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WO2025127545A1 - Procédé d'élimination d'impuretés dans des déchets d'aluminium fondu - Google Patents

Procédé d'élimination d'impuretés dans des déchets d'aluminium fondu Download PDF

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Publication number
WO2025127545A1
WO2025127545A1 PCT/KR2024/019300 KR2024019300W WO2025127545A1 WO 2025127545 A1 WO2025127545 A1 WO 2025127545A1 KR 2024019300 W KR2024019300 W KR 2024019300W WO 2025127545 A1 WO2025127545 A1 WO 2025127545A1
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WO
WIPO (PCT)
Prior art keywords
molten metal
aluminum
boron
stirring
impurities
Prior art date
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Pending
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PCT/KR2024/019300
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English (en)
Korean (ko)
Inventor
김지혜
손정길
장진혁
노정영
김원호
연창한
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Posco M Tech Co Ltd
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Posco M Tech Co Ltd
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Publication date
Priority claimed from KR1020240142847A external-priority patent/KR102820014B1/ko
Application filed by Posco M Tech Co Ltd filed Critical Posco M Tech Co Ltd
Publication of WO2025127545A1 publication Critical patent/WO2025127545A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • 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
    • C22B21/00—Obtaining aluminium
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/06—Obtaining aluminium refining
    • 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
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • 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
    • 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
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for appropriately controlling impurity elements other than aluminum contained in aluminum scrap in order to recycle the aluminum scrap and use it by dividing it by grade according to its appropriate use.
  • Aluminum is manufactured and used in various ways. Currently, the most common way to produce aluminum is to obtain aluminum ingots (primary ingots) through ore treatment/smelting/refining from bauxite. The next way is to collect aluminum scraps and re-melt them.
  • the former method generates CO2 , various chlorine ( Cl2 ) gases, and red mud during the aluminum manufacturing process.
  • the amount of CO2 generated at this time is 16.5 t CO2eq per ton of aluminum ingot produced, whereas when aluminum scraps are used, the CO2 generated from the raw materials used is zero, and about 0.5 to 0.7 t CO2eq is derived from the energy fuel used to operate the melting furnace, so it can be said that there is a significant CO2 reduction effect.
  • the purpose of the present invention is to provide a method for controlling impurities in a molten aluminum scrap.
  • a method for controlling impurities in a molten aluminum scrap comprising: a step of melting a metal material including aluminum to form a molten aluminum and an impurity remover including boron; a step of reacting at least a portion of the impurities included in the metal material with the boron in the molten aluminum to form a reactant; and a step of separating the reactant from the molten aluminum, wherein the impurity includes a transition metal, the transition metal includes at least one of titanium, chromium, vanadium, and zirconium, and the reactant is in the form of MB 2 , wherein M is the transition metal, and the impurity remover is an alloy of boron and the aluminum.
  • the above boron alloy comprises 1 to 20 wt% boron, an additional component and the remainder aluminum, wherein the additional component comprises at least one of chromium, titanium, vanadium and zirconium, and the weight of the additional component can be 0.2 to 1.5 wt% of the boron.
  • the step of separating the reactants from the molten metal may include a step of first stirring the molten metal; a first dross removal step of removing dross after the first stirring; a step of precipitating the reactants in the molten metal after the first dross removal; a step of second stirring the molten metal after the precipitation; and a second dross removal step of removing dross after the second stirring.
  • the above precipitation can be performed for 30 minutes to 8 hours.
  • the temperature of the molten metal during the above precipitation may be 850 to 950°C.
  • the formation of the molten metal and the formation and removal of the impurities are performed in a melting furnace, and after the removal of the impurities, the step of discharging the molten metal from the melting furnace into a bath; and the step of injecting an impurity remover into the molten metal in the bath may be further included.
  • the above impurity remover can be added to the molten metal flowing in a straight direction without stirring from the outside of the melting furnace.
  • the amount of impurity remover added to the molten metal in the above bath may be 0.5 g to 2.0 g per kg of the molten metal.
  • the amount of impurity remover added to the molten metal in the above-mentioned bath may be 8% to 30% of the amount of impurity remover supplied to the molten metal in the melting furnace per molten metal weight.
  • the above-mentioned bath includes a spout, an upstream bath, a pond, a middle bath, a heating furnace, and a downstream bath, which are arranged sequentially along the direction of progression of the molten metal, and the impurity remover can be supplied to the upstream bath.
