EP1280619A1 - Method for cleaning oxidized hot rolled copper rods - Google Patents

Method for cleaning oxidized hot rolled copper rods

Info

Publication number
EP1280619A1
EP1280619A1 EP01943060A EP01943060A EP1280619A1 EP 1280619 A1 EP1280619 A1 EP 1280619A1 EP 01943060 A EP01943060 A EP 01943060A EP 01943060 A EP01943060 A EP 01943060A EP 1280619 A1 EP1280619 A1 EP 1280619A1
Authority
EP
European Patent Office
Prior art keywords
descaling
reduction
liquid
cooling
reducing agent
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.)
Withdrawn
Application number
EP01943060A
Other languages
German (de)
French (fr)
Inventor
Michael Schwarze
Herbert Berendes
Jürgen JACOB
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.)
SMS Siemag AG
Original Assignee
SMS Demag AG
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
Application filed by SMS Demag AG filed Critical SMS Demag AG
Publication of EP1280619A1 publication Critical patent/EP1280619A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/04—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C43/00—Devices for cleaning metal products combined with or specially adapted for use with machines or apparatus provided for in this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/04—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing
    • B21B45/08—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing hydraulically
    • 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
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B2003/005—Copper or its alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B3/003—Rolling non-ferrous metals immediately subsequent to continuous casting, i.e. in-line rolling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0203—Cooling
    • B21B45/0206—Coolants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0203—Cooling
    • B21B45/0209—Cooling devices, e.g. using gaseous coolants
    • B21B45/0215—Cooling devices, e.g. using gaseous coolants using liquid coolants, e.g. for sections, for tubes
    • B21B45/0224—Cooling devices, e.g. using gaseous coolants using liquid coolants, e.g. for sections, for tubes for wire, rods, rounds, bars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0239—Lubricating
    • B21B45/0242—Lubricants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0269—Cleaning
    • B21B45/0275—Cleaning devices

Definitions

  • the invention relates to a method for cleaning oxidized, hot-rolled copper rods (copper wire rod) which, after casting, emerge from a rolling mill connected downstream thereof in a continuously operating continuous casting device and which have oxidized layers on their surface when they emerge from the rolling mill.
  • the invention relates to the controlled cooling and cleaning of the cast and rolled rod before it is wound up and / or subjected to a drawing treatment for producing fine wire.
  • the strand leaving the casting device is generally immediately hot rolled.
  • the rod As the rod is exposed to the atmosphere, it oxidizes and scale forms on the surface, which is a mixture of copper oxide CuO (red) and copper oxide Cu 2 0 (black).
  • CuO red
  • Cu 2 0 black
  • These oxides must be removed or converted back to the metallic state before the rod can be subjected to a drawing treatment to produce a tradable wire product. The removal of the oxides is also necessary to prevent premature wear of the drawing tools and the like.
  • copper is intended to include copper alloys in the present context.
  • This process is characterized by high investment costs and high operating costs, which result from the need to use acid-resistant materials and to avoid ecological problems associated with the emission of spent acids.
  • oxide scale can be removed by first exposing the rod to reducing gases or vapors at high temperature and then immediately quenching it in a cooling bath before exposing the rod to the atmosphere.
  • gas reduction appears to have some advantages over acid pickling, there are certain disadvantages to gas reduction.
  • the gases or vapors designated as suitable for reducing copper rods are flammable, toxic, or both, and therefore require special handling to avoid the risk of explosion or suffocation or the like.
  • oxygen-free atmospheres of elevated temperature must be provided, which requires special seals.
  • Another disadvantage of the gas reduction processes consists in the fact that the reaction rates are considerably slower than in the processes in which a liquid is brought into contact with the strand.
