brown oil phase above the aqueous phase.
  • the clear aqueous phase contained by analysis 13.1 g / l TOC, 0.6 ml / l brightener and 21.8 ml / l additional solution.
  • Testing by Hull cell after adjustment of the pH to the working range (pH 5) showed a uniformly shiny sheet with low fogging in the low current density range.
  • the cloud point of the bath before treatment was 50 ° C, after treatment and adjustment at 85 ° C.
  • the separated oil phase consists of 10-15% of functional bath additives and 85-90% of impurities.
  • the separation unit (3 ') comprised a crystallizer from Carbolux.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (17)

  1. Procédé de dépôt de couches fonctionnelles à partir de bains de zinc ou de bains d'alliage de zinc acides ou alcalins comprenant des additifs organiques choisis parmi des brillanteurs, des agents mouillants et des agents complexants, un sel de zinc soluble et éventuellement d'autres sels métalliques choisis parmi les sels de Fe, Ni, Co, Sn, comprenant les étapes suivantes consistant à :
    (i) mettre à disposition le bain de zinc ou le bain d'alliage de zinc comprenant les composants cités ci-dessus,
    (ii) déposer une couche de zinc ou d'alliage de zinc sur la pièce devant recevoir le revêtement selon des procédés connus en soi,
    (iii) prélever une portion du bain de zinc ou du bain d'alliage de zinc et transférer la portion prélevée dans un dispositif de séparation de phases,
    (iv) additionner d'un acide ou d'une base la portion acide ou alcaline prélevée,
    (v) ajuster la température pour accélérer la séparation des phases,
    (vi) séparer la phase organique et éventuellement les phases solides,
    (vii) recycler la phase aqueuse dans le bain de zinc ou le bain d'alliage de zinc de sorte que le pH ou la teneur en hydroxyde du bain de zinc ou du bain d'alliage de zinc demeure dans sa plage de fonctionnement normal et qu'ainsi le bain puisse être exploité sans interruption, et
    (viii) compléter les composants du bain de zinc ou du bain d'alliage de zinc ayant été consommés.
  2. Procédé selon la revendication 1, caractérisé en ce que le prélèvement de la portion du bain de zinc et son recyclage sont effectués de façon continue ou discontinue.
  3. Procédé selon la revendication 1, caractérisé en ce que l'adjonction de l'acide et la séparation des phases sont effectuées à une température dans la plage de 5 à 90 °C, et de préférence de 20 à 50 °C.
  4. Procédé selon la revendication 1, caractérisé en ce que l'adjonction de la base et la séparation des phases sont effectuées à une température dans la plage de -5 à 30 °C, et de préférence de 0 à 8 °C, et en ce qu'après la séparation de la phase organique, le bain est refroidi à une température dans la plage de -5 à 20 °C, et de préférence de 0 à 8 °C, afin d'obtenir une phase inorganique solide, qui est séparée avant que la phase aqueuse soit recyclée dans le bain de zinc ou le bain d'alliage de zinc.
  5. Procédé selon la revendication 1, caractérisé en ce que l'on utilise en tant qu'acide un acide minéral, en particulier de l'acide chlorhydrique, et en tant que base des hydroxydes alcalins ou alcalino-terreux, en particulier de l'hydroxyde de sodium.
  6. Procédé selon la revendication 1, caractérisé en ce que le taux de régénération est compris entre 0,1 et 20 % du volume du bain par jour.
  7. Procédé selon la revendication 1, caractérisé en ce que le recyclage de la phase aqueuse est effectué de telle sorte que le pH ou la concentration en ions hydroxyde du bain de zinc ou du bain d'alliage de zinc demeure constant(e).
  8. Procédé selon la revendication 1, caractérisé en ce que la formation de la phase organique dans le réservoir est décelée par l'intermédiaire d'un détecteur, le détecteur initiant le retrait de la phase organique du réservoir.
