EP2872656A1 - Fil fourré et procédé de traitement de fer ou d'acier liquides - Google Patents

Fil fourré et procédé de traitement de fer ou d'acier liquides

Info

Publication number
EP2872656A1
EP2872656A1 EP13742174.9A EP13742174A EP2872656A1 EP 2872656 A1 EP2872656 A1 EP 2872656A1 EP 13742174 A EP13742174 A EP 13742174A EP 2872656 A1 EP2872656 A1 EP 2872656A1
Authority
EP
European Patent Office
Prior art keywords
melt
treatment
filling
cored wire
bitumen
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Withdrawn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
EP13742174.9A
Other languages
German (de)
English (en)
Inventor
Mechthilde DÖRING-FREISSMUTH
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP2872656A1 publication Critical patent/EP2872656A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/11—Treating the molten metal
    • B22D11/116—Refining the metal
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/02—Dephosphorising or desulfurising
    • C21C1/025—Agents used for dephosphorising or desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C21C7/0645—Agents used for dephosphorising or desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0075—Treating in a ladle furnace, e.g. up-/reheating of molten steel within the ladle
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum

Definitions

  • the invention relates to a flux cored wire for the treatment of iron or steel melts.
  • the invention also relates to a process for the treatment of iron or steel melts.
  • Iron smelting especially molten steel, undergoes treatment by means of pyrophoric metals, such as magnesium, calcium, aluminum and by means of corresponding alloys thereof, in particular in finely divided form, for deoxidation, desulfurization, dephosphorization, decarburization and for seeding of cast iron.
  • pyrophoric metals such as magnesium, calcium, aluminum and by means of corresponding alloys thereof, in particular in finely divided form, for deoxidation, desulfurization, dephosphorization, decarburization and for seeding of cast iron.
  • pyrophoric metals such as magnesium, calcium, aluminum and by means of corresponding alloys thereof, in particular in finely divided form
  • the patent DE 39 24 558 C1 describes a means in the form of a cored wire and a method for its production, the use of which is in the treatment of cast iron melts with a magnesium-containing silicon alloy.
  • the advantage of the filler wire described is to be seen in the shift of the precipitation form of the cast iron carbon in the direction of spheroidal graphite by alloying magnesium and rare earth metals, as well as in the reduction of the steps desulfurization, magnesium treatment and inoculation of cast iron melts on a single, simultaneously carried out treatment measure.
  • EP-A-0 066 305 describes the use of passivated magnesium or calcium as a wire filling.
  • the passivation of these metals is achieved with a surface coating consisting essentially of alumina, magnesia, finely divided silica, graphite or coke powder. Due to the reaction-retarding effect of the coating, the premature reaction of the reactive agent is suppressed exclusively during the treatment process, for example, the premature melting and evaporation of the magnesium core to be overcome.
  • the method has serious drawbacks, such as afterglow or afterburning of the wire, and release of harmful metal oxides during and after treatment.
  • DE 102 36 354 B4 discloses a process for the continuous or discontinuous treatment of steel melts by introducing a wire-shaped additive encased in a composite wire, wherein the additive is a solid at room temperature, gas-releasing agent having a decomposition temperature in the range of 100 ° C up to a temperature of 150 ° C above the melting temperature of the molten steel is used.
  • Ladle furnaces heated by graphite electrodes are equipped with flushing nozzles in the bottom of the ladle and usually have up to three wire-winding machines.
  • the cored wires that can be processed serve primarily for adjusting the carbon content, for deoxidizing and for alloying the molten iron.
  • the known fillers correspond to the standard agents, such as CaSi for deoxidizing, calcium carbide or carbon for carburizing.
  • the object of the present invention is to avoid the disadvantages of the prior art, and in particular to provide a means and a method for the treatment of iron or steel melts, which is characterized by high efficiency and controllable effort in the field, especially to low oxygen and To obtain phosphorus levels.
  • effective components i. Petroleum or petroleum derivatives, in particular bitumen or white oils, in particular paraffins or paraffin oils, introduced into the melt in the form of filler wire.
  • the product obtained from petroleum is preferably bitumen granules with optional additives, such as iron powder and / or lime compounds, such as calcium oxide.
  • bitumen can advantageously be minced easily, is inexpensive and generally available.
  • the production of a filler wire according to the invention is preferably carried out via a filler wire folded or welded from a strip of flat steel into a tube, preferably 0.2 mm thick and 0.4 mm thick.
  • These production methods are known; they allow the production of very long cored wires with diameters, eg of 9 mm, 13 mm or 16 mm, eg with fine grain usually with CaSi or FeSi; similar to DE 26 03 412 A1.
  • the filling with the material according to the invention or the material mixture according to the invention in principle, similar to the filling of the cored wires with the known fine-grained alloys, such as with CaSi or Mg alloys.
  • the function of the flux cored wire was described by G.
  • the filled wire proved to be decisive for the metallurgical efficiency, because this measure secures the entry of the petroleum derivative without influence of the environment.
  • the cored wire flat steel has in special cases the same or similar composition as the iron or steel melt to be treated, thereby preventing the melt from being contaminated and, if necessary, the filler wire may also be an alloy so as to provide the melt with certain dopants.
  • the filler wire may also be rectangular in shape, for example 16 mm wide and 7 mm thick
  • These round or rectangular wires are filled according to the invention with petroleum products, preferably with solid, fine-grained bitumen or white oil (paraffin / paraffin oil) and after completion of the filling - And / or folding process closed and wound up on coils t.
  • bitumen is understood to mean a heavy, dark-colored multi-substance mixture of organic substances consisting of high molecular weight, long-chain, aliphatic and aromatic hydrocarbon compounds, produced by vacuum distillation from crude oil.
  • the properties of the different types of bitumen are determined by special test methods. These are defined in the DIN standards (Europanorm EN 12591) for road bitumen (softening point RuK (EP RuK), breaking point according to Fraigne, determination of needle penetration). By adding additional components, the physical properties can be changed in a targeted manner.
  • white oils in particular paraffin and / or paraffin oils
