WO2022092231A1 - 再生アルミニウムの製造方法、製造装置、製造システム、再生アルミニウム、及び、アルミニウム加工物 - Google Patents

再生アルミニウムの製造方法、製造装置、製造システム、再生アルミニウム、及び、アルミニウム加工物 Download PDF

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WO2022092231A1
WO2022092231A1 PCT/JP2021/039898 JP2021039898W WO2022092231A1 WO 2022092231 A1 WO2022092231 A1 WO 2022092231A1 JP 2021039898 W JP2021039898 W JP 2021039898W WO 2022092231 A1 WO2022092231 A1 WO 2022092231A1
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Prior art keywords
aluminum
aluminum alloy
cathode
anode
recycled
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English (en)
French (fr)
Japanese (ja)
Inventor
徹也 長坂
鴻民 朱
岳人 平木
シン ルー
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Tohoku University NUC
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Tohoku University NUC
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Priority to JP2022559245A priority Critical patent/JPWO2022092231A1/ja
Priority to CN202180072703.3A priority patent/CN116615578A/zh
Priority to US18/033,516 priority patent/US20230392273A1/en
Priority to DE112021004433.8T priority patent/DE112021004433T5/de
Publication of WO2022092231A1 publication Critical patent/WO2022092231A1/ja
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    • 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
    • C25C3/24—Refining
    • 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
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • 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
    • C25C3/18—Electrolytes
    • 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
    • C22B21/0038—Obtaining aluminium by other processes
    • C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
    • 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 is configured to be operable by wiring a plurality of recycled aluminum manufacturing methods, recycled aluminum manufacturing devices, recycled aluminum manufactured from the manufacturing method and manufacturing devices, and recycled aluminum manufacturing devices as one system. Regarding the manufacturing system of recycled aluminum and aluminum processed products processed from recycled aluminum. This application claims priority based on Japanese Patent Application No. 2020-180899 filed in Japan on October 28, 2020, the contents of which are incorporated herein by reference.
  • Aluminum is a typical metal material that consumes about 1.8 million tons of bullion in Japan and 58 million tons in the world (both in 2017), and is recognized as one of the three major social base metal materials along with iron and copper. ing.
  • aluminum having a purity of about 99.7% to 99.98% is manufactured by a combination of the Bayer method and the Hall-Héroult method for a long time (primary electrolytic refining).
  • the Bayer method is a method for producing alumina by dissolving and extracting the alumina content in bauxite in caustic soda
  • the Hall-Héroult method is a method for producing aluminum by dissolving the alumina in an electrolytic bath and electrolyzing it. ..
  • the Hall-Héroult method is a method that can electrolyze alumina with a melting point of over 2000 ° C at an operating temperature of about 1000 ° C.
  • the electrolytic bath was discovered by Mr. Hall and Mr. Eru about 120 years ago, and aluminum. Has developed as an industrial manufacturing method.
  • two types of methods are industrially adopted.
  • One is a three-layer electrolysis method, and one is a fractional crystallization method.
  • the three-layer electrolysis method is similar to the Hall-Héroult method described above.
  • Primary electrolytic aluminum which is the raw material, is inserted into the alloy layer containing copper (Cu), and by passing electricity, only aluminum, which has a lighter specific gravity than copper, is removed.
  • Non-Patent Document 1 discloses the structure of an electrorefining furnace, an electrolysis bath (mass%), an electrolysis temperature, and the like.
  • the fractional crystallization method is a method in which high-purity aluminum having a purity of about 99.98 to 99.996% is crystallized and separated by melting primary electrolytic aluminum as a raw material and locally cooling the aluminum.
  • these three major social base metal materials are extremely rarely used as pure metals except for copper as a conductive material (electrocopper: purity 99.99%), and in most cases, some other element is used. It is used as an alloy containing.
  • Aluminum is recognized as a metal that is well recycled in terms of quantity, but in terms of quality (composition), as the number of times of recycling increases, alloying elements accumulate and the downgrade of secondary products progresses. This is the actual situation of aluminum recycling. Except for a few cases where partial sorting is performed in a dislike of mixing some elements, scrap sorting by standard is not performed. That is, used aluminum products such as building materials such as aluminum cans and sashes or cast aluminum products are melted together as scrap and reused as secondary aluminum, but the composition cannot be controlled, so the component specifications are strict. It is extremely rarely used in materials, and is used in cast products that allow a large amount of alloying elements to be contained.