  • the above pond may have a vertical cross-sectional area in the direction of progression of the molten metal that is 3 to 30 times greater than that of the above upstream tank.
  • UBC Unsed Beverage Can
  • the present invention provides a method for controlling impurities in the process of manufacturing an aluminum deoxidizer and alloy using collected aluminum scrap.
  • Figure 1 is a flow chart of an impurity control method according to one embodiment of the present invention.
  • FIGS 2 and 3 show the melting furnace type used in the experimental example.
  • Figure 4 is a schematic diagram of a cross-section of a sample obtained in an experimental example.
  • Figure 5 is a schematic diagram of a cross-section of the molten metal in an experimental example.
  • Figure 6 shows the tank used in Experimental Example 7.
  • Figure 7 is a plan view of the heating furnace in Experimental Example 7.
  • Aluminum scrap uses various types of scrap as shown in Table 1.
  • the Ti content in each scrap can vary from 0.001 to 0.15 wt%.
  • the Cr content in each scrap can vary from 0.002 to 0.40 wt%. Although not limited thereto, the Cr content can be higher than the Ti content.
  • Other elements can be included to the extent of examples in Table 1. At this time, the content of impurities cannot be limited, and the type appears differently depending on the type of scrap.
  • the following description mainly exemplifies a process for manufacturing an aluminum deoxidizer from which impurities are removed (reduced) from aluminum scrap, but the present invention is not limited thereto.
  • the removal of impurities is mainly exemplified by the removal of titanium, but the present invention is not limited thereto.
  • % means weight % unless otherwise stated.
  • Scrap is mixed appropriately based on aluminum for each raw material, targeting the deoxidizer (S2).
  • the moisture and oil are dried in a drying zone (150 ⁇ 400°C) inside the melting furnace for several minutes to several tens of minutes, and then melting is carried out in the molten metal.
  • the melting temperature may be 700°C to 1300°C when radiant heat is used, and 550°C to 870°C or 650°C to 900°C when direct heat is used.
  • the melting time may take 1 hour to 8 hours depending on the mass to be dissolved.
  • S0 impurity remover or additive
  • pre-melted S0 B, Al-Bx, Al-Ti-B, etc.
  • a method of putting the additive in an additive tank and injecting it into a melting furnace can be used.
  • Figure 2 shows a case where a reflector furnace is used as a melting furnace
  • Figure 3 shows a case where a rotary furnace, induction furnace, or electric furnace is used as a melting furnace.
  • each reference number represents 1 for the melting furnace, 100 for the additive, 101 for the additive tank, 200 for the aluminum melt, 201 for the EMS, 202 for the melting furnace, 203a and 203b for the burners, and 204 for the atmosphere.
  • each instruction number indicates that 2 represents a melting furnace, 100 represents an additive, 101 represents an additive tank, 103 represents an additive inlet, 200 represents molten aluminum, 204 represents the atmosphere, 300 and 301 represent impellers, and 304 represents a spout.
  • S0 may be an aluminum-boron alloy.
  • the boron alloy may contain 0.1 to 20 wt % or 0.1 to 5 wt % boron and the remainder aluminum.
  • Boron in S0 forms an intermetallic compound with aluminum, specifically, it can be AlB 2 or AlB 12 , and it can be in the form of AlxByM1z with a third element (additional component) M1 in addition to aluminum and boron.
  • M1 contains V, Ti, Cr, Zr, etc., and it is also possible to use a material in which Ti is not present at all.
  • the weight of M1 can be 0.2 to 1.5% or 0.2 to 0.4% of the weight of B.
  • the amount of S0 used can be adjusted to be 0.1 to 5.0 times or 0.8 to 2.0 times the molar ratio of the transition metal in the scrap to be removed.
  • the amount of S0 used can be adjusted to 0.0005 to 1.2 times or 0.002 to 0.08 times the weight ratio of the metal material (aluminum scrap).
  • Equation 1 An example of the formation of a reactant (MB 2 ) is as shown in Equation 1 below.
  • Equation 1 AlB 2 (s,l) + M(l) ⁇ Al(l) + MB 2 (S)
  • Equation 2 AlB 12 (s,l) + M(l) ⁇ Al(l) + MB 2 (S)
  • the molten metal is stirred or ultrasonically treated to increase the effective collision number of AlB 2 or AlB 12 that did not react.
  • Primary stirring can be performed at 100 rpm to 400 rpm for 30 minutes to 8 hours or 3 hours to 5 hours.
