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WO2009107339A1 - Procédé de fabrication pour métal réducteur et appareil électrolytique à utiliser dans ce procédé - Google Patents

Procédé de fabrication pour métal réducteur et appareil électrolytique à utiliser dans ce procédé Download PDF

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Publication number
WO2009107339A1
WO2009107339A1 PCT/JP2009/000614 JP2009000614W WO2009107339A1 WO 2009107339 A1 WO2009107339 A1 WO 2009107339A1 JP 2009000614 W JP2009000614 W JP 2009000614W WO 2009107339 A1 WO2009107339 A1 WO 2009107339A1
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WO
WIPO (PCT)
Prior art keywords
cathode
reducing metal
electrolytic bath
molten salt
anode
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2009/000614
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English (en)
Japanese (ja)
Inventor
山口雅憲
小野有一
山中理
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toho Titanium Co Ltd
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Toho Titanium Co Ltd
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Filing date
Publication date
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Priority to JP2010500546A priority Critical patent/JPWO2009107339A1/ja
Publication of WO2009107339A1 publication Critical patent/WO2009107339A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C22B34/1272—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • 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
    • C25C3/04—Electrolytic production, recovery or refining of metals by electrolysis of melts of magnesium
    • 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
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • 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 a method for producing a reducing metal from a metal chloride by molten salt electrolysis and an apparatus therefor.
  • the FFC method (for example, refer to Patent Document 1) in which titanium oxide is directly reduced as a raw material with metal calcium to directly produce titanium metal, or titanium tetrachloride as a raw material is used as a metal calcium.
  • a JTS method in which metal titanium ingot is continuously produced by reducing the plasma to produce metal titanium ingot has been conceived and studied (for example, see Patent Document 2).
  • metallic calcium is used as a reducing agent for obtaining titanium. Therefore, metallic titanium is generated along with the reduction reaction, and calcium chloride is also produced as a by-product.
  • the calcium chloride can be regenerated into metallic calcium and chlorine gas by molten salt electrolysis.
  • the concentration of metallic calcium produced by molten salt electrolysis of calcium chloride is as high as possible.
  • the metal calcium is partially dissipated in the electrolytic bath, and a certain amount of calcium chloride is mixed in the recovered metal calcium, so that it is recovered. There is still room for improvement in terms of recovery yield and purity of metallic calcium.
  • the present invention relates to a preferred method for producing a reducing metal suitable for a reduction reaction of titanium tetrachloride and titanium oxide, and a molten salt electrolysis apparatus used therefor, and in particular, reduction of a molten state efficiently by molten salt electrolysis.
  • An object of the present invention is to provide a method for producing a porous metal and a molten salt electrolysis apparatus for producing a metal using the same.
  • a method for producing a reducing metal using a molten salt electrolysis apparatus which is formed by being floated after being produced in an electrolytic bath in a cathode chamber constituting the electrolysis apparatus.
  • a high concentration of the reducing metal can be produced by continuously extracting the reducing metal from the system while keeping the thickness of the reduced metal layer constant. It has been found that by using a reducing metal, the reduction reaction of titanium tetrachloride or titanium oxide can be advanced efficiently, and the present invention has been completed.
  • the present invention is a method for producing a reducing metal in which a molten salt electrolytic cell is filled with an electrolytic bath made of a reducing metal chloride, and an anode and a cathode are immersed and arranged to perform molten salt electrolysis.
  • the partition wall is divided into an anode chamber and a cathode chamber by partition walls, and a formed metal extraction tube is immersed on the cathode chamber side, and after forming in an electrolytic bath in the cathode chamber, the thickness of the reducible metal layer formed by floating is set. It is characterized in that the reducing metal in the reducing metal layer is continuously extracted out of the system by a generated metal extraction pipe while being kept constant.
  • the anode chamber and the cathode chamber are an anode partition and a cathode partition surrounding the anode and the cathode.
  • the present invention has a preferred aspect of performing molten salt electrolysis while controlling the lower end surface of the reducing metal layer in a range deeper than the lower end surface of the generated metal extraction tube and shallower than the lower end surface of the cathode, Also, from the start of molten salt electrolysis until the thickness of the reducible metal layer in a steady state is reached, the reducible metal produced in the cathode chamber diffuses into the electrolytic bath outside the cathode chamber without extracting the reducible metal. It is a preferable aspect to perform molten salt electrolysis at a speed larger than the speed of the heat treatment.
  • the cathode chamber means an electrolytic bath existing inside a cathode partition including a cathode and an upper space thereof.