  • the recycled aluminum (secondary aluminum) melted from the scraps is cast materials, die castings, etc. (hereinafter referred to as die casting). It may be described as "casting material"), which is a major industrial problem. That is, the current aluminum is limited to use for downgrade recycling.
  • the inventors have diligently studied and at a temperature at which recycled aluminum (secondary aluminum) melted from aluminum cast material scrap is in a solid state and the molten salt is in a liquid state, the alloy anode and cathode made of the recycled aluminum are used. Removal of alloying elements from aluminum cast material scrap and regeneration / recovery as high-purity aluminum by a purification method that reduces impurity elements from the regenerated aluminum (secondary aluminum) by means of molten salt electrolysis energized between and. Demonstrated what can be done. Not only can-to-can horizontal recycling, which is not possible at present, but also upgrade recycling from cast materials to wrought materials is possible. The industrial impact of the latter is enormous, and even if the demand for cast materials drops sharply, it will be possible to produce wrought materials domestically without importing new aluminum metal from overseas.
  • the present invention has been made in view of the above circumstances, and is a method, manufacturing apparatus, manufacturing system, recycled aluminum, and a method for manufacturing recycled aluminum in which the concentration of alloying elements contained is significantly reduced as compared with the original aluminum alloy material. , Aims to provide aluminum workpieces.
  • the "method for producing recycled aluminum” means that alloying elements can be removed from recycled aluminum (secondary aluminum) melted from such aluminum casting scrap and recycled / recovered as high-purity aluminum.
  • the method is abbreviated as "method for manufacturing recycled aluminum”. That is, in the present specification, "recycled aluminum” means "high-purity regenerated aluminum” in which the concentration of alloying elements is significantly reduced from “recycled aluminum (secondary aluminum)", and the original aluminum casting.
  • the aluminum alloy melted from the material scrap (recycled aluminum (secondary aluminum)) is described as "aluminum alloy” to distinguish the notation.
  • the present invention provides the following means for solving the above problems.
  • the aluminum alloy anode and the cathode are arranged facing each other in the molten salt, the aluminum alloy anode is in a solid state, and the molten salt is formed. It has a step of energizing between the aluminum alloy anode and the cathode at a temperature in which the aluminum alloy is in a liquid state to ionize and elute aluminum from the aluminum alloy anode and deposit aluminum precipitates on the cathode.
  • the method for producing recycled aluminum according to the above aspect is such that the aluminum alloy anode and the cathode have a flat plate shape, and the flat plate-shaped aluminum alloy anode and the flat plate-shaped cathode are arranged so as to face each other.
  • the cathode may be rod-shaped, and a plate-shaped aluminum alloy anode arranged concentrically around the rod-shaped cathode may face the cathode.
  • anode mud anode slime containing an impurity element that does not ionize may be further precipitated from the aluminum alloy anode.
  • the method for producing recycled aluminum according to the above aspect may be one produced by a method having an anode manufacturing step for manufacturing the aluminum alloy anode by melting aluminum alloy scrap.
  • the conductivity of the molten salt may be 1Sm -1 or more.
  • the temperature may be room temperature or higher and 660 ° C. or lower.
  • the molten salt may contain 1.5 to 35% by mass of AlF 3 in the molten salt.
  • the method for producing recycled aluminum according to the above aspect may include a step of taking out the settling anode mud.
  • the direction in which the aluminum alloy anode and the cathode are arranged facing each other may be arranged in substantially the same direction as gravity.
  • the aluminum alloy anode and the cathode are arranged in the molten salt so as to face each other, the aluminum alloy anode is in a solid state, and the molten salt is present.
  • a means for energizing between the aluminum alloy anode and the cathode at a temperature in which is in a liquid state is provided, aluminum is ionized from the aluminum alloy anode, aluminum is deposited on the cathode, and the aluminum alloy anode is not ionized.
  • Anode mud (anode slime) containing an impurity element can be settled.
  • a plurality of anodes and cathodes in which the aluminum alloy anode and the cathode are arranged facing each other may be arranged in the molten salt.
