WO2007026565A1 - PROCÉDÉ D’ÉLECTROLYSE DE SEL FONDU, PILE ÉLECTROLYTIQUE, ET PROCÉDÉ DE PRODUCTION DE Ti À L’AIDE DUDIT PROCÉDÉ - Google Patents

PROCÉDÉ D’ÉLECTROLYSE DE SEL FONDU, PILE ÉLECTROLYTIQUE, ET PROCÉDÉ DE PRODUCTION DE Ti À L’AIDE DUDIT PROCÉDÉ Download PDF

Info

Publication number
WO2007026565A1
WO2007026565A1 PCT/JP2006/316348 JP2006316348W WO2007026565A1 WO 2007026565 A1 WO2007026565 A1 WO 2007026565A1 JP 2006316348 W JP2006316348 W JP 2006316348W WO 2007026565 A1 WO2007026565 A1 WO 2007026565A1
Authority
WO
WIPO (PCT)
Prior art keywords
molten salt
electrolytic cell
metal
electrolysis
force sword
Prior art date
Application number
PCT/JP2006/316348
Other languages
English (en)
Japanese (ja)
Inventor
Tadashi Ogasawara
Makoto Yamaguchi
Toru Uenishi
Masahiko Hori
Kazuo Takemura
Katsunori Dakeshita
Original Assignee
Osaka Titanium Technologies 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 Osaka Titanium Technologies Co., Ltd. filed Critical Osaka Titanium Technologies Co., Ltd.
Priority to CA002620402A priority Critical patent/CA2620402A1/fr
Priority to US11/991,072 priority patent/US20090152122A1/en
Priority to AU2006285971A priority patent/AU2006285971A1/en
Priority to EA200800718A priority patent/EA200800718A1/ru
Priority to EP06796611A priority patent/EP1942210A1/fr
Publication of WO2007026565A1 publication Critical patent/WO2007026565A1/fr
Priority to NO20080952A priority patent/NO20080952L/no

Links

Classifications

    • 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
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • 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
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts

Definitions

  • the present invention electrolyzes a molten salt containing a metal fog-forming metal (for example, Ca, Li, Na, A1, etc.), particularly a molten salt containing Ca C1, to obtain a molten salt with an increased Ca concentration.
  • a metal fog-forming metal for example, Ca, Li, Na, A1, etc.
  • the present invention relates to a molten salt electrolysis method, an electrolytic cell used therefor, and a Ti production method using the method.
  • metal Ti is manufactured through a reduction process and a vacuum separation process.
  • the reduction process liquid TiCl supplied from above in the reaction vessel is melted by molten Mg.
  • Reduced, particulate metal Ti is generated, and then sinks downward to obtain sponge-like metal Ti.
  • sponge metal T unreacted Mg and by-product MgCl in the reaction vessel are removed.
  • the supplied TiCl reacts as unreacted TiCl gas or insufficiently reduced TiCl gas.
  • the reaction is performed only in the vicinity of the surface of the molten Mg liquid in the reaction vessel, so that the heat generation area is narrow. Therefore, if TiCl is supplied at high speed, the cooling will not be in time.
  • the generated Ti powder settles in an aggregated state, and during the sedimentation, it is sintered by the heat of the high-temperature melt and grows. However, it is difficult to recover outside the reaction vessel. For this reason, metal Ti cannot be manufactured continuously, and production Sex is inhibited.
  • US Pat. No. 2,205,854 describes that, for example, Ca can be used as a reducing agent for Ti C1 in addition to Mg.
  • the upper force also supplies metallic Ca powder to dissolve Ca in the molten salt, and TiCl gas is supplied from below to react the dissolved Ca and TiCl in the molten CaCl salt.
  • the metal Ca powder used as the reducing agent is extremely expensive, and when purchased and used, the production cost is higher than that of the crawl method. Therefore, it cannot be established as an industrial Ti manufacturing method. It is difficult to handle Ca, which is highly reactive, and this is also a major factor that hinders the industrial process of Ti production by Ca reduction.
  • This method is a kind of direct oxide reduction method.
  • this method requires the use of expensive high-purity TiO.
  • JP-A-2005-133195 (hereinafter referred to as “Reference 3”) and JP-A-2005-133196 (hereinafter referred to as “Reference 4”),
  • the inventors of the present invention based on the OYIK method as a basic configuration, and as part of the development of a metal Ti manufacturing process that can perform stable and efficient operation, electrolysis of molten CaCl
  • the manufacturing method of the T-fired Ti alloy of the present invention is based on the initials of “Ogasawara, Yamaguchi, Takahashi, Kanazawa” who were deeply involved in the development and completion of the idea. Law) ”.
  • An object of the present invention is to electrolyze a molten salt containing a metal fog forming metal chloride such as Ca, Li, Na, A1, etc., in particular, a molten salt containing CaCl to increase the Ca concentration.
  • the object is to provide a molten salt electrolysis method capable of continuously electrolyzing 2, an electrolytic cell used therefor, and a Ti production method to which the method is applied.
  • the gist of the present invention resides in the following (1) molten salt electrolysis method, (2) electrolytic cell, and (3) Ti production method using the method.
  • the "metal fog forming metal” as used herein has a property that the metal itself dissolves in a salt of metal such as Ca, Li, Na, A1, etc. (that is, Ca is CaCl, also Li Is a metal that dissolves LiCl) and reduces TiCl.
  • the anode surface and the force sword surface face each other and are arranged in a substantially vertical direction, and a partition wall configured to allow a part of the diaphragm or the molten salt to flow between the anode and the force sword. If the electrolytic cell provided is used, it is easy to recover the chlorine gas generated on the anode side. Moreover, the back reaction which returns to CaCl by the reaction of metal fog forming metal (for example, Ca) generated by electrolysis and chlorine (C1) can be suppressed.
  • metal fog forming metal for example, Ca
  • the first embodiment it is desirable (hereinafter referred to as the first embodiment).
  • the force sword is hollow and has a gap or a hole through which the molten salt can flow into the force sword.
  • the metal fog forming metal concentrated molten salt that has flowed into the force sword is removed from the electrolytic cell. If an embodiment that can be extracted is adopted, knock reaction can be effectively suppressed (hereinafter referred to as the second embodiment).
  • the metal fog forming metal concentration of the molten salt in the electrolytic cell is controlled to be less than the saturation solubility, the Ca concentration is increased to increase the TiCl generation rate,
  • Defects such as blockage inside the electrolytic cell can be suppressed (hereinafter referred to as the third embodiment).
  • a molten salt supply port is provided at one end in the longitudinal direction of the electrolytic cell container so that molten salt can be supplied between the anode and the cathode, and the molten salt is provided at the other end.
  • An electrolytic cell provided with a molten salt extraction port for extracting molten salt with increased Ca concentration generated by electrolysis out of the electrolytic cell.
  • the electrolytic cell is arranged in a substantially vertical direction with the anode surface and the force sword surface facing each other, and further, a partition wall configured to allow a part of a diaphragm or a molten salt to flow between the anode and the force sword. If provided, it can be suitably used for carrying out the electrolysis method of the first embodiment.
  • a reduction process for producing Ti grains in the salt a separation process for separating the Ti grains produced in the molten salt by the molten salt force, and electrolyzing the molten salt in which the Ca concentration is reduced as Ti grains are produced. And the electrolysis process for increasing the Ca concentration.
  • a method for producing Ti that uses elevated molten salt for the reduction of TiCl in the reduction step the method comprising:
  • a method for producing Ti wherein the molten salt electrolysis method according to (1) is applied in the solution step.
  • the molten salt electrolysis method of the present invention is a method for recovering a molten salt in which the concentration of metal fog forming metal is increased on the outlet side of the electrolytic cell by electrolyzing the molten salt while flowing in one direction near the surface of the force sword. It is. According to this electrolysis method, knock reaction is suppressed and high current efficiency is maintained, and only the molten salt enriched with metal fog forming metal such as Ca can be effectively taken out. Large quantities of molten CaCl can be continuously electrolyzed. This person
  • the method can be easily carried out by the electrolytic cell of the present invention.
  • molten salt electrolysis method of the present invention is applied to the production of Ti by Ca reduction, a molten salt enriched with Ca can be obtained relatively stably, so that metal Ti can be produced efficiently. it can.
  • FIG. 1 is a longitudinal sectional view showing a configuration example of a main part of the electrolytic cell of the present invention.
  • FIG. 2 is a diagram schematically showing a partial configuration of an electrolytic cell using a hollow sword, which is another configuration example of the electrolytic cell of the present invention.
  • FIG. 3 is a diagram showing a process example when the Ti manufacturing method of the present invention is carried out.