  • aqueous solutions consisting of alcohols, ketones or amine compounds were used, which are used to reduce the said oxides.
  • the surface quality achieved measured as the residual oxide layer thickness of the cooled end product, depends to such an extent on the reagents used, the product throughput rate and the reaction rate, so that these reduction lines by no means reach the values of an acid pickle.
  • metal strips are electrolytically pickled, two successive containers filled with aqueous electrolytes being provided and cathodic treatment being carried out in the first container and anodic treatment in the second container.
  • the invention is based on the object of specifying a method by means of which the oxidic surface layers in copper rods can be removed in a particularly simple and advantageous manner without the use of acidic solutions.
  • This object is achieved according to the invention in a method for cleaning oxidized, rolled copper bars which, after casting, emerge from a rolling mill connected downstream thereof in a continuously operating continuous caster and which have oxidic layers on their surface when they leave the rolling mill, in that the roll strand initially already is wetted in the hot rolling process with an emulsion to which a hydrocarbon-containing reducing agent has been added in order to at least prevent oxidation of the hot rolling strand during the rolling process.
  • the oxidized, finished-rolled rod is then passed through one or more reduction zones at a temperature of approximately 650 ° C., a dilute, aqueous hydrocarbon-containing solution being used as the reduction liquid (s) in the reduction zone (s).
  • the amount of reducing liquid used in the descaling section is limited to approx. 10% to 35% of the total circulating amount of the liquid for the descaling and cooling section.
  • the oxidized layers of the rod will be converted to metal.
  • the non-acidic, liquid reducing agent is continuously recirculated, cooled and the pH value and the chemical composition of the recirculating reducing agent are kept constant.
  • the speed of the chemical reactions taking place to reduce the two types of oxide present is so intensified by generating a bath turbulence by means of one or more ultrasound sources that the surface quality is improved and the length of the reduction zone is reduced.
  • the rolled rod is cooled intensively with a large amount of the reducing liquid and before the deoxidized rod is coated with a wax to protect it from renewed oxidation, the rod is dried by means of mechanical and compressed-air strippers.
  • this is achieved by the turbulent flow of the pickling medium generated by means of the ultrasonic transducers, these operating in the frequency range from 20-3000 kHz.
  • the method according to the invention is to be explained below using a system shown in the drawings.
  • Fig. 1 in the upper part is a schematic side view of a system
  • Fig. 4 details of the cooling section.
  • the shaft melting furnace is designated by 2 in FIG. This is preceded by a charging device, by means of which the feed is fed to the furnace.
  • the charging and melting are monitored from the main furnace control room 3.
  • the melt leaving the shaft melting furnace passes through a holding furnace 4 into a double-belt casting machine 5, the monitoring and control of the casting process taking place in the control station 6. Downstream of the casting machine are a driving device 7, a pendulum shear 8 and an edge milling machine 9.
  • the rolling mill and 10 the cooling and descaling section which is explained in detail in the remaining figures, are designated by 10.
  • At the end of the system there is a winding layer 12, a ring formation chamber 13 and a coil carriage 14.
  • a crane 15 is used to move the coils.
  • an emulsion system 16 which has an automatic emulsion filter, a cleaner circulation system 17, an oil circulation system 18, the cooling water sump 19 for the casting machine, the hydraulic system 20, the electrics 21, with the transformer room 23 and finally the workshop 24th
  • the cooling section 11 is shown enlarged in FIG.
  • mechanical wipers 24, cooling pipes 25, cooling nozzles 26 and air wipers 27 are provided along the cooling section.
  • FIG. 3 shows - again enlarged - the ultrasonic transducers 28 arranged between the mechanical stripper 24 and the cooling nozzle 26, by means of which the reducing liquid in the cooling section 11 is moved intensively.