  9. Dispositif pour la mise en oeuvre du procédé selon la revendication 1, comprenant un réservoir (1) destiné à recevoir un bain de zinc ou un bain d'alliage de zinc, un dispositif de mélange (2) relié à celui-ci, lequel est connecté à un autre dispositif de dosage (7) destiné à recevoir une solution acide ou alcaline ou un solide alcalin, au moins un dispositif de séparation (3) et (3') destiné à recevoir la portion prélevée du bain de zinc ou du bain d'alliage de zinc, un réservoir (8) destiné à recevoir la phase organique provenant du dispositif de séparation (3), éventuellement un réservoir (8') destiné à recevoir la phase solide provenant du dispositif de séparation (3'), et les conduites nécessaires à la réception et qui permettent la séparation de la phase organique et/ou de la phase solide.
  10. Dispositif selon la revendication 9, comprenant un réservoir (1) destiné à recevoir un bain de zinc ou un bain d'alliage de zinc, un dispositif de mélange (2) relié à celui-ci par l'intermédiaire d'une pompe (9) et connecté à un dispositif de dosage (7) destiné à recevoir une solution acide ou alcaline ou un solide alcalin par l'intermédiaire d'une pompe ou d'une glissière de déversement (9), au moins un dispositif de séparation (3) et (3') destiné à recevoir la portion prélevée du bain de zinc ou du bain d'alliage de zinc, un réservoir (8) destiné à recevoir la phase organique provenant du dispositif de séparation (3), éventuellement un réservoir (8') destiné à recevoir la phase solide provenant du dispositif de séparation (3'), et les conduites et vannes nécessaires à la réception.
  11. Dispositif selon la revendication 9, comprenant un réservoir (1) destiné à recevoir un bain de zinc ou un bain d'alliage de zinc, un dispositif de mélange (2) relié à celui-ci par l'intermédiaire d'une pompe (9), un dispositif de séparation (3) relié au dispositif de mélange (2) et destiné à recevoir la portion prélevée du bain de zinc ou du bain d'alliage de zinc, comprenant une partie inférieure pour séparer la phase aqueuse (3a) et une partie supérieure plus étroite pour séparer la phase organique (3b) et pourvu d'un orifice d'évacuation supérieur pour la phase organique (3c) et d'un orifice d'évacuation inférieur pour la phase aqueuse purifiée (3d), un dispositif de dosage (7) destiné à recevoir une solution acide ou alcaline ou un solide alcalin, relié par l'intermédiaire d'une pompe ou d'une glissière de déversement (9) au dispositif de mélange (2), et au moins un réservoir (8) et (8') destiné à recevoir la phase solide ou organique provenant du dispositif de séparation (3) et (3').
  12. Dispositif selon la revendication 11, caractérisé en ce qu'il comprend en outre un dispositif de séparation supplémentaire (3') pour séparer la phase solide.
  13. Dispositif selon les revendications 9 à 12, caractérisé en ce que le dispositif de séparation (3) ou (3') comporte des dispositifs de brassage (4) et de contrôle de la température (5), lesquels sont reliés à une unité de commande.
  14. Dispositif selon les revendications 9 à 13, caractérisé en ce qu'il comporte en outre un dispositif (6) destiné à recevoir la phase aqueuse provenant du dispositif de séparation (3) ou (3').
  15. Dispositif selon les revendications 9 à 13, caractérisé en ce que le dispositif de mélange (2) et le dispositif de séparation (3) ne sont pas séparés spatialement.
  16. Dispositif selon les revendications 9, 10 ou 12, caractérisé en ce que les dispositifs de séparation (3) et (3') sont réalisés en une seule et même unité.
  17. Dispositif selon les revendications 9 à 16, caractérisé en ce qu'il comprend en outre un réservoir destiné à recevoir la phase aqueuse régénérée, d'où peut s'effectuer le recyclage de la phase aqueuse selon le procédé selon la revendication 7.
EP05808579A 2004-12-20 2005-11-28 Procede d'exploitation continue de bains de zinc ou de bains d'alliage de zinc, acides ou alcalins Revoked EP1831435B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004061255A DE102004061255B4 (de) 2004-12-20 2004-12-20 Verfahren für den kontinuierlichen Betrieb von sauren oder alkalischen Zink- oder Zinklegierungsbädern und Vorrichtung zur Durchführung desselben
PCT/EP2005/012689 WO2006066689A2 (fr) 2004-12-20 2005-11-28 Procede d'exploitation continue de bains de zinc ou de bains d'alliage de zinc, acides ou alcalins

Publications (2)