  • the anode chamber means an electrolytic bath existing inside an anode partition including an anode and a space above the electrolytic bath.
  • the thickness of the reducing metal layer in the electrolytic bath can be detected by measuring the electrical resistance in the electrolytic bath held in the cathode chamber.
  • the electrolytic bath of the raw material is uniformly supplied from above with respect to the electrolytic bath surface held in the anode chamber.
  • metallic calcium containing the electrolytic bath produced by the above method can be used as a reducing agent for titanium tetrachloride.
  • a molten salt electrolyzer for producing a reducing metal includes an electrolytic cell, an electrolytic bath that fills the electrolytic cell, an anode and a cathode that are immersed in the electrolytic bath, and surrounds the anode and defines an anode chamber.
  • An anode partition and a cathode partition surrounding the cathode and partitioning the cathode chamber are provided.
  • a sensor for measuring electrical conductivity is immersed in an electrolytic bath.
  • the preferred embodiment is that the cathode is inserted and arranged in the electrolytic bath from the bottom of the cathode chamber.
  • a raw material electrolytic bath supply nozzle is disposed in the space above the bath surface of the anode chamber.
  • the anode partition is made of porous alumina and the cathode partition is made of dense silicon nitride.
  • the reducing metal can be produced with high yield.
  • the reducing metal is used as a reducing agent for titanium tetrachloride or titanium oxide, the reduction reaction can be carried out stably.
  • SYMBOLS 1 Electrolytic cell, 11 ... Electrolytic bath, 12 ... Anode chamber, 13 ... Cathode chamber, 2 ... Anode, 21 ... Anode, 3 ... Cathode, 31 ... Cathode, 32 ... Cathode insulator, 33 ... Cathode, 4 ... Partition DESCRIPTION OF SYMBOLS 41 ... Anode partition, 42 ... Cathode partition, 5 ... Electrolytic bath supply pipe, 6 ... Reducing metal discharge pipe, 7 ... Reducing metal layer, 71 ... Chlorine gas, 8 ... Electric resistance measuring sensor, 9 ... Fan.
  • FIG. 1 shows an apparatus configuration example according to a preferred molten salt electrolysis apparatus for carrying out the production of the reducing metal of the present invention.
  • an electrolytic bath 1 is filled with a molten electrolytic bath 11, an anode 2 and a cathode 3 are immersed, and an anode partition wall 41 so as to surround the anode 2 and the cathode 3.
  • a cathode barrier 42 is provided.
  • the electrolytic bath 11 and its upper space surrounded by the anode partition 41 and the cathode partition 42 are defined as an anode chamber 12 and a cathode chamber 13, respectively.
  • this molten salt electrolysis apparatus when a voltage is applied between the anode 2 and the cathode 3 to start electrolysis, a reducing metal is generated in the cathode chamber 13 and chlorine gas 71 is generated in the anode chamber 12.
  • the contact between the molten reducing metal generated on the surface of the cathode 3 and the chlorine gas 71 generated on the anode 2 can be effectively performed. Can be suppressed.
  • the generated reducible metal is concentrated to form the reducible metal layer 7, it is extracted by the generated metal extraction pipe 6 and used in the next step.
  • the electrolytic bath 11 consumed by the molten salt electrolysis is replenished to the anode chamber 12 from the electrolytic bath supply pipe 5.
  • the present invention is a method for producing a reducing metal by using a molten salt electrolysis apparatus as described above and subjecting the electrolytic bath 11 held in the electrolytic cell 1 to molten salt electrolysis, and is configured in the electrolytic cell 1.
  • the layer thickness of the reducing metal layer 7 on the surface of the electrolytic bath suspended in the cathode chamber 13 is kept constant, The metal is continuously extracted from the system.
  • the lower end surface of the generated metal extraction pipe 6 immersed and held in the reducing metal layer 7 is reduced to the reducing metal layer 7. It can always be held in the reducing metal layer 7 so as not to protrude from the inside, and as a result, it is possible to effectively suppress the entrainment of the electrolytic bath 11 in contact with the lower end surface of the reducing metal layer 7. It plays. As a result, there is an effect that the concentration of the reducing metal extracted from the generated metal extraction pipe 6 to the outside of the system can be maintained almost constant.
  • the thickness of the reducing metal layer 7 is preferably maintained at 5% or more with respect to the entire depth of the electrolytic bath held in the cathode partition wall 42.
  • the concentration of metal calcium in the electrolytic bath held in the cathode partition wall 42 can be maintained in a saturated state, and as a result, the metal calcium generated in the cathode 3 can be kept in the reducing metal layer 7. The effect is that it can be efficiently combined.
