WO2015111698A1 - スカンジウム濃縮物の製造方法 - Google Patents

スカンジウム濃縮物の製造方法 Download PDF

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Publication number
WO2015111698A1
WO2015111698A1 PCT/JP2015/051828 JP2015051828W WO2015111698A1 WO 2015111698 A1 WO2015111698 A1 WO 2015111698A1 JP 2015051828 W JP2015051828 W JP 2015051828W WO 2015111698 A1 WO2015111698 A1 WO 2015111698A1
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WIPO (PCT)
Prior art keywords
scandium
aluminum
electrolysis
potential
molten
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PCT/JP2015/051828
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English (en)
French (fr)
Japanese (ja)
Inventor
高橋　純一
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住友金属鉱山株式会社
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Priority to EP15740883.2A priority Critical patent/EP3081671B1/de
Publication of WO2015111698A1 publication Critical patent/WO2015111698A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on 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
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32

Definitions

  • the present invention relates to a method for producing a scandium concentrate, and more particularly to a method for reusing an alloy containing scandium and aluminum as aluminum and scandium concentrate.
  • Aluminum scandium alloy containing aluminum and scandium (hereinafter also referred to as “Al—Sc alloy”) has characteristics of light weight and high strength, and is used not only for sports equipment but also in fields requiring impact resistance. . In addition, in the future, it is expected to be used as a structural material for aircraft, electric cars, high-speed railways and the like. However, scandium is very expensive because it produces very little. Therefore, it is not easy to use scandium widely industrially.
  • the scandium quality of these waste products and the like is much higher than the scandium quality of nickel oxide ore and the like, and it is expected that the scandium is recovered from the waste products and reused.
  • the quality of scandium such as waste is high, the element contained in the Al—Sc alloy is aluminum, and the scandium content is very small compared to the aluminum content. It is not possible to effectively recover the scandium concentrate simply by melting.
  • the present invention has been made to solve the above-described problems, and its purpose is to effectively recover a scandium concentrate from an Al—Sc alloy. More specifically, in a structure or the like, an Al—Sc alloy having a Sc concentration of 0.1 to 1% is often used. As described above, the Sc concentration of the Al—Sc master alloy is 1 to 2%.
  • the present invention efficiently produces a scandium concentrate that can be directly used as an Al—Sc master alloy from scrap products of an Al—Sc alloy having an Sc concentration of about 0.1 to 1% used in structures and the like. The purpose is to collect.
  • the present inventors contacted and melted an alloy containing aluminum and scandium, and then subjected the molten mixture to electrolysis under predetermined conditions.
  • the inventors have found that the above object can be achieved and have completed the present invention.
  • the present invention provides the following.
  • the present invention provides a molten mixture producing step of producing a molten mixture of aluminum chloride and scandium chloride by bringing chlorine into contact with and melting an alloy containing aluminum and scandium; A first electrolysis step that generates a molten aluminum by subjecting to a first electrolysis at a potential between a potential and a metalization potential of scandium, and after the molten aluminum generation step, the molten mixture is recovered and scandium is recovered. A second electrolysis step of subjecting to a second electrolysis at a possible potential to produce a scandium concentrate.
  • the alloy contacted with the chlorine may be applied to a chloride salt or eutectic salt melt having a melting point or eutectic temperature higher than 500 ° C.
  • the scandium concentrate can be effectively recovered from the Al—Sc alloy.
  • This scandium concentrate can be reused as it is as a high-quality Al—Sc master alloy. Further, scandium can be recovered through the solvent extraction or the like extremely efficiently compared to the case of recovery from nickel oxide ore.
  • FIG. 1 is a schematic view showing a method for producing a scandium concentrate according to the present invention.
  • This method includes a molten mixture generating step S1 in which a molten mixture of aluminum chloride and scandium chloride is produced by contacting and melting chlorine in an alloy containing aluminum and scandium, and the molten mixture is converted into a metallization potential of aluminum.
  • Scandium can be recovered from the molten mixture after the first electrolysis step S2 for producing molten aluminum by subjecting it to the first electrolysis at a potential between the metalization potential of scandium and the molten aluminum producing step S2.
  • a second electrolysis step S3 that is subjected to a second electrolysis at a low potential to produce a scandium concentrate.