  • white oils are understood as meaning mixtures of saturated hydrocarbons having the general empirical formula C n H 2 n + 2, where the number n is between 18 and 32.
  • oil or petroleum derivative heavy means or light oil, such as petroleum, diesel fuel or fuel oil understood.
  • These new active components ie petroleum or petroleum derivatives, in particular bitumen or white oils, in particular paraffins or paraffin oils, can advantageously be mixed with other components which are to become active, ie which are to be introduced into the melt. A corresponding mixture of the above-mentioned components can finally be introduced into a flux-cored wire.
  • magnesium is suitable, in particular for the inoculation of cast iron.
  • special alloys such as cerium misch metal, metallurgically very effective metal hydrides, such as NaBH 4 or LiAlH 4 can be introduced as additional components in a cored wire according to the invention.
  • the additional components are homogeneously distributed, preferably in bitumen or paraffin, or mixed with bitumen or paraffin. This has the advantage that the components are largely safe to handle, so as to achieve specific metallurgical reactions within the molten iron, such as the formation of cast iron graphite molds vermicular or spherical (globular), or in steel influencing the inclusion forms.
  • the contents i. mixing a mixture of effective components and optionally additional components with inactive substances or components, such as to slow down or weaken the reaction in the melt.
  • inactive substances or components such as to slow down or weaken the reaction in the melt.
  • magnesium granules are used together with active components, i. Petroleum or petroleum derivatives, especially bitumen or white oils, especially paraffins or paraffin oils are to be introduced into cast iron melts.
  • active components i. Petroleum or petroleum derivatives, especially bitumen or white oils, especially paraffins or paraffin oils are to be introduced into cast iron melts.
  • a dilution, by up to 50 wt .-%, for example with iron be advantageous.
  • a filler wire according to the invention is the incorporation of the oxides of valuable elements, such as rare earths or sulfides from roasting process. These are mixed homogeneously with petroleum or petroleum derivatives, in particular bitumen or white oils, in particular paraffins or paraffin oils, and then introduced into a flux-cored wire in order to be finally fed into the melt. The oxides are reduced, the metals thus released go into solution. In addition to the economic advantage, the high yield of up to 80% of the metal content of the metals introduced as oxide is to be considered.
  • the active components and optionally other components are liquid, viscous or plastic, they can be in a thin-walled, tubular shell, for example made of plastic, filled.
  • This filled plastic shell can finally be inserted in a known manner in a cored wire with a corresponding diameter or during the folding of a flat wire. From this, inventive annular cored wires but also rods with larger diameters, in particular up to 21 mm in cross-section produced.
  • a filler wire according to the invention in particular with bitumen, as a fining agent for steel and as an inoculant for cast iron, in conjunction with the inoculating metal, shows a particular effectiveness, which can not be explained by the known teachings of metallurgy. It is believed that the released hydrogen as well as the carbon from the pyrolysis process achieves these extraordinary effects.
  • the object defined at the outset is also achieved by a process for the treatment of iron or steel melts.
  • effective components i. Petroleum or petroleum derivatives, in particular bitumen or white oils, in particular paraffins or paraffin oils, introduced in the form of at least one filler wire in the melt.
  • the cored wire or wires are deeply inserted into the molten bath of the molten iron to be treated with special Einspul machines.
  • the effective material of Guhett sleepllung - such as fine-grained bitumen - can be blown.
  • Advantageous is the fact that this eliminates the often necessary intensive rinsing of the melts with argon through bottom nozzles, but at least can be significantly reduced.
  • the wires according to the invention are introduced deep with Einspul- machines in the melt, the wire wrap protects the contents and only then melts and releases the contents when the filler wire has reached the greatest possible depth. About the Conveying speed, a melting of the wire sheath in the lowest point of the melt can be achieved.
  • the inventive method is particularly suitable for ladle metallurgy.
  • the use of the method is also suitable for use in Verg cordofen.
  • only certain process steps and process parameters such as temperature setting, cover slag or alloy correction, adapt.
  • the treatment of molten steel can be done when the melt has been placed on the continuous casting plant, but also when the melt enters the tundish. Since a subset of the ladle contents can be treated in the tundish, it is advantageous to use a relatively thin filler wire which is fed continuously or intermittently, depending on the casting progress.
  • the active components in particular bitumen, alone or with minor additions of other metallurgically active substances in the melt (steel), z. B. be blown with argon.
  • the bitumen must be fine-grained.
  • the filler wires filled with the metallurgically active petroleum derivatives can have any desired cross-sectional shape and can also be produced in rod or rod form and pushed into the melt with a specially designed feed device.
  • Example 1 shows that these new agents allow reduction of metal oxides and alloying of the reduced metals in the melt.
  • a 140 t EAF melt is tapped with the addition of the alloying agent, brought to the pan treatment station, pre-oxidized, alloyed, and then added with slags and finally heated. Thereafter, the heater is switched off and filler wire with bitumen in the bath wound. This may optionally be supplemented with gentle argon purging of the melt. With a bitumen cored wire of 13 mm in diameter, and 0.02 wt .-% bitumen, which corresponds to approximately 135 m, it is possible to reduce the sulfur, oxygen and phosphorus concentration according to the results table. Result:
  • An LD molten steel of 270 t was pre-oxidized during tapping.
  • a lid was placed, with openings for a lance and for the cored wire.
  • With the lance was injected 0.035 wt .-% of a mixture of 90% bitumen and 10% iron powder.
  • the blowing time was 6 min.
  • the final sulfur content was 0.001 wt%
  • the final phosphorus content was 0.0035 wt%
  • the final oxygen content was 0.0018 wt%.
  • a melt according to Example 2 with 140 t was immediately oxidized immediately before the start of continuous casting with 125 m bitumen cored wire with a diameter of 9 mm and desulfurized as soon as it was placed in the casting position. Before the start of casting, the cored wire was filled with unmixed bitumen powder, finely ground, and reeled in. The oxygen content of the melt was 0.0008 wt .-%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Abstract