Publication Number Publication Date
EP1831435A2 EP1831435A2 (fr) 2007-09-12
EP1831435B1 true EP1831435B1 (fr) 2008-11-05

Family

ID=36051511

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05808579A Revoked EP1831435B1 (fr) 2004-12-20 2005-11-28 Procede d'exploitation continue de bains de zinc ou de bains d'alliage de zinc, acides ou alcalins

Country Status (11)

Country Link
US (1) US8475874B2 (fr)
EP (1) EP1831435B1 (fr)
JP (1) JP4764886B2 (fr)
KR (1) KR101237037B1 (fr)
CN (1) CN101278077B (fr)
AT (1) ATE413479T1 (fr)
BR (1) BRPI0519144A2 (fr)
CA (1) CA2591932A1 (fr)
DE (2) DE102004061255B4 (fr)
ES (1) ES2313434T3 (fr)
WO (1) WO2006066689A2 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007040005A1 (de) 2007-08-23 2009-02-26 Ewh Industrieanlagen Gmbh & Co. Kg Verfahren zum Abscheiden funktioneller Schichten aus einem Galvanikbad
DE102008058086B4 (de) * 2008-11-18 2013-05-23 Atotech Deutschland Gmbh Verfahren und Vorrichtung zur Reinigung von galvanischen Bädern zur Abscheidung von Metallen
CN102234795B (zh) * 2011-06-02 2016-09-07 杭州震达五金机械有限公司 用于双金属复合线材加工的锌基多元合金沉积液
CN102324276B (zh) * 2011-06-02 2017-02-22 杭州震达五金机械有限公司 铜包铝镁双金属导线生产工艺
US9120111B2 (en) 2012-02-24 2015-09-01 Rain Bird Corporation Arc adjustable rotary sprinkler having full-circle operation and automatic matched precipitation
US9156043B2 (en) 2012-07-13 2015-10-13 Rain Bird Corporation Arc adjustable rotary sprinkler with automatic matched precipitation
CN103668192A (zh) * 2012-09-01 2014-03-26 无锡新大中薄板有限公司 一种铝合金板用四元浸锌锡镍铁工艺
CN104911683A (zh) * 2015-05-05 2015-09-16 武汉科技大学 一种侧线脱除硫酸锌电镀液中铁离子的方法