Landscapes

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

Abstract

The invention relates to a method for cleaning oxidized, rolled copper rods coming out after casting from a rolling mill mounted downstream of a continuos casting device and having oxidic layers on their surfaces after exiting from the rolling mill. The method is characterized in that the oxidized, finish milled rod is guided through one or several reduction zones at a temperature of approximately 650° C; a diluted, aqueous solution containing hydrocarbon is used in the reduction zone(s) as reduction liquid and the speed of the ongoing chemical reactions for the reduction of the two existing types of oxides is intensified by generating a bath turbulence with the aid of one or more ultrasound sources.

Description

Verfahren zum Säubern oxidierter, warmgewalzter KupferstäbeProcess for cleaning oxidized, hot-rolled copper rods
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zum Säubern oxidierter, warmgewalzter Kupferstäbe (Kupferwalzdraht) die nach dem Gießen in einer kontinuierlich arbeitenden Stranggießeinrichtung aus einem derselben nachgeschalteten Walzwerk austreten und die beim Austritt aus dem Walzwerk auf ihrer Oberfläche oxydierte Schichten aufweisen.The invention relates to a method for cleaning oxidized, hot-rolled copper rods (copper wire rod) which, after casting, emerge from a rolling mill connected downstream thereof in a continuously operating continuous casting device and which have oxidized layers on their surface when they emerge from the rolling mill.
Insbesondere betrifft die Erfindung das gesteuerte Kühlen und Säubern des gegossenen und gewalzten Stabes, bevor dieser aufgewickelt und/oder einer Ziehbehandlung zum Herstellen feinen Drahtes unterzogen wird.In particular, the invention relates to the controlled cooling and cleaning of the cast and rolled rod before it is wound up and / or subjected to a drawing treatment for producing fine wire.
Bei der Herstellung kontinuierlich gegossener Kupferstäbe wird der die Gießeinrichtung verlassende Strang im allgemeinen unverzüglich warmgewalzt. Da der Stab der Atmosphäre ausgesetzt wird, oxidiert er, und es setzt sich an der Oberfläche Zunder an, der eine Mischung aus Kupferoxidul CuO (rot) und Kupferoxid Cu20 (schwarz) darstellt. Diese Oxide müssen entfernt bzw. zum metallischen Zustand zurück umgewandelt werden, bevor der Stab einer Ziehbehandlung zur Herstellung eines handelsfähigen Drahterzeugnisses unterworfen werden kann. Das Entfernen der Oxide ist auch deshalb notwendig, um einen vorzeitigen Verschleiß der Ziehwerkzeuge und dergleichen zu verhindern.In the production of continuously cast copper bars, the strand leaving the casting device is generally immediately hot rolled. As the rod is exposed to the atmosphere, it oxidizes and scale forms on the surface, which is a mixture of copper oxide CuO (red) and copper oxide Cu 2 0 (black). These oxides must be removed or converted back to the metallic state before the rod can be subjected to a drawing treatment to produce a tradable wire product. The removal of the oxides is also necessary to prevent premature wear of the drawing tools and the like.
Zum Entfernen der Oxide von der Oberfläche von auf der Grundlage von Kupfer hergestellten Erzeugnissen wurden bislang verschiedene Verfahren vorgeschlagen. Es sei bemerkt, daß der Ausdruck "Kupfer" im vorliegenden Rahmen auch Kupferlegierungen umfassen soll. Einige typische, zum Entzundern vorgeschlagene Verfahren sind folgende:Various methods have been proposed to remove the oxides from the surface of copper-based products. It should be noted that the term "copper" is intended to include copper alloys in the present context. Some typical descaling processes are as follows:
1. Mechanisches Entfernen des Zunders, beispielsweise durch Sandstrahlen, Schaben, Schälen oder dgl., 2. Entfernen des Zunders durch Säure (Beizen)1. Mechanical removal of the scale, for example by sandblasting, scraping, peeling or the like. 2. Remove the scale by acid (pickling)
3. Dampf- bzw. Gasreduktion des Zunders3. Steam or gas reduction of the scale
4. Reduktion des Zunders durch Einsatz von Alkohol-Benzol-Wassergemischen4. Reduction of scale by using alcohol-benzene-water mixtures