  • the metal fog forming metal is the same when reducing TiCl to produce Ti.
  • FIG. 1 is a longitudinal sectional view showing a configuration example of a main part of an electrolytic cell used when carrying out the molten salt electrolysis method of the present invention.
  • This electrolytic cell 1 has a pipe (cylindrical) shape that is long in one direction and holds a molten salt containing CaCl.
  • An electrolytic cell container la a cylindrically shaped anode 2 disposed in the container la along the longitudinal direction of the electrolytic cell container la, and a cylindrical force sword 3, and the electrolytic cell container
  • a molten salt supply port 6 is provided at one end (bottom plate 4) in the longitudinal direction of la, and a molten salt discharge port 7 is provided at the other end (upper cover 5).
  • the anode surface and the force sword surface Further, a diaphragm 8 is disposed between the anode 2 and the force sword 3 so as to suppress the passage of Ca generated by the electrolysis of the molten salt.
  • a cooler 9 is attached to the outer surface of the anode 2.
  • the molten salt electrolysis method of the present invention includes a metal fog forming metal (Ca) chloride (CaCl 3).
  • a molten salt containing CaCl is used.
  • the one end force of the electrolytic cell 1 is also supplied continuously or intermittently between the anode 2 and the force sword 3.
  • the “molten salt containing CaCl” means only molten CaCl or molten CaCl.
  • 2 2 2 2 is a molten salt containing KC1, CaF, etc. for adjusting the melting point and viscosity. Less than
  • the electrolytic cell 1 Since the electrolytic cell 1 is long in one direction and has a shape (in the example shown, it is elongated in the vertical direction! /, A pipe (cylindrical) shape), the molten salt is applied to one end of the electrolytic cell 1.
  • a flow rate in one direction is given to the molten salt near the surface of the force sword 3, and the molten salt flows in one direction near the surface of the force sword 3.
  • the entire molten salt between the anode 2 and the force sword 3 may flow in one direction.
  • the term “near the force sword surface” refers to a region adjacent to the force sword surface where Ca generated on the force sword surface is present.
  • the supply of the molten salt is usually performed continuously, the supply of the molten salt may be continued intermittently, that is, even if the supply of the molten salt is temporarily stopped in relation to the post-process and the like.
  • the flow of molten salt near the surface of the power sword is also stopped. Therefore, strictly speaking, the “flow velocity” when “giving a one-way flow velocity to the molten salt near the surface of the force sword” includes a state where the flow velocity is zero without any flow.
  • the force electrolysis cell 1 is one in which molten salt is electrolyzed while flowing in the vicinity of the surface of the force sword to generate Ca on the surface of the force sword.
  • the distance between the anode 2 and the force sword 3 is made relatively small in order to keep the electrolysis voltage low.
  • Molten salt supply port 6 Prevents mixing of molten salt near the molten salt extraction port 7 and molten salt near the Ca concentration by electrolysis, effectively extracting only the Ca-concentrated molten salt I can do it.
  • TiC titanium carbide
  • the document 2 describes a technique of "forming a molten salt flow in the vicinity of a force sword in the production of Ti by Ca reduction in a molten salt".
  • the anode and the force sword are placed facing each other along the longitudinal direction in the electrolytic cell, it is formed near the force sword surface or between the force sword surface and the diaphragm when a diaphragm is provided.
  • a molten salt flow in one direction along the surface of the force sword is formed and the molten salt with increased Ca concentration is recovered on the outlet side of the electrolytic cell by electrolysis in that state.
  • Ming's technical philosophy is not to indicate a statement that suggests it!
  • the molten salt electrolysis method of the present invention is completely different from the technique described in the above-mentioned document 2, even though they are common in that a one-way flow is formed in the molten salt in the electrolytic cell.
  • the anode surface and the force sword surface are opposed to each other in a substantially vertical direction, and a diaphragm or a part of the molten salt is interposed between the anode and the force sword.
  • This is a method using an electrolytic cell provided with partition walls configured to be able to flow.
  • the term “substantially” in the above “substantially vertical direction” means “substantially” and “substantially”, and “substantially vertical direction” is slightly inclined toward the horizontal direction or the direction force thereof. The direction.
  • the electrolysis method according to the first embodiment can be preferably carried out by using the electrolytic cell illustrated in FIG. Note that in the electrolytic cell illustrated in FIG.
  • the anode surface and the force sword surface face each other in a substantially vertical direction, while the molten salt near the force sword surface is given a flow rate in one direction. Therefore, the flow direction of the molten salt is vertical, and the chlorine gas generated on the anode side floats easily, so it is easy to recover.
  • Examples of the diaphragm provided between the anode and the force sword include, for example, many kinds including yttria (Y 2 O 3).
  • Porous ceramic bodies can be used.
  • a porous ceramic body made by firing yttria has a selective permeability that allows Ca and chlorine ions to pass through but does not allow metal Ca to pass through. It also reduces by Ca, which has strong reducing power. It has an excellent calcium resistance reduction property, and is suitable as a diaphragm in the molten salt electrolysis method of the present invention.
  • Electrolysis can be carried out with high current efficiency at which knock reaction is unlikely to occur.
  • a partition configured to allow a part of the molten salt to flow therethrough may be used.
  • the partition wall does not allow molten salts such as Ca and chlorine ions as well as metallic Ca, but by providing slits or holes through which molten salt can pass in a part of the partition wall, electrolysis can be achieved, while metal Ca It is possible to limit knock reaction by restricting the passage to some extent.
  • the cathode is hollow, and the molten salt flows into the force sword surface force force sword (ie, the hollow portion).
  • This is a method that has a gap or hole that can be formed, and allows the Ca-concentrated molten salt flowing into the power sword to be extracted outside the electrolytic cell.
  • FIG. 2 is a diagram schematically showing a configuration example of a part of an electrolytic cell using a hollow force sword.
  • the anode 2 and the hollow power sword 3a are arranged in a substantially vertical direction facing each other along the longitudinal direction in the electrolytic cell 1, and the anode 2 and the power sword 3a A diaphragm 8 is provided between them.
  • the force sword 3a is provided with a gap or a hole through which molten salt can flow into the force sword from the surface of the force sword.
  • the electrolytic cell configured as described above, the molten salt is extracted from above the hollow portion of the force sword 3a, so that the inner side from the outer surface side of the force sword is indicated by the white arrow in the figure.
  • the molten salt flow is formed in the outer surface of the force sword 3a, and the Ca generated on the outer surface of the force sword 3a is immediately taken into the force sword 3a without diffusing and moving toward the anode. Thereby, back reaction can be effectively