EP2878685B1 - Method for conditioning a slag on molten metal from the processing of iron and steel in a metallurgical vessel - Google Patents

Method for conditioning a slag on molten metal from the processing of iron and steel in a metallurgical vessel Download PDF

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Publication number
EP2878685B1
EP2878685B1 EP13195334.1A EP13195334A EP2878685B1 EP 2878685 B1 EP2878685 B1 EP 2878685B1 EP 13195334 A EP13195334 A EP 13195334A EP 2878685 B1 EP2878685 B1 EP 2878685B1
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EP
European Patent Office
Prior art keywords
slag
mass
mixture
iron
carbon
Prior art date
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EP13195334.1A
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German (de)
French (fr)
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EP2878685B9 (en
EP2878685A1 (en
Inventor
Alexander Cepak
Thomas Kollmann
Oliver Zach
Marcus Kirschen
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Refractory Intellectual Property GmbH and Co KG
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Refractory Intellectual Property GmbH and Co KG
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Priority to RS20150849A priority Critical patent/RS54471B1/en
Priority to PT131953341T priority patent/PT2878685E/en
Application filed by Refractory Intellectual Property GmbH and Co KG filed Critical Refractory Intellectual Property GmbH and Co KG
Priority to HUE13195334A priority patent/HUE026614T2/en
Priority to SI201330101T priority patent/SI2878685T1/en
Priority to ES13195334.1T priority patent/ES2559024T3/en
Priority to EP13195334.1A priority patent/EP2878685B9/en
Priority to PL13195334T priority patent/PL2878685T3/en
Priority to PCT/EP2014/071022 priority patent/WO2015082093A1/en
Priority to US15/038,735 priority patent/US20160376672A1/en
Priority to MX2016005055A priority patent/MX2016005055A/en
Priority to CN201480062204.6A priority patent/CN105705662A/en
Publication of EP2878685A1 publication Critical patent/EP2878685A1/en
Publication of EP2878685B1 publication Critical patent/EP2878685B1/en
Priority to HRP20151446TT priority patent/HRP20151446T1/en
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    • 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
    • C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal

Definitions

  • the invention relates to a mixture comprising magnesium, carbon and aluminum for introduction into the slag present on a molten metal in iron and steel metallurgy, to the use of such a mixture and to a method for conditioning a metallurgical one in iron and steel metallurgy on a molten metal Container, for example in a converter, in an electric arc furnace or in a pan, slag.
  • the pig iron melt is separated from unwanted components before it is cast.
  • the crude steel melt is produced by the melting of scrap, pig iron, molten iron and / or sponge iron and other raw materials.
  • the slag must be specifically influenced or conditioned with regard to chemical and physical properties.
  • the basicity ie the mass or molar ratio of the basic components to the other components of the slag (which can be calculated, for example, according to the following formula: [xCaO + MgO] / [xSiO 2 + Al 2 O 3 + other components])
  • the first acidic or non-basic slag are increased to the corrosive attack of the slag on the basic delivery of the metallurgical vessel, in the the molten metal is to reduce and thereby reduce the wear of the delivery and to increase their service life.
  • slag conditioners have a component that increases the basicity of the slag, in particular lime, dolomitic lime or dolomite.
  • the viscosity of the slag may be desirable to adjust the viscosity of the slag by the slag conditioner.
  • the viscosity of the slag during refining is as low as possible in order to be able to incorporate the iron companion oxidized by the applied oxygen well into the slag.
  • This applied slag layer a corrosive attack of a molten metal can be reduced to the delivery of the converter.
  • the process of applying the slag to the converter is also referred to as "maintenance" of the converter.
  • the foamed slag has insulating properties, so that the heat losses from the melt can be reduced and energy can be saved. Furthermore, components of the metallurgical vessel in which the molten iron is located can be protected from heat radiation by the foamed slag.
  • the object of the invention is to provide a slag conditioner by means of which the basicity and the MgO content of the slag can be increased rapidly in order to prevent the slag from attacking the refractory lining of the metallurgical vessel, in which the slag conditioner Molten metal with the slag on it is able to reduce.
  • a further object of the invention is to provide a slag conditioner by means of which the viscosity of the slag can be adjusted in a targeted manner.
  • Another object of the invention is to provide a slag conditioner by which foaming of the slag can be achieved.
  • a further object of the invention is to provide a slag conditioner by which an increase in the iron yield of the primary metallurgical process can be achieved.
  • a mixture or a slag conditioner for introduction into the slag contained in a molten metal in iron and steel metallurgy, the mixture comprising magnesium, carbon and aluminum in the following proportions by mass: MgO: 45-90% by mass; C: 5-40 mass%; and Al 2 O 3 : 1-20 mass%.
  • the mixture according to the invention or the slag conditioner according to the invention is suitable for introduction into slags on molten metals in any metallurgical vessel, but in particular for slags in converters, electric arc furnaces and ladles.
  • magnesium and aluminum in the mixture according to the invention are given as fractions of their oxides MgO and Al 2 O 3 in the mixture, as usual in refractory technology.
  • magnesium and especially aluminum may also be used as described herein other than in oxide form in the mixture according to the invention, for example in metallic form or, with regard to aluminum, in the form of carbide.
  • the proportion of MgO in the mixture according to the invention By the proportion of MgO in the mixture according to the invention, the MgO saturation of the slag is reached faster, so that the corrosive attack of the slag is reduced to the refractory lining of the metallurgical vessel holding the molten metal. Furthermore, the viscosity of the slag increases with increasing MgO content.
  • Magnesium is preferably present in the mixture according to the invention as an oxide, ie in the form of MgO.
  • the proportions of magnesium in the mixture according to the invention are preferably exclusively in the form of MgO, particularly preferably in the form of sintered or fused magnesia.
  • MgO can be present in the mixture according to the invention in proportions of at least 45% by mass, that is also for example in proportions of at least 48, 50, 52, 54, 56, 57, 58, 59, 60 or 61% by mass. Furthermore, MgO may be present in the mixture in proportions of at most 90% by weight, that is to say, for example, in proportions of at most 88, 86, 84, 82, 80, 78, 76, 74, 72, 70, 69, 68, 67, 66 , 65, 64 or 63% by mass.
  • the proportion of carbon of the mixture according to the invention reacts when entering the mixture into the slag with oxygen in the slag to form carbon oxides, in particular to carbon monoxide CO and carbon dioxide CO 2 .
  • the carbon of the mixture oxidizes immediately and violently with oxygen fractions of the slag, so that it foams spontaneously when introducing the mixture.
  • the slag thus rises, as in slag-foaming, in the air and covers the refractory lining of the metallurgical vessel.
  • the Electric arc furnace is shielded by the increased volume of the foamed slag, the radiation of the arcs partially or completely with respect to the furnace wall. Due to the increased content of MgO, the slag simultaneously obtains the necessary viscosity in order to adhere to the wall during and after foaming.
  • the carbon of the mixture can react directly with oxygen of the molten metal and extract oxygen from the molten metal.
  • This extracted from the molten metal oxygen must not be removed later in additional steps by deoxidizer, such as aluminum, from the molten metal.
  • At least part of the oxygen with which the carbon introduced into the slag from the mixture according to the invention reacts originates from iron oxides in the slag, which are reduced by the carbon to metallic iron.
  • iron oxides are fluxes which reduce the viscosity of the slag.
  • the viscosity of the slag can be increased.
  • the yield of recovered iron is increased in the overall process.
  • Due to the proportion of carbon in the mixture can thus be achieved on the one foaming of the slag. Furthermore, the viscosity of the slag can be increased. By the proportion of carbon in the mixture can thus be adjusted in a targeted manner the extent of foaming of the slag and its viscosity.
  • the carbon in the mixture, can be present substantially in pure form, for example in the form of graphite or coke, but also, for example, communitized with other constituents, for example with aluminum fractions or magnesium fractions of the mixture.
  • the proportions of carbon according to the invention in the mixture is present partially, substantially or even completely in the form of aluminum carbide (Al 4 C 3 ).
  • Carbon is present in the mixture according to the invention in proportions of at least 5% by mass, for example also in proportions of at least 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 21, 22 or 23 mass%. Furthermore, carbon is present in the mixture according to the invention in proportions of at most 40% by mass, ie for example also in proportions of at most 38, 36, 34, 32, 31, 30, 29, 28, 27, 26 or 25% by mass.
  • Aluminum, calculated as Al 2 O 3 can be present in a proportion of at least 1% by mass in the mixture, ie also in a proportion of at least 2, 3, 4 or 5% by mass. Furthermore, aluminum, calculated as Al 2 O 3 , may be present in proportions of at most 20% by mass in the mixture, that is to say for example also in proportions of at most 18, 16, 14, 13, 12, 11, 10, 9, 8 or 7 Dimensions-%.
  • the proportion of aluminum in the mixture according to the invention is herein calculated as Al 2 O 3 , although the proportions of aluminum in the mixture preferably not in oxide form as Al 2 O 3 , but preferably partially, substantially or completely in metallic form and / or in the form of carbide, ie as Al 4 C 3 .
  • this aluminum carbide simultaneously forms a carrier of both the aluminum and the carbon content in the mixture.
  • the aluminum carbide component is particularly advantageous insofar as both the aluminum and the carbon of the aluminum carbide can react with oxygen fractions of the slag and thereby reduce oxidic constituents of the slag, in particular iron oxides can be. With corresponding reactions, the aluminum content of the aluminum carbide oxidizes to Al 2 O 3 and the carbon content of the aluminum carbide to CO 2 .
  • slag conditioners include magnesium, they have this regularly in the form of magnesium carbonate (MgCO 3 ), dolomite or partially in the form of magnesium hydroxide (Mg (OH) 2 ).
  • MgCO 3 magnesium carbonate
  • dolomite magnesium hydroxide
  • Mg (OH) 2 magnesium hydroxide
  • the mixture according to the invention in contrast to the prior art, is formulated such that the component comprising magnesium, in particular in the form of MgO, is provided solely for increasing the basicity and the MgO content in the mixture, while the foaming of the slag by other components the mixture is caused, in particular by the components comprising carbon and aluminum.
  • the resource efficiency is higher, that is, the specific consumption and the total weight of slag conditioner to be introduced and transported into the slag is lower than in the prior art.
  • the emissions of carbon dioxide can be reduced by the slag conditioner according to the invention, as far as carbonate-containing slag formers are replaced by the slag former according to the invention.
  • the mixture has a proportion of magnesium carbonate of less than 10% by mass, that is to say, for example, a proportion of less than 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5% by mass.
  • the mixture has a content of Mg (OH) 2 of less than 10% by mass, that is to say for example also a fraction of 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 Dimensions-%.
  • the mixture has a proportion of dolomite, in particular of crude dolomite, less than 10% by mass, so for example, a proportion of 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 mass%.
  • the mixture has a proportion of calcium carbonate or of limestone below 10% by mass, ie, for example, a proportion of 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 mass -%.
  • the mixture is present in a relatively small particle size, for example at least 70% by mass, 80% by mass or at least 90% by mass or else 100% by mass in a particle size of less than 0.5 mm.
  • the mixture according to the invention can meet, for example, only one of the following conditions in terms of particle size: ⁇ 1 mm: 100% by mass; ⁇ 500 ⁇ m: 100% by mass; ⁇ 315 ⁇ m: at least 90 or 95% by mass and at most 100% by mass; ⁇ 200 ⁇ m: at least 85 or 90% by mass and at most 95 or 100% by mass; ⁇ 100 ⁇ m: at least 65 or 70% by mass and at most 75 or 80% by mass; ⁇ 63 ⁇ m: at least 45 or 50% by mass and at most 65 or 70% by mass.
  • the mixture according to the invention having this very small average particle size, it is possible to effect a particularly good and uniform distribution and, in particular, rapid dissolution of the mixture in a slag.
  • a mixture according to the invention which in particular can have the previously described particle size distribution, is pressed into pellets without additions of additives.
  • these pellets may have an almond-shaped, rod-shaped or spherical shape, for example with a maximum length of, for example, 50 mm, 40 mm or 30 mm.
  • the pellets may also have, for example, a minimum diameter of 5, 10, 15, 20 or 25 mm.
  • the mixture according to the invention has a proportion of calcium oxide (CaO), as by this the basicity of the slag can be further increased and the attack of the slag can be reduced to the refractory lining of the metallurgical vessel.
  • the CaO of the mixture has, in particular, an advantageous basicity-reducing effect if the ratio of CaO to SiO 2 in the mixture does not exceed a certain level.
  • the basicity of the slag can be increased by the CaO, in particular, if the ratio of mass fractions of CaO to SiO 2 in the mixture is not less than 0.7. It can therefore be provided that the ratio of the mass fractions of CaO to SiO 2 in the mixture according to the invention is not less than 0.7.
  • SiO 2 can essentially be introduced into the mixture according to the invention via impurities in the raw materials of the mixture according to the invention.
  • CaO can be present in proportions of at least 0.1 or 0.2 or 0.5 or 1 or 1.5 or 2% by mass in the mixture and, for example, in proportions of at most 10, 9, 8, 7, 6, 5, 4, 3 or 2.5 mass%.
  • SiO 2 can be present in the mixture in proportions of at least 0.1 or 0.2 or 0.5 or 1 or 1.5 or 2 mass% and, for example, in proportions of at most 7, 6, 5, 4, 3 or 2.5% by mass.
  • the mixture in the form of pellets, wherein the mixture is compressed into pellets without the addition of additives.
  • additives are used to compress the mixture into pellets
  • the mixture may be envisioned to use CaO as such a pressing additive.
  • the mixture contrary to the previously disclosed concept of the invention, according to which the mixture has proportions of CaO of at most 10% by mass of CaO, may have proportions of CaO of up to 40% by mass.
  • the mixture preferably has no additive for pressing, so that the proportion of CaO in the mixture, as stated above, is not more than 10% by mass.
  • Iron oxide stands for the sum of all iron oxides in the mixture, ie in particular FeO and Fe 2 O 3 , but also, for example, Fe 3 O 4 and Fe 2 O.
  • Iron oxides may also be present in the mixture in proportions of at least 0.1% by mass, 0.2% by mass, 0.4% by mass, 0.6% by mass or 0.8% by mass, for example at most in Proportions of 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2.8 mass%, 2.6 mass%, 2.4 mass%, 2, 2% by mass or 2% by mass.
  • the mixture comprises, in addition to the aforementioned components, ie MgO, C, Al, Al 4 C 3 , CaO, SiO 2 , iron oxides and optionally Al 2 O 3 only small proportions of other components, for example in proportions below 5% by mass, 4% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass or else less than 1% by mass.
  • the aforementioned components ie MgO, C, Al, Al 4 C 3 , CaO, SiO 2 , iron oxides and optionally Al 2 O 3 only small proportions of other components, for example in proportions below 5% by mass, 4% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass or else less than 1% by mass.
  • the mixture comprises fractions of the following components below the mass fractions indicated below: Cr 2 O 3 : ⁇ 0.2% by mass; P 2 O 5 : ⁇ 0.2% by mass; TiO 2 : ⁇ 0.2% by mass; K 2 O + Na 2 O: ⁇ 0.5 mass%; Zr 2 : ⁇ 0.2 mass%.
  • magnesia-carbon products which have been used in the steel industry, in particular as wear linings of oxygen blowing converters, in electric arc furnaces or in pans, are partly suitable as raw material for the mixture according to the invention.
  • correspondingly recycled magnesia-carbon products can be used partially, largely or exclusively as raw material for the mixture according to the invention.
  • the invention also relates to the use of recycled gastric carbon products as raw material for the mixture according to the invention or the use of such recycled magnesia-carbon products as inventive slag conditioners.
  • magnesia in particular sintered magnesia
  • carbon in particular graphite
  • corundum aluminum carbide
  • the mixture may, as described herein, be provided, for example, in compacted or compressed form, for example in the form of pellets.
  • the mixture provided is added to the slag and sinks into it so that it can unfold its effect there according to the invention.
  • the mixture according to the invention is fundamentally suitable as a slag conditioner for slags on a molten metal in any metallurgical vessel, for example for molten metals in converters, electric arc furnaces or ladles.
  • the mixture according to the invention is particularly preferably used as a slag conditioner for slags on molten metals which are located in a metallurgical vessel with a basic feed, ie in particular with a feed based on at least one of the following materials: magnesia, magnesia-carbon, doloma or dolomite. Carbon.
  • the invention furthermore relates to the use of a mixture according to the invention described herein for conditioning a slag present in iron and steel metallurgy on a molten metal in a metallurgical vessel.
  • a mixture which comprises magnesium, carbon and aluminum as well as further components in the proportions by mass according to Table 1.
  • Table 1 component Mass shares [%] MgO 62.6 C 24.6 Al 2 O 3 6.4 CaO 2,4 SiO 2 2.3 Fe 2 O 3 1.3 Cr 2 O 3 0.05 P 2 O 5 0.08 TiO 2 0.08 K 2 O 0.05 Na 2 O 0.08 ZrO 2 0.06
  • the carbon was present in the mixture in the form of graphite and aluminum carbide.
  • Aluminum was present in the mixture in the form of metallic aluminum and in the form of aluminum carbide.
  • the raw materials used were exclusively recycled magnesia-carbon products.
  • the mixture was provided in the form of almond-shaped pellets having a thickness of about 15 mm and a length of about 30 mm pressed without additional additives.
  • the particle size distribution of the mixture in the pellets is given in Table 2.
  • the mixture was used as a slag conditioner for a slag on a molten metal in an oxygen converter.
  • the mixture was applied to the slag contained on the melt.
  • its basicity could be increased.
  • by the proportions of carbon, aluminum and aluminum carbide in the mixture foaming of the slag could be achieved.
  • the viscosity of the slag could be adjusted to the desired level.

Description

Die Erfindung betrifft eine Magnesium, Kohlenstoff und Aluminium umfassende Mischung zur Einbringung in die bei der Eisen- und Stahlmetallurgie auf einer Metallschmelze befindlichen Schlacke, die Verwendung einer solchen Mischung sowie ein Verfahren zur Konditionierung einer bei der Eisen- und Stahlmetallurgie auf einer Metallschmelze in einem metallurgischen Gefäß, beispielsweise in einem Konverter, in einem Elektrolichtbogenofen oder in einer Pfanne, befindlichen Schlacke.The invention relates to a mixture comprising magnesium, carbon and aluminum for introduction into the slag present on a molten metal in iron and steel metallurgy, to the use of such a mixture and to a method for conditioning a metallurgical one in iron and steel metallurgy on a molten metal Container, for example in a converter, in an electric arc furnace or in a pan, slag.