  • the thickness of the reducible metal layer 7 is less than 5%, the inside of the cathode chamber 13 does not reach the metal calcium saturation concentration, and the generated metal calcium diffuses. Moreover, there exists a possibility that the production
  • the upper limit of the thickness of the reducing metal layer 7 is preferably controlled so that the bottom surface of the reducing metal layer 7 does not exceed the lower end of the cathode 3.
  • the bottom surface of the reducing metal layer 7 grows below the lower end surface of the cathode 3
  • the bottom surface of the reducing metal layer 7 itself forms a cathode, and metallic calcium is generated on the surface.
  • the metallic calcium tends to flow out of the bath from the bottom of the cathode partition wall 42, which is not preferable.
  • the reducing metal produced in the cathode chamber 13 diffuses into the electrolytic bath outside the cathode chamber until the layer thickness of the reducing metal layer 7 maintained in a steady state is reached after the start of molten salt electrolysis. It is preferable that the molten salt electrolysis is performed at a speed higher than the speed of the heating.
  • the reducing metal according to the present invention is metallic calcium, it has a certain solubility in the electrolytic bath, and as a result, part of the metallic calcium produced at the cathode may flow out of the cathode chamber. is there. For this reason, molten salt electrolysis is started while maintaining the generation rate of the reducing metal at the cathode to be higher than the flow rate of the reducing metal from the cathode chamber to the outside. Until the calcium concentration falls within the above-described range, it is preferable to operate so as not to extract the reducing metal bath and to supply the raw electrolytic bath.
  • the thickness of the reducing metal layer 7 in the electrolytic bath held in the cathode chamber can be stably maintained at a predetermined thickness, and as a result, the dissolution loss of metallic calcium generated in the cathode is effectively reduced. There is an effect that it can be suppressed.
  • the electric resistance measurement sensor 8 it is preferable to immerse the electric resistance measurement sensor 8 in the reducing metal layer 7 surrounded by the cathode partition wall 42 and the electrolytic bath below the reducing metal layer 7.
  • the reducing metal is metallic calcium
  • the electrolytic bath is calcium chloride
  • the metallic calcium has solubility with respect to calcium chloride, so that the calcium chloride in which metallic calcium is dissolved flows out from the cathode chamber 13 to the outside.
  • the case where the metal calcium concentration which exists in the electrolytic bath in the cathode chamber 13 falls is assumed.
  • the sensor 8 described above has an effect that such a state can be accurately detected from the outside.
  • the sensor 8 can be composed of, for example, two conductive wires in which only the tip of the insulator is opened. By applying a constant voltage between the tips of the wires, it is possible to detect the change in the electrical resistance of the electrolytic bath in contact with the tips from the outside.
  • the electrolytic bath supply pipe 5 disposed in the present invention is preferably disposed in the upper space in the anode chamber 12, and a plurality of electrolytic baths are uniformly supplied to the entire surface of the electrolytic bath 11. More preferably, it is configured as a pipe.
  • the raw material electrolytic bath is uniformly supplied from the upper space of the electrolytic bath 11 existing in the anode chamber 12 toward the electrolytic bath surface, thereby generating bubbles of chlorine gas generated on the surface of the anode 2.
  • the accompanying upward flow of the electrolytic bath 11 can be effectively suppressed. As a result, it is possible to effectively avoid the invasion of metallic calcium flowing out from the cathode chamber 13 to the outside.
  • the anode 2 is preferably composed of graphite. By configuring the anode 2 with graphite, corrosion from chlorine gas generated at the anode 2 can be effectively suppressed.
  • the material of the anode partition wall 41 is preferably a material that can withstand chlorine gas, and specifically, it is preferably composed of ceramics such as alumina or magnesia. Further, the anode partition wall 41 preferably has pores such that the electrolytic bath 11 can flow and chlorine gas cannot pass through, and specifically has a porosity of about 10 to 30%. Preferably it is.
  • the cathode 3 is preferably composed of a metal that is not easily corroded by the metal in order to generate the reducing metal layer 7 in a molten state.
  • a metal that is not easily corroded by the metal in order to generate the reducing metal layer 7 in a molten state.
  • it is preferable to comprise with carbon steel or stainless steel.
  • other high melting point metals such as titanium, tantalum or tungsten can be used.
  • the cathode partition 42 provided around the cathode 3 is preferably made of a material that can withstand the reducing metal produced by the cathode 3, and is preferably made of a dense material that does not penetrate the reducing metal. Silicon nitride is preferred as such a material. This is because the silicon nitride has a low reactivity with the reducing metal produced at the cathode 3 and is suitable as a constituent material of the cathode partition wall 42, and a dense grade of silicon nitride can be obtained relatively easily.