  • EMS Electro magnetic stirrer
  • it can be 10 to 350 Hz, 100 to 300 Hz, 200 to 250 Hz or 150 to 250 Hz.
  • the molten metal injection method can provide convenience in terms of shortening the reaction time, safety during the operation process, environment, etc., and workability.
  • the next process is the first dross removal process, which is a process to remove dross generated after stirring and reaction of S0 (S5).
  • inert gas can be injected into the molten metal to remove impurities more effectively.
  • the use of inert gas can improve castability by surfacing and removing H + and oxides when manufacturing alloys.
  • S6 is a step for precipitating the reactants after stirring. This is done to increase the particle size of TiB 2 through precipitation and to facilitate removal of the precipitated ones from the bottom. In addition, by providing precipitation time, the reaction time of Ti and B can be increased.
  • the precipitation time can be from 30 minutes to 8 hours or from 1 hour to 2 hours.
  • the precipitation temperature can be from 680 to 950°C or from 720 to 800°C. Stirring may not be performed during the precipitation.
  • Secondary stirring can be performed at 100 rpm to 400 rpm for 30 minutes to 8 hours or 3 hours to 5 hours.
  • EMS Electro magnetic stirrer
  • it can be 10 to 350 Hz, 100 to 300 Hz, 200 to 250 Hz or 150 to 250 Hz.
  • the aluminum product has a constant chemical composition.
  • S0 once more (S10) added to the melting pot during the melting process, a product is manufactured in which the impurity content is stably maintained at a low level.
  • the amount of S0 supplied to the molten metal from the hot-water bath is 0.5 g to 2.0 g or 0.7 g to 1.3 g per kg of molten metal being poured.
  • the amount of S0 supplied to the molten metal from the hot-water bath is 8% to 30% or 10% to 20% of the amount of S0 supplied to the molten metal from the melting furnace per weight of the molten metal.
  • the hot water tank may be composed of a melting furnace wall (c1), a spout (c2), an upstream hot water tank (c3), a pond (c4), a midstream hot water tank (c5), a heating furnace (c6), a downstream hot water tank (c7), a filter zone (c8), and a casting (c9).
  • S0 may be injected from the double upstream hot water tank (c3), and the injection may be intermittent or continuous.
  • the tank especially the upper tank, may be a trench-shaped tank with a cover provided on the upper part.
  • S0 may be poured into the upper part of the molten metal by opening a part of the cover or by providing an inlet in the cover.
  • the molten metal into which S0 is injected in the upper stream flows in one direction without separate stirring.
  • the one direction can be a straight line.
  • the pond is intended to provide overflow protection. It can have a length and width that are two to five times larger than the upstream tank.
  • the reaction of Ti + B mainly occurs in the pond.
  • agitation may be applied to the pond to increase the reaction rate.
  • the reaction product of Ti + B exists in a space below the heater, so it accumulates there and can be periodically removed.
  • Table 3 compares the change in titanium concentration according to stirring time when S0 is introduced as a solution and when it is introduced by dissolving it in a solid.
  • this compares the case where S0 is melted at 700°C and then introduced, and the case where S0 is introduced as a solid at room temperature (25°C).
  • the reaction conditions were 780°C, 200rpm stirring speed, 500kg of aluminum raw material, and 1kg of additive 4 as S0.
  • the melting furnace type used was the same as that in Fig. 3.
  • the composition of the aluminum raw material is as shown in Table 4.
  • scraps 1, scraps 2, and scraps 5 were applied to manufacture aluminum deoxidizer molten sample 1
  • scraps 4 scraps 6, scraps 8, scraps 9, and scraps 10 were applied to manufacture aluminum deoxidizer molten sample 2, and an experiment was conducted.
  • S0 can be of the form AlxByM1z with a third element M1 other than aluminum and boron, examples of which are as follows.
  • the scrap was passed through S1 and S2 and then put into the melting furnace.
  • the melting furnace used type 3 and the scrap used was scrap 2 collected from UBC beverage cans generated domestically.
  • the basic reaction conditions were temperature 800°C, stirring speed 300rpm, 1.5kg of molten aluminum, 1 hour of melting, 7.5g of S0 addition, followed by S4 for 2 hours and S6 for 4 hours.
  • the initial Ti content in the molten metal was 244ppm.