Bei der Stahl- und Eisenmetallurgie wird die Roheisenschmelze vor dem Vergießen von unerwünschten Bestandteilen getrennt.In steel and iron metallurgy, the pig iron melt is separated from unwanted components before it is cast.

Soweit ein Konverter verwendet wird, wird hierzu bei dem heutzutage am weitesten verbreiteten LD-Verfahren Sauerstoff mittels einer Lanze auf die in einem mit einem basischen feuerfesten Material zugestellten Konverter befindliche Roheisenschmelze aufgeblasen. Der Vorgang dieses Aufblasens von Sauerstoff auf die Roheisenschmelze wird auch als Frischen bezeichnet. Beim Frischen werden Eisenbegleiter, insbesondere Eisenbegleiter in Form von Kohlenstoff, Mangan, Silicium und Phosphor durch den eingeblasenen Sauerstoff oxidiert und bilden zusammen mit zugesetztem gebranntem Kalk eine auf der Metallschmelze aufschwimmende Schlackenschicht.As far as a converter is used, this is in the most widely used today LD method oxygen by means of a lance on the in inflated molten pig iron contained in a converter supplied with a basic refractory material. The process of this inflation of oxygen on the pig iron melt is also referred to as fresh. When fresh iron companion, especially iron companion in the form of carbon, manganese, silicon and phosphorus are oxidized by the injected oxygen and form together with added quicklime on the molten metal floating slag layer.

Im Elektrolichtbogenofen wird die Rohstahlschmelze durch das Einschmelzen von Schrott, Roheisen, Flüssigeisen und/oder Eisenschwamm und anderer Rohstoffe erzeugt.In the electric arc furnace, the crude steel melt is produced by the melting of scrap, pig iron, molten iron and / or sponge iron and other raw materials.

Nachdem die im primärmetallurgischen Aggregat gefrischte Metallschmelze die gewünschten Eigenschaften aufweist, wird diese zur sekundärmetallurgischen Behandlung durch den Abstichkanal in die Pfanne abgestochen.After the reflowed in the primary metallurgical aggregate molten metal has the desired properties, this is tapped for secondary metallurgical treatment through the tapping channel in the pan.

Die Schlacke muss hinsichtlich chemischer und physikalischer Eigenschaften gezielt beeinflusst beziehungsweise konditioniert werden.The slag must be specifically influenced or conditioned with regard to chemical and physical properties.

Zur Konditionierung der Schlacke ist es bekannt, die Schlacke mit sogenannten Schlackenkonditionierern zu versehen, um die Eigenschaften der Schlacke verändern zu können.To condition the slag, it is known to provide the slag with so-called slag conditioners in order to be able to change the properties of the slag.

So muss die Basizität, also das Massen- oder Molverhältnis der basischen Komponenten zu den anderen Komponenten der Schlacke (das beispielsweise nach der folgenden Formel berechnet werden kann: [xCaO+MgO] / [xSiO2+Al2O3+weitere Komponenten]), der zunächst sauren beziehungsweise nicht-basischen Schlacke erhöht werden, um den korrosiven Angriff der Schlacke auf die basische Zustellung des metallurgischen Gefäßes, in dem sich die Metallschmelze befindet, zu reduzieren und dadurch den Verschleiß der Zustellung zu vermindern und deren Lebensdauer zu erhöhen. Hierzu weisen Schlackenkonditionierer eine die Basizität der Schlacke erhöhende Komponente auf, insbesondere Kalk, dolomitischen Kalk oder Dolomit. Zusätzlich ist es sinnvoll, den Gehalt an MgO in der Schlacke durch Zugabe eines Schlackenkonditionierers so einzustellen, dass dieser im Bereich der Sättigung an MgO in der Schlacke liegt und dadurch ein korrosiver Angriff der Schlacke auf die Zustellung vermindert wird.Thus, the basicity, ie the mass or molar ratio of the basic components to the other components of the slag (which can be calculated, for example, according to the following formula: [xCaO + MgO] / [xSiO 2 + Al 2 O 3 + other components]) , the first acidic or non-basic slag are increased to the corrosive attack of the slag on the basic delivery of the metallurgical vessel, in the the molten metal is to reduce and thereby reduce the wear of the delivery and to increase their service life. For this purpose, slag conditioners have a component that increases the basicity of the slag, in particular lime, dolomitic lime or dolomite. In addition, it is useful to adjust the content of MgO in the slag by adding a slag conditioner so that it is in the range of saturation of MgO in the slag and thereby a corrosive attack of the slag is reduced to the delivery.

In WO 99/05466 wird beispielweise die Basizität und Viskosität der Schlacke in Zusammenhang mit einer konkreten Ausmauerung kontrolliert.In WO 99/05466 For example, the basicity and viscosity of the slag are controlled in connection with a concrete lining.

Ferner kann es gewünscht sein, die Viskosität der Schlacke durch den Schlackenkonditionierer einzustellen. So ist es häufig gewünscht, dass die Viskosität der Schlacke während des Frischens möglichst gering ist, um die durch den aufgebrachten Sauerstoff oxidierten Eisenbegleiter gut in die Schlacke einbinden zu können. Ferner kann es während des Abstichs oder nach dem Abstich gewünscht sein, dass die Schlacke eine hohe Viskosität aufweist, um die nach dem Abstich im Konverter verbliebene Schlacke besser auf die feuerfeste Zustellung des Konverters auftragen zu können. Durch diese aufgetragene Schlackenschicht kann ein korrosiver Angriff einer Metallschmelze auf die Zustellung des Konverters reduziert werden. Der Vorgang des Auftragens der Schlacke auf den Konverter wird auch als "Pflege" des Konverters bezeichnet. Bei den bekannten Methoden zur Pflege des Konverters handelt es sich zum einen um das sogenannte "Slag-Washing", bei dem die Schlacke durch Schwenken des Konverters auf die Abstich- und Chargierseite verteilt wird. Ein weitere Pflegemethode ist das sogenannte "Slag-Splashing", bei dem die Schlacke mit Hilfe eines Stickstoff-Gasstroms einer Lanze mechanisch verspritzt wird. Schließlich wird beim sogenannten "Slag-Foaming" Schlacke durch Zugabe eines Kohlenstoffträgers chemisch aufgeschäumt. Die beim Slag-Foaming aufgeschäumt Schlacke wird auch als "Schaumschlacke" bezeichnet.Further, it may be desirable to adjust the viscosity of the slag by the slag conditioner. Thus, it is often desired that the viscosity of the slag during refining is as low as possible in order to be able to incorporate the iron companion oxidized by the applied oxygen well into the slag. Furthermore, it may be desired during tapping or after tapping that the slag has a high viscosity in order to better apply the slag remaining after tapping in the converter to the refractory lining of the converter. By this applied slag layer, a corrosive attack of a molten metal can be reduced to the delivery of the converter. The process of applying the slag to the converter is also referred to as "maintenance" of the converter. In the known methods for the maintenance of the converter is on the one hand to the so-called "slag-washing", in which the slag is distributed by pivoting the converter on the tapping and Chargierseite. Another method of care is the so-called slag-splashing, in which the slag is mechanically sprayed with the aid of a nitrogen gas stream of a lance. Finally, in the so-called "slag-foaming" slag is chemically foamed by adding a carbon carrier. The slag foam foamed slag is also known as "foamed slag".

Neben der Pflege des Konverters durch die Schaumschlacke, hat diese weitere vorteilhafte Wirkungen. So weist die Schaumschlacke isolierende Eigenschaften auf, so dass die Wärmeverluste aus der Schmelze vermindert und Energie gespart werden kann. Ferner können Komponenten des metallurgischen Gefäßes, in dem sich die Eisenschmelze befindet, durch die Schaumschlacke vor Wärmestrahlung geschützt werden.In addition to the care of the converter by the foam slag, this has further beneficial effects. Thus, the foamed slag has insulating properties, so that the heat losses from the melt can be reduced and energy can be saved. Furthermore, components of the metallurgical vessel in which the molten iron is located can be protected from heat radiation by the foamed slag.

Um im Elektrolichtbogenofen eine Schaumschlacke zu erzeugen, wird zusätzlich in die Schlacke eingeblasener Kohlenstoff mittels Sauerstoff zu Kohlenmonoxid verbrannt und das zum Schäumen notwendige Kohlenmonoxidgas derart bereitgestellt. Im Fall des Einschmelzprozesses im Elektrolichtbogenofen ist ein Aufschäumen der Schlackenschicht von Bedeutung, da diese durch Volumenvergrößerung die Lichtbogen abschirmt, Strahlungsverluste auf die Ofenwand vermindert, die Energieübertragung auf die Schmelze verbessert und dadurch ebenfalls Energie gespart wird.In order to produce a foamed slag in the electric arc furnace, additionally injected into the slag carbon is burned by means of oxygen to carbon monoxide and provided the necessary for foaming carbon monoxide gas. In the case of the smelting process in the electric arc furnace, foaming of the slag layer is important, since this shields the arc by increasing the volume, reduces radiation losses on the furnace wall, improves the energy transfer to the melt and thus energy is also saved.

