EP0838542B1 - Procédé et dispositif pour le décapage électrolytique de bandes métalliques - Google Patents

Procédé et dispositif pour le décapage électrolytique de bandes métalliques Download PDF

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Publication number
EP0838542B1
EP0838542B1 EP97117775A EP97117775A EP0838542B1 EP 0838542 B1 EP0838542 B1 EP 0838542B1 EP 97117775 A EP97117775 A EP 97117775A EP 97117775 A EP97117775 A EP 97117775A EP 0838542 B1 EP0838542 B1 EP 0838542B1
Authority
EP
European Patent Office
Prior art keywords
strip
electrodes
electrolyte
process according
anodes
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.)
Expired - Lifetime
Application number
EP97117775A
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German (de)
English (en)
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EP0838542A1 (fr
Inventor
Wilhelm Dr. Techn. Karner
Jovan Dipl.-Ing. Dr. Starcevic
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.)
Andritz AG
Original Assignee
Andritz AG
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Filing date
Publication date
Application filed by Andritz AG filed Critical Andritz AG
Publication of EP0838542A1 publication Critical patent/EP0838542A1/fr
Application granted granted Critical
Publication of EP0838542B1 publication Critical patent/EP0838542B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/06—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/08—Refractory metals

Definitions

  • the invention relates to a method and an apparatus for electrolytic pickling of metallic strips, in particular Stainless steel bands, bands made of titanium, aluminum or nickel, the Electric current indirectly, i.e. without electrically conductive contact between tape and electrodes, is passed through the tape, the Band vertically and the electrolyte liquid between the band and the electrodes are inserted.
  • GB 2140036 further describes a device for electrochemical treatment of metal strips with vertical Belt guide, indirect power supply and by gravity forced electrolyte flow in the gap between the band and the electrodes.
  • the Srom has to travel long distances in the band, taking the danger there is that it is derived at the deflection rollers and in others Episode is not available for the pickling process.
  • the invention is characterized in that the anode and cathode on Band are connected in direct succession. This is the way of Current through the tape is very short and the losses are low. Consequently much higher current rates can also be transmitted.
  • An advantageous development of the invention is characterized in that that the distance between the anodes and cathodes depending on the Band dimension is changeable. It is achieved that at different Band dimensions the maximum current yield at the lowest Tension can be achieved. Are the anode and cathode too close to each other? arranged, there is a direct current flow. On the other hand, it increases with their distance the voltage drop in the band. Naturally depends this voltage drop together with the band cross section. There are therefore an optimal distance for each band dimension.
  • a favorable embodiment of the invention is characterized in that that the amount of electrolyte in the gap, between the electrodes and the volume, regulated. This allows the belt to be hydraulically accurate be stabilized in the middle between the electrodes. So the distance between electrodes and band can be reduced to a minimum.
  • An advantageous variant of the invention is characterized in that the temperature, electrolyte concentration and charge density (Coulomb per unit area) can be specifically adjusted to the strip to be pickled. As a result, the pickling conditions can be applied to every strip dimension, line speed, Treatment time, type of scale etc. optimally set become.
  • An advantageous embodiment of the invention is characterized in that that the gap between the electrodes and the band is changed. So the distance can be easily adapted to the band ripple.
  • a favorable further development of the invention is characterized in that that the band ripple is determined and the electrodes are removed from the band be avoided so that contact between the tape and the electrode becomes. This prevents contact between the band and the electrodes that would lead to short circuits.
  • the invention also relates to a device for electrolytic pickling made of metallic strips, in particular stainless steel strips Titanium, aluminum or nickel, the electrical current being indirect, i.e. without electrically conductive contact between the band and the electrodes the tape is guided, the tape being vertical and between Electrodes and tape a vertical gap is provided in the Electrolyte liquid is introduced. It is characterized in that Anode and cathode are arranged one behind the other on the strip. As a result, the path of the current through the belt is very short, and so is that Losses low. This means that significantly higher current rates can also be used be transmitted.
  • a favorable further development of the invention is characterized in that that anodes and cathodes are staggered in the direction of the tape are, i.e. the tape runs between two opposite Anodes or two opposite cathodes. This results in a uniform current flow and at the band edge thus an even pickling effect.
  • an advantageous embodiment of the invention is characterized in that the anode surface, or the anodes entirely, are preferably made of lead, or lead alloys, or iridium oxide or graphite.
  • the material from which the anodes are made results in a chemical passivation against the anodic attack of the electrolyte anions.
  • Lead with sulfate ions (SO 4 2- ) and iridium oxide with sulfate and / or chloride ions (Cl - ) are preferably used.
  • Graphite with various anions or mixtures thereof can also be used.
