WO2023027567A1 - Method and apparatus for producing a ferrotitanium alloy having high content of titanium - Google Patents

Method and apparatus for producing a ferrotitanium alloy having high content of titanium Download PDF

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Publication number
WO2023027567A1
WO2023027567A1 PCT/LV2021/050008 LV2021050008W WO2023027567A1 WO 2023027567 A1 WO2023027567 A1 WO 2023027567A1 LV 2021050008 W LV2021050008 W LV 2021050008W WO 2023027567 A1 WO2023027567 A1 WO 2023027567A1
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Prior art keywords
iron
rutile
melting
alloy
titanium
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PCT/LV2021/050008
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English (en)
French (fr)
Inventor
Toms BEINERTS
Jurijs GEĻFGATS
Kalvis KALNIŅŠ
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Latvijas Universitāte
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Publication of WO2023027567A1 publication Critical patent/WO2023027567A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/18—Electroslag remelting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1295—Refining, melting, remelting, working up of titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/06—Alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/006—Making ferrous alloys compositions used for making ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C35/00—Master alloys for iron or steel
    • C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present invention relates to the field of ferrous metallurgy, in particular for the production of a ferrotitanium alloy having high titanium content - ferrotitanium - obtained by the melting process of a molten composite electrode and used as an alloying component in the production of steel alloys having high physical and mechanical properties.
  • titanium-based casting alloys containing aluminium, molybdenum, zirconium, niobium (UA 51032) or those containing aluminium, zirconium, molybdenum, vanadium, yttrium (UA 58671) are known. These alloys are obtained in the form of traditional casting techniques by melting a combination of porous titanium and the specified alloying components mainly in arc furnaces and casting the material into crystallization moulds obtaining bars of said alloys.
  • a titanium alloy powder with magnesium is known (UA 51917), which is obtained by melting in an electric arc furnace a consumable electrode consisting of porous titanium, which is melted in vacuum arc furnaces in an amount of 80-90% and reduced by a magnesium thermal method by grinding to a fraction of 5 to 70 mm, mixed with 1 to 5 mm of magnesium granules containing 0,3 to 5% by weight and with the remaining magnesium chloride (up to 5% by weight).
  • magnesium and magnesium chloride vapours due to their high partial pressure (several times higher than the titanium vapour pressure) ensure sublimation of the electrode material in the titanium-magnesium alloy in the form of spherical particles.
  • the volume of the final product (titanium alloy powder) in the best case is 43.5% (with a fraction size of 1.0 + 0.5 mm), 20.2% (with a fraction size of 0.5 + 0.315 mm), 12.2% (with a fraction size of 0.315 + 0.2 mm), 17.8% (with a fraction size of 0.2 + 0.09 mm) and 5.4% with a fraction size of less than 0.09 mm.
  • the disadvantages of the final product of the known material are its predominant maximum casting fraction volume (1.0-0.5 mm), as the addition of a titanium-containing alloy such as an alloy, for example in a converter at a melting point of 1500-1700 °C or in an alloy processing process outside the furnace in the ladle 1450- 1600 °C, will increase titanium losses.
  • alloy steel production is in the tens of thousands of tonnes per year and (taking into account the volumes of the alloying component) requires hundreds of tonnes of titanium alloy powder due to its low density, which in turn means the need to build new, high capacity, energy-intensive titanium powder plants.
  • the resulting iron alloy contains a certain amount of oxygen, which it obtains from the air by easily combining with titanium.
  • the access of gaseous oxygen to the ferrous alloy is not stopped by a significant layer of chips. According to quality standards, high-quality alloy steels must not contain more than 0.004-0.007% by weight of oxygen.
  • the iron alloy thus obtained contains 55-60% by weight of titanium, the rest is iron and up to 1.5% by weight - impurities.
  • the final ferrotitanium obtained under the known solution contains from 55 to 60% by weight of titanium, which is not sufficient for the particular application of the ligature, as it would mean that it would have to be added in excessive amounts during its production process.
  • Another disadvantage is that in the second stage of the process there is no protection against oxidation with oxygen in the air, which significantly reduces the quality of the final product obtained and reduces the amount of useful product at the end of the process.
  • the main disadvantage of this solution is that it is not possible to obtain the final product in the form of a ferrotitanium bar.
  • Ferrotitanium after two stages of regeneration and melting, comes out in the form of crumbs that are incorporated into the slag mass. Thus, additional steps are needed to remove these crumbs from the slag and alloys, which increase the unit price of the resulting product.
  • the object of the proposed invention is to obtain an iron alloy with a high titanium content in the final product - not less than 70% by weight, to reduce the unit cost of the product, to prevent the possibility of contamination of the iron alloy with air oxygen during titanium regeneration, to provide the conditions for obtaining a finished product in the form of a compact ferrotitanium bar with a certain content of the main component.