  • a molten salt electrolysis method is used in which an ionic solid is melted at a high temperature and electrolyzed.
  • the melting point of aluminum is 660.5 ° C. and the molten salt is heated to a temperature higher than this melting point, the molten salt needs to have a melting point or eutectic temperature higher than 500 ° C.
  • the heating is performed to a temperature higher than the melting point of aluminum at the time of electrolysis, if the melting point or eutectic temperature is significantly lower than the melting point of aluminum, the activity of the salt increases as the temperature increases. Doing so increases the vapor pressure of the chloride and causes the salt to volatilize.
  • the salt composition gradually changes, and the electrolysis voltage continuously changes accordingly, making it difficult to appropriately control the electrolysis. For this reason, it is not preferable to use a molten salt whose melting point or eutectic temperature is significantly lower than that of aluminum.
  • the eutectic temperature of LiCl—KCl eutectic salt is 350 ° C., which is not preferable because the eutectic temperature is significantly lower than the melting point of aluminum.
  • molten salt whose melting point or eutectic temperature is close to the melting point of aluminum in that it does not require heating more than necessary during electrolysis.
  • the molten salt requires that the difference between the metalation potential of aluminum and the metalation potential of scandium be 0.8 V or more.
  • the electrolytic potential of the element varies depending on the type and composition of the molten salt.
  • the molten salt since aluminum and scandium coexist, only aluminum is generated in the first electrolysis, and scandium is generated for the first time in the second electrolysis. Therefore, the molten salt has the metalation potential of aluminum. Therefore, it is necessary to have a certain difference from the metalation potential of scandium.
  • the difference is preferably larger, more preferably 1.0 V or more, and further preferably 1.2 V or more.
  • the metallization potential of Al 3+ in the Ag + / Ag electrode system at 450 ° C. of the LiCl—KCl eutectic salt is ⁇ 1.04 V
  • the metallization potential of Sc 3+ is ⁇ 1.83 V.
  • the difference between the two is about 0.8 V, which is sufficient to suppress the formation of both aluminum and scandium in the first electrolysis.
  • a chloride-based salt does not cause a significant difference in the metalation potential even if the types of metal elements constituting the salt are different.
  • the scandium concentrate can be efficiently recovered.
  • NaCl—KCl eutectic salt eutectic temperature: 660 ° C.
  • the stability is high and the change in composition can be suppressed. Further, it is not necessary to heat more than necessary during electrolysis. And it can suppress that both aluminum and a scandium produce
  • the heating temperature of the molten salt is sufficient if it can sufficiently melt the Al—Sc alloy.
  • the liquidus temperature of the Al—Sc alloy varies depending on the concentration of scandium contained in the Al—Sc alloy.
  • the liquidus temperature of the Al—Sc alloy can be obtained by referring to a known phase diagram of the Al—Sc alloy. For example, when the scandium concentration is about 0.2 to 0.4%, the liquidus temperature of the Al—Sc alloy is about 660 ° C. which is the eutectic temperature. On the other hand, the higher the scandium concentration contained in the Al—Sc alloy, the higher the liquidus temperature.
  • the liquidus temperature when the scandium concentration is 1% is about 730 ° C., and the liquidus temperature when the scandium concentration is 2%.
  • the line temperature exceeds 800 ° C.
  • the above mixture that is, a mixture of aluminum chloride and scandium chloride is dissolved in a molten salt heated to such an extent that the Al—Sc alloy can be sufficiently melted. Since the saturated vapor pressure of aluminum chloride is different from the saturated vapor pressure of scandium chloride, when the mixture is dissolved in the molten salt, a part of aluminum chloride (AlCl 3 ) is volatilized, while the remaining aluminum chloride and Scandium chloride (ScCl 3 ) is easily melted into the eutectic salt and becomes a uniform melt.
  • first electrolysis step S2 Subsequently, the first electrolysis step S2 will be described.
  • the molten mixture obtained in the molten mixture generation step S1 is subjected to the first electrolysis at a potential between the metalation potential of aluminum and the scandium metalization potential to produce molten aluminum. To do.
  • the type of electrode is not particularly limited, and examples thereof include using silver as a reference electrode, graphite as an anode, and nickel as a cathode.
  • the potential in the first electrolysis needs to be between the metalation potential of aluminum and the metalation potential of scandium, more specifically, not more than the metalation potential of aluminum and not less than the metalation potential of scandium. If it is not in this range, not only molten aluminum but also scandium can be generated at the cathode, which is not preferable.