  • An advantageous variant of the invention is characterized in that a control device for the amount of electrolyte is provided is, with one per liquid channel between the band and the electrode separate control device can be provided. This can on the one hand the flow is adapted to the bandwidth and also for Bands of different widths can be optimally adjusted. Through the Resulting hydraulic guidance of the belt can change the position of the Band can be set between the electrodes.
  • the conventional ones Systems usually require two rectifiers per cell - one for the underside of the band and one for the top of the band.
  • the cell according to the invention can be a rectifier for one or for multiple cells can be installed. Thanks to the hydraulic belt guide, which is made possible by regulating the amount of electrolyte added now e.g. the top of the tape, if more scaled, closer to the Electrodes are pressed and thus stained more intensely.
  • a favorable embodiment of the invention is characterized in that that a device for adjusting or controlling the distance is provided between anodes and cathodes.
  • the adjustable distance between the anode and cathode allows the current flow to be adjusted and subsequently a reduction in electricity costs.
  • An advantageous development of the invention is characterized in that that a device for adjusting the gap between the tape and Electrode is provided. So the distance can easily match the band ripple be adjusted.
  • a cheap variant of the invention is characterized in that a device for detecting the band ripple is provided, which with the adjusting device of the electrodes is connected. This will Avoid contact between the tape and electrodes, which leads to short circuits could lead.
  • the rectifier current was increased at a constant system speed of approx. 50 m / min. With a current of 6000A (4x1500 A) the belt was completely free of scale. With a current application of 8000 A there was an improved gloss of the strip surface. Here, with a current density of approx. 200 A / dm 2 , there were no problems in the cell with electrolyte overheating, excessive local heating of the strip or insufficient gas discharge. The evaluation of the tests also consisted of determining the uniformity of the current application. This was done through the gloss and color measurements. It was found that the fluctuations were not larger than that of the starting material. The particularly scaled band edges were completely descaled.
  • 1 shows the diagram of a conventional pickling plant with neutral electrolyte
  • 2 shows a plant according to the inventive method
  • Figure 3 illustrates a cell according to the invention.
  • Fig. 1 shows a pickling tank 1 according to the prior art.
  • the metal strip 2 is passed through the electrolyte 3, for example Na 2 SO 4 , between the cathodes 4 and anodes 5.
  • the distance between the electrodes and the band is usually approximately 70 to 150 mm, the band 2 having a certain sag, which can be reduced by support rollers, for example in the middle of the system.
  • the electrolyte 3 is fed from a pump 7 via a line 6 into the pickling tank 1 and, via a line 8, for example into an intermediate tank 9, from where the electrolyte 3 is recirculated.
  • Fig. 2 shows a system with a decoiler 11 and a decoiler 18, the it enables the belt to travel at a speed of up to 60 m / min to pull through the treatment.
  • the treatment consists of chemical degreasing 12 to clean the oiled tape and an electrolytic cell 13.
  • the cell is connected to 4 rectifiers. Each of them has an output of max. 3000A / 32 V.
  • the arrangement of the electrodes 15, 16 was chosen so that only an anode (15) - cathode (16) pair is connected to a rectifier.
  • the belt 2 is deflected here via rollers 14, 14 '.
  • Fig. 3 shows an electrolytic cell according to the invention.
  • the metallic Volume 2 e.g. B. stainless steel strip, is in the gap between the electrodes 15, 16 out.
  • the electrodes, e.g. the cathode 16 can in Direction 20 are moved so that the distance between anode 15 and Cathode 16 is adjustable. This enables optimal use of electricity.
  • the electrolyte is in turn pump 7 via a line 6, wherein lines 21, 21 ', 21 ", 21"' are provided which connect the electrolyte 3 into the columns 24, 24 ', 24 ", 24"' between the electrodes 15, 16 and the Feed in volume 2.
  • the electrolyte can now be controlled by regulators 22, 22 ', 22 ", 22"' to be adapted to the required conditions. After passage between the electrodes, the electrolyte 3 is in the lower Part 23 of the electrolytic cell 13 collected and again the Pump 7 supplied.
  • the new cell has higher performance than the conventional ones. At same electrical power can be achieved by the lower voltage drop more electricity is passed through the belt. At the same time, however new cell flow mechanically designed so that very high Mass transfer numbers and heat transfer values can be achieved. This results from high turbulence due to the small gap between the electrodes and the band as well as by the band movement i.e. it dissolves the metals and the heat from the Reaction zone removed very effectively.
  • the main advantage of cell according to the invention compared to the flooded cell according to the prior art the technology (see Fig. 1) lies in the better tape guidance and higher mass and heat exchange. This results in a higher one Pickling performance.
  • the conventional cells have rectifier performance from 11000 A (2 x 5500). Depending on the distance between electrodes and Band (approx. 50 - 150 mm) the voltage drop is between 25 and 40 V.
  • the cell according to the invention can apply 50,000 A to the band at approximately 17 V. transfer.
  • the invention is not limited by the embodiments shown. Rather, all known variants of the circuit and Arrangement of the electrodes, e.g. corresponding polarization or shorter anodes and longer cathodes to increase chemical Treatment, can be used analogously.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (20)