  • the main conditions at this time were that S0 was not added, additive 4 of Table 2 in the AlxByM1z form and additive 5 in the AlxBy form were added respectively, and after going through steps S4, S5, and S6, it was quenched in a water tank.
  • the sample was cut from the deep part of the cut surface to the outside as shown in the schematic diagram of Fig. 4 and analysis was performed.
  • the cross-section was divided into six parts, and each side was cut into a grid pattern to conduct an analysis, divided into upper (1,2), middle (3,4), and lower (5,6).
  • Component analysis was conducted using ICP and S-OES, and the Ti precipitate at the bottom was analyzed using OM/SEM/EDS.
  • the Ti content was 2,900 ppm, and it was confirmed through the ICP results that a large amount of Ti was precipitated. It was confirmed that Ti, Cr, and V were concentrated in the lower part of 300 ⁇ m or less.
  • Table 6 shows the experimental results for Ti control according to stirring time.
  • Scrap was manufactured by appropriately mixing scrap 1, scrap 2, scrap 5, scrap 8, and scrap 9 of Table 1, which are UBC, Talic, and Taboo types, and the Al content was 94.5 wt% and the Ti content was 446 ppm.
  • the melting temperature was 850°C
  • the melting furnace type of Fig. 3 was used
  • the aluminum molten metal capacity was 1 ton
  • S0 additive 3 0.5 kg
  • the S4 times were 0 minutes, 30 minutes, 60 minutes, 90 minutes, 120 minutes, 160 minutes, 180 minutes, 210 minutes, and 240 minutes
  • S9 was performed directly without going through steps S5, S6, S7, and S8.
  • Table 6 shows the experimental results, which are the results of analyzing the Ti concentration using ICP/OES.
  • EMS Electro magnetic stirrer
  • EMP Electro magnetic pump
  • the agitator uses an impeller, and both EMS and EMP methods can be used in Melting Furnace 1, but only the agitator and EMP methods can be used in Melting Furnace 2.
  • an inert gas is injected during stirring to float the inclusions and oxygen in the molten metal, and after adding S0, the products such as TiBx, CrBx, CrMnx, and VBx can also be floated and removed with dross.
  • the melting temperature was 750°C, and type 2 of the melting furnace of Fig. 2 was used.
  • 200 kg of sample 3 1.6 kg of S0 additive 3, stirring speed 300 rpm, S4 was performed for 120 minutes, and then S4 was performed for an additional hour while purging Ar gas (25 LPM).
  • S7 was performed for 1 hour, and S9 was performed without performing S8.
  • the amount of Ti that can be removed by levitation was 37.2%, and the remaining 40% was removed by precipitation, so the total removal rate was 72.7%. From this, it can be confirmed that some Ti can be removed by levitation only by stirring. If the dross is removed after the first stirring, the Ti, Cr, etc. present in the molten metal can be reduced, and some of the remaining molten metal can be used for the next process.
  • the most important factors in precipitation reaction are temperature and time.
  • the temperature can be 680 ⁇ 950°C or 720 ⁇ 770°C.
  • high temperatures such as 850 ⁇ 950°C, rather than helping the precipitation reaction of aluminum, some TiB2 type compounds may float upward, which may hinder precipitation.
  • Table 8 shows the average results of analyzing the upper, middle, and lower parts of the sample after the reaction.
  • the sedimentation time showed a sedimentation removal rate of over 90% at 90 minutes and 240 minutes.
  • Fig. 8 when the lower part at 90 minutes and 240 minutes was observed by SEM, it was confirmed that the lower sedimentation layer was formed and sedimented.
  • the size increased further and formed a T-shape.
  • the results of analyzing the sample after the experiment showed that there were differences by section.
  • Table 8 shows the average analyzed by dividing the molten metal into levels as in Fig. 9, and Table 9 shows the results when the precipitation temperature is 900°C, from 30 to 240 minutes, with level 90 or higher being marked as the upper part, or “upper”, and level 30 or lower being marked as the lower part, or “lower” in the levels of Fig. 9.
  • the precipitation temperature is 850°C or higher
  • only the middle level of 30 to 90% can be used.
  • the Ti concentration in the upper part is high except for 90 minutes and 240 minutes.
  • the optimal time may be 90 minutes or 240 minutes, and S5 performance may be accompanied for the remaining times.
  • the molten metal can be discharged at the level of the controlled middle part by changing the height of the discharge port during discharge by dividing it by the level of the molten metal.