  • the potential in the first electrolysis is preferably close to the metalation potential of aluminum. Specifically, it is preferably in the range of ⁇ 1.50 V or more and ⁇ 1.04 V or less, and ⁇ 1.30 V. More preferably, it is in the range of ⁇ 1.10 V or less.
  • the temperature of the molten salt is not particularly limited as long as it is higher than the melting point of aluminum. However, from the viewpoint of minimizing the energy cost and suppressing the generated aluminum from becoming a solid, the temperature of 380 ° C. to 500 ° C. It is preferable that it is °C or less, more preferably 390 ° C or more and 450 ° C or less.
  • the first electrolysis it is preferable to store aluminum together with the molten salt in a storage container in advance. Since the inside of the storage container is heated to a temperature higher than the melting point of aluminum, the stored aluminum is used as an aluminum electrode (cathode) through the nickel. Then, through the first electrolysis, new aluminum generated by the electrolysis of the Al—Sc alloy is dissolved in the already melted aluminum. As a result, the concentration of scandium contained in the molten salt increases.
  • a part of the aluminum obtained by the first electrolysis is taken out of the storage container by tilting the storage container before performing the second electrolysis.
  • the type of electrode is not particularly limited, and the same electrode as that used in the first electrolysis can be used.
  • the potential in the second electrolysis needs to be able to recover scandium, more specifically, it must be less than or equal to the metalization potential of scandium. If it is not within this range, the liquid scandium does not dissolve in the liquid aluminum obtained by the first electrolysis at the cathode, which is not preferable.
  • the potential in the second electrolysis may be ⁇ 1.83 V or less, but it is preferably ⁇ 2.0 V or less in consideration of the stability of operation.
  • the amount of aluminum stored in advance in the storage container can be arbitrarily set according to the target scandium quality of the scandium concentrate.
  • the temperature of the molten salt is not particularly limited as long as it is higher than the temperature of the liquid phase line of the Al—Sc alloy contained in the molten salt. However, in view of operational stability, the liquid phase line of the Al—Sc alloy is not limited.
  • the temperature is preferably 5 ° C. or higher, more preferably 10 ° C. or higher.
  • the scandium concentrate of the present invention may be reused as it is as a high-quality Al—Sc master alloy, or may be reused after remelting to form a master alloy. Further, by recovering scandium from a scandium concentrate by a known method such as solvent extraction, scandium can be recovered extremely efficiently as compared with the case of recovering from nickel oxide ore.
  • FIG. 2 is a schematic diagram illustrating the configuration of the electrolyzer 1 used in this embodiment.
  • the electrolysis apparatus 1 includes a quartz container 2 that encloses an Al—Sc alloy together with a dissolved salt, one opening, a quartz tube 3 that accommodates the quartz container 2 from the opening, and a rubber plug 4 that seals the quartz tube 3.
  • chlorine was brought into contact with an Al—Sc alloy having a scandium concentration of 1% to chlorinate the alloy.
  • the resulting chloride had a scandium grade of about 10%.
  • chlorine gas is introduced into the quartz tube 3 through the gas replacement unit 8 at a flow rate of 0.1 liter / min. Feed for minutes.
  • the reference electrode (silver) 5, the anode (graphite) 6 and the cathode (nickel) 7 are immersed in the position shown in FIG. 2, and the potential of the Ag + / Ag reference electrode 5 is kept at a potential of ⁇ 1.25V.
  • a first electrolysis was performed. As a result, aluminum was recovered from the bottom of the quartz container 2 through the cathode 7.
  • the energization was stopped once, the inside of the quartz tube 3 was depressurized, and about 10 g of aluminum produced by the first electrolysis was sucked out.
  • the inside of the quartz tube 3 was heated to 880 ° C., and second electrolysis was performed.
  • aluminum remaining in the bottom of the quartz container 2 was mixed with aluminum and scandium eluted from the Al—Sc alloy contained in the molten salt, and a scandium concentrate was obtained.
  • the inside of the quartz tube 3 was cooled to room temperature. Then, the salt 12 (mixture of aluminum and NaCl—KCl eutectic salt) and the scandium concentrate 13 solidified by this cooling were taken out.
  • Each of the aluminum recovered by the first electrolysis and the scandium concentrate 13 recovered by the second electrolysis was analyzed using a fluorescent X-ray analyzer (XRF) and ICP mass spectrometry.
  • the purity of the aluminum metal contained in the aluminum recovered by the first electrolysis exceeded 98%, and the scandium concentrate 13 recovered by the second electrolysis was approximately 3.5%. From this, the aluminum recovered by the first electrolysis can be reused as aluminum, and the scandium concentrate 13 recovered by the second electrolysis can be reused as a high-grade Al—Sc master alloy. confirmed.