Fil fourré pour le traitement de fer ou d'acier liquide, caractérisé en ce qu'il contient du pétrole ou des dérivés de pétrole, en particulier du bitume ou des huiles blanches, en particulier des paraffines ou des huiles de paraffine en tant que matière de charge, et une gaine métallique entourant cette matière de charge. La présente invention concerne également un procédé de traitement de fer ou d'acier liquides.
EP13742174.9A 2012-07-10 2013-07-08 Fil fourré et procédé de traitement de fer ou d'acier liquides Withdrawn EP2872656A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201210013662 DE102012013662A1 (de) 2012-07-10 2012-07-10 Füllldraht und Verfahren zur Behandlung von Eisenschmelzen
PCT/EP2013/064419 WO2014009327A1 (fr) 2012-07-10 2013-07-08 Fil fourré et procédé de traitement de fer ou d'acier liquides

Publications (1)

Publication Number Publication Date
EP2872656A1 true EP2872656A1 (fr) 2015-05-20

Family

ID=48877206

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13742174.9A Withdrawn EP2872656A1 (fr) 2012-07-10 2013-07-08 Fil fourré et procédé de traitement de fer ou d'acier liquides

Country Status (3)

Country Link
EP (1) EP2872656A1 (fr)
DE (1) DE102012013662A1 (fr)
WO (1) WO2014009327A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022117315A1 (fr) * 2020-12-03 2022-06-09 Compagnia Commerciale Srl Procédé de fusion de métaux ferreux, de métaux non ferreux, de déchets d'usinage et de ferraille et d'acier

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3018524B1 (fr) * 2014-03-11 2017-03-10 Affival Procede de desulfuration d'une fonte liquide et fil fourre pour sa mise en oeuvre
CN111318659B (zh) * 2020-02-29 2021-12-07 邯郸钢铁集团有限责任公司 解决小方坯连铸生产高硫易切削齿轮钢水口堵塞的方法

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WO1986004359A1 (fr) * 1985-01-24 1986-07-31 Vallourec Procede de traitement de metaux liquides par fil fourre contenant du calcium
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DE4324494C2 (de) * 1993-07-21 1995-04-20 Sueddeutsche Kalkstickstoff Verfahren zum Behandeln von Gußeisenschmelzen
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022117315A1 (fr) * 2020-12-03 2022-06-09 Compagnia Commerciale Srl Procédé de fusion de métaux ferreux, de métaux non ferreux, de déchets d'usinage et de ferraille et d'acier

Also Published As

Publication number Publication date
DE102012013662A1 (de) 2014-01-16
WO2014009327A1 (fr) 2014-01-16

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