Vor diesem Hintergrund liegt der Erfindung die Aufgabe zugrunde, einen Schlackenkonditionierer zur Verfügung zu stellen, durch den die Basizität und der MgO-Gehalt der Schlacke schnell erhöht werden können, um den Angriff der Schlacke auf die feuerfeste Zustellung des metallurgischen Gefäßes, in dem sich die Metallschmelze mit der darauf befindlichen Schlacke befindet, reduzieren zu können.Against this background, the object of the invention is to provide a slag conditioner by means of which the basicity and the MgO content of the slag can be increased rapidly in order to prevent the slag from attacking the refractory lining of the metallurgical vessel, in which the slag conditioner Molten metal with the slag on it is able to reduce.

Eine weitere Aufgabe der Erfindung besteht darin, einen Schlackenkonditionierer zur Verfügung zu stellen, durch den die Viskosität der Schlacke gezielt eingestellt werden kann.A further object of the invention is to provide a slag conditioner by means of which the viscosity of the slag can be adjusted in a targeted manner.

Eine weitere Aufgabe der Erfindung besteht darin, einen Schlackenkonditionierer zur Verfügung zu stellen, durch den ein Aufschäumen der Schlacke erreicht werden kann.Another object of the invention is to provide a slag conditioner by which foaming of the slag can be achieved.

Schließlich liegt eine weitere Aufgabe der Erfindung darin, einen Schlackenkonditionierer zur Verfügung zu stellen, durch den eine Erhöhung der Eisenausbringung des primärmetallurgischen Prozesses erreicht werden kann.Finally, a further object of the invention is to provide a slag conditioner by which an increase in the iron yield of the primary metallurgical process can be achieved.

Zur Lösung dieser Aufgabe wird erfindungsgemäß zur Verfügung gestellt eine Mischung beziehungsweise ein Schlackenkonditionierer zur Einbringung in die bei der Eisen- und Stahlmetallurgie auf einer Metallschmelze befindliche Schlacke, wobei die Mischung Magnesium, Kohlenstoff und Aluminium in folgenden Massenanteilen umfasst: MgO: 45-90 Masse-%; C: 5-40 Masse-%; und Al2O3: 1-20 Masse-%. To achieve this object, a mixture or a slag conditioner is provided according to the invention for introduction into the slag contained in a molten metal in iron and steel metallurgy, the mixture comprising magnesium, carbon and aluminum in the following proportions by mass: MgO: 45-90% by mass; C: 5-40 mass%; and Al 2 O 3 : 1-20 mass%.

Die erfindungsgemäße Mischung beziehungsweise der erfindungsgemäße Schlackenkonditionierer eignet sich zum Einbringen in Schlacken auf Metallschmelzen in einem beliebigen metallurgischen Gefäß, insbesondere jedoch für Schlacken in Konvertern, Elektrolichtbogenöfen und Pfannen.The mixture according to the invention or the slag conditioner according to the invention is suitable for introduction into slags on molten metals in any metallurgical vessel, but in particular for slags in converters, electric arc furnaces and ladles.

Sämtliche der hierin gemachten Angaben in % sind Angaben in Masse-%, jeweils bezogen auf die Gesamtmasse der erfindungsgemäßen Mischung.All of the statements made herein in% are in mass%, in each case based on the total mass of the mixture according to the invention.

Die Anteile an Magnesium und Aluminium in der erfindungsgemäßen Mischung sind als Anteile an deren Oxiden MgO und Al2O3 in der Mischung angegeben, wie in der Feuerfesttechnologie üblich. Allerdings können Magnesium und insbesondere Aluminium auch, wie hierin ausgeführt, in anderer Form als in Oxidform in der erfindungsgemäßen Mischung vorliegen, beispielsweise in metallischer Form oder, in Hinblick auf Aluminium, in Form von Carbid.The proportions of magnesium and aluminum in the mixture according to the invention are given as fractions of their oxides MgO and Al 2 O 3 in the mixture, as usual in refractory technology. However, magnesium and especially aluminum may also be used as described herein other than in oxide form in the mixture according to the invention, for example in metallic form or, with regard to aluminum, in the form of carbide.

Durch den Anteil an MgO in der erfindungsgemäßen Mischung wird die MgO-Sättigung der Schlacke schneller ereicht, so dass der korrosive Angriff der Schlacke auf die feuerfeste Zustellung des die Metallschmelze haltenden metallurgischen Gefäßes reduziert wird. Ferner erhöht sich die Viskosität der Schlacke mit steigendem MgO-Gehalt.By the proportion of MgO in the mixture according to the invention, the MgO saturation of the slag is reached faster, so that the corrosive attack of the slag is reduced to the refractory lining of the metallurgical vessel holding the molten metal. Furthermore, the viscosity of the slag increases with increasing MgO content.

Magnesium liegt in der erfindungsgemäßen Mischung bevorzugt als Oxid, also in Form von MgO vor. Bevorzugt liegen die Anteile an Magnesium in der erfindungsgemäßen Mischung ausschließlich in Form von MgO vor, besonders bevorzugt in Form von Sinter- oder Schmelzmagnesia.Magnesium is preferably present in the mixture according to the invention as an oxide, ie in the form of MgO. The proportions of magnesium in the mixture according to the invention are preferably exclusively in the form of MgO, particularly preferably in the form of sintered or fused magnesia.

MgO kann in der erfindungsgemäßen Mischung in Anteilen von wenigstens 45 Masse-% vorliegen, also beispielsweise auch in Anteilen von wenigstens 48, 50, 52, 54, 56, 57, 58, 59, 60 oder 61 Masse-%. Ferner kann MgO in der Mischung in Anteilen von höchstens 90 Masse-% vorliegen, also beispielsweise auch in Anteilen von höchstens 88, 86, 84, 82, 80, 78, 76, 74, 72, 70, 69, 68, 67, 66, 65, 64 oder 63 Masse-%.MgO can be present in the mixture according to the invention in proportions of at least 45% by mass, that is also for example in proportions of at least 48, 50, 52, 54, 56, 57, 58, 59, 60 or 61% by mass. Furthermore, MgO may be present in the mixture in proportions of at most 90% by weight, that is to say, for example, in proportions of at most 88, 86, 84, 82, 80, 78, 76, 74, 72, 70, 69, 68, 67, 66 , 65, 64 or 63% by mass.

Der Anteil an Kohlenstoff der erfindungsgemäßen Mischung reagiert bei Eingabe der Mischung in die Schlacke mit in der Schlacke befindlichem Sauerstoff zu Kohlenstoffoxiden, insbesondere zu Kohlenmonoxid CO und Kohlendioxid CO2. Bei Einbringen der Mischung in die Schlacke oxidiert der Kohlenstoff der Mischung umgehend und heftig mit Sauerstoffanteilen der Schlacke, so dass diese bei Einbringen der Mischung spontan aufschäumt. Die Schlacke steigt hierdurch, wie beim Slag-Foaming, in die Höhe und bedeckt die feuerfeste Zustellung des metallurgischen Gefäßes. Im Elektrolichtbogenofen wird durch das erhöhte Volumen der aufgeschäumten Schlacke die Strahlung der Lichtbögen teilweise oder vollständig gegenüber der Ofenwand abgeschirmt. Durch den erhöhten Gehalt an MgO erhält die Schlacke gleichzeitig die notwendige Viskosität um auch während und nach dem Aufschäumen an der Wand haften zu bleiben.The proportion of carbon of the mixture according to the invention reacts when entering the mixture into the slag with oxygen in the slag to form carbon oxides, in particular to carbon monoxide CO and carbon dioxide CO 2 . When introducing the mixture into the slag, the carbon of the mixture oxidizes immediately and violently with oxygen fractions of the slag, so that it foams spontaneously when introducing the mixture. The slag thus rises, as in slag-foaming, in the air and covers the refractory lining of the metallurgical vessel. in the Electric arc furnace is shielded by the increased volume of the foamed slag, the radiation of the arcs partially or completely with respect to the furnace wall. Due to the increased content of MgO, the slag simultaneously obtains the necessary viscosity in order to adhere to the wall during and after foaming.

Soweit die Mischung in unmittelbaren Kontakt mit der Metallschmelze tritt, beispielsweise weil es durch einen Spüler zu einer Öffnung der Schlackenschicht kommt, kann der Kohlenstoff der Mischung direkt mit Sauerstoff der Metallschmelze reagieren und der Metallschmelze Sauerstoff entziehen. Dieser der Metallschmelze entzogene Sauerstoff muss später nicht mehr in zusätzlichen Schritten durch Desoxidationsmittel, beispielsweise Aluminium, aus der Metallschmelze entfernt werden.As far as the mixture comes into direct contact with the molten metal, for example because it comes through a spinner to an opening of the slag layer, the carbon of the mixture can react directly with oxygen of the molten metal and extract oxygen from the molten metal. This extracted from the molten metal oxygen must not be removed later in additional steps by deoxidizer, such as aluminum, from the molten metal.

