EP0766751B1 - Verfahren zum ätzen von metallischen werkstoffen - Google Patents

Verfahren zum ätzen von metallischen werkstoffen Download PDF

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Publication number
EP0766751B1
EP0766751B1 EP95922577A EP95922577A EP0766751B1 EP 0766751 B1 EP0766751 B1 EP 0766751B1 EP 95922577 A EP95922577 A EP 95922577A EP 95922577 A EP95922577 A EP 95922577A EP 0766751 B1 EP0766751 B1 EP 0766751B1
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EP
European Patent Office
Prior art keywords
solution
pickling
spraying
oxygen
enclosure
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EP95922577A
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English (en)
French (fr)
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EP0766751A1 (de
Inventor
Didier Paul
Bernard Vialatte
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USINOR SA
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USINOR SA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • 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
    • C23G1/36—Regeneration of waste pickling liquors
    • 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
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • 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
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • C23G3/023—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously by spraying

Definitions

  • the present invention relates to a pickling process acid from metallic materials, especially alloy steel, steel stainless steel or titanium alloys.
  • pickling of steel materials is done in a bath consisting of aqueous solution containing ferric ions and hydrofluoric acid.
  • This bath has the advantage of not containing nitric acid and therefore of do not generate toxic compounds derived from nitric acid during pickling.
  • mineral acids such as sulfuric acid or phosphoric acid can also enter into the composition of such pickling baths.
  • the baths can be regenerated by introducing an oxidizing agent so as to increase their lifespan. For this can be done by bubbling air or an oxygen-containing gas in the bath, or introduce an oxidant stronger than gaseous oxygen such as ozone, hydrogen peroxide or a compound such as peroxide, peracid or parsley.
  • the pickling solution is sprayed on the part to be stripped, the solution is recovered after contact with the part and it is recycled in a closed circuit of solution of pickling.
  • the solution is usually regenerated by performing a bubbling of air or an oxygen-containing gas at a point in the recirculation of the pickling solution.
  • the object of the invention is to provide a pickling process acid of metal parts by spraying, in which the speed of pickling is significantly improved throughout the duration of using the same solution.
  • the invention also aims to improve in a way particularly economical the etching speed of the processes of the aforementioned type.
  • the invention relates to a process for pickling metallic materials, by a pickling solution S containing ferric ions in an acid medium comprising at least one acid chosen from a halogenated acid, a mineral acid and non-oxidizing organic acids from iron in which said solution is sprayed on the material, recovered and recycled in a closed circuit pickling solution and said spraying is carried out in an atmosphere confined in a spray enclosure with an oxygen supply by introduction into the spraying enclosure of a gas G containing oxygen.
  • metallic materials can be cited alloy steel, stainless steel or titanium alloys.
  • the pickling method of the invention can also be applied to alloys based on zirconium, cobalt or nickel, or on non-alloy steels.
  • the acid used according to the invention preferably as halogenated acid, hydrofluoric acid, as mineral acid, sulfuric or phosphoric acid and as non-oxidizing organic acids in iron, formic acid or acetic acid.
  • the materials to be stripped can be in the form of strips, any wires, tubes, plates or metal parts.
  • the introduction into the confined atmosphere of a gas containing the oxygen makes it possible to maintain a speed of high pickling.
  • the oxygen contained in said gas can be introduced, even partially, in the form of ozone.
  • This oxygen supply can advantageously be carried out continuously in maintaining the circulation in the spraying enclosure of a gas G containing oxygen, and very advantageously by uniformly distributing the continuous circulation of said gas in the enclosure for ensure a homogeneous composition of the atmosphere in the enclosure.
  • the oxygen content of said gas G containing oxygen is more than 10%.
  • the gas may for example be air.
  • the flow rate of said gas G containing the oxygen is at least equal to the spray rate of said solution S.
  • the flow rate of said gas G makes it possible to renew the atmosphere in the spray enclosure on average at least all fifteen minutes, and preferably every five minutes.
  • the oxygen supply maintains an oxygen content of the atmosphere in the spray enclosure at least equal to 10%.
  • the ratio between the flow of spraying of said solution S on the metal surface expressed in liters / minute and the surface to be stripped per unit of time expressed in meters squares per minute is at least five.
  • the solution of pickling be sprayed as small droplets which provide a large exchange surface between the sprayed liquid and the atmosphere prevailing in the spray enclosure.