  • the method for producing a reducible metal using the molten salt electrolysis apparatus maintains a constant thickness of the reducible metal layer 7 suspended on the electrolytic bath surface in the cathode chamber constituting the molten salt electrolyzer. However, the reducing metal is continuously extracted from the system.
  • both the electrolytic bath 11 is continuously supplied into the anode chamber 12 and the reducing metal layer 7 retained and held in the cathode chamber 13 is extracted from the system by the generated metal extraction pipe 6. This can be achieved by adjusting the amount balance.
  • the electrical resistance in the electrolytic bath 11 held in the cathode chamber 13 is withdrawn while being appropriately monitored by the sensor 8 immersed in the electrolytic bath.
  • the generated metal extraction tube immersed in the reducing metal layer 7 in the cathode chamber 13 is detected.
  • the senor 8 is separately provided in the vicinity of the lower end surface of the cathode 3.
  • the sensor 8 detects the vertical position of the lower end surface of the reducible metal layer 7 at an early stage, and effectively avoids the state in which the reducible metal layer 7 is generated below the lower end of the cathode 3. It has the effect of being able to.
  • the reducing metal layer 7 grows downward beyond the lower end surface of the cathode 3, it is not preferable because it is electrically integrated with the cathode 3 to form a so-called molten cathode.
  • a sensor 8 is separately provided in the vicinity of the lower end surface of the cathode 3 to control the position of the lower end surface of the reducing metal layer 7 so as not to extend below the lower end surface of the cathode 3.
  • the senor 8 is preferably immersed not only in the electrolytic bath in the cathode chamber 13 but also outside the cathode chamber 13. If the molten salt electrolysis reaction is continued for a long time, the reducing metal concentration in the electrolytic bath 11 gradually increases, and as a result, the electrical resistance of the electrolytic bath 11 may decrease, and it may be difficult to continue the molten salt electrolysis. It is. By separately disposing the sensor 8 in the electrolytic bath 11, the above-described state can be detected from the outside at an early stage.
  • FIG. 2 shows another preferred embodiment according to the present invention.
  • the cathode 31 is disposed through the electrolytic bath 11 from the bottom surface of the cathode chamber through the insulator 32.
  • the reducing metal generated at the cathode 31 is separated from the cathode 31 and floats and accumulates on the bath surface, so that the above-described reducing metal layer 7 and the cathode 31 are integrated as a molten cathode. Can be effectively suppressed.
  • the phenomenon that the reducing metal layer 7 flows out to the anode side via the lower end portion of the partition wall 4 is suppressed.
  • the reducible metal layer 7 can be retained to the maximum extent in the cathode-side electrolytic bath partitioned by (1). By ensuring a sufficient amount of retention of the reducing metal layer 7, it is possible to stabilize the supply amount of metallic calcium supplied to the reduction process.
  • the lower end surface of the reducible metal layer 7 is located deeper than the generated metal extraction pipe 6 immersed in the reducible metal layer 7 and is immersed in the electrolytic bath 11. It is preferable to arrange at a position shallower than the upper end of the cathode 31.
  • the reducing metal layer 7 By disposing the reducing metal layer 7 in such a range, not only can the reducing metal layer 7 be extracted from the system more efficiently than the generated metal extraction tube 8, but also the contact with the cathode 31 is effective. As a result, it is possible to proceed with efficient electrolysis.
  • the temperature of the electrolytic bath 11 is preferably kept at a temperature higher than the melting point (845 ° C.) of metallic calcium.
  • heating the temperature of the electrolytic bath too much is not preferable because it causes evaporation loss of the reductive metal produced electrolytically. Therefore, it is preferable to heat and hold the electrolytic bath up to 900 ° C.
  • the electrolytic bath used in the present invention is preferably constituted by adding calcium chloride alone or a second component such as potassium chloride or calcium fluoride.
  • a second component such as potassium chloride or calcium fluoride.
  • potassium chloride it is particularly preferable to add potassium chloride to calcium chloride.
  • the addition amount is preferably in the range of 5 to 25 mol% with respect to the whole.
  • the solubility of metallic calcium produced at the cathode can also be effectively suppressed.
  • the melting point of calcium chloride alone is 780 ° C.
  • the melting point of the electrolytic bath can be lowered to 756 ° C. to 640 ° C. by adding 5 to 25 mol% of potassium chloride as the second component. This has the effect that it can be easily extracted.
