WO2006003865A1 - Procédé de production de métal par électrolyse ignée - Google Patents

Procédé de production de métal par électrolyse ignée Download PDF

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Publication number
WO2006003865A1
WO2006003865A1 PCT/JP2005/011751 JP2005011751W WO2006003865A1 WO 2006003865 A1 WO2006003865 A1 WO 2006003865A1 JP 2005011751 W JP2005011751 W JP 2005011751W WO 2006003865 A1 WO2006003865 A1 WO 2006003865A1
Authority
WO
WIPO (PCT)
Prior art keywords
molten salt
metal
cathode
anode
calcium
Prior art date
Application number
PCT/JP2005/011751
Other languages
English (en)
Japanese (ja)
Inventor
Masanori Yamaguchi
Yuichi Ono
Susumu Kosemura
Eiji Nishimura
Original Assignee
Toho Titanium Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toho Titanium Co., Ltd. filed Critical Toho Titanium Co., Ltd.
Publication of WO2006003865A1 publication Critical patent/WO2006003865A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing

Definitions

  • the present invention relates to recovery of metal from metal salts, and more particularly to a method for producing metal by molten salt electrolysis.
  • Patent document l WO99Z064638
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2003-129268
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2003-306725
  • Patent Document 4 US 3226311
  • the present invention has been made in view of the above situation, and it is possible to efficiently recover, for example, a metal used to reduce an acid or a salt of metal titanium.
  • the object is to provide a method for producing a metal by molten salt electrolysis which can be carried out by an inexpensive method.
  • the method for producing a metal by molten salt electrolysis comprises an anode and a cathode, and an electrolysis cell having a diaphragm composed of graphite and disposed between the anode and the cathode. It is characterized in that molten salt is filled and molten salt electrolysis is performed. Also, the voltage applied between the anode and the cathode is characterized in that it is not more than twice the theoretical decomposition voltage of the molten salt.
  • the reaction occurs in proportion to the voltage applied between the anode and the cathode, but an intermediate electrode (conductor) is placed between the anode and the cathode and it is necessary for the electrolysis.
  • this intermediate pole is polarized, and electrolysis occurs not only between the anode and the cathode but also between the anode and the intermediate pole, and in two regions of the intermediate pole and the cathode. Chlorine is generated on one side of the intermediate electrode and metal is deposited on the other side of the cathode and the intermediate electrode.
  • the diaphragm composed of graphite is disposed between the anode and the cathode, the chlorine generated at the anode and the metal deposited at the cathode are separated, and the reverse reaction can be suppressed.
  • a voltage equal to or less than twice the theoretical decomposition voltage of the molten salt is applied, the reaction can be promoted efficiently without polarization of the membrane.
  • FIG. 1 shows an example of a preferred apparatus configuration for practicing the present invention.
  • reference numeral 1 denotes an electrolytic cell, the inside of which is filled with an electrolytic bath 2 consisting of calcium chloride (melting point 780 ° C.), and the heating means (not shown) It is heated and kept molten.
  • Reference numeral 3 is an anode
  • reference numeral 4 is a cathode, which are immersed in the electrolytic bath 2.
  • a diaphragm 5 made of, for example, graphite is disposed between the anode 3 and the cathode 4.
  • chloride ions in the electrolytic bath 2 are attracted to the anode 3 to emit electrons and chlorine It is released out of the system as gas 6.
  • Calcium ions are attracted to the cathode 4 to receive electrons, and become metallic calcium 7 and deposit on the surface of the cathode 4.
  • solid metallic calcium is deposited on the cathode 4 by setting the temperature of the electrolytic bath 2 to the melting point of metallic calcium (845 ° C.) and the melting point of calcium chloride (780 ° C.) or higher. be able to.
  • the present invention can be practiced even if the temperature of the electrolytic bath 2 is selected to be higher than the melting point of metallic calcium.
  • the metallic calcium deposited on the cathode 4 floats in the electrolytic bath 2 while a part thereof is dissolved, and stays on the surface of the electrolytic bath 2.
  • the metallic calcium and the electrolytic bath enriched with metallic calcium can be used, for example, as a reducing agent by direct electrolysis of titanium oxide.
  • Chlorine gas and metallic calcium generated as described above tend to diffuse and cause reverse reaction with each other, but in the present invention, since a diaphragm is provided between the anode and the cathode, the reverse reaction is suppressed. can do.
  • the amount of current supplied to the electrolytic cell 1 is increased, and the metal deposition rate can be increased.
  • both surfaces of the diaphragm 5 are polarized as the applied voltage increases, and when the applied voltage reaches twice the theoretical decomposition voltage, metal is deposited on the anode side of the diaphragm 5 and the cathode side of the diaphragm 5 Begins to generate chlorine gas.
  • the chlorine gas generated on the cathode side of the diaphragm 5 causes a reverse reaction with the metal deposited on the cathode 4 to lower the yield of calcium metal.
  • the voltage applied to the anode 3 and the cathode 4 is preferably an electrolytic voltage which does not cause the polarization of the diaphragm 5.
  • Such a voltage range is not less than the theoretical decomposition voltage of calcium chloride and not more than twice thereof, and specifically, 3.2 V to 6.4 V It is a range.
  • the anode used in the present invention is required to be a material resistant to high-temperature chlorine gas, and graphite is preferable as such a material. Not only does Graphite withstand high temperature chlorine gas, it is also durable in high temperature electrolytic baths and has good conductivity and conductivity.
  • the anode may be formed by immersing the upper lid of the electrolytic cell 1 (not shown) into the electrolytic bath 2 so that the surface of the anode 3 made of graphite penetrating the upper lid may be coated with ceramic. . With such a configuration, wear and tear on graphite can be minimized.
  • any material resistant to high temperature molten salt can be used, and it can be made of common carbon steel or stainless steel.
  • Carbon steel is preferred to withstand high temperature molten salts or metallic calcium. It is also cheap, durable and practical.
  • the diaphragm used in the present invention is required to be made of a material resistant to high temperature calcium chloride or chlorine gas, and specifically, Graphite is preferable. Even if the entire septum is made of graphite, the strength at high temperature can be maintained for a long time by making the center part of ceramic and making the outside part of dolaphyte.
  • the diaphragm is required to be as compact as possible, the porosity of the diaphragm is to be within the scope of the present invention even if there is a gap that metal calcium produced in the cathode 4 does not penetrate and move to the anode side. There is no hindrance to the above. Also, the lower end of the diaphragm does not have to reach the bottom of the electrolytic cell, and the calcium metal formed at the cathode 4 or the calcium chloride layer enriched with metal calcium can not move to the anode. It is enough.
  • the generated chlorine gas is extracted out of the system and can be used, for example, for chlorination reaction of titanium ore.
  • metallic calcium can be used for the reduction reaction of titanium oxide or titanium chloride using a molten salt.
  • the diaphragm is made of graphite and the voltage applied to the anode and the cathode is equal to or higher than the theoretical decomposition voltage of calcium chloride and equal to or lower than twice the theoretical decomposition voltage.
  • the metal calcium can be efficiently generated without generating chlorine gas due to the polarization on the diaphragm surface.
  • Example 1 when the molten salt electrolysis of calcium chloride was performed by setting the voltage applied to the anode and the cathode to 7. OV, metallic calcium corresponding to 20% of the theoretical value could not be recovered.
  • the acid oxide of metallic titanium can efficiently recover the metal used to reduce chloride.
  • FIG. 1 is a schematic cross-sectional view showing an electrolytic cell in molten salt electrolysis of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