In der Kupferwalzdrahtproduktion werden Prozesse genutzt, bei denen saures Beizen zum Entzundern von Kupferstäbe durchgeführt wird, indem die Stäbe in eine verdünnte, wässrige Säurelösung getaucht werden, beispielsweise in Schwefelsäure, nachdem die gegossenen Stäbe das Walzwerk verlassen, jedoch die Aufwickeleinrichtung noch nicht erreicht haben. Um optimale Betriebsbedingungen in Bezug auf das Säubern aufrechtzuerhalten, muß die Beizlösung fortwährend regeneriert werden. Dazu wird die benutzte Lösung durch eine Elektrolysiereinrichtung zur Rückgewinnung des Kupfers hindurchgeführt, außerdem wird periodisch frische Säure zugeführt.In copper wire rod production, processes are used in which acid pickling is carried out to descale copper bars by immersing the bars in a dilute, aqueous acid solution, for example in sulfuric acid, after the cast bars have left the rolling mill but have not yet reached the winding device. In order to maintain optimal operating conditions with regard to cleaning, the pickling solution must be continuously regenerated. For this purpose, the solution used is passed through an electrolyzer for recovering the copper, and fresh acid is also added periodically.
Dieses Verfahren ist durch hohe Investitionskosten und hohe Betriebskosten gekennzeichnet, die sich durch die Notwendigkeit ergeben, säurebeständige Werkstoffe zum Einsatz zu bringen, und um ökologische Probleme zu vermeiden, die mit dem Ausstoß verbrauchter Säuren zusammenhängen.This process is characterized by high investment costs and high operating costs, which result from the need to use acid-resistant materials and to avoid ecological problems associated with the emission of spent acids.
Andere Techniken, bei denen ein oder mehrere Gase oder Dämpfe als Reduktionsmittel benutzt werden, um oxidierte Kupferstäbe zu behandeln, sind in der einschlägigen Literatur beschrieben. Es wird aufgezeigt, daß der Oxidzunder dadurch entfernt werden kann, daß der Stab zunächst reduzierenden Gasen oder Dämpfen hoher Temperatur ausgesetzt und unmittelbar anschließend in einem Kühlbad abgeschreckt wird, bevor der Stab der Atmo- ■ Sphäre ausgesetzt wird.Other techniques using one or more gases or vapors as reducing agents to treat oxidized copper rods are described in the relevant literature. It is shown that the oxide scale can be removed by first exposing the rod to reducing gases or vapors at high temperature and then immediately quenching it in a cooling bath before exposing the rod to the atmosphere.
Obwohl diese Gas-Reduktion einige Vorteile gegenüber dem Säurebeizen zu haben scheint, ergeben sich bei der Gas-Reduktion gewissen Nachteile. So sind beispielsweise die Gase oder Dämpfe, die für das Reduzieren von Kupferstäben als geeignet bezeichnet werden, entflammbar, giftig oder beides und erfordern daher eine besondere Handhabung, um eine Explosionsgefahr oder Erstickungsgefahr oder dgl. zu vermeiden. Außerdem müssen sauerstofffreie Atmosphären von erhöhter Temperatur vorgesehen werden, was spezielle Abdichtungen erforderlich macht. Ein weiterer Nachteil der Gas-Reduktionsprozesse besteht darin, daß die Reaktionsgeschwindigkeiten wesentlich geringer sind als bei den Prozessen, bei denen eine Flüssigkeit mit dem Strang in Berührung gebracht wird.Although this gas reduction appears to have some advantages over acid pickling, there are certain disadvantages to gas reduction. For example, the gases or vapors designated as suitable for reducing copper rods are flammable, toxic, or both, and therefore require special handling to avoid the risk of explosion or suffocation or the like. In addition, oxygen-free atmospheres of elevated temperature must be provided, which requires special seals. Another disadvantage of the gas reduction processes consists in the fact that the reaction rates are considerably slower than in the processes in which a liquid is brought into contact with the strand.
Zur Ablösung der Säurebeize kam es zur Anwendung von wässrigen Lösungen bestehend aus Alkoholen, Ketonen bzw. Amin-Verbindungen, die zur Reduktion der besagten Oxide genutzt werden.To remove the acid stain, aqueous solutions consisting of alcohols, ketones or amine compounds were used, which are used to reduce the said oxides.
Die erreichte Oberflächenqualität gemessen als Restoxidschichtdicke des abgekühlten Endproduktes ist jedoch in solchem Maße von den eingesetzten Reagenzien, der Produktdurchlaufgeschwindigkeit und der Reaktionsgeschwindigkeit abhängig, so daß diese Reduktionslinien die Werte einer Säurebeize bei weitem nicht erreichen.However, the surface quality achieved, measured as the residual oxide layer thickness of the cooled end product, depends to such an extent on the reagents used, the product throughput rate and the reaction rate, so that these reduction lines by no means reach the values of an acid pickle.