  • the apparatus for producing recycled aluminum according to the above aspect further includes means for wiring a plurality of anodes and cathodes in which the aluminum alloy anode and the cathode are arranged so as to face each other and energizing them in parallel or in series. May be good.
  • the recycled aluminum manufacturing system according to the third aspect of the present invention is configured to be operable by wiring a plurality of the recycled aluminum manufacturing devices as one system.
  • the recycled aluminum according to the fourth aspect of the present invention is recycled aluminum produced by the above-mentioned method for producing recycled aluminum.
  • the recycled aluminum according to the above aspect has a Si concentration of 0.001% by mass or more and 1% by mass or less and a Cu concentration of 0.001% by mass or more and 0.5% by mass or less.
  • the aluminum work piece according to the fifth aspect of the present invention is an aluminum work piece processed from the above-mentioned recycled aluminum.
  • the anode slime according to the sixth aspect of the present invention is obtained by producing recycled aluminum by using the above-mentioned method for producing recycled aluminum.
  • recycled aluminum having high aluminum purity with a significantly reduced concentration of alloying elements can be produced from an aluminum alloy material such as cast aluminum scrap with low energy consumption.
  • FIG. 1 This is an example of a schematic vertical cross-sectional view in which a plate-shaped aluminum alloy anode arranged concentrically around a rod-shaped cathode is arranged so as to face the cathode in a solid electrolyzer energized by the method for manufacturing recycled aluminum.
  • (A) is an aluminum alloy anode used as a raw material in the method for producing recycled aluminum according to the embodiment of the present invention, anodized mud (anodide slime) by-produced by energization, and aluminum deposited on the cathode side by energization.
  • FIG. 1 is a manufacturing process flow diagram showing a flow of a manufacturing process included in an example of the method for manufacturing recycled aluminum according to an embodiment of the present invention.
  • FIG. 3 is a schematic vertical sectional view showing an example of a solid electrolysis apparatus for carrying out a solid electrolysis step of a method for producing recycled aluminum.
  • “recycled aluminum” is not limited to high-purity aluminum (purity of about 99.98% to 99.998%), which is generally called pure aluminum, and is derived from aluminum scrap raw materials having various compositions. It includes all those containing an alloy element, which are regenerated by reducing the alloy element (impurity element) by the method of the present invention. Further, the "recycled aluminum” is not limited in shape, and is included in the “recycled aluminum” if it is made of recycled aluminum such as an ingot, a plate material, a bar material, a foil material, an amorphous lump, and fine particles. .. Further, “regeneration” means that the concentration of alloying elements is reduced as compared with the original aluminum alloy material.
  • an aluminum alloy anode formed from an aluminum scrap raw material is regenerated into aluminum having higher purity by removing alloying elements in the aluminum alloy by the method for producing recycled aluminum of the present invention.
  • a method for manufacturing recycled aluminum As the aluminum alloy anode, for example, when an aluminum casting scrap melted and processed into an anode shape is used, the content concentration of the aluminum casting material is reduced as compared with the alloy element of the original aluminum casting scrap. It can be recycled into aluminum wrought materials.
  • each manufacturing step in the case of having a step of manufacturing an aluminum alloy anode will be described with reference to FIGS. 1 and 3.
  • the aluminum alloy scrap melting step 101 is performed as necessary when manufacturing the aluminum alloy anode, and can be arbitrarily performed by a known aluminum alloy melting method. In the method for producing recycled aluminum of the present invention, it is not an essential step when the aluminum alloy material of the raw material to be recycled can be used as it is as an anode.
  • the “aluminum alloy scrap” typically includes scraps of used aluminum products, but is not limited to this, and includes all aluminum alloy scraps to be recycled. Further, the number of "aluminum alloy scraps" to be melted may be one or a plurality. Examples of the “aluminum alloy scrap” include scrap of cast material, scrap of wrought material, and mixed scrap of cast material and wrought material.
  • alloying elements contained in "aluminum alloy scrap" include more than 50 types shown in JIS standards, and typical ones are Mg, Cu, Si, and Fe. , Zn, Mn and the like. When it is regenerated into a high-purity aluminum alloy by the method for producing recycled aluminum of the present invention, it means that the concentration of one or more of these alloying elements has been reduced.