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PCT/JP2015/051828 2014-01-27 2015-01-23 スカンジウム濃縮物の製造方法 WO2015111698A1 (ja)

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Application Number Priority Date Filing Date Title
EP15740883.2A EP3081671B1 (de) 2014-01-27 2015-01-23 Scandiumkonzentratherstellungsverfahren

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JP2014-012667 2014-01-27
JP2014012667A JP5907188B2 (ja) 2014-01-27 2014-01-27 スカンジウム濃縮物の製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115011805A (zh) * 2022-01-19 2022-09-06 昆明理工大学 一种从冶炼渣中回收钪和铝的方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TR201704220A2 (tr) * 2017-03-21 2018-03-21 Minertek Mineral Teknolojileri Madencilik Sanayi Ve Ticaret Anonim Sirketi (NH4)2NaScF6 formundaki skandiyum bileşiğinden elde edilen ScF3 bileşiğine, CaCl2 ve/veya MgCl2 bileşiklerinin ilavesiyle oluşturulan, skandiyum tuz karışımlarından elektroliz yöntemi vasıtasıyla skandiyum metali ve Al-Sc alaşımlarının üretim metodu
CN107630234B (zh) * 2017-09-18 2019-09-17 江西理工大学 一种利用氯盐氧化物体系熔盐电解制备铝钪中间合金的方法
JP7361058B2 (ja) * 2018-03-15 2023-10-13 エフイーエー マテリアルズ エルエルシー アルミニウム－スカンジウム合金の製造方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2003171724A (ja) 2001-12-07 2003-06-20 Aomori Prefecture Ａｌ−Ｓｃ母合金の製造法およびその方法によって得られたＡｌ−Ｓｃ母合金
JP2007254822A (ja) * 2006-03-23 2007-10-04 Taiheiyo Kinzoku Kk スカンジウム含有合金の製造方法およびこの方法により得られたスカンジウム含有合金
JP2012136766A (ja) * 2010-12-28 2012-07-19 Kyoto Univ 電気分解による金属の製造方法

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US2874039A (en) * 1954-06-17 1959-02-17 Pechiney Prod Chimiques Sa Extraction of scandium from its ores
US6808695B1 (en) * 2000-05-22 2004-10-26 Toth Aluminum Corporation Process for continuously producing aluminum from clays
JP5472897B2 (ja) * 2008-12-09 2014-04-16 株式会社東芝 画像処理装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003171724A (ja) 2001-12-07 2003-06-20 Aomori Prefecture Ａｌ−Ｓｃ母合金の製造法およびその方法によって得られたＡｌ−Ｓｃ母合金
JP2007254822A (ja) * 2006-03-23 2007-10-04 Taiheiyo Kinzoku Kk スカンジウム含有合金の製造方法およびこの方法により得られたスカンジウム含有合金
JP2012136766A (ja) * 2010-12-28 2012-07-19 Kyoto Univ 電気分解による金属の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115011805A (zh) * 2022-01-19 2022-09-06 昆明理工大学 一种从冶炼渣中回收钪和铝的方法

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JP2015140446A (ja) 2015-08-03
JP5907188B2 (ja) 2016-04-26
EP3081671A1 (de) 2016-10-19
EP3081671A4 (de) 2016-12-21
EP3081671B1 (de) 2017-08-02

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