  • the size of droplets depend on the flow rates of liquid and especially gas in said pregnant and is advantageously in the range corresponding to atomization processes.
  • a part at less of the pickling solution is introduced into said enclosure by atomization.
  • the pickling process can be discontinuous, the spraying parts to be stripped taking place in a closed enclosure provided with means for introducing oxygen.
  • This enclosure can example be a spray tunnel.
  • the enclosure also has means for introducing oxygen.
  • an etching solution S which contains hydrofluoric acid and Fe 3+ ions, present in the form of fluorinated complexes, the concentration of ferric ions Fe 3+ being included between 1 and 150 grams per liter, and which has a pH between 0 and 3; it also contains Fe 2+ ions and its redox potential measured with respect to a saturated calomel reference electrode is between -200 mV and + 800 mV; such a pickling solution is described in particular in European patent application No. 0 188 975 filed by the applicant.
  • the etching speed remains permanently much higher that the pickling speed that would be obtained by immersion of said parts in said solution and oxidative regeneration by bubbling oxygen in said solution.
  • the pickling process can be implemented by checking the redox potential of the solution.
  • We can maintain the value of the potential to a predetermined value by modifying the flow rate of gas G introduced, by adding an oxidizing agent to solution S in the circuit recirculation or by changing the spray rate of solution S.
  • Checking the redox potential of the pickling solution is particularly advantageous in the context of the present invention because it allows to use the recycled pickling solution for a very long lasting with good stripping efficiency while spacing out equipment maintenance interruptions.
  • the present inventors have been able to determine that one can spray pickling with a solution having a sufficiently high redox potential, to ensure good efficiency of pickling, but low enough to limit precipitation and crystallizations of ferric compounds and thus limit the risks of clogging in the installation, in particular at the level of the spray.
  • the measurement of the redox potential of the solution pickling allows, by comparison with the initial value of the potential of the solution at the start of pickling, to assess the aging of said solution or detect any anomalies. So although one of the goals of the invention either to avoid resorting to strong oxidants but expensive, depending on the value of the redox potential, you may need a strong oxidation means temporarily and / or locally completing the action oxygen carrier gas introduced into the spray enclosure to quickly return to an advantageous redox potential allowing a good pickling.
  • the method according to the invention can be used for pickling with solutions containing ferric ions in acidic media containing acids other than hydrofluoric acid, in particular organic acids, used in a closed circuit and therefore requiring regeneration by an oxidizing agent, for example by a gas containing oxygen or hydrogen peroxide, regeneration controlled by measuring the redox potential of the solution.
  • an oxidizing agent for example by a gas containing oxygen or hydrogen peroxide
  • the pickling solution is maintained within a predetermined temperature range, preferably at a constant temperature within operating variations, in the circuit closed solution recirculation.
  • an operation of heating and / or heating at any point of the recirculation circuit using any suitable technique.
  • we circulate in the solution a stream of hot gas containing oxygen, advantageously a current of hot air, so as to achieve at the same time reheating and regeneration of the pickling solution.
  • reheating preferably takes place just before spraying the solution.
  • the method according to the invention applies to pickling in continuous, in particular of metal strips, and discontinuously, in particular of crowns of metal wire or metal parts.
  • the device according to the invention may further comprise means for maintaining the temperature of said solution, capable of ensuring a reheating or cooling.
  • the pickling processes employ solutions above room temperature that have tendency to cool down during use.
  • the means of maintaining temperature are therefore preferably means for reheating the pickling solution.
  • Reheating means may include a tray conventional conduction heater or means of insufflation in the solution of a hot gas containing oxygen, in particular air hot, these two types of means possibly being associated. They are preferably arranged just upstream of the spraying means.
  • the device can further comprise liquid / solid separation means, in particular by decantation, for rid the pickling solution circulating in closed circuit of solid particles from pickling which are entrained with the solution in the receiving tank.
  • said means of separation can be provided with means for blowing hot gas containing oxygen in the area where the liquid resides.
  • the device can advantageously include control means comprising at least one measurement probe, in particular the temperature, pH or redox potential of the solution, located at any point on the solution recirculation circuit pickling.
  • control means may include in particular a redox potential measurement probe for the solution of pickling.
  • the device may further comprise means for injecting an oxidizing agent, in particular hydrogen peroxide, in the recirculation circuit of said solution, slaved to said probe potential measurement.