  • the molten metal was discharged at the level of the middle part where Ti was controlled by changing the height of the discharge port at the time of discharge by dividing it by the level of the molten metal. After S6, stirring (S7) was performed to increase the temperature for discharge again, and then discharge was performed.
  • the dross removal part of S8 can be omitted, but it can be confirmed that there is a removal effect of some Ti when the dross is removed. Since most of the dross and the surfaced Ti are removed in S5, it can be proceeded directly to S9.
  • Experiment A was conducted from S1 to S4, Experiment B from S1 to S6, and Experiment C from S1 to S7, and then the water was drained.
  • the results of analyzing the reactants of each experiment are shown in Table 11.
  • Fig. 6 shows the appearance of the discharge channel for discharging molten metal from the furnace.
  • the discharge channel appearance is described in detail here.
  • the depth of the discharge channel is approximately 400 mm, the width is 300 mm, and the total length is more than 3 m.
  • transition metal impurities in molten aluminum that adversely affect the decrease in electrical conductivity can be removed with an efficiency of 90% or more based on titanium by adding an appropriate boron alloy (aluminum boron master alloy) without facility investment or process change.
  • boron alloy aluminum boron master alloy

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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Abstract

La présente invention concerne un procédé d'élimination d'impuretés dans des déchets d'aluminium fondu, comprenant les étapes consistant à : faire fondre un matériau métallique contenant de l'aluminium, ce qui permet de former un métal fondu et un agent d'élimination d'impuretés contenant du bore ; faire réagir, dans le métal fondu, le bore avec au moins certaines des impuretés contenues dans le matériau métallique, ce qui permet de former un produit de réaction ; et séparer le produit de réaction du métal fondu, les impuretés contenant un métal de transition, le métal de transition comprenant au moins l'un parmi le titane, le chrome, le vanadium et le zirconium, le produit de réaction étant sous la forme de MB2, M étant le métal de transition, et l'agent d'élimination d'impuretés étant un alliage de bore et d'aluminium.
PCT/KR2024/019300 2023-12-11 2024-11-29 Procédé d'élimination d'impuretés dans des déchets d'aluminium fondu Pending WO2025127545A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2023-0178226 2023-12-11
KR20230178226 2023-12-11
KR1020240142847A KR102820014B1 (ko) 2023-12-11 2024-10-18 알루미늄 스크랩의 용탕 내 불순물 제어 방법
KR10-2024-0142847 2024-10-18

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09194964A (ja) * 1996-01-19 1997-07-29 Showa Alum Corp アルミニウムの精製方法
KR19990052862A (ko) * 1997-12-23 1999-07-15 신현준 붕화물 결정 제조방법
JP2000104128A (ja) * 1998-07-27 2000-04-11 Sumitomo Chem Co Ltd アルミニウムの精製方法および得られたアルミニウムの用途
JP2002173718A (ja) * 2000-12-06 2002-06-21 Nippon Light Metal Co Ltd アルミニウム処理方法
JP2002194453A (ja) * 2000-12-25 2002-07-10 Nippon Light Metal Co Ltd Ｔｉ，Ｖ，Ｂを低減するアルミニウム溶湯処理法
JP2007119855A (ja) * 2005-10-28 2007-05-17 Showa Denko Kk アルミニウム合金溶湯の処理方法、処理装置、鍛造用アルミニウム合金鋳塊の鋳造方法、鍛造成型品及びアルミニウム合金鋳塊の鋳造設備

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09194964A (ja) * 1996-01-19 1997-07-29 Showa Alum Corp アルミニウムの精製方法
KR19990052862A (ko) * 1997-12-23 1999-07-15 신현준 붕화물 결정 제조방법
JP2000104128A (ja) * 1998-07-27 2000-04-11 Sumitomo Chem Co Ltd アルミニウムの精製方法および得られたアルミニウムの用途
JP2002173718A (ja) * 2000-12-06 2002-06-21 Nippon Light Metal Co Ltd アルミニウム処理方法
JP2002194453A (ja) * 2000-12-25 2002-07-10 Nippon Light Metal Co Ltd Ｔｉ，Ｖ，Ｂを低減するアルミニウム溶湯処理法
JP2007119855A (ja) * 2005-10-28 2007-05-17 Showa Denko Kk アルミニウム合金溶湯の処理方法、処理装置、鍛造用アルミニウム合金鋳塊の鋳造方法、鍛造成型品及びアルミニウム合金鋳塊の鋳造設備

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