Aus dem Bereich der Fe-Verarbeitung sind Technologien zur Intensivierung des Säuberungsprozesses bekannt, wo durch Einsatz von elektrolytischen Ketten bzw. Ultraschallquellen der Prozeß des Säurebeizens (d. h. das Auflösen und in Lösung bringen der Oxide) beschleunigt wird. Es sind auch Prozesse bekannt, wo allein die durch die Ultraschallquelle hervorgerufene Kavitation einen mechanischen Abreinigungsprozeß z. B. von Fetten, Emulsionen etc. bewirkt.Technologies for intensifying the cleaning process are known from the field of Fe processing, where the process of acid pickling (i.e. dissolving and dissolving the oxides) is accelerated by using electrolytic chains or ultrasound sources. Processes are also known where only the cavitation caused by the ultrasound source causes a mechanical cleaning process, e.g. B. caused by fats, emulsions, etc.
So ist es aus der US-PS 5409594 bekannt, die Oberfläche von langgestreckten metallischen Gegenständen, wie beispielsweise Draht, mittels Ultraschall zu reinigen, wobei der Draht durch ein mit Reinigungslösung gefülltes Bad geführt wird, in dem sich zwei Ultraschallwandler befinden. Die durch diese erzeugten hochfrequenten Ultraschallwellen erzeugen Druckstöße durch die der Zunder dann vom Draht abgelöst wird.It is known from US Pat. No. 5,409,594 to use ultrasound to clean the surface of elongated metallic objects such as wire, the wire being passed through a bath filled with cleaning solution, in which two ultrasound transducers are located. The high-frequency ultrasonic waves generated by this generate pressure surges which then detach the scale from the wire.
Bei dem Verfahren nach der EP 0518 850 A1 erfolgt ein elektrolytisches Beizen von Metallbändern, wobei zwei aufeinanderfolgende, mit wäßrigen Elektrolyten gefüllte, Behälter vorgesehen sind und im ersten Behälter eine kathodische und im zweiten Behälter eine anodische Behandlung durchgeführt wird.In the process according to EP 0518 850 A1, metal strips are electrolytically pickled, two successive containers filled with aqueous electrolytes being provided and cathodic treatment being carried out in the first container and anodic treatment in the second container.
Da die für die Kupferwalzdrahtindustrie eingesetzten Verfahren Säurebeize oder Reduktion durch Alkohole durch hohe lnvestitions-/Prozeßkosten bzw. durch unzureichende Oberflächenqualität gekennzeichnet werden, auf der anderen Seite die zunehmende Automati- siation der Ziehereibetriebe und Weiterentwicklung der Ziehereitechnik zu Vielfachzieh- maschinen immer höhere Anforderungen an die Oberflächenqualität des Kupfervorproduktes stellen, ist ein intensiveres und effizienteres Reinigungsverfahren notwendig geworden.On the other hand, since the processes used in the copper wire rod industry for acid pickling or reduction by alcohols are characterized by high investment / process costs or inadequate surface quality, the increasing automation of drawing plants and the further development of drawing technology into multiple drawing machines place ever increasing demands on the surface quality of the copper preliminary product, a more intensive and efficient cleaning process has become necessary.
Der Erfindung liegt die Aufgabe zu Grunde, ein Verfahren anzugeben, mittels dessen die oxydischen Oberflächenschichten bei Kupferstäben auf besonders einfache und vorteilhafte Weise ohne Verwendung saurer Lösungen entfernbar sind.The invention is based on the object of specifying a method by means of which the oxidic surface layers in copper rods can be removed in a particularly simple and advantageous manner without the use of acidic solutions.
Gelöst wird diese Aufgabe erfindungsgemäß bei einem Verfahren zum Säubern oxidierter, gewalzter Kupferstäbe, die nach dem Gießen in einer kontinuierlich arbeitenden Stranggießeinrichtung aus einem derselben nachgeschalteten Walzwerk austreten und die beim Austritt aus dem Walzwerk auf ihrer Oberfläche oxidische Schichten aufweisen, dadurch dass der Walzstrang zunächst bereits im Prozeß des Warmwalzens mit einer Emulsion benetzt wird, der ein kohlenwasserstoffhaltiges Reduktionsmittel zugemischt wurde, um einer Oxidation des heißen Walzstranges während des Walzprozesses zumindest vorzubeugen. Anschließend wird der oxidierte, fertiggewalzte Stab bei einer Temperatur von ca. 650°C durch eine oder mehrere Reduktionszonen hindurchgeführt, wobei in der/den Reduktions- zone(n) als Reduktionsflüssigkeit eine verdünnte, wässrige kohlenwasserstoffhaltige Lösung eingesetzt wird.This object is achieved according to the invention in a method for cleaning oxidized, rolled copper bars which, after casting, emerge from a rolling mill connected downstream thereof in a continuously operating continuous caster and which have oxidic layers on their surface when they leave the rolling mill, in that the roll strand initially already is wetted in the hot rolling process with an emulsion to which a hydrocarbon-containing reducing agent has been added in order to at least prevent oxidation of the hot rolling strand during the rolling process. The oxidized, finished-rolled rod is then passed through one or more reduction zones at a temperature of approximately 650 ° C., a dilute, aqueous hydrocarbon-containing solution being used as the reduction liquid (s) in the reduction zone (s).