  1. Procédé de décapage électrolytique des bandes métalliques, surtout des bandes en acier inoxydable, des bandes en titane, aluminium ou nickel, avec passage indirect du courant électrique dans la bande, i.e. sans contact électro-conducteur entre la bande et les électrodes, avec marche de la bande au sens vertical et alimentation du liquide électrolytique dans l'espace entre la bande et les électrodes, caractérisé en ce que l'anode et la cathode sont mises en place sur la bande en série directe.
  2. Procédé selon la revendication 1, caractérisé en ce que l'espace entre les anodes et les cathodes est variable en fonction de la dimension de la bande.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la quantité d'électrolyte qui est amenée dans la fente entre les électrodes et la bande est contrôlée.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la température est spécifiquement réglée en fonction de la bande à décaper.
  5. Procédé selon la revendication 4, caractérisé en ce que la température de l'électrolyte s'élève à entre 20 et 85°C, de préférence au-dessous de 70°C.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la concentration de l'électrolyte est spécifiquement réglée en fonction de la bande à décaper.
  7. Procédé selon la revendication 6, caractérisé en ce que la concentration de l'électrolyte en Na2SO4 s'élève à 100 jusqu'à 350 g/l, de préférence autour de 150 g/l.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que la densité de charge (coulombs par unité de surface) est spécifiquement réglée en fonction de la bande à décaper.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que les densités de courant s'élèvent à entre 20 A/dm2 et 250 A/dm2, avec par exemple, environ 130 A/dm2 pour les anodes en plomb et environ 180 A/dm2 pour les anodes en iridium.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que la fente entre les électrodes et la bande est modifiée.
  11. Procédé selon la revendication 10, caractérisé en ce que l'ondulation de la bande est mesurée et les électrodes sont éloignées de la bande afin d'éviter tout contact entre la bande et l'électrode.
  12. Dispositif de décapage électrolytique des bandes métalliques, surtout des bandes en acier inoxydable, des bandes en titane, aluminium ou nickel, avec passage indirect du courant électrique dans la bande, i.e. sans contact électro-conducteur entre la bande et les électrodes, avec marche de la bande au sens vertical et avec fente verticale prévue entre la bande et les électrodes, dans laquelle le liquide électrolytique est alimenté, caractérisé en ce que l'anode et la cathode sont mises en place sur la bande en série directe.
  13. Dispositif selon la revendication 12, caractérisé en ce que les anodes et les cathodes sont échelonnées les unes envers les autres.
  14. Dispositif selon la revendication 12 ou 13, caractérisé en ce que la surface des anodes ou bien les anodes entières sont, de préférence, en plomb ou alliages de plomb, ou en oxyde d'iridium ou en graphite.
  15. Dispositif selon l'une des revendications 12 à 14, caractérisé en ce qu'un dispositif de contrôle du débit d'alimentation de l'électrolyte est prévu.
  16. Dispositif selon la revendication 15, caractérisé en ce qu'un dispositif de contrôle séparé est prévu pour chacun des conduits de liquide entre la bande et l'électrode.
  17. Dispositif selon l'une des revendications 12 à 16, caractérisé en ce qu'un dispositif de réglage respectivement de contrôle de l'espace entre les anodes et les cathodes est prévu.
  18. Dispositif selon l'une des revendications 12 à 17, caractérisé en ce qu'un dispositif de réglage de la fente entre la bande et l'électrode est prévu.
  19. Dispositif selon la revendication 18, caractérisé en ce qu'un dispositif de détection de l'ondulation de la bande est prévu, qui est relié au dispositif de réglage des électrodes.
  20. Dispositif selon l'une des revendications 12 à 19, caractérisé en ce que les électrodes et la bande sont espacées de 5 à 15 mm.
EP97117775A 1996-10-25 1997-10-14 Procédé et dispositif pour le décapage électrolytique de bandes métalliques Expired - Lifetime EP0838542B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0187296A AT406385B (de) 1996-10-25 1996-10-25 Verfahren und vorrichtung zum elektrolytischen beizen von metallischen bändern
AT1872/96 1996-10-25
AT187296 1996-10-25

Publications (2)