  • the concentration of alloying elements contained in "aluminum alloy scrap” is not limited in principle, but is, for example, 30% or less when scrap of used aluminum products is used.
  • the "concentration” and “purity” of alloying elements and aluminum mean mass% unless otherwise specified.
  • concentration of the contained alloying element is 20% or less.
  • concentration of the alloy element contained is 10% or less.
  • the aluminum alloy anode manufacturing step 102 typically includes processing into the shape of the anode (for example, processing into a plate shape), but other steps performed for manufacturing the aluminum alloy anode in general. Is included. In the method for producing recycled aluminum of the present invention, it is not an essential step when the aluminum alloy material to be recycled can be used as it is as an anode.
  • the aluminum alloy anode and the cathode are arranged and immersed in the molten salt so as to face each other, and the aluminum alloy anode and the cathode are immersed at a temperature at which the aluminum alloy anode is in the solid state and the molten salt is in the liquid state. It is a step of melting the aluminum alloy anode by energizing between the two, and at the same time, the aluminum precipitate is deposited on the cathode.
  • a configuration in which the aluminum alloy anode and the cathode are arranged facing each other for example, a configuration in which the flat plate-shaped aluminum alloy anode and the flat plate-shaped cathode are arranged facing each other (FIG. 4, etc.) or a rod shape is used. It is possible to exemplify a configuration in which plate-shaped aluminum alloy anodes are arranged concentrically around the cathode of the above and face each other. In addition to these configurations, known configurations usually used in electrolysis can be used.
  • the aluminum alloy anode and the cathode are arranged so as to face each other substantially in parallel. This is because the distance between the electrodes is constant over the entire surface of the electrodes because they are substantially parallel, so that the aluminum ions are uniformly separated from the surface of the aluminum alloy anode.
  • FIG. 2 shows an SEM image of a cross section of the aluminum alloy anode after performing the solid electrolysis step.
  • the SEM image was obtained by FE-SEM (JXA-8530F (manufactured by JEOL Ltd.)) at an acceleration voltage of 15 kV.
  • As the electric field conditions LiCl-KCl-5 mol% AlF 3 at 500 ° C. was used in an electrolytic bath, an aluminum cast alloy AC2A was used as an aluminum alloy anode, a pure aluminum plate was used as a cathode, and the anode current density was 200 mAcm -2 . Electrolysis was performed for hours. From the SEM image, it can be seen that the surface side of the aluminum alloy anode has a porous structure.
  • Table 1 also shows the results of composition analysis (ICP-AES) of the aluminum alloy anode before electrolysis and the porous structure after electrolysis. It can be seen that the proportion of Al is significantly reduced in the porous structure after electrolysis. From the SEM image and the result of the composition analysis, it is considered that the porous structure formed on the surface side of the aluminum alloy anode is caused by the aluminum ions escaping from the surface of the aluminum alloy anode in the solid state. .. Further, in the porous structure after electrolysis, the concentrations of impurities such as Si and Cu are significantly increased. Therefore, it is shown that impurities such as Si and Cu are the main elements constituting the skeleton of the porous structure.
  • ICP-AES composition analysis
  • the impurity element in the aluminum alloy anode may settle as anode mud (slime) depending on its concentration and the like.
  • the impurity element when the impurity concentration is high to some extent, the impurity element remains in the porous structure on the surface side, but a part of this porous structure may fall off to become slime, and when the impurity concentration is low. Settles as slime, as is known in copper electrolysis.
  • the precipitation separation of the anode mud precipitates in the direction of gravity of the aluminum alloy anode and the cathode, the anode mud can be easily separated and taken out. Therefore, the direction in which the aluminum alloy anode and the cathode are arranged so as to face each other is arranged in substantially the same direction as gravity.
  • FIG. 3 is a schematic vertical sectional view of an example of a solid electrolyzer included in the recycled aluminum manufacturing apparatus according to the embodiment of the present invention.
  • the solid electrolysis apparatus 10 for carrying out the solid electrolysis step includes an anode holding portion 2 for holding an aluminum alloy anode 1, a cathode 3, and an electrolytic cell 5 for accommodating a molten salt 4.
  • the aluminum alloy anode 1 is provided with a heating device 6 capable of holding the molten salt 4 at a temperature in which the molten salt 4 is in a liquid state, and a power source 7 for energizing between the aluminum alloy anode 1 and the cathode 3.