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2434191A (en) * 1942-02-02 1948-01-06 Du Pont Removing organic impurities from copper-cyanide electroplating baths
US2861927A (en) * 1956-04-25 1958-11-25 Westinghouse Electric Corp Process for adjusting the components in aqueous alkali cyanide electrolytes
US3821095A (en) * 1972-09-26 1974-06-28 M & T Chemicals Inc Zinc electroplating process and electrolyte therefor
US3887445A (en) * 1974-04-26 1975-06-03 R O Hull & Company Inc Method for the reduction of zinc ion concentration and removal of organic impurities in a neutral or acidic, aqueous zinc plating bath
JPS5262136A (en) * 1975-11-18 1977-05-23 Kosaku Kk Regeneration method of inferion plating bath
DE3138792C2 (de) 1981-09-30 1986-08-21 Basf Ag, 6700 Ludwigshafen Verwendung von Benzalaceton in roher Form als Spitzenglanzbildner in sauren galvanischen Zinkbädern
JPS6096781A (ja) 1983-11-01 1985-05-30 Ube Ind Ltd 水酸化カリウム電解液の再生方法
JPH0726239B2 (ja) * 1989-07-04 1995-03-22 三菱電機株式会社 メッキ液の回収方法
US5246591A (en) * 1990-07-13 1993-09-21 Pact, Incorporated Separation of metal ions on an anion exchange resin by chromatographic elution
DE4200774C2 (de) 1992-01-15 1993-11-25 Rene Leutwyler Verfahren zum Entfernen von Carbonaten aus galvanischen Bädern
DE4410347A1 (de) * 1994-03-25 1995-09-28 Rene Leutwyler Verfahren zum Entfernen von anorganischen Metallverbindungen aus Lösungen
DE19525509C2 (de) 1994-07-22 1997-10-02 Lpw Anlagen Gmbh Anwendung der UV/H¶2¶O¶2¶-Oxidationsbehandlung zur betriebsmäßigen Wiederverwendungs- oder Weiterverwendungsaufbereitung eines Bades für die galvanotechnische Beschichtung von Gegenständen mit metallischen Überzügen
DE19506297A1 (de) * 1995-02-23 1996-08-29 Schloemann Siemag Ag Verfahren und Anlage zum Regenerieren von Sulfatelektrolyt bei der Stahlband-Verzinkung
DE19810859A1 (de) 1998-03-13 1999-09-16 A C K Aqua Concept Gmbh Wasser Kombinationsverfahren zur Behandlung eines schäumend eingestellten galvanischen Bads
DE19834353C2 (de) * 1998-07-30 2000-08-17 Hillebrand Walter Gmbh & Co Kg Alkalisches Zink-Nickelbad
US6391209B1 (en) * 1999-08-04 2002-05-21 Mykrolis Corporation Regeneration of plating baths
DE19956666B4 (de) 1999-11-25 2009-10-29 Enthone Gmbh Verfahren zur kontinuierlichen Abscheidung blendfreier Metallüberzüge auf einer metallischen Oberfläche
US6602395B1 (en) * 2000-04-11 2003-08-05 Innovative Technology Licensing, Llc Patterning of polymer light emitting devices using electrochemical polymerization
JP2001316894A (ja) * 2000-05-08 2001-11-16 Tokyo Electron Ltd 液処理装置、液処理システム、及び液処理方法
JP3568460B2 (ja) 2000-07-03 2004-09-22 大日本スクリーン製造株式会社 メッキ液再生装置及び基板メッキ装置並びにメッキシステム
JP2002253899A (ja) 2001-02-27 2002-09-10 Emiko Watanabe 衣類干し補助具
JP2002322599A (ja) * 2001-04-23 2002-11-08 Shigeo Hoshino ３価クロムめっき方法
DE10225203A1 (de) * 2002-06-06 2003-12-18 Goema Ag Verfahren und Vorrichtung zur Spülwasserrückführung und Reinigung eines Prozessbades

Also Published As

Publication number Publication date
JP4764886B2 (ja) 2011-09-07
WO2006066689A2 (fr) 2006-06-29
US8475874B2 (en) 2013-07-02
DE102004061255B4 (de) 2007-10-31
CN101278077A (zh) 2008-10-01
CA2591932A1 (fr) 2006-06-29
CN101278077B (zh) 2013-01-09
WO2006066689A3 (fr) 2007-11-08
ATE413479T1 (de) 2008-11-15
JP2008524436A (ja) 2008-07-10
US20090130315A1 (en) 2009-05-21
EP1831435A2 (fr) 2007-09-12
KR101237037B1 (ko) 2013-02-25
BRPI0519144A2 (pt) 2008-12-30
ES2313434T3 (es) 2009-03-01
DE102004061255A1 (de) 2006-06-29
DE502005005921D1 (de) 2008-12-18
KR20070086772A (ko) 2007-08-27