Die Menge der eingesetzten Reduktionsflüssigkeit ist dabei in der Entzunderungsstrecke auf ca. 10 % bis 35 % der Gesamtumlaufmenge der Flüssigkeit für die Entzunderungs- und Kühlstrecke begrenzt.The amount of reducing liquid used in the descaling section is limited to approx. 10% to 35% of the total circulating amount of the liquid for the descaling and cooling section.
Dadurch, dass der oxidierte, gewalzte Stab mit dem kühleren, nichtsauren, flüssigen Reduktionsmittel in Berührung gebracht wird, werden die oxidierten Schichten des Stabes in Metall umgewandelt werden.By bringing the oxidized, rolled rod into contact with the cooler, non-acidic, liquid reducing agent, the oxidized layers of the rod will be converted to metal.
Das nichtsaure, flüssige Reduktionsmittel wird kontinuierlich rezirkuliert, gekühlt und der PH-Wert und die chemische Zusammensetzung des rezirkulierten Reduktionsmittels werden konstant gehalten.The non-acidic, liquid reducing agent is continuously recirculated, cooled and the pH value and the chemical composition of the recirculating reducing agent are kept constant.
Die Geschwindigkeit der ablaufenden chemischen Reaktionen zur Reduktion der beiden vorhandenen Oxidtypen wird durch Erzeugung einer Badturbulenz mittels einer oder mehrere Ultraschallquellen so intensiviert, dass sowohl die Oberflächenqualität verbessert als auch die Länge der Reduktionszone verringert wird. In einem oder mehreren anschließenden Kühlsegmenten erfolgt die Abkühlung des gewalzten Stabes mit einer hohen Menge der Reduktionsflüssigkeit intensiv und vor der Beschichtung des deoxidierten Stabes mit einem Wachs zum Schutz vor einer neuerlichen Oxidation erfolgt eine Trocknung des Stabes mittels mechanischer und druckluftbeaufschlagter Abstreifer.The speed of the chemical reactions taking place to reduce the two types of oxide present is so intensified by generating a bath turbulence by means of one or more ultrasound sources that the surface quality is improved and the length of the reduction zone is reduced. In one or more subsequent cooling segments, the rolled rod is cooled intensively with a large amount of the reducing liquid and before the deoxidized rod is coated with a wax to protect it from renewed oxidation, the rod is dried by means of mechanical and compressed-air strippers.
Vorzugsweise Ausgestaltungen ergeben sich aus den Unteransprüchen.Refinements preferably result from the subclaims.
Die Besonderheit der Entzunderung von warmgewalzten Kupferstäben im Vergleich zur Zunderentfernung von Stahl oder Eisenprodukten ist im Aufbau der Oxidschichten auf der Kupferoberfläche, ihrer unterschiedlichen Anhaftung an der Oberfläche und ihrem Reaktionsvermögen mit Säuren bzw. Reduktionsmitteln begründet. In einem Aufsatz von Prof. Horace Pops and Daniel R. Hennessy "The Role of Surface Oxide and its measurement in the Copper Wire Industry" Essex Group Incl, United Technology Corp. Metals Laboratory wird die Problematik tiefgreifend dargestellt.The peculiarity of the descaling of hot-rolled copper rods in comparison to the descaling of steel or iron products is due to the structure of the oxide layers on the copper surface, their different adhesion to the surface and their reactivity with acids or reducing agents. In an essay by Prof. Horace Pops and Daniel R. Hennessy "The Role of Surface Oxide and its measurement in the Copper Wire Industry" Essex Group Incl, United Technology Corp. The problem is presented in depth in Metals Laboratory.
Die Reduktion der Oxidschichten mit Kohlenwasserstoffverbindungen findet unter Bildung von flüssigen Reaktionsprodukten statt,The reduction of the oxide layers with hydrocarbon compounds takes place with the formation of liquid reaction products,
z.B. CuO + CmHnOp -> Cu + Cm Hn.20p + H20e.g. CuO + C m H n O p -> Cu + C m H n . 2 0 p + H 2 0