  • the aluminum alloy anode 1 is attached to the anode holding portion 2, and the molten salt 4 is placed in the electrolytic cell 5.
  • molten salt a chloride-based molten salt, a fluoride-based molten salt, a bromide-based molten salt, a mixed salt thereof, or the like can be used.
  • chloride-based molten salt for example, KCl, NaCl, CaCl 2 , LiCl, RbCl, CsCl, SrCl 2 , BaCl 2 , MgCl 2 , or a mixed salt thereof can be used.
  • the fluoride-based molten salt for example, LiF, NaF, KF, RbF, CsF, MgF 2 , CaF 2 , SrF 2 , BaF 2 , AlF 3 , or a mixed salt thereof can be used.
  • AlF 3 is contained in the molten salt.
  • AlF 3 is preferably contained in the molten salt in the range of 1.5 to 35% by mass, more preferably in the range of 3 to 25% by mass, and in the range of 6 to 15% by mass. It is more preferably contained in.
  • AlF 3 is preferably contained in the molten salt in the range of 1 to 28 mol%, more preferably in the range of 2 to 14 mol%, and contained in the range of 4 to 10 mol%. It is more preferable to be done. Further, from the viewpoint of lowering the melting point of the molten salt, it is effective to positively contain an aluminum halide.
  • the aluminum halide include aluminum fluoride (AlF 3 ), aluminum chloride (AlCl 3 ), aluminum bromide (AlBr 3 ) and the like.
  • AlF 3 aluminum fluoride
  • AlCl 3 aluminum chloride
  • AlBr 3 aluminum bromide
  • the use of aluminum fluoride is preferable to aluminum chloride from the viewpoint of reducing changes in the composition of the electrolytic bath due to evaporation and from the viewpoint of facilitating continuous electrolysis.
  • the molten salt may intentionally contain other components as unavoidable impurities or other components as long as the effects of the present invention are exhibited.
  • aluminum alloy scrap may usually contain an element of Mg, and therefore Mg is mixed with the molten salt in the solid electrolysis step.
  • a chloride-based molten salt such as LiCl-KCl eutectic salt (Example) or NaCl-KCl
  • MgCl 2 such as MgCl 2 -LiCl-KCl or MgCl 2 -NaCl-KCl. It may be a eutectic salt, but even in this case, the effect of the present invention is exhibited.
  • an inexpensive MgCl 2 -NaCl-KCl system can be preferably used as the chloride-based molten salt.
  • the applicable temperature range of the molten salt can be adjusted, which is preferable.
  • MgCl 2 is preferably in the range of 1 to 70% by mass, preferably in the range of 10 to 60% by mass, and more preferably in the range of 20 to 50% by mass in the molten salt of the MgCl 2 -NaCl-KCl system.
  • an ionic liquid made of a known organoaluminum compound can be used as the molten salt.
  • organoaluminum compounds are ions composed of aluminum chloride (AlCl 3 ) and 1-ethyl-3-methylimidazolium chloride ([EtMeIm] Cl). Examples include liquids (light metals, Vol. 69, No. 1 (2019), 15-21).
  • the density of the molten salt is preferably as small as possible in order to facilitate precipitation separation of alloy components such as Cu and Si from the aluminum alloy anode as slime. From this point of view, for example, a molten salt having a density equal to or lower than that of pure aluminum (2.70 g / cm 3 near room temperature and 2.375 g / cm 3 near the melting point (660 ° C.)) can be used.
  • the cathode is not limited to these, and any electrode material from which the deposited aluminum can be peeled off may be used, and for example, stainless steel, carbon, nickel, iron and the like can be used.
  • the temperature at which the solid electrolysis step is performed is the temperature at which the aluminum alloy anode is in the solid state and the molten salt is in the liquid state.
  • the temperature can be set in the range of room temperature or higher and 660 ° C or lower.
  • the temperature at which the solid electrolysis step is performed is preferably in the range of 150 to 600 ° C, more preferably in the range of 300 to 550 ° C, and further preferably in the range of 450 to 550 ° C. preferable.
  • the temperature does not exceed 660 ° C. because the melting point of pure aluminum is 660 ° C. and the melting point is lowered when the alloy component enters.
  • the melting point drops to about 570 ° C.