Zumindest ein Teil des Sauerstoffs, mit dem der aus der erfindungsgemäßen Mischung in die Schlacke eingebrachte Kohlenstoff reagiert, stammt aus Eisenoxiden in der Schlacke, die durch den Kohlenstoff zu metallischem Eisen reduziert werden. Eisenoxide stellen im Gegensatz zu metallischem Eisen jedoch Flussmittel dar, die die Viskosität der Schlacke reduzieren. Indem der Anteil an Eisenoxiden in der Schlacke durch die Zugabe der Mischung reduziert wird, kann somit die Viskosität der Schlacke erhöht werden. Ferner wird das Ausbringen an gewonnenem Eisen im Gesamtprozess erhöht.At least part of the oxygen with which the carbon introduced into the slag from the mixture according to the invention reacts originates from iron oxides in the slag, which are reduced by the carbon to metallic iron. However, in contrast to metallic iron, iron oxides are fluxes which reduce the viscosity of the slag. Thus, by reducing the proportion of iron oxides in the slag by the addition of the mixture, the viscosity of the slag can be increased. Furthermore, the yield of recovered iron is increased in the overall process.

Durch den Anteil an Kohlenstoff in der Mischung kann somit zum einen ein Aufschäumen der Schlacke erreicht werden. Zum weiteren kann die Viskosität der Schlacke erhöht werden. Durch den Anteil an Kohlenstoff in der Mischung kann somit der Umfang des Aufschäumens der Schlacke sowie deren Viskosität gezielt eingestellt werden.Due to the proportion of carbon in the mixture can thus be achieved on the one foaming of the slag. Furthermore, the viscosity of the slag can be increased. By the proportion of carbon in the mixture can thus be adjusted in a targeted manner the extent of foaming of the slag and its viscosity.

In der Mischung kann der Kohlenstoff im Wesentlichen in reiner Form vorliegen, beispielsweise in Form von Graphit oder Koks, aber beispielsweise auch vergemeinschaftet mit weiteren Bestandteilen, beispielsweise mit Aluminiumanteilen oder Magnesiumanteilen der Mischung. Insbesondere kann vorgesehen sein, dass die erfindungsgemäßen Anteile an Kohlenstoff in der Mischung teilweise, weitgehend oder auch vollständig in Form von Aluminiumcarbid (Al4C3) vorliegt.In the mixture, the carbon can be present substantially in pure form, for example in the form of graphite or coke, but also, for example, communitized with other constituents, for example with aluminum fractions or magnesium fractions of the mixture. In particular, it can be provided that the proportions of carbon according to the invention in the mixture is present partially, substantially or even completely in the form of aluminum carbide (Al 4 C 3 ).

Kohlenstoff liegt in der erfindungsgemäßen Mischung in Anteilen von wenigstens 5 Masse-% vor, also beispielsweise auch in Anteilen von wenigstens 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 oder 23 Masse-%. Ferner liegt Kohlenstoff in der erfindungsgemäßen Mischung in Anteilen von höchstens 40 Masse-% vor, also beispielsweise auch in Anteilen von höchstens 38, 36, 34, 32, 31, 30, 29, 28, 27, 26 oder 25 Masse-%.Carbon is present in the mixture according to the invention in proportions of at least 5% by mass, for example also in proportions of at least 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 21, 22 or 23 mass%. Furthermore, carbon is present in the mixture according to the invention in proportions of at most 40% by mass, ie for example also in proportions of at most 38, 36, 34, 32, 31, 30, 29, 28, 27, 26 or 25% by mass.

Aluminium kann, berechnet als Al2O3, in einem Anteil von wenigstens 1 Masse-% in der Mischung vorliegen, also beispielsweise auch in einem Anteil von wenigstens 2, 3, 4 oder 5 Masse-%. Ferner kann Aluminium, berechnet als Al2O3, in Anteilen von höchstens 20 Masse-% in der Mischung vorliegen, also beispielsweise auch in Anteilen von höchstens 18, 16, 14, 13, 12, 11, 10, 9, 8 oder 7 Masse-%.Aluminum, calculated as Al 2 O 3 , can be present in a proportion of at least 1% by mass in the mixture, ie also in a proportion of at least 2, 3, 4 or 5% by mass. Furthermore, aluminum, calculated as Al 2 O 3 , may be present in proportions of at most 20% by mass in the mixture, that is to say for example also in proportions of at most 18, 16, 14, 13, 12, 11, 10, 9, 8 or 7 Dimensions-%.

Der Anteil an Aluminium in der erfindungsgemäßen Mischung ist hierin, wie zuvor ausgeführt, als Al2O3 berechnet, wobei die erfindungsgemäßen Anteile an Aluminium in der Mischung jedoch bevorzugt nicht in Oxidform als Al2O3, sondern bevorzugt teilweise, weitgehend oder auch vollständig in metallischer Form und/oder in Form von Carbid, also als Al4C3 vorliegen.The proportion of aluminum in the mixture according to the invention is herein calculated as Al 2 O 3 , although the proportions of aluminum in the mixture preferably not in oxide form as Al 2 O 3 , but preferably partially, substantially or completely in metallic form and / or in the form of carbide, ie as Al 4 C 3 .

Soweit Aluminium als Carbid in der Mischung vorliegt, bildet dieses Aluminiumcarbid gleichzeitig einen Träger sowohl des Anteils an Aluminium als auch des Kohlenstoffs in der Mischung.As far as aluminum is present as a carbide in the mixture, this aluminum carbide simultaneously forms a carrier of both the aluminum and the carbon content in the mixture.

Soweit Kohlenstoff und Aluminium in der Mischung in Form von Aluminiumcarbid vorliegen, ist die Aluminiumcarbid-Komponente insoweit besonders vorteilhaft, als dass sowohl das Aluminium als auch der Kohlenstoff des Aluminiumcarbids mit Sauerstoffanteilen der Schlacke reagieren können und hierdurch oxidische Bestandteile der Schlacke, insbesondere Eisenoxide, reduziert werden können. Bei entsprechenden Reaktionen oxidiert der Aluminiumanteil des Aluminiumcarbids zu Al2O3 und der Kohlenstoffanteil des Aluminiumcarbids zu CO2.Insofar as carbon and aluminum are present in the mixture in the form of aluminum carbide, the aluminum carbide component is particularly advantageous insofar as both the aluminum and the carbon of the aluminum carbide can react with oxygen fractions of the slag and thereby reduce oxidic constituents of the slag, in particular iron oxides can be. With corresponding reactions, the aluminum content of the aluminum carbide oxidizes to Al 2 O 3 and the carbon content of the aluminum carbide to CO 2 .

Soweit Schlackenkonditionierer gemäß dem Stand der Technik Magnesiumanteile umfassen, weisen sie diese regelmäßig in Form von Magnesiumcarbonat (MgCO3), Dolomit oder teilweise auch in Form von Magnesiumhydroxid (Mg(OH)2) auf. Insoweit wird gemäß dem Stand der Technik als vorteilhaft angesehen, dass bei Kontakt dieser Komponenten der betreffenden Schlackenkonditionierer mit der Schlacke das Magnesiumcarbonat in Magnesiumoxid und Kohlendioxid, der Dolomit in Magnesium- und Calziumoxid sowie Kohlendioxid beziehungsweise das Magnesiumhydroxid in Magnesiumoxid und Wasserdampf aufgespalten wird. Dabei bewirken das Kohlendioxid und der Wasserdampf ein Aufschäumen der Schlacke.As far as slag conditioners according to the prior art include magnesium, they have this regularly in the form of magnesium carbonate (MgCO 3 ), dolomite or partially in the form of magnesium hydroxide (Mg (OH) 2 ). In that regard, it is considered advantageous according to the prior art that upon contact of these components of the relevant slag conditioner with the slag, the magnesium carbonate is split into magnesium oxide and carbon dioxide, the dolomite in magnesium and calcium oxide and carbon dioxide or magnesium hydroxide in magnesium oxide and water vapor. The carbon dioxide and the steam cause foaming of the slag.

Erfindungsgemäß wurde jedoch festgestellt, dass in Form von Magnesiumcarbonat, Dolomit oder Magnesiumhydroxid vorliegendes Magnesium nur zu einer verzögerten Erhöhung der Basizität und des MgO-Gehaltes der Schlacke führen. Ferner wurde erfindungsgemäß festgestellt, dass die Basizität und der MgO-Gehalt der Schlacke wesentlich schneller und effektiver dadurch erhöht werden können, dass Magnesium in Form von Magnesiumoxid in die Schlacke eingegeben wird. Insofern ist die erfindungsgemäße Mischung in Abwendung vom Stand der Technik derart konfektioniert, dass die Magnesium umfassende Komponente, insbesondere in Form von MgO, allein zur Erhöhung der Basizität und des MgO-Gehaltes in der Mischung vorgesehen ist, während das Aufschäumen der Schlacke durch andere Komponenten der Mischung verursacht wird, insbesondere durch die Kohlenstoff und Aluminium umfassenden Komponenten. Indem durch den erfindungsgemäßen Schlackenkonditionierer ferner keine weiteren Carbonate in den primärmetallurgischen Prozess eingebracht werden müssen, ist die Ressourceneffizienz höher, das heißt der spezifische Verbrauch und das in die Schlacke einzutragende und zu transportierende Gesamtgewicht an Schlackenkonditionierer geringer als im Stand der Technik. Darüber hinaus können die Emissionen an Kohlendioxid durch den erfindungsgemäßen Schlackenkonditionierer reduziert werde, soweit carbonathaltige Schlackenbildner durch den erfindungsgemäßen Schlackenbildner ersetzt werden.According to the invention, however, it has been found that magnesium present in the form of magnesium carbonate, dolomite or magnesium hydroxide only leads to a delayed increase in the basicity and the MgO content of the slag. Furthermore, it has been found according to the invention that the basicity and the MgO content of the slag are substantially faster and can be increased more effectively by adding magnesium in the form of magnesium oxide in the slag. In this respect, the mixture according to the invention, in contrast to the prior art, is formulated such that the component comprising magnesium, in particular in the form of MgO, is provided solely for increasing the basicity and the MgO content in the mixture, while the foaming of the slag by other components the mixture is caused, in particular by the components comprising carbon and aluminum. Furthermore, by not having to introduce further carbonates into the primary metallurgical process by the slag conditioner of the invention, the resource efficiency is higher, that is, the specific consumption and the total weight of slag conditioner to be introduced and transported into the slag is lower than in the prior art. Moreover, the emissions of carbon dioxide can be reduced by the slag conditioner according to the invention, as far as carbonate-containing slag formers are replaced by the slag former according to the invention.