Daraus wird ersichtlich, dass entscheidend für den schnellen Abschluß dieser Reaktion die kontinuierliche Zuführung frischen Reduktionsmittels bzw. die Abführung der Reaktionsprodukte von der Grenzfläche der Kupferstäbe ist. Aus diesem Grunde kommt der aktivierenden Wirkung durch intensivere Vermischung der grenznahen Schichten mit dem Rest des Mediums durch die Ultraschallquelle entscheidende Bedeutung bei der Zerstörung der laminaren Schichtstruktur der Flüssigkeit um den Stab in den Überführungen der Entzunderungsstrecke zu.From this it can be seen that the decisive factor for the rapid completion of this reaction is the continuous supply of fresh reducing agent or the removal of the reaction products from the interface of the copper rods. For this reason, the activating effect through more intensive mixing of the layers near the border with the rest of the medium by the ultrasound source is of crucial importance in the destruction of the laminar layer structure of the liquid around the rod in the overpasses of the descaling section.
Bei dem erfindungsgemäßen Verfahren wird dieses durch die mittels der Ultraschallwandler erzeugte turbulente Strömung des Beizmediums erreicht, wobei diese im Frequenzbereich von 20-3000 kHz arbeiten. Das erfindungsgemäße Verfahren soll nachfolgend an einer in den Zeichnungen gezeigten Anlage erläutert werden.In the method according to the invention, this is achieved by the turbulent flow of the pickling medium generated by means of the ultrasonic transducers, these operating in the frequency range from 20-3000 kHz. The method according to the invention is to be explained below using a system shown in the drawings.
Dabei zeigt:It shows:
Fig. 1 im oberen Teil eine schematische Seitenansicht einer Anlage undFig. 1 in the upper part is a schematic side view of a system and
Fig. 2 die Aufsicht,2 the supervision,
Fig. 3 die Kühlstrecke,3 the cooling section,
Fig. 4 Details der Kühlstrecke.Fig. 4 details of the cooling section.
In der Figur 1 ist der Schachtschmelzofen mit 2 bezeichnet. Diesem ist eine Chargiervorrichtung vorgeschaltet, mittels der das Einsatzmaterial dem Ofen zugeführt wird. Die Überwachung des Chargierens und Schmelzens erfolgt von der Hauptofenwarte 3 aus.The shaft melting furnace is designated by 2 in FIG. This is preceded by a charging device, by means of which the feed is fed to the furnace. The charging and melting are monitored from the main furnace control room 3.
Die den Schachtschmelzofen verlassende Schmelze gelangt über einen Halteofen 4 in eine Doppelband-Gießmaschine 5, wobei die Überwachung und Steuerung des Gießvorganges im Steuerstand 6 erfolgt. Der Gießmaschine nachgeschaltet sind ein Treibapparat 7, eine Pendelschere 8 und eine Kantenfräsmaschine 9. Mit 10 ist das Walzwerk und mit 11 die Kühl- und Entzunderungsstrecke bezeichnet, die im Detail in den übrigen Figuren erläutert wird. Am Ende der Anlage befinden sich ein Windungsleger 12, eine Ringbildekammer 13 und ein Coilwagen 14. Zum Umsetzen der Coils wird ein Kran 15 benutzt. Weiterhin sind in der Zeichnung angedeutet eine Emulsionsanlage 16, die über einen automatischen Emulsionsfilter verfügt, eine Cleaner-Umlaufanlage 17, eine Ölumlaufanlage 18, der Kühlwassersumpf 19 für die Gießmaschine, die Hydraulikanlage 20, die Elektrik 21 , mit dem Transformatorraum 23 und schließlich die Werkstatt 24.The melt leaving the shaft melting furnace passes through a holding furnace 4 into a double-belt casting machine 5, the monitoring and control of the casting process taking place in the control station 6. Downstream of the casting machine are a driving device 7, a pendulum shear 8 and an edge milling machine 9. The rolling mill and 10 the cooling and descaling section, which is explained in detail in the remaining figures, are designated by 10. At the end of the system there is a winding layer 12, a ring formation chamber 13 and a coil carriage 14. A crane 15 is used to move the coils. Also indicated in the drawing are an emulsion system 16, which has an automatic emulsion filter, a cleaner circulation system 17, an oil circulation system 18, the cooling water sump 19 for the casting machine, the hydraulic system 20, the electrics 21, with the transformer room 23 and finally the workshop 24th
In der Figur 2 ist die Kühlstrecke 11 vergrößert dargestellt. Im Einzelnen sind entlang der Kühlstrecke mechanische Abstreifer 24, Kühlrohre 25, Kühldüsen 26 und Luftabstreifer 27 vorgesehen. Die Figur 3 zeigt - nochmals vergrößert - die zwischen dem mechanischen Abstreifer 24 und der Kühldüse 26 angeordneten Ultraschallwandler 28, mittels der die Reduktionsflüssigkeit in der Kühlstrecke 11 intensiv bewegt wird. The cooling section 11 is shown enlarged in FIG. In detail, mechanical wipers 24, cooling pipes 25, cooling nozzles 26 and air wipers 27 are provided along the cooling section. FIG. 3 shows - again enlarged - the ultrasonic transducers 28 arranged between the mechanical stripper 24 and the cooling nozzle 26, by means of which the reducing liquid in the cooling section 11 is moved intensively.