  • an oxidizing agent in particular hydrogen peroxide
  • said ventilation means can be equipped with a gas flow control valve controlled by said gas probe potential measurement.
  • said spraying means can be equipped with a solution flow control valve controlled by said probe potential measurement.
  • the device shown in Figure 1 includes a spray enclosure, means for spraying a solution of pickling in said enclosure, means of ventilation of said enclosure, control means, recirculation means, processing means and means for maintaining said temperature solution.
  • Said spray enclosure comprises a tunnel 1 provided a receiving tank 2 and a cover 3, an airlock 4A and a 4B exit airlock for the strip to be stripped and transfer means said strip composed of rollers 5 which define a strip path or stripping plan P.
  • the spraying means include spray bars 6 parallel to the rollers 5, regularly spaced and arranged above and below said plane pickling P, as shown in detail in Figure 2; ramps 6 are rigid tubular conduits which open into a multitude of spray nozzles 7 arranged regularly along the boom 6.
  • Said spray nozzles 7 are of a type known from itself intended to produce a flat spray.
  • the distance between the orifices of the nozzles 7 from the plane of pickling P along the direction of the jet is between 5 cm and 70 cm, and preferably equal to approximately 30 cm.
  • the nozzles 7 of the same ramp 6 are oriented to create flat jets that span the width of the strip path and the distance between the nozzles 7 is less than the width of the jet at the level of the stripping plane P so that the flat jets of each nozzle of a same ramp partially overlap over the entire width of the path strip, as shown in Figure 2.
  • the means of ventilation include a supply circuit and a gas exhaust circuit the enclosure. These circuits are preferably adapted in a known manner in itself to ensure a homogeneous composition of the atmosphere of the enclosure.
  • the ventilation means of the tunnel include a fan 8 connected to one end of the tunnel by a gas supply pipe and a gas evacuation chimney 9 located at the other end of the tunnel.
  • the intake of fan 8 is connected to a mouth air intake not shown and the fan is fitted with a flow control not shown; the chimney 9 is connected to a device gas treatment not shown which allows the recovery of a part of the mist or droplets discharged into the gas stream.
  • Said recirculation means comprise a tank buffer 10 connected to the receiving tank 2 and a pump 11 for reinjecting under pressure the solution from the buffer tank 10 to each ramps 6.
  • the pump 11 has characteristics which make it possible to supply said ramps at a pressure of between 0.5 ⁇ 10 5 and 7.10 5 Pa, and preferably equal to 3.10 5 Pa; the pump 11 is provided with a flow control valve not shown.
  • the buffer tank 10 is provided with a feed orifice, in particular to supplement the quantity of pickling solution S.
  • Said control means consist of a redox potential measurement located at the buffer tank 10, not represented.
  • said probe for measuring redox potential can be installed at other points in the recirculation of the pickling solution.
  • Said processing means comprise a decanter 12.
  • Decanter 12 is installed on a recirculation circuit secondary connected to the buffer tank 10 whose flow rate is regulated by a 12 'pump; the decanter 12, known in itself, is not described here in detail and has a solid residue discharge R.
  • Said temperature maintenance means comprise a heater 13 which is installed on the pipe connecting the pump 11 to ramps 6; the heater 13, known in itself, is not described here in detail.
  • the method according to the invention is used here for pickling a stainless steel strip B of width Lb.
  • the buffer tank 10 is filled with a pickling solution S containing ferric ions in hydrofluoric acid medium.
  • the spraying and recirculation means are started, treatment and heating of the pickling solution as well as the ventilation means of the spray tunnel 1.
  • Band B is continuously passed through the tunnel spraying 1 on the rollers 5 at a running speed Vb, successively by the entry airlock 4A then the exit airlock 4B.
  • the total volume of the spray tunnel being V in m 3 , using the fan flow control valve 8, the air flow pushed by said fan 8 into said tunnel is adjusted to V / 15 m 3 / minutes, so that the atmosphere of said tunnel is renewed on average at least every fifteen minutes, and preferably every five minutes.
  • the strip B When passing through spray tunnel 1, and especially between the spray bars 6, the strip B is sprayed with homogeneously on both sides by the pickling solution S sprayed by the nozzles 7 of the booms 6.
  • the spent solution comprising solid residues of pickling in suspension pours by gravity into the receiving tank 2 then in the buffer tank 10.