  • FIG. 1 - schematic representation of the electroslag remelting equipment provided by an electromagnetic system in the crystallization zone;
  • Fig. 2 - a consumable electrode obtained by placing a mixture of raw materials in a metal (iron, steel or cast iron) shell;
  • Fig. 3 - a permanent magnet system which is located around the crystallization reservoir to create a strong permanent magnetic field in the region of fluxes and crystallization;
  • Fig. 4 - a capacitor block adapted for generating a pulsed current for generating a pulsed magnetic field in the crystallization region;
  • Fig. 5 - a diagram showing the dependence of the current of the coil on the time obtained with the pulse battery
  • Fig. 6 the trajectories of the droplets in the region of the liquid melt and their radial distribution in the crystallizer, as well as the flow in the region of the liquid melt: Fig. 6.A - without magnetic field, Fig. 6.B with transverse magnetic field;
  • Fig. 7 one embodiment of the arrangement of permanent magnets according to the proposed invention.
  • the proposed method for obtaining a high titanium content ferrotitanium compound from a rutile-based mixture of chemical elements by an electromagnetically supplemented electroslag remelting method comprising the following sequential steps: (i) providing an electrode adapted for its melting, by placing a mixture of powdered chemical elements based on rutile in a metal shell; (ii) melting electrode in the molten flux layer (5), subjecting the molten metal layer (6) and the crystallizing alloy to a combined action of a permanent magnetic and pulsed electromagnetic field source (the permanent magnetic field creates a cross field with respect to the molten flux layer (5), the molten metal layer (6) and/or the cooled crystallizer (4), while the pulsed electromagnetic field has an axial direction), wherein, the permanent magnetic field is selected in the range of 200-400 mT and the pulsed magnetic field in the range of 400- 800 mT with a pulse frequency of 1-10 Hz; (iii) after melting the electrode - cooling the mol
  • the composition of the consumable electrode is selected from the group consisting of rutile, iron (can be also cast iron or steel, which is the source of iron), carbon, coke, quicklime and aluminium powder having fraction in the range of 600-900 ⁇ m .
  • the material of the metal shell may be cast iron, iron, steel or other iron-based alloys.
  • the electroslag prior to melting of the electrode on step (ii), can be melted in an electric arc furnace, by first melting the cast iron or steel electroslag, removing the smelting slag from the furnace and adding a mixture of rutile and reducer - carbon or coke - to the top of the liquid metal bath, optionally also adding limestone or lime to the mixture.
  • the slag-free melt product is subjected to melting in an induction furnace to form a high titanium content ferrotitanium rod.
  • the apparatus (Fig. 1) for carrying out the method comprises: an electrode holder (1); a closed atmosphere reservoir (2); a consumable electrode (3); a coolable crystallizer (4); a coolable base (9) and an electromagnetic system (8) located outside the reservoir (2) at the level of the molten flux layer (5), the molten metal layer (6) and/or at the level of the cooled crystallizer (4), the electromagnetic system (8) comprising permanent magnets and an inductor connected to a capacitor unit for pulsed current generation; the electromagnetic system (8) is adapted to generate a permanent magnetic field, which is a cross field with respect to the molten flux layer (5), the molten metal layer (6) and a coolable crystallizer (4), as well as a pulsed electromagnetic field, which is an axial field in relation to the molten flux layer (5), the molten metal layer (6) and the coolable crystallizer (4), wherein the permanent magnets being adapted to generate a permanent magnetic field in the range of 200 to 400 mT and
  • the set goal is reached by obtaining an iron alloy with a high titanium content from the mixture (rutile, cast iron and/or steel scrap, crushed electrodes or coke, lime and/or limestone and aluminium) placed in a metal shell (Fig. 2) and melted as a consumable electrode in an electric slag remelting furnace under the melt layer. Additional sources of electromagnetic fields are connected to the standard electric melting furnace - placed around the crystallization region: permanent magnet system - Fig. 3, which creates a cross field of 200-400 mT in relation to the crystallization reservoir.
  • a single-winding inductor powered by a capacitor bank (Fig. 4) which, with a pulsed current (Fig. 5), generates a pulsed axial magnetic field reaching 400-800 mT with a pulse frequency of 1-10 Hz.
  • a capacitor bank (Fig. 4) which, with a pulsed current (Fig. 5), generates a pulsed axial magnetic field reaching 400-800 mT with a pulse frequency of 1-10 Hz.
  • the combination of pulsed and permanent magnetic field created interacts with the discharge current and, firstly, causes movement in liquid fluxes and molten droplets, which promotes melting of molten material and, consequently, increases chemical reaction rates, and secondly, crystallization of the ingot, significantly reducing the formation of possible dentrides and other irregularities (including pores, gas inclusions).
  • Intense stirring of the reaction medium allows it to proceed with less residue, reducing the amount of residual impurities and allowing a higher titanium content to be achieved.
  • the permanent magnetic field is created by a permanent magnetic system comprising pieces of permanent magnets arranged in a toroidal shape as shown in Fig. 7, where the top of the toroidally arranged magnets has a magnetization directed radially in the axial direction, but at the bottom - in the opposite direction.