Claims

Patentansprüche claims
1 . Verfahren zum Säubern oxidierter, gewalzter Kupferstäbe, die nach dem Gießen in einer kontinuierlich arbeitenden Stranggießeinrichtung aus einem derselben nachgeschalteten Walzwerk austreten und die beim Austritt aus dem Walzwerk auf ihrer Oberfläche oxidische Schichten aufweisen, dadurch gekennzeichnet:1 . Process for cleaning oxidized, rolled copper bars which, after casting in a continuously operating continuous caster, emerge from a rolling mill connected downstream thereof and which have oxide layers on their surface when they emerge from the rolling mill, characterized in:
a) dass der Walzstrang bereits im Prozeß des Warmwalzens mit einer Emulsion benetzt wird, der ein kohlenwasserstoffhaltiges Reduktionsmittel zugemischt wurde,a) that the rolling train is already wetted with an emulsion in the process of hot rolling, to which a hydrocarbon-containing reducing agent has been added,
b) dass der oxidierte, fertiggewalzte Stab bei einer Temperatur von ca. 650°C durch eine oder mehrere Reduktionszonen hindurchgeführt wird,b) the oxidized, finished-rolled rod is passed through one or more reduction zones at a temperature of approximately 650 ° C.,
c) dass in der/den Reduktionszone(n) als Reduktionsflüssigkeit eine verdünnte, wässrige kohlenwasserstoffhaltige Lösung eingesetzt wird,c) that a dilute, aqueous hydrocarbon-containing solution is used as the reduction liquid in the reduction zone (s),
d) wobei die Menge der eingesetzten Reduktionsflüssigkeit in der Entzunderungsstrecke auf ca. 10 % bis 35 % der Gesamtumlaufmenge der Flüssigkeit für die Entzunderungs- und Kühlstrecke begrenzt ist,d) the amount of the reducing liquid used in the descaling section being limited to approximately 10% to 35% of the total circulating amount of the liquid for the descaling and cooling section,
e) dass das nichtsaure, flüssige Reduktionsmittel kontinuierlich rezirkuliert, gekühlt und der PH-Wert und die chemische Zusammensetzung des rezirkulierten Reduktionsmittels konstant gehalten werden,e) that the non-acidic, liquid reducing agent is continuously recirculated, cooled and the pH and the chemical composition of the recirculating reducing agent are kept constant,
f) dass die Geschwindigkeit der ablaufenden chemischen Reaktionen zur Reduktion der beiden vorhandenen Oxidtypen durch Erzeugung einer Badturbulenz mittels einer oder mehrere Ultraschallquellen intensiviert wird,f) the speed of the chemical reactions taking place to reduce the two types of oxide present is increased by generating a bath turbulence by means of one or more ultrasound sources,
g) dass in einem oder mehreren anschließenden Kühlsegmenten die Abkühlung des gewalzten Stabes mit einer hohen Menge der Reduktionsflüssigkeit intensiv erfolgt und h) dass vor der Beschichtung des deoxidierten Stabes mit einem Wachs zumg) in one or more subsequent cooling segments, the cooling of the rolled rod is carried out intensively with a large amount of the reducing liquid, and h) that before coating the deoxidized rod with a wax for
Schutz vor einer neuerlichen Oxidation eine Trocknung des Stabes mittels mechanischer und druckluftbeaufschlagter Abstreifer erfolgt.Protection against renewed oxidation, the rod is dried by means of mechanical and compressed air strippers.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass ein oder mehrere im Frequenzbereich von 20 - 100 kHz arbeitende Ultraschallquellen zur Intensivierung der chemischen und physikalischen Vorgänge in den Entzunderungssegmenten eingesetzt werden.2. The method according to claim 1, characterized in that one or more ultrasonic sources operating in the frequency range of 20-100 kHz are used to intensify the chemical and physical processes in the descaling segments.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass ein oder mehrere im Frequenzbereich von 100 - 500 kHz arbeitende Ultraschallquellen zur Intensivierung der chemischen und physikalischen Vorgänge in den Entzunderungssegmenten eingesetzt werden.3. The method according to claim 1, characterized in that one or more ultrasound sources operating in the frequency range of 100-500 kHz are used to intensify the chemical and physical processes in the descaling segments.
4. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass ein oder mehrere im Frequenzbereich von 500 - 3000 kHz arbeitende Ultraschallquellen zur Intensivierung der chemischen und physikalischen Vorgänge in den Entzunderungssegmenten eingesetzt werden.4. The method according to claim 1, characterized in that one or more ultrasound sources operating in the frequency range from 500 to 3000 kHz are used to intensify the chemical and physical processes in the descaling segments.
5. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass auch in den Kühlsegmenten zur Aktivierung bzw. Intensivierung der Kühlprozesse eine oder mehrere Ultraschallquellen eingesetzt werden.5. The method according to any one of the preceding claims, characterized in that one or more ultrasound sources are used in the cooling segments for activating or intensifying the cooling processes.
6. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass bei a) als Emulsion ein Wasser-Öl-Alkoholgemisch verwendet wird. 6. The method according to claim 1, characterized in that in a) a water-oil-alcohol mixture is used as the emulsion.
7. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als kohlenwasserstoffhaltiges Reduktionsmittel Isopropylalkohoi verwendet wird.7. The method according to claim 1, characterized in that isopropyl alcohol is used as the hydrocarbon-containing reducing agent.
8. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als kohlenstoffhaltiges Reduktionsmittel Äthanol verwendet wird. 8. The method according to claim 1, characterized in that ethanol is used as the carbon-containing reducing agent.
EP01943060A 2000-05-10 2001-05-08 Method for cleaning oxidized hot rolled copper rods Withdrawn EP1280619A1 (en)

Applications Claiming Priority (3)

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DE10023480A DE10023480A1 (en) 2000-05-10 2000-05-10 Process for skimming oxidic rolled copper bars after casting in a continuous casting machine comprises wetting the casting with an emulsion mixed with reductant, and injecting a diluted aqueous hydrocarbon-containing solution as reductant
DE10023480 2000-05-10
PCT/DE2001/001791 WO2001087509A1 (en) 2000-05-10 2001-05-08 Method for cleaning oxidized hot rolled copper rods

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CN110670082B (en) * 2019-10-18 2024-06-18 南京华新有色金属有限公司 Copper rod non-pickling system, copper rod non-pickling method and copper rod production system
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