  • the redox potential measurement probe allows to measure the redox potential of solution S in buffer tank 10.
  • the solid residues of solution S are separated by the decanter 12 at the time of the passage of said solution in the circuit of secondary recirculation connected to the buffer tank 10.
  • the heater 13 advantageously maintains the temperature of the solution between 15 and 80 ° C, and preferably between 40 and 70 ° C.
  • solution S is continuously sprayed on the said strip in an atmosphere constantly renewed in oxygen and recirculates in a closed circuit in the pickling device.
  • the nozzles of spray 7 are replaced by pneumatic atomizing nozzles as previously supplied with liquid by the pump 11 and supplied with pressurized gas by an air or gas compressor containing oxygen.
  • Pneumatic atomization nozzles are known by themselves and are not described here; pump features 11 are adapted to the liquid supply specifications of said liquid nozzles.
  • the solution S is advantageously sprayed on both sides of the strip pickling and the atmosphere of the pickling tunnel is advantageously renewed at the level of the spraying means themselves by atomization pneumatic itself.
  • the spray tunnel is vertical; this arrangement can be advantageous for pickling metal wires or tubes.
  • the device is suitable for stripping crowns or coils of wire. he comprises a spray enclosure, provided with a support for the crown, means for spraying a pickling solution on the crown in said enclosure, control means, means of recirculation, treatment means and means for maintaining temperature of said solution.
  • Figure 3 shows a detail of such a device and illustrates spraying a crown of wire.
  • the device comprises a hook-shaped support 14 which supports on its lower part a crown of metallic wire C.
  • the spraying means comprise two booms of spray 6 arranged above and below the wire crown metallic C and fitted with spray nozzles 7 similar to the nozzles 7 shown in Figure 2, supplied with pickling solution S by a pipe connected to the recirculation circuit of said solution.
  • the ramps 6 are arranged horizontally in the enclosure one above the other, the nozzles 7 of the upper rail opposite the nozzles 7 of the lower ramp. They are enough spaced so that the coil C carried by the support 14 can be inserted in the intermediate space.
  • the power and orientation of the jets produced by the nozzles 7 are such that the entire crown is brought into contact with the pickling solution.
  • This spraying device can be integrated into a wire stripping device discontinuously, the support 14 being fixed relative to the closed and ventilated stripping chamber. he can also be integrated into a continuous pickling device wire crowns which includes several pairs of ramps 6 defining a horizontal space in which circulate mobile supports 14 carrying crowns C and into which the pickling solution S is sprayed on the succession of crowns C.
  • Pickling of a steel plate is carried out by immersion in a pickling bath containing ferric ions and acid hydrofluoric.
  • aqueous pickling solution About 1 liter of an aqueous pickling solution is prepared containing 30 grams per liter of hydrofluoric acid (expressed as HF), 30 grams per liter of total iron in solution with potential 250 mV redox compared to a reference electrode at saturated calomel, measured at 60 ° C.
  • This solution is placed in a pickling tank provided a redox potential measurement probe and air bubbling means in the bottom of the tank to stir the solution in the tank.
  • Said plate is etched by immersion in the tank and bubbled air there at a rate of between 10 and 20 l / minute.
  • the bath temperature is maintained between 50 and 60 ° C and the pH is maintained at its initial value by addition of hydrofluoric acid.
  • the same rectangular plate 20 is stripped mm x 50 mm of AISI 430 grade steel, using a spray.
  • the spray device models a tunnel spray and includes an enclosure with a cover and a tank filled with pickling solution S and equipped with a measurement probe redox potential.
  • a spray nozzle supplied with spray solution by a pump including the inlet pipe plunges into said tank.
  • the stripping plate is placed horizontally above from the tank, approximately 30 cm below the spray nozzle.
  • a fan ventilates the spray enclosure continuously.
  • the pickling solution S is sprayed homogeneously over the entire surface of the plate; the used solution is collected by the tank under the plate; the pump extracts the collected solution and returns it to the spray nozzle.
  • the temperature of the solution is maintained between 50 and 60 ° C and the pH is maintained at its initial value by addition of acid hydrofluoric.
  • the average change in weight over 3 hours is 10 g / m 2 / min.
  • the average change in weight over 3 hours is 14 g / m 2 / min.
  • the oxygenated jet process of the invention remains economical since it makes it possible to halve the quantity of this expensive reagent for achieve equal efficiency.