  • a so-called ferromagnetic yoke can be used on the outer side surface of the toroid of the magnetic system.
  • the size of the magnetic system (toroid dimensions, magnet magnetization, magnetic yoke dimensions) must be selected according to the reactor dimensions so that a constant magnetic field of 200- 400 mT is reached on the axis.
  • the toroidal arrangement relative to the reactor is designed so that its centre coincides with the lower surface of the flux (5) - the initial crystallization front - and at the same time with the central plane of one winding inductor.
  • the steel and rutile can be pre-fused in an electric arc furnace.
  • cast iron or steel scrap is melted.
  • a mixture of rutile and a reducing agent carbon or coke
  • Limestone or lime (depending on the purity of the rutile used) is added to the rutile composition used to burn any remaining impurities and other rocks, which requires a source of TiO 2 of at least 95% by mass.
  • the iron oxide normally present in the composition is reduced. Recovered iron is converted into a metallic melt, which causes an increase in the concentration of titanium oxide in the generated slag.
  • the mixture of rutile, iron and aluminium powder having a fraction in the range of 600-900 ⁇ m is first prepared.
  • the mixture is placed in a metal shell, which is then used as a consumable electrode in an electrical slag remelting plant.
  • a consumable electrode formed by a metal shell filled with the above mixture is connected to the positive pole of the power supply source and lowered into the molten flux layer at the bottom of the melting reservoir until it contacts the bottom where the negative pole of the power supply source is fed.
  • a mixture of aluminium and calcium oxides is provided in the fluxes.
  • the melt is continuously affected by a pulsed magnetic field from melting to crystallization, which there causes pulsed pressure fluctuations, which in turn improves the reaction rate and, secondly, creates micromotion in each drop, which in turn improves reagent transport and, accordingly, reaction rate.
  • the fluxes have a relatively low electrical conductivity, due to the flowing current, the external magnetic field creates a macroscopic flow in these fluxes as well, which in turn means that it ensures more efficient removal of other impurities from the melt droplets.
  • Electrode chips with a carbon content of 86% by weight and aluminium powder PA-2 (800 ⁇ m ) were used as reducing agents.
  • Rutile concentrate (TiO 2 > 95%) and steel (0.5-3mm) were used to form the consumable electrode.
  • Ferrotitanium smelting was performed by reducing the oxides of titanium, iron and silicon present in the main mixture of rutile and steel chips (at least 82% by weight TiO 2 , max 9% by weight Fe 2 O 3 , the rest: admixture of oxides of aluminium, silicon, vanadium and manganese, and possibly sulphur and phosphorus) with aluminium by melting the consumable electrode under protective melt.
  • the composition of the raw materials (from which the consumable electrode is formed) is: rutile - 48-55%; aluminium powder - 22-25%, iron - 12-16%, lime or limestone - 10-15% and other impurities 0-7%.
  • the main mixture used as a consumable electrode filler contained crushed slag (titanium oxide, aluminium powder and liquid glass as a binder of the above composition). The flow of silica was ensured by the limestone added to the mixture. After dosing the slag, aluminium powder and liquid glass, the composition of the main mixture was stirred to make its composition more even.
  • the prepared mixture was placed in a consumable electrode steel shell and sealed with pressing equipment. [027]
  • the prepared consumable electrode was connected to the positive pole of the DC supply and the bottom of the melting reservoir - to the negative pole. By use of an electric mechanism, the electrode was lowered until it made contact with the bottom of the melting reservoir, passing through the protective melt layer at the bottom of the reservoir.
  • Sample 2 of Tables 1 and 2 shows a high (79% by weight) titanium content in the ferrotitanium alloy, but the aluminium content is increased as well.
  • the quality of the casting obtained is high, while the amount of other impurities, including silicon, manganese, vanadium and sulphur, does not exceed 2.6% by weight.

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  • Manufacturing & Machinery (AREA)
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PCT/LV2021/050008 2021-08-26 2021-09-01 Method and apparatus for producing a ferrotitanium alloy having high content of titanium WO2023027567A1 (en)

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LVLVP2021000049 2021-08-26
LVP-21-49A LV15720B (lv) 2021-08-26 2021-08-26 Paņēmiens un iekārta augsta titāna satura dzelzs sakausējuma iegūšanai elektrosārņu pārkausēšanas procesā

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2398908C2 (ru) * 2007-10-11 2010-09-10 Сергей Николаевич Чепель Установка для получения ферротитана путем электродугового плавления титансодержащего материала под слоем защитного флюса

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2398908C2 (ru) * 2007-10-11 2010-09-10 Сергей Николаевич Чепель Установка для получения ферротитана путем электродугового плавления титансодержащего материала под слоем защитного флюса

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KOMPAN YA ET AL: "Magnetically controlled electroslag melting of titanium alloys", MAGNETOHYDRODYNAMICS, vol. 46, no. 3, 1 January 2010 (2010-01-01), pages 317 - 324, XP055911787, Retrieved from the Internet <URL:http://www.mhd.sal.lv/contents/2010/3/MG.46.3.9.R.html> *

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