Cette invention concerne un procédé de production de métal par électrolyse ignée, caractérisée en ce que cette électrolyse ignée est réalisée à l’aide d’une cuve d’électrolyse comprenant une anode, une cathode et un diaphragme composé de graphite et disposé entre l’anode et la cathode, et remplie de sel fondu contenant un chlorure métallique. La tension électrique appliquée entre l’anode et la cathode ne dépasse pas le double de la tension électrique appliquée pour la décomposition théorique du sel fondu.
PCT/JP2005/011751 2004-06-30 2005-06-27 Procédé de production de métal par électrolyse ignée WO2006003865A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-192955 2004-06-30
JP2004192955A JP4199703B2 (ja) 2004-06-30 2004-06-30 溶融塩電解による金属の製造方法

Publications (1)

Publication Number Publication Date
WO2006003865A1 true WO2006003865A1 (fr) 2006-01-12

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/011751 WO2006003865A1 (fr) 2004-06-30 2005-06-27 Procédé de production de métal par électrolyse ignée

Country Status (2)

Country Link
JP (1) JP4199703B2 (fr)
WO (1) WO2006003865A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012092868A1 (fr) * 2011-01-07 2012-07-12 青海北辰科技有限公司 Appareil d'électrolyse du chlorure de magnésium et procédé d'électrolyse
CN105103349A (zh) * 2013-03-27 2015-11-25 Jsr株式会社 蓄电设备用粘结剂组合物

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6270446B2 (ja) * 2013-12-06 2018-01-31 東邦チタニウム株式会社 溶融塩電解による金属の製造方法
JP7127984B2 (ja) * 2017-12-27 2022-08-30 東邦チタニウム株式会社 溶融塩電解槽の操業方法及び、溶融金属の製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03115592A (ja) * 1989-09-28 1991-05-16 Osaka Titanium Co Ltd 溶融塩電解槽

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03115592A (ja) * 1989-09-28 1991-05-16 Osaka Titanium Co Ltd 溶融塩電解槽

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012092868A1 (fr) * 2011-01-07 2012-07-12 青海北辰科技有限公司 Appareil d'électrolyse du chlorure de magnésium et procédé d'électrolyse
CN105103349A (zh) * 2013-03-27 2015-11-25 Jsr株式会社 蓄电设备用粘结剂组合物

Also Published As

Publication number Publication date
JP4199703B2 (ja) 2008-12-17
JP2006016633A (ja) 2006-01-19

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