  • the pickling solution used in the examples can be used for continuous pickling, in a tunnel spraying of a steel strip of AISI 304 grade.
  • the spray tunnel has a total volume of 50 m 3 . It is equipped at one end with a fan connected to an air intake vent blowing air into the tunnel at a rate of 3.5 m 3 / minute.
  • the steel strip 1.3 m wide, runs in the tunnel at a speed of 25 m / min.
  • Common type spray bars are equipped with spray nozzles spaced 30 cm apart.
  • the pickling solution pumped into the receiving tank of the tunnel supplies the spraying booms under a pressure of 3.10 5 Pa for a flow rate of 2 m 3 / min.
  • a heating device helps maintain the pickling solution temperature between 50 and 60 ° C.
  • This pickling device was able to operate for periods of several weeks while retaining a satisfactory redox potential with good pickling quality.
  • This solution is used to continuously strip cold-rolled AISI 304 stainless steel strips in a spray tunnel with a volume of approximately 31 m 3 .
  • This tunnel has three outlets connected to an air suction device and the suction air flow is 160 m 3 / min; the three mouths are arranged regularly along one of the side walls of the enclosure, parallel to the strip running path.
  • the tunnel has 32 spray bars arranged about 25 cm below and above the scroll strip and distributed regularly along the tunnel; each ramp has spray nozzles uniformly spaced 35 cm apart.
  • the ramps are supplied with pickling solution under a pressure of 3.10 5 Pa (3 bar) and deliver a total of 2 m 3 / min of solution.
  • a heating device keeps the solution pickling temperature of around 75 ° C.
  • the steel strip, with a width of 1.24 m runs through the tunnel at a speed of 48 m / min.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)

Claims (27)

  1. Verfahren zum Ätzen von metallischen Werkstoffen durch eine Ätzlösung, die Eisenionen in saurem Medium enthält, das wenigstens eine Säure umfaßt, die unter einer halogenierten Säure, einer Mineralsäure und organischen, Eisen nicht-oxidierenden Säuren ausgewählt wurde, in dem besagte Lösung über dem Werkstoff versprüht, rückgewonnen und in einem geschlossenem Ätzlösungskreislauf zwückgeführt wird und besagte Versprühung in einer von einer Sprühkammer begrenzten Atmosphäre unter Sauerstoffzufuhr durch Einführen eines sauerstoffhaltigen Gases in besagte Kammer durchgeführt wird.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß der Umlauf in der Sprühkammer von einem sauerstoffhaltigen Gas unterhalten wird.
  3. Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Sauerstoffgehalt des besagten sauerstoffhaltigen Gases höher als 10 % ist.
  4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Durchflußmenge des besagten sauerstoffhaltigen Gases wenigstens gleich der Durchflußmenge der Versprühung der besagten Lösung ist.
  5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es der Umlauf des besagten sauerstoffhaltigen Gases erlaubt, die Atmosphäre in der Sprühkammer durchschnittlich wenigstens aller 15 Minuten und vorzugsweise aller 5 min zu erneuern.
  6. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Sauerstoffgehalt der besagten Atmosphäre höher als 10 % gehalten wird.
  7. Verfahren gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet daß das Verhältnis zwischen der Durchflußmenge der Versprühung besagter Lösung, ausgedrückt in Litern pro Minute, und der zu ätzenden Oberfläche pro Zeiteinheit, ausgedrückt in Quadratmetern pro Minute, wenigstens gleich fünf ist.
  8. Verfahren gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß ein Teil wenigstens der Ätzlösung in besagte Kammer durch Zerstäubung eingeführt wird.
  9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Redoxpotential der Ätzlösung bei einem vorbestimmten Wert gehalten wird.
  10. Verfahren gemäß Anspruch 9, dadurch gekennzeichnet, daß das besagte Redoxpotential auf besagten vorbestimmten Wert eingestellt wird, indem die Durchflußmenge der Einführung des besagten sauerstoffhaltigen Gases verändert wird.
  11. Verfahren gemäß Anspruch 9 oder 10, dadurch gekennzeichnet, daß das besagte Redoxpotential auf besagten vorbestimmten Wert eingestellt wird, indem ein Oxidationsmittel zu der Ätzlösung hinzugefügt wird.