Erfindungsgemäß kann insoweit vorgesehen sein, dass die Mischung einen Anteil an Magnesiumcarbonat unter 10 Masse-% aufweist, also beispielsweise auch einen Anteil unter 9, 8, 7, 6, 5, 4, 3, 2, 1 oder 0,5 Masse-%.According to the invention, it may be provided that the mixture has a proportion of magnesium carbonate of less than 10% by mass, that is to say, for example, a proportion of less than 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5% by mass. ,

Ferner kann vorgesehen sein, dass die Mischung einen Anteil an Mg(OH)2 unter 10 Masse-% aufweist, also beispielsweise auch einen Anteil unter 9, 8, 7, 6, 5, 4, 3, 2, 1 oder 0,5 Masse-%.Furthermore, it can be provided that the mixture has a content of Mg (OH) 2 of less than 10% by mass, that is to say for example also a fraction of 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 Dimensions-%.

Ferner kann vorgesehen sein, dass die Mischung einen Anteil an Dolomit, insbesondere an Roh-Dolomit, unter 10 Masse-% aufweist, also beispielsweise auch einen Anteil unter 9, 8, 7, 6, 5, 4, 3, 2, 1 oder 0,5 Masse-%.Furthermore, it can be provided that the mixture has a proportion of dolomite, in particular of crude dolomite, less than 10% by mass, so for example, a proportion of 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 mass%.

Ferner kann vorgesehen sein, dass die Mischung einen Anteil an Kalziumcarbonat beziehungsweise an Kalkstein unter 10 Masse-% aufweist, also beispielsweise auch einen Anteil unter 9, 8, 7, 6, 5, 4, 3, 2, 1 oder 0,5 Masse-%.Furthermore, it can be provided that the mixture has a proportion of calcium carbonate or of limestone below 10% by mass, ie, for example, a proportion of 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 mass -%.

Bevorzugt ist vorgesehen, dass die Mischung in einer verhältnismäßig geringen Korngröße vorliegt, beispielsweise zu wenigstens 70 Masse-%, 80 Masse-% oder zu wenigstens 90 Masse-% oder auch zu 100 Masse-% in einer Korngröße unter 0,5 mm.It is preferably provided that the mixture is present in a relatively small particle size, for example at least 70% by mass, 80% by mass or at least 90% by mass or else 100% by mass in a particle size of less than 0.5 mm.

Beispielsweise kann vorgesehen sein, dass die Korngröße der Komponenten der erfindungsgemäßen Mischung unterhalb der nachfolgend angegebenen Korngrößen in den jeweils angegebenen Massenanteilen vorliegt, wobei die erfindungsgemäße Mischung beispielsweise auch nur eine der nachfolgenden Bedingungen hinsichtlich ihrer Korngröße erfüllen kann: < 1 mm: 100 Masse-%; < 500µm: 100 Masse-%; < 315µm: wenigstens 90 oder 95 Masse-% und höchstens 100 Masse-%; < 200µm: wenigstens 85 oder 90 Masse-% und höchstens 95 oder 100 Masse-%; < 100µm: wenigstens 65 oder 70 Masse-% und höchstens 75 oder 80 Masse-%; < 63µm: wenigstens 45 oder 50 Masse-% und höchstens 65 oder 70 Masse-%. For example, it may be provided that the particle size of the components of the mixture according to the invention below the particle sizes given below in each of the specified proportions by mass, the mixture according to the invention can meet, for example, only one of the following conditions in terms of particle size: <1 mm: 100% by mass; <500μm: 100% by mass; <315μm: at least 90 or 95% by mass and at most 100% by mass; <200μm: at least 85 or 90% by mass and at most 95 or 100% by mass; <100μm: at least 65 or 70% by mass and at most 75 or 80% by mass; <63μm: at least 45 or 50% by mass and at most 65 or 70% by mass.

Indem die erfindungsgemäße Mischung diese sehr geringe, mittlere Korngröße aufweist, kann eine besonders gute und gleichmäßige Verteilung und insbesondere auch eine schnelle Auflösung der Mischung in einer Schlacke bewirkt werden.By virtue of the mixture according to the invention having this very small average particle size, it is possible to effect a particularly good and uniform distribution and, in particular, rapid dissolution of the mixture in a slag.

Um trotz dieser geringen Korngröße der Mischung ein gutes Handling der erfindungsgemäßen Mischung erreichen zu können, kann vorgesehen sein, die Mischung in kompaktierter oder gepresster Form, beispielsweise in Form von Pellets zur Verfügung zu stellen. Um die Mischung in Form von Pellets zur Verfügung zu stellen, kann vorgesehen sein, dass eine erfindungsgemäße Mischung, die insbesondere die zuvor beschriebene Korngrößenverteilung aufweisen kann, ohne Zugaben von Additiven zu Pellets verpresst wird. Beispielsweise können diese Pellets eine mandelförmige, stäbchenförmige oder kugelige Form aufweisen, beispielsweise mit einer maximalen Länge von beispielsweise 50 mm, 40 mm oder 30 mm. Die Pellets können ferner beispielsweise einen Mindestdurchmesser von 5, 10, 15, 20 oder 25 mm aufweisen. Pellets mit einer entsprechenden Größe sind gut handhabbar, jedoch gleichzeitig noch so klein, dass sie nach Eingabe in eine Schlacke dort schnell zerfallen und die Vorteile der erfindungsgemäßen, geringen Korngrößenverteilung dort schnell zum Tragen kommen können.In order to be able to achieve good handling of the mixture according to the invention in spite of this small particle size of the mixture, it can be provided to provide the mixture in compacted or pressed form, for example in the form of pellets. In order to provide the mixture in the form of pellets, it can be provided that a mixture according to the invention, which in particular can have the previously described particle size distribution, is pressed into pellets without additions of additives. For example, these pellets may have an almond-shaped, rod-shaped or spherical shape, for example with a maximum length of, for example, 50 mm, 40 mm or 30 mm. The pellets may also have, for example, a minimum diameter of 5, 10, 15, 20 or 25 mm. Pellets of an appropriate size are easy to handle, but at the same time so small that they quickly disintegrate there after entering a slag and the benefits of the invention, small particle size distribution can quickly come to fruition there.

Es kann vorgesehen sein, dass die erfindungsgemäße Mischung einen Anteil an Calciumoxid (CaO) aufweist, da durch diesen die Basizität der Schlacke weiter erhöht werden kann und der Angriff der Schlacke auf die feuerfeste Zustellung des metallurgischen Gefäßes gesenkt werden kann. Das CaO der Mischung hat insbesondere dann eine vorteilhafte, die Basizität reduzierende Wirkung, wenn das Verhältnis von CaO zu SiO2 in der Mischung ein bestimmtes Maß nicht überschreitet.It can be provided that the mixture according to the invention has a proportion of calcium oxide (CaO), as by this the basicity of the slag can be further increased and the attack of the slag can be reduced to the refractory lining of the metallurgical vessel. The CaO of the mixture has, in particular, an advantageous basicity-reducing effect if the ratio of CaO to SiO 2 in the mixture does not exceed a certain level.

Erfindungsgemäß hat sich herausgestellt, dass die Basizität der Schlacke insbesondere dann durch das CaO erhöht werden kann, wenn das Verhältnis von Massenanteilen von CaO zu SiO2 in der Mischung nicht unter 0,7 liegt. Es kann daher vorgesehen sein, dass das Verhältnis der Massenanteile von CaO zu SiO2 in der erfindungsgemäßen Mischung nicht unter 0,7 liegt.According to the invention, it has been found that the basicity of the slag can be increased by the CaO, in particular, if the ratio of mass fractions of CaO to SiO 2 in the mixture is not less than 0.7. It can therefore be provided that the ratio of the mass fractions of CaO to SiO 2 in the mixture according to the invention is not less than 0.7.

SiO2 kann im Wesentlichen über Verunreinigungen der Rohstoffe der erfindungsgemäßen Mischung in diese gelangt sein.SiO 2 can essentially be introduced into the mixture according to the invention via impurities in the raw materials of the mixture according to the invention.