Publication Number Publication Date
EP0838542A1 EP0838542A1 (fr) 1998-04-29
EP0838542B1 true EP0838542B1 (fr) 2001-06-13

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EP97117775A Expired - Lifetime EP0838542B1 (fr) 1996-10-25 1997-10-14 Procédé et dispositif pour le décapage électrolytique de bandes métalliques

Country Status (14)

Country Link
US (1) US6120671A (fr)
EP (1) EP0838542B1 (fr)
KR (1) KR100487646B1 (fr)
CN (1) CN1195905C (fr)
AT (1) AT406385B (fr)
BR (1) BR9705144A (fr)
CA (1) CA2218765A1 (fr)
DE (1) DE59703769D1 (fr)
ES (1) ES2159076T3 (fr)
ID (1) ID18748A (fr)
MX (1) MX9708212A (fr)
MY (1) MY123861A (fr)
RU (1) RU2205254C2 (fr)
TW (1) TW531570B (fr)

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IT1302202B1 (it) 1998-09-11 2000-07-31 Henkel Kgaa Processo di decapaggio elettrolitico con soluzioni esenti da acidonitrico.
DE19951324C2 (de) * 1999-10-20 2003-07-17 Atotech Deutschland Gmbh Verfahren und Vorrichtung zum elektrolytischen Behandeln von elektrisch leitfähigen Oberflächen von gegeneinander vereinzelten Platten- und Folienmaterialstücken sowie Anwendung des Verfahrens
DE19951325C2 (de) 1999-10-20 2003-06-26 Atotech Deutschland Gmbh Verfahren und Vorrichtung zum elektrolytischen Behandeln von elektrisch gegeneinander isolierten, elektrisch leitfähigen Strukturen auf Oberflächen von elektrisch isolierendem Folienmaterial sowie Anwendungen des Verfahrens
DE10153171B4 (de) * 2001-10-27 2004-09-16 Atotech Deutschland Gmbh Verfahren und Vorrichtung zum elektrolytischen Behandeln von Teilen in Durchlaufanlagen
AT413697B (de) * 2001-11-07 2006-05-15 Andritz Ag Maschf Verfahren zur behandlung säurehältiger abwässer
AT413707B (de) * 2004-07-19 2006-05-15 Voest Alpine Ind Anlagen Verfahren und vorrichtung zum beizen von metallen
JP4531777B2 (ja) * 2007-01-18 2010-08-25 日本メクトロン株式会社 プリント配線板のめっき前処理方法
US20130233702A1 (en) * 2012-03-09 2013-09-12 Chung-Shan Institute of Science and Technology, Armaments, Bureau, Ministry of National Defense Multi-Stationed Continuous Electro-Polishing System
DE102013022030B4 (de) * 2013-12-19 2017-10-05 Schlenk Metallfolien Gmbh & Co. Kg Verfahren zur elektrolytischen Oberflächenmodifizierung von flächigen Metallwerkstücken in sulfatometallhaltigen Kupfersulfat-Behandlungsflüssigkeiten, flächiges Metallwerkstück und dessen Verwendung
JP6233334B2 (ja) * 2015-03-04 2017-11-22 Ｊｆｅスチール株式会社 方向性電磁鋼帯の連続電解エッチング方法および方向性電磁鋼帯の連続電解エッチング装置
IT201700097032A1 (it) * 2017-08-29 2019-03-01 Qualital Servizi Srl Impianto e procedimento per il trattamento elettrochimico in continuo di nastri in materiale metallico
CN109750307B (zh) * 2019-03-11 2021-04-13 中冶东方工程技术有限公司 一种不锈钢板的酸洗系统和方法
CN111621840A (zh) * 2020-05-26 2020-09-04 大连理工大学 一种钛合金表面铁污染的双极电化学清除方法
CN111676493B (zh) * 2020-06-12 2021-02-19 广东嘉元科技股份有限公司 一种用于电解铜箔剥离和表面处理的多功能装置

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Also Published As

Publication number Publication date
ES2159076T3 (es) 2001-09-16
CN1192488A (zh) 1998-09-09
CN1195905C (zh) 2005-04-06
EP0838542A1 (fr) 1998-04-29
ID18748A (id) 1998-05-07
MX9708212A (es) 1998-04-30
MY123861A (en) 2006-06-30
KR19980033150A (ko) 1998-07-25
US6120671A (en) 2000-09-19
BR9705144A (pt) 1999-02-23
ATA187296A (de) 1999-09-15
DE59703769D1 (de) 2001-07-19
CA2218765A1 (fr) 1998-04-25
TW531570B (en) 2003-05-11
AT406385B (de) 2000-04-25
KR100487646B1 (ko) 2005-09-02
RU2205254C2 (ru) 2003-05-27

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