  12. Verfahren gemäß einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, daß das besagte Redoxpotential auf besagten vorbestimmten Wert eingestellt wird, indem die Durchflußmenge der Versprühung der Lösung verändert wird.
  13. Verfahren gemäß einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß in die Ätzlösung ein warmer Luftstrom, der Sauerstoff enthält, eingeblasen wird.
  14. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die zu ätzenden metallischen Werkstoffe legierter Stahl, nichtrostender Stahl oder Titanlegierungen sind.
  15. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die halogenierte Säure Fluorwasserstoffsäure ist, die Mineralsäure Schwefelsäure oder Phosphorsäure ist und die organischen, Eisen nicht-oxidierenden Säuren Ameisensäure oder Essigsäure sind.
  16. Vorrichtung zum Ätzen durch Besprühung von metallischen Oberflächen, die eine Sprühkammer (1), die mit einem Sammelgefäß (2) ausgestattet ist, Mittel zum Versprühen (6) einer Ätzlösung S in besagter Kammer, Mittel zur Rückführung (11) der besagten Lösung zwischen besagtem Gefäß (2) und besagten Mitteln zum Versprühen (6) und Mittel zur Belüftung der besagten Kammer (8), (9) durch ein Gas G, das Sauerstoff enthält, umfaßt.
  17. Vorrichtung gemäß Anspruch 16, dadurch gekennzeichnet, daß die besagten Mittel zur Belüftung (8), (9) besagtes sauerstoffhaltiges Gas bei einer minimalen Durchflußmenge, die das Volumen des besagten Tunnels wiedergibt, wenigstens aller fünfzehn Minuten und vorzugsweise aller fünf Minuten freisetzen.
  18. Vorrichtung gemäß Anspruch 16 oder 17, dadurch gekennzeichnet, daß die besagten Mittel zum Versprühen (6) der besagten Ätzlösung vom Typ der pneumatischen Zerstäubung sind.
  19. Vorrichtung gemäß Anspruch 16 oder 17, dadurch gekennzeichnet, daß die besagten Mittel zum Versprühen (6) der besagten Ätzlösung Mittel vom Typ des herkömmlichen Besprühens und vom Typ der pneumatischen Zerstäubung umfassen.
  20. Vorrichtung gemäß einem der Ansprüche 16 bis 19, dadurch gekennzeichnet, daß sie außerdem Mittel zur Temperaturhaltung (13) der besagten Lösung umfaßt.
  21. Vorrichtung gemäß Anspruch 20, dadurch gekennzeichnet, daß die besagten Mittel zur Temperaturhaltung Mittel zur Einblasung in besagte Lösung von einem heißen Gas, das Sauerstoff enthält, umfassen.
  22. Vorrichtung gemäß einem der Ansprüche 16 bis 21, dadurch gekennzeichnet, daß sie außerdem Mittel zur Flussigkeit/Feststoff-Trennung umfaßt, die gegebenenfalls mit Mitteln zur Einblasung eines heißen Gases, das Sauerstoff enthält, in die Zone, in der die Flüssigkeit vorliegt, ausgestattet ist.
  23. Vorrichtung gemäß einem der Ansprüche 16 bis 22, dadurch gekennzeichnet, daß sie außerdem Kontrollvorrichtungen umfaßt, die wenigstens eine Sonde zur Messung besonders der Temperatur, des pH-Wertes oder des Redoxpotentials besagter Lösung umfaßt, die an irgendeinem Punkt des Kreislaufes der Rückfuhrung besagter Lösung eingesetzt sind.
  24. Vorrichtung gemäß Anspruch 23, dadurch gekennzeichnet, daß die besagten Kontrollvorrichtungen eine Sonde zur Messung des Redoxpotentials besagter Ätzlösung umfassen.
  25. Vorrichtung gemäß Anspruch 24, dadurch gekennzeichnet, daß sie außerdem Mittel zur Einspritzung eines Oxidationsmittels, insbesondere von Wasserstoffperoxid, in den Kreislauf der Rückfuhrung besagter Lösung umfaßt, die von besagter Potentialmeßsonde abhängen.
  26. Vorrichtung gemäß einem der Ansprüche 24 oder 25, dadurch gekennzeichnet, daß die besagten Mittel zur Belüftung mit einem Schieber zur Regelung der Durchflußmenge des Gases G ausgestattet sind, der von der besagten Potentialmeßsonde abhängt.