Es kann vorgesehen sein, dass die Mischung Calciumoxid und Siliciumdioxid in folgenden Massenanteilen umfasst:

  • CaO: 0 bis 10 Masse-%,
  • SiO2: 0 bis 7 Masse-%.
It can be provided that the mixture comprises calcium oxide and silicon dioxide in the following proportions by weight:
  • CaO: 0 to 10 mass%,
  • SiO 2 : 0 to 7% by mass.

CaO kann ferner beispielsweise in Anteilen von wenigstens 0,1 oder 0,2 oder 0,5 oder 1 oder 1,5 oder 2 Masse-% in der Mischung vorliegen und beispielsweise in Anteilen von höchstens 10, 9, 8, 7, 6, 5, 4, 3 oder 2,5 Masse-%.Furthermore, CaO can be present in proportions of at least 0.1 or 0.2 or 0.5 or 1 or 1.5 or 2% by mass in the mixture and, for example, in proportions of at most 10, 9, 8, 7, 6, 5, 4, 3 or 2.5 mass%.

SiO2 kann beispielsweise in Anteilen von wenigstens 0,1 oder 0,2 oder 0,5 oder 1 oder 1,5 oder 2 Masse-% in der Mischung vorliegen und beispielsweise in Anteilen von höchstens 7, 6, 5, 4, 3 oder 2,5 Masse-%.For example, SiO 2 can be present in the mixture in proportions of at least 0.1 or 0.2 or 0.5 or 1 or 1.5 or 2 mass% and, for example, in proportions of at most 7, 6, 5, 4, 3 or 2.5% by mass.

Wie zuvor ausgeführt, kann vorgesehen sein, die Mischung in Form von Pellets zur Verfügung zu stellen, wobei die Mischung ohne die Zugabe von Additiven zu Pellets verpresst wird. Soweit jedoch Additive zur Verpressung der Mischung zu Pellets verwendet werden, kann vorgesehen sein, CaO als ein solches Pressadditiv zu verwenden. In diesem Fall kann die Mischung, in Abwendung von dem zuvor offenbarten Erfindungsgedanken, wonach die Mischung Anteile an CaO von höchstens 10 Masse-% CaO aufweist, Anteile an CaO von bis zu 40 Masse-% aufweisen. Bevorzugt weist die Mischung jedoch kein Additiv zum Verpressen auf, so dass der Anteil an CaO in der Mischung, wie oben ausgeführt, nicht über 10 Masse-% liegt.As stated above, it can be provided to provide the mixture in the form of pellets, wherein the mixture is compressed into pellets without the addition of additives. However, where additives are used to compress the mixture into pellets, it may be envisioned to use CaO as such a pressing additive. In this case, the mixture, contrary to the previously disclosed concept of the invention, according to which the mixture has proportions of CaO of at most 10% by mass of CaO, may have proportions of CaO of up to 40% by mass. However, the mixture preferably has no additive for pressing, so that the proportion of CaO in the mixture, as stated above, is not more than 10% by mass.

Es kann vorgesehen sein, dass die Mischung Eisenoxide in folgenden Massenanteilen umfasst:

  • Eisenoxid: 0 bis 7 Masse-%.
It can be provided that the mixture comprises iron oxides in the following proportions by weight:
  • Iron oxide: 0 to 7% by mass.

Eisenoxid steht dabei für die Summe sämtlicher Eisenoxide in der Mischung, also insbesondere FeO und Fe2O3, aber beispielsweise auch Fe3O4 und Fe2O.Iron oxide stands for the sum of all iron oxides in the mixture, ie in particular FeO and Fe 2 O 3 , but also, for example, Fe 3 O 4 and Fe 2 O.

Eisenoxide können in der Mischung beispielsweise auch in Anteilen von wenigstens 0,1 Masse-%, 0,2 Masse-%, 0,4 Masse-%, 0,6 Masse-% oder 0,8 Masse-% vorliegen und beispielsweise höchstens in Anteilen von 7 Masse-%, 6 Masse-%, 5 Masse-%, 4 Masse-%, 3 Masse-%, 2,8 Masse-%, 2,6 Masse-%, 2,4 Masse-%, 2,2 Masse-% oder 2 Masse-%.Iron oxides may also be present in the mixture in proportions of at least 0.1% by mass, 0.2% by mass, 0.4% by mass, 0.6% by mass or 0.8% by mass, for example at most in Proportions of 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2.8 mass%, 2.6 mass%, 2.4 mass%, 2, 2% by mass or 2% by mass.

Erfindungsgemäß hat sich herausgestellt, dass die hierin beschriebenen, vorteilhaften Wirkungen der erfindungsgemäßen Mischung als Schlackenkonditionierer durch die Anwesenheit von weiteren Komponenten in der Mischung nachteilig beeinflusst werden können.According to the invention, it has been found that the advantageous effects of the mixture according to the invention described herein as a slag conditioner can be adversely affected by the presence of further components in the mixture.

Es kann daher vorgesehen sein, dass die Mischung neben den vorgenannten Komponenten, also MgO, C, Al, Al4C3, CaO, SiO2, Eisenoxiden und gegebenenfalls Al2O3 nur geringe Anteile an weiteren Komponenten umfasst, zum Beispiel in Anteilen unter 5 Masse-%, 4 Masse-%, 3 Masse-%, 2,5 Masse-%, 2 Masse-%, 1,5 Masse-% oder auch unter 1 Masse-%.It can therefore be provided that the mixture comprises, in addition to the aforementioned components, ie MgO, C, Al, Al 4 C 3 , CaO, SiO 2 , iron oxides and optionally Al 2 O 3 only small proportions of other components, for example in proportions below 5% by mass, 4% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass or else less than 1% by mass.

Beispielsweise kann vorgesehen sein, dass die Mischung Anteile an den folgenden Komponenten unterhalb der nachfolgend angegebenen Massenanteile umfasst: Cr2O3: < 0,2 Masse-%; P2O5: < 0,2 Masse-%; TiO2: < 0,2 Masse-%; K2O + Na2O: < 0,5 Masse-%; Zr2: < 0,2 Masse-%. For example, it may be provided that the mixture comprises fractions of the following components below the mass fractions indicated below: Cr 2 O 3 : <0.2% by mass; P 2 O 5 : <0.2% by mass; TiO 2 : <0.2% by mass; K 2 O + Na 2 O: <0.5 mass%; Zr 2 : <0.2 mass%.

Überraschenderweise hat sich erfindungsgemäß herausgestellt, dass Magnesia-Kohlenstoff-Erzeugnisse, die in der Stahlindustrie benutzt worden sind, insbesondere als Verschleißfutter von Sauerstoffblaskonvertern, in Elektrolichtbogenöfen oder in Pfannen, sich teilweise als Rohstoff für die erfindungsgemäße Mischung eignen. Insofern können entsprechend recycelte Magnesia-Kohlenstoff-Erzeugnisse teilweise, weitgehend oder ausschließlich als Rohstoff für die erfindungsgemäße Mischung verwendet werden. Gegenstand der Erfindung ist insoweit auch die Verwendung von recycelten Magensia-Kohlenstoff-Erzeugnissen als Rohstoff für die erfindungsgemäße Mischung beziehungsweise die Verwendung solch recycelter Magnesia-Kohlenstoff-Erzeugnisse als erfindungsgemäßer Schlackenkonditionierer.Surprisingly, it has been found according to the invention that magnesia-carbon products which have been used in the steel industry, in particular as wear linings of oxygen blowing converters, in electric arc furnaces or in pans, are partly suitable as raw material for the mixture according to the invention. In this respect, correspondingly recycled magnesia-carbon products can be used partially, largely or exclusively as raw material for the mixture according to the invention. The invention also relates to the use of recycled gastric carbon products as raw material for the mixture according to the invention or the use of such recycled magnesia-carbon products as inventive slag conditioners.

Beispielsweise kann vorgesehen sein, als Rohstoffe für die erfindungsgemäße Mischung neben recycelten Magnesia-Kohlenstoff-Erzeugnissen wenigstens einen der folgenden weiteren Rohstoffe zu wählen: Magnesia (insbesondere Sintermagnesia), Kohlenstoff (insbesondere Graphit), Korund oder Aluminiumcarbid.For example, it may be provided to select at least one of the following further raw materials as raw materials for the mixture according to the invention in addition to recycled magnesia-carbon products: magnesia (in particular sintered magnesia), carbon (in particular graphite), corundum or aluminum carbide.

Gegenstand der Erfindung ist ferner ein Verfahren zur Konditionierung einer bei der Eisen- und Stahlmetallurgie auf einer Metallschmelze in einem metallurgischen Gefäß befindlichen Schlacke mit folgenden Schritten:

  • Zur Verfügungstellung einer hierin beschriebenen, erfindungsgemäßen Mischung;
  • Einbringen der Mischung in die auf der Metallschmelze in dem metallurgischen Gefäß befindliche Schlacke.
The invention furthermore relates to a method for conditioning a slag contained in a metallurgical vessel during iron and steel metallurgy, comprising the following steps:
  • Providing a mixture of the invention described herein;
  • Introducing the mixture into the slag located on the molten metal in the metallurgical vessel.