Similar Documents

Publication Publication Date Title
EP1831435B1 (fr) Procede d'exploitation continue de bains de zinc ou de bains d'alliage de zinc, acides ou alcalins
EP0158910B1 (fr) Procédé pour la récupération de cuivre à partir d'une solution ammoniacale de décapage de cuivre et régénération de ladite solution
DE2447323A1 (de) Wiedergewinnung von metallen aus abfallschlaemmen
WO2012031753A1 (fr) Anode et son utilisation dans un bain galvanique alcalin
EP1979511A2 (fr) Procédé et dispositif pour revêtir les surfaces d'un substrat
DE4318168C2 (de) Verfahren zum direkten elektrochemischen Raffinieren von Kupferabfällen
DE2250072A1 (de) Verfahren zur rueckgewinnung von kupfer aus verbrauchten aetzloesungen, sowie einrichtung zur durchfuehrung des verfahrens
EP0240589B1 (fr) Procédé et appareillage pour la régénération d'un bain de dépôt chimique de cuivre
DE2724724B2 (de) Verfahren und Anlage zum Aufbereiten von schwermetallhaltigen Abwässern unter Rückgewinnung von Schwermetallen
DE4405741C1 (de) Verfahren zur elektrolytischen Abscheidung von Metallen aus Elektrolyten mit Prozeßorganik
EP2352859B1 (fr) Procédé et installation de décapage
DE2739970A1 (de) Verfahren zur rueckgewinnung des zinks aus dieses enthaltenden rueckstaenden, und bei diesem verfahren benutzbare elektrolysevorrichtung
EP2384800B1 (fr) Régénération d'électrolytes zinc-nickel alcalins par la suppression d'ions de cyanure
DE4315411C2 (de) Verfahren zur Regenerierung von verbrauchten Chromsäurelösungen
DE2057606A1 (de) Verfahren und Einrichtung zur Rueckgewinnung von Nickel und/oder von anderen der Eisengruppe des periodischen Systems angehoerenden,vorzugsweise hoeherwertigen Metallen
DE2929305C2 (de) Verfahren und Vorrichtung zur kontinuierlichen galvanischen Abscheidung von Mangan auf Stahl
DE69912999T2 (de) Verfahren und anlage zum auflösen von metallen in einem elektrolyten zur metallabscheidung
EP2039810A2 (fr) Procédé et dispositifs pour prolonger la durée d'utilisation d'une solution de procédé utilisée dans un processus de revêtement métallique par réduction chimique
EP0612359A1 (fr) Procede et dispositif pour la regeneration de decapants recuperes.
EP0079032B1 (fr) Appareil pour le dépôt électrolytique d'une pièce métallique
EP0519987B1 (fr) Procede et dispositif de regeneration de reactifs alcalins d'attaque micrographique de l'aluminium
DE2636552A1 (de) Verfahren zur galvanischen abscheidung einer ferro-nickel-legierung
EP2431500B1 (fr) Régénération d'électrolytes alcalins en nickel-zinc par suppression de cyanidions à l'aide de composés solubles d'ammonium quaternaire
DE10342291A1 (de) Verfahren zur elektrolytischen Abscheidung von Zinnlegierungen mit elektropositiveren Metallen
DE4231879C2 (de) Verfahren zum Beizen von Aluminiumoberflächen unter Gewinnung von Natriumaluminatlösung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070524

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

R17D Deferred search report published (corrected)

Effective date: 20071108

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20080307

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502005005921

Country of ref document: DE

Date of ref document: 20081218

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2313434

Country of ref document: ES

Kind code of ref document: T3

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
LTIE Lt: invalidation of european patent or patent extension

Effective date: 20081105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090305

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

BERE Be: lapsed

Owner name: ATOTECH DEUTSCHLAND G.M.B.H.

Effective date: 20081130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081130

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090205

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090205

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090406

26 Opposition filed

Opponent name: DR.ING. MAX SCHLOETTER GMBH & CO. KG

Effective date: 20090723

26 Opposition filed

Opponent name: DR. HESSE GMBH & CIE KG

Effective date: 20090803

Opponent name: DR.ING. MAX SCHLOETTER GMBH & CO. KG

Effective date: 20090723

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081130

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081128

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

R26 Opposition filed (corrected)

Opponent name: DR. HESSE GMBH & CIE KG

Effective date: 20090803

Opponent name: DR.ING. MAX SCHLOETTER GMBH & CO. KG

Effective date: 20090723

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20091128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081128

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090506

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091130

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091130

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091128

RIC2 Information provided on ipc code assigned after grant

Ipc: C25D 21/18 20060101ALI20120202BHEP

Ipc: C25D 3/56 20060101AFI20120202BHEP

Ipc: C25D 3/22 20060101ALI20120202BHEP

Ipc: C25D 21/14 20060101ALI20120202BHEP

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: ATOTECH DEUTSCHLAND GMBH

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: DR. HESSE GMBH & CIE KG

Effective date: 20090803

Opponent name: DR.ING. MAX SCHLOETTER GMBH & CO. KG

Effective date: 20090723

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20161121

Year of fee payment: 12

Ref country code: CZ

Payment date: 20161125

Year of fee payment: 12

Ref country code: FR

Payment date: 20161118

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20161110

Year of fee payment: 12

Ref country code: IT

Payment date: 20161123

Year of fee payment: 12

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 502005005921

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 502005005921

Country of ref document: DE

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20171002

REG Reference to a national code

Ref country code: AT

Ref legal event code: MA03

Ref document number: 413479

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171002