  • an anode partition and a cathode partition are provided, and in FIG. 2, only one partition is provided.
  • the present invention is not limited to these embodiments.
  • an anode barrier and a cathode barrier can also be provided.
  • Electrolytic cell 1 Titanium Anode 2: Graphite
  • Cathode 3 Carbon steel Anode-side partition wall 41: Alumina tube (porosity; 20%)
  • Cathode side partition 42 Silicon nitride tube
  • Sensor 10 Electrode material: Stainless steel 2
  • Electrolytic bath Bath composition Calcium chloride (85 mol%) + Potassium chloride (15 mol%) Bath temperature: 880 ° C 3) Results Under the above conditions, the sensor 8 detects the electrical conductivity in the reducing metal layer 7 shown in FIG. 1 while the lower end surface of the reducing metal layer 7 is moved from the lower end surface of the generated metal extraction pipe 6.
  • the molten salt was electrolyzed with calcium chloride so as to have a constant layer thickness while maintaining the depth deeper and shallower than the lower end surface of the cathode 3. As a result, it was possible to stably extract a reducing metal containing metallic calcium having a concentration of 90 to 95 wt%. The current efficiency at this time was 85%.
  • Example 2 In Example 1, molten metal electrolysis of calcium chloride was performed under the same conditions except that FIG. 2 was used, and the reducing metal produced at the cathode 31 was detected while the electrical conductivity in the reducing metal layer 7 was detected by the sensor 8. The metal calcium which comprises the layer 7 was extracted out of the system. The metal calcium concentration in the extracted reducing metal layer 7 was in the range of 90 to 95 wt%. The current efficiency at this time was 85%.
  • Reference numeral 33 denotes a cylindrical cathode, which is provided with a flow hole for an electrolytic bath communicating with the outside and the inside.
  • the electrolytic bath is supplied from the outside of the electrode by the supply of the electrolytic bath by the electrolytic bath supply pipe 5 and the rotation of the fan 9. It flows toward the inside.
  • the metallic calcium produced in the cylindrical cathode 33 is retained inside the cylindrical cathode by the flow of the electrolytic bath from the outside to the inside of the electrode, and the retained molten metallic calcium is continuously formed. I pulled it out. The current efficiency achieved when the test was conducted remained at about 70-80%.

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Abstract

L'invention concerne un procédé pour fabriquer efficacement, par l'intermédiaire d'une électrolyse dans des sels fondus, un métal réducteur approprié pour la réaction de réduction du tétrachlorure de titane ou du titane, et un appareil électrolytique à sels fondus à utiliser dans ce procédé. Le procédé de fabrication d'un métal réducteur décrit implique le remplissage d'une cuve électrolytique à sels fondus avec un bain électrolytique comportant un chlorure de métal réducteur, l'immersion de l'anode et de la cathode et la réalisation d'une électrolyse dans des sels fondus ; ladite cuve électrolytique étant divisée en une chambre d'anode et une chambre de cathode en utilisant une cloison et un tube d'extraction pour le métal produit étant immergé dans la chambre de cathode. Le métal produit dans le bain électrolytique à l'intérieur de la chambre de cathode remonte et forme une couche de métal réducteur qui est maintenue à une épaisseur constante alors que le métal réducteur présent dans la couche de métal réducteur est extrait en continu par l'intermédiaire du tube d'extraction. L'invention concerne également un appareil électrolytique à sels fondus à utiliser dans le procédé de fabrication de ce métal réducteur.
PCT/JP2009/000614 2008-02-27 2009-02-17 Procédé de fabrication pour métal réducteur et appareil électrolytique à utiliser dans ce procédé Ceased WO2009107339A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015110815A (ja) * 2013-12-06 2015-06-18 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
CN110760893A (zh) * 2019-11-22 2020-02-07 龙南龙钇重稀土科技股份有限公司 一种连续悬浮式电解装置
KR102209438B1 (ko) * 2019-09-03 2021-01-29 (주)진합 전해를 이용한 크로메이트 용액 재생장치

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CN113279022B (zh) * 2021-05-14 2022-04-19 奥勇新材料科技（上海）有限公司 一种还原性熔盐介质及其制备方法

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JP2015110815A (ja) * 2013-12-06 2015-06-18 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
KR102209438B1 (ko) * 2019-09-03 2021-01-29 (주)진합 전해를 이용한 크로메이트 용액 재생장치
CN110760893A (zh) * 2019-11-22 2020-02-07 龙南龙钇重稀土科技股份有限公司 一种连续悬浮式电解装置

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