Die Mischung kann, wie hierin beschrieben, beispielsweise in kompaktierter oder gepresster Form, beispielsweise in Form von Pellets zur Verfügung gestellt werden.The mixture may, as described herein, be provided, for example, in compacted or compressed form, for example in the form of pellets.

Die zur Verfügung gestellte Mischung wird auf die Schlacke gegeben und sinkt in diese ein, so dass sie dort ihre erfindungsgemäße Wirkung entfalten kann.The mixture provided is added to the slag and sinks into it so that it can unfold its effect there according to the invention.

Die erfindungsgemäße Mischung eignet sich grundsätzlich als Schlackenkonditionierer für Schlacken auf einer Metallschmelze in einem beliebigen metallurgischen Gefäß, beispielsweise für Metallschmelzen in Konvertern, Elektrolichtbogenöfen oder Pfannen. Besonders bevorzugt wird die erfindungsgemäße Mischung als Schlackenkonditionierer für Schlacken auf solchen Metallschmelzen verwendet, die sich in einem metallurgischen Gefäß mit einer basischen Zustellung befinden, also insbesondere mit einer Zustellung auf Basis wenigstens eines der folgenden Werkstoffe: Magnesia, Magnesia-Kohlenstoff, Doloma oder Doloma-Kohlenstoff.The mixture according to the invention is fundamentally suitable as a slag conditioner for slags on a molten metal in any metallurgical vessel, for example for molten metals in converters, electric arc furnaces or ladles. The mixture according to the invention is particularly preferably used as a slag conditioner for slags on molten metals which are located in a metallurgical vessel with a basic feed, ie in particular with a feed based on at least one of the following materials: magnesia, magnesia-carbon, doloma or dolomite. Carbon.

Gegenstand der Erfindung ist ferner die Verwendung einer hierin beschriebenen, erfindungsgemäßen Mischung zur Konditionierung einer bei der Eisen- und Stahlmetallurgie auf einer Metallschmelze in einem metallurgischen Gefäß befindlichen Schlacke.The invention furthermore relates to the use of a mixture according to the invention described herein for conditioning a slag present in iron and steel metallurgy on a molten metal in a metallurgical vessel.

Die Verwendung kann dabei wie hierin offenbart erfolgen.The use can be carried out as disclosed herein.

Sämtliche der hierin offenbarten Merkmale der Erfindung können, einzeln oder in Kombination, beliebig miteinander kombiniert sein.All of the features of the invention disclosed herein may be combined with each other singly or in combination.

Die Erfindung wird anhand des nachfolgenden Ausführungsbeispiels näher erläutert.The invention will be explained in more detail with reference to the following embodiment.

Zunächst wurde im Ausführungsbeispiel eine Mischung zur Verfügung gestellt, die Magnesium, Kohlenstoff und Aluminium sowie weitere Komponenten in den Massenanteilen gemäß Tabelle 1 umfasst. Tabelle 1 Komponente Massenanteile [%] MgO 62,6 C 24,6 Al2O3 6,4 CaO 2,4 SiO2 2,3 Fe2O3 1,3 Cr2O3 0,05 P2O5 0,08 TiO2 0,08 K2O 0,05 Na2O 0,08 ZrO2 0,06 First, in the exemplary embodiment, a mixture was provided which comprises magnesium, carbon and aluminum as well as further components in the proportions by mass according to Table 1. Table 1 component Mass shares [%] MgO 62.6 C 24.6 Al 2 O 3 6.4 CaO 2,4 SiO 2 2.3 Fe 2 O 3 1.3 Cr 2 O 3 0.05 P 2 O 5 0.08 TiO 2 0.08 K 2 O 0.05 Na 2 O 0.08 ZrO 2 0.06

Der Kohlenstoff lag in der Mischung in Form von Graphit sowie Aluminiumcarbid vor.The carbon was present in the mixture in the form of graphite and aluminum carbide.

Aluminium lag in der Mischung in Form von metallischem Aluminium sowie in Form von Aluminiumcarbid vor.Aluminum was present in the mixture in the form of metallic aluminum and in the form of aluminum carbide.

Als Rohstoffe wurden ausschließlich recyclierte Magnesia-Kohlenstoff-Erzeugnisse verwendet.The raw materials used were exclusively recycled magnesia-carbon products.

Die Mischung wurde in Form von ohne zusätzliche Additive gepressten, mandelförmigen Pellets mit einer Dicke von etwa 15 mm und einer Länge von etwa 30 mm zur Verfügung gestellt.The mixture was provided in the form of almond-shaped pellets having a thickness of about 15 mm and a length of about 30 mm pressed without additional additives.

Die Korngrößenverteilung der Mischung in den Pellets ist in Tabelle 2 angegeben. Tabelle 2 Korngröße Massenanteile [%] < 63 µm 55 < 100 µm 72 < 200 µm 92 < 250 µm 97 < 500 µm 100 The particle size distribution of the mixture in the pellets is given in Table 2. Table 2 grain size Mass shares [%] <63 μm 55 <100 μm 72 <200 μm 92 <250 μm 97 <500 μm 100

Die Mischung wurde verwendet als Schlackenkonditionierer für eine Schlacke auf einer in einem Sauerstoffkonverter befindlichen Metallschmelze. Dabei wurde die Mischung auf die auf der Schmelze befindliche Schlacke aufgegeben. Durch die Aufgabe der Mischung auf die Schlacke konnte deren Basizität erhöht werden. Ferner konnte durch die Anteile an Kohlenstoff, Aluminium und Aluminiumcarbid in der Mischung eine Schaumbildung der Schlacke erreicht werden. Schließlich konnte die Viskosität der Schlacke auf das gewünschte Maß eingestellt werden.The mixture was used as a slag conditioner for a slag on a molten metal in an oxygen converter. The mixture was applied to the slag contained on the melt. By abandoning the mixture to the slag, its basicity could be increased. Furthermore, by the proportions of carbon, aluminum and aluminum carbide in the mixture foaming of the slag could be achieved. Finally, the viscosity of the slag could be adjusted to the desired level.

Claims (6)

  1. A method for conditioning a slag located on a metal melt in a metallurgical vessel in iron and steel metallurgy, said method comprising the following steps:
    1.1 providing a mixture comprising magnesium, carbon and aluminium in the following mass proportions: MgO: 45 to 90 mass %; C: 12 to 40 mass %; Al2O3: 1 to 20 mass %;
    1.2 introducing the mixture into the slag located on the metal melt in the metallurgical vessel.
  2. The method according to claim 1, in which the mixture contains a proportion of MgCO3 less than 10 mass %.
  3. The method according to at least one of the preceding claims, in which the mixture is present in the form of pellets.
  4. The method according to at least one of the preceding claims, with a mixture of which the granularity is present in a grain size less than 0.5 mm to an extent of at least 70 mass %.
  5. The method according to at least one of the preceding claims, with a mixture comprising calcium oxide and silicon dioxide in the following mass proportions:
    CaO: 0 to 10 mass %;
    SiO2: 0 to 7 mass %.
  6. The method according to at least one of the preceding claims, with a mixture comprising iron oxide in the following mass proportions: iron oxide: 0 to 7 mass %.
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PL13195334T PL2878685T3 (en) 2013-12-02 2013-12-02 Method for conditioning a slag on molten metal from the processing of iron and steel in a metallurgical vessel
HUE13195334A HUE026614T2 (en) 2013-12-02 2013-12-02 Method for conditioning a slag on molten metal from the processing of iron and steel in a metallurgical vessel
SI201330101T SI2878685T1 (en) 2013-12-02 2013-12-02 Method for conditioning a slag on molten metal from the processing of iron and steel in a metallurgical vessel
ES13195334.1T ES2559024T3 (en) 2013-12-02 2013-12-02 Procedure for conditioning a slag found on a metal melt in a metallurgical vessel in iron and steel metallurgy
EP13195334.1A EP2878685B9 (en) 2013-12-02 2013-12-02 Method for conditioning a slag on molten metal from the processing of iron and steel in a metallurgical vessel
PT131953341T PT2878685E (en) 2013-12-02 2013-12-02 Method for conditioning a slag on molten metal from the processing of iron and steel in a metallurgical vessel
RS20150849A RS54471B1 (en) 2013-12-02 2013-12-02 Method for conditioning a slag on molten metal from the processing of iron and steel in a metallurgical vessel
PCT/EP2014/071022 WO2015082093A1 (en) 2013-12-02 2014-10-01 Mixture, use of this mixture and process for conditioning a slag located on a metal melt in a metallurgical vessel in iron and steel metallurgy
MX2016005055A MX2016005055A (en) 2013-12-02 2014-10-01 Mixture, use of this mixture and process for conditioning a slag located on a metal melt in a metallurgical vessel in iron and steel metallurgy.
US15/038,735 US20160376672A1 (en) 2013-12-02 2014-10-01 Mixture, use of this mixture and process for conditioning a slag located on a metal melt in a metallurgical vessel in iron and steel metallurgy
CN201480062204.6A CN105705662A (en) 2013-12-02 2014-10-01 Mixture, use of this mixture and process for conditioning a slag located on a metal melt in a metallurgical vessel in iron and steel metallurgy
HRP20151446TT HRP20151446T1 (en) 2013-12-02 2015-12-31 Method for conditioning a slag on molten metal from the processing of iron and steel in a metallurgical vessel

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