  • the molten salt is in a liquid state
  • the molten salt is in a molten state
  • FIGS. 4, 6 and 9 are schematic vertical cross-sectional views showing another example of the solid electrolysis apparatus for carrying out the solid electrolysis step of the method for producing recycled aluminum.
  • Figures 4 and 9 also include figures, letters, and symbols for conceptually explaining the phenomena that occur in the solid electrolysis process.
  • the aluminum alloy anode 11 and the cathode 13 are alternately arranged in the molten salt 14 in the electrolytic cell 15 substantially parallel to each other and facing each other. That is, in the molten salt, the anode and the cathode in which the aluminum alloy anode 11 and the cathode 13 are arranged substantially in parallel and facing each other are arranged in a plurality of pairs. Further, the anode and the cathode do not have to be paired (FIG. 5), and the anode and the cathode may be arranged facing each other and alternately. In FIG.
  • reference numeral 20 is an anode slime, and the case where the anode slime has settled is shown as an example.
  • FIG. 4 shows an enlarged view of a portion where the aluminum alloy anode 11, the cathode 13, and the anode slime 20 are close to each other, which are indicated by circles.
  • a basket may be provided below the aluminum alloy anode 11, for collecting the anode slime that has fallen from the aluminum alloy anode 11.
  • four plate-shaped aluminum alloy anodes 21 arranged concentrically are arranged around the rod-shaped cathode 23. The configuration facing the cathode 23 is illustrated.
  • the plate-shaped aluminum alloy anode 21 is arranged in an arc shape when viewed from above.
  • the plate-shaped aluminum alloy anode 21 is not limited to four, and may be two, six, eight, or the like. Further, it may be a single cylindrical shape connected without a break.
  • the one plate-shaped aluminum alloy anode 21 does not necessarily have to be arranged in an arc shape when viewed from above, and may be four flat plates arranged in a square peripheral shape, and may be arranged in a regular hexagonal peripheral shape. It may be 6 flat plates, or 8 flat plates arranged in a regular octagonal circumferential shape.
  • the porous body include, but are not limited to, glass cloth and ceramic fiber molded products having a high alumina content.
  • a large-scale device provided with means for energizing a plurality of pairs (pairs) of an anode and a cathode in which an aluminum alloy anode and a cathode are arranged facing each other in parallel or in series. You may do it.
  • the current density is desired to be high from the viewpoint of increasing the aluminum precipitation rate and improving the productivity.
  • it can be 5 to 2000 mA / cm 2 .
  • the formed state of the precipitated aluminum does not matter, so that the current density can be determined mainly from the viewpoint of production efficiency.
  • the current flowing between the aluminum alloy anode 11 and the cathode 13 can be a constant current.
  • the aluminum alloy anode becomes a porous structure from the surface side. Since the resistance increases in the porous structure, the voltage increases in order to maintain a constant current as the portion of the porous structure expands. Therefore, it is preferable to provide a voltage monitoring device to monitor the voltage during the production of recycled aluminum.
  • the aluminum precipitate recovery step 104 is a step of recovering the aluminum precipitate deposited on the cathode in the solid electrolysis step.
  • a known method can be used as a method for recovering the aluminum precipitate deposited on the cathode. For example, it can be used for industrially usable alloy applications by mechanically scraping off aluminum precipitates, or if the cathode is of aluminum or aluminum alloy type, it is melted together with aluminum precipitates. ..
  • the recovery step 105 of the recovered aluminum precipitate is a step of melting the recovered aluminum precipitate in the above-mentioned aluminum precipitate recovery step.
  • the step of melting the aluminum precipitate can be performed, for example, by the same method as the step of melting the aluminum alloy scrap.
  • By adding the alloy component it is also possible to produce a recycled aluminum alloy material having a desired concentration.
  • aluminum alloy elements such as silicon (Si) and copper (Cu), which are abundantly contained in aluminum casting scraps and the like, can be significantly removed, and high-purity aluminum can be recycled or recovered. ..
  • the purity of aluminum was 99.9%, and in Example 2, the purity was 99.88%.
  • the silicon (Si) concentration can be reduced to, for example, in the range of 1000 to 10 ppm.
  • aluminum processed products having various shapes and sizes can be obtained by a known processing technique.