  27. Vorrichtung gemäß einem der Ansprüche 24 bis 26, dadurch gekennzeichnet, daß die besagten Mittel zur versprühung mit einem Schieber zur Regelung der Durchflußmenge der Lösung S ausgestattet sind, der von der besagten Potentialmeßsonde abhängt.
EP95922577A 1994-06-15 1995-06-07 Verfahren zum ätzen von metallischen werkstoffen Expired - Lifetime EP0766751B1 (de)

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Application Number Priority Date Filing Date Title
FR9407328 1994-06-15
FR9407328A FR2721328B1 (fr) 1994-06-15 1994-06-15 Procédé de décapage de matériaux métalliques, notamment en acier allié, en acier inoxydable ou en alliage de titane, par une solution du type contenant des ions ferriques en milieu acide.
PCT/FR1995/000744 WO1995034695A1 (fr) 1994-06-15 1995-06-07 Procede de decapage de materiaux metalliques

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EP0766751B1 true EP0766751B1 (de) 1999-05-06

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IT1296932B1 (it) * 1997-12-05 1999-08-03 Acciai Speciali Terni Spa Procedimento di decapaggio a spruzzo per nastro d'acciaio ed apparecchiatura per attuare detto procedimento
DE19833990A1 (de) * 1998-07-29 2000-02-10 Metallgesellschaft Ag Beizmittel für Edelstähle
US6494961B2 (en) * 2001-03-30 2002-12-17 Alcan International Limited Method of controlling solution concentration in strip cleaning line
FR2917097A1 (fr) * 2007-06-06 2008-12-12 Siemens Vai Metals Tech Sas Installation de decapage de bandes metalliques,notamment en acier
KR100926610B1 (ko) 2007-10-24 2009-11-11 주식회사 포스코 혼산슬러지 자동 제거 장치
CN101275231B (zh) * 2008-05-27 2010-06-02 洛阳双瑞金属复合材料有限公司 不锈钢复合板喷淋酸洗、抛光、钝化的方法及装置配置
KR101242877B1 (ko) * 2010-12-28 2013-03-12 주식회사 포스코 근적외선-적정법을 이용한 Ｏｎ-ｌｉｎｅ 산액 분석 방법
JP2019150866A (ja) * 2018-03-06 2019-09-12 日本製鉄株式会社 線材コイルの水冷装置、及び、線材コイルの結束方法
WO2021140612A1 (ja) * 2020-01-09 2021-07-15 Ｐｒｉｍｅｔａｌｓ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｊａｐａｎ株式会社 鋼板の酸洗方法及び酸洗装置
CN111607800A (zh) * 2020-06-24 2020-09-01 江苏苏讯新材料科技有限公司 一种不锈钢带盐酸酸洗循环系统及其方法
CN112593240A (zh) * 2020-11-26 2021-04-02 江苏欧姆圣智能装备股份有限公司 一种全封闭的酸洗槽体
CN113774397B (zh) * 2021-09-24 2024-07-23 中冶南方工程技术有限公司 一种降低冷轧酸液消耗的工艺及其设备

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CA1063809A (en) * 1975-12-11 1979-10-09 Cominco Ltd. Hydrometallurgical process for metal sulphides
FR2587369B1 (fr) * 1985-09-19 1993-01-29 Ugine Gueugnon Sa Procede de decapage acide de produits en acier inoxydable
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DE4240572A1 (de) * 1992-12-03 1994-06-09 Schloemann Siemag Ag Beizanlage und Verfahren zum Betreiben der Beizanlage

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JP3735691B2 (ja) 2006-01-18
FR2721328A1 (fr) 1995-12-22
DE69509527D1 (de) 1999-06-10
ES2132680T3 (es) 1999-08-16
CA2190779C (fr) 2004-08-03
KR100361114B1 (ko) 2003-10-22
KR970703449A (ko) 1997-07-03
WO1995034695A1 (fr) 1995-12-21
EP0766751A1 (de) 1997-04-09
KR100427795B1 (ko) 2004-04-28
JPH10503805A (ja) 1998-04-07
US6033485A (en) 2000-03-07
DE69509527T2 (de) 1999-09-02
FR2721328B1 (fr) 1996-09-06
ATE179763T1 (de) 1999-05-15
CA2190779A1 (fr) 1995-12-21
KR20030097597A (ko) 2003-12-31

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