  • the step 106 for producing recycled aluminum is a step of collecting the aluminum precipitates dissolved in the above-mentioned melting step of the recovered alumnium precipitates, for example, as an aluminum ingot.
  • the aluminum alloy anode becomes a porous structure from the surface side, but the core side remains the aluminum alloy having the original composition. Therefore, the aluminum alloy anode may be taken out after the production of the recycled aluminum or during the production of the recycled aluminum, and the core side thereof may be used as a raw material for producing the aluminum alloy anode.
  • the electrolytic residue having a porous structure formed on the surface side of the aluminum alloy anode can be used as a raw material for producing any impurity metal (for example, copper) contained therein.
  • the recycled aluminum according to the present invention is produced by the above-mentioned method for producing recycled aluminum.
  • the recycled aluminum is aluminum having a reduced impurity concentration as compared with the aluminum alloy material used for the anode as a raw material.
  • the impurity concentration in the recycled aluminum can be, for example, 0.001 to 1% by mass, 0.001 to 0.5% by mass, or 0.001 to 0.1% by mass with respect to Si. It can also be mass%.
  • the impurity concentration in the recycled aluminum can be, for example, 0.001 to 0.5% by mass, 0.001 to 0.2% by mass, or 0.001 for Cu. It can also be ⁇ 0.1% by mass.
  • electrolysis In the electrolysis step, about 300 g of the pre-dissolved molten salt for an electrolytic bath was weighed, placed in a graphite crucible, heated to 500 ° C. under an Ar atmosphere, and maintained. A general-purpose aluminum die-cast alloy AD12.1 plate (see FIG. 7B) was used for the anode, and an aluminum plate was used for the cathode. As shown in FIG. 5, an anode was installed in the center and two cathodes were arranged facing each other on both sides of the anode in order to perform stable electrolysis. Electrolysis was performed in 2 hours with an anode current density of 200 mAcm -2 and a cathode current density of 100 mA cm -2 .
  • Table 2 shows the composition of the anode used.
  • FIG. 10 shows the cyclic voltamogram curve of aluminum deposited on the cathode, and showed the ideal redox oxidation / reduction wave of aluminum.
  • the equilibrium potential of chloride generation was measured using the same Ag / AgCl reference electrode, and the potential of the used Ag / AgCl reference electrode was -1.18 V (vs. Cl 2 / Cl ⁇ ).
  • the CV potential is shown in terms of the reference potential (Cl 2 / Cl ⁇ ) based on the chlorine generation equilibrium potential.
  • the electrolysis step the anode and cathode were removed and the composition was analyzed using XRF (X-ray fluorescence analysis). The result is shown in FIG. 7 (a). Almost pure aluminum was deposited on the cathode, and Si and the like in the AD12.1 alloy used as the anode were left as the anode slime.
  • the aluminum precipitate (FIG. 7 (c)) peeled off from the cathode was redissolved and collected as an ingot (FIG. 7 (d)).
  • Table 2 the results of composition analysis of the obtained ingot (recycled aluminum) show that the aluminum purity is 99.9%, Si is quantified by 0.005%, and Cu is quantified by about 0.002%. rice field.
  • the yield of aluminum before and after the electrolysis step was 95.6%, and a small part of the yield was transferred to the anode slime (see FIG. 7 (e)).
  • Example 2 The preparation of the electrolysis bath and the electrolysis experiment were carried out in the same manner as in Example 1. A typical cast aluminum alloy AC2A was used for the anode. A pure aluminum plate was used as the cathode as well. Electrolysis was performed in 2 hours with an anode current density of 200 mAcm -2 and a cathode current density of 100 mA cm -2 .
  • composition of the cast aluminum alloy AC2A used as the anode is also shown in Table 2.
  • the anode potential and cathode potential were stable during the electrolysis process, and the tank voltage was about 0.3 V.
  • the anode and cathode were removed and the composition was analyzed using XRF.
  • the results are also shown in Table 2. Almost pure aluminum was deposited on the cathode.
  • electrolyzed anode slime was collected and the components were identified by XRD. The results are shown in FIG. From the XRD analysis results, it was found that the anode slime left after electrolysis was mainly composed of Si and Al 2 Cu, and Al, which is the main component of the cast aluminum alloy AC2A, was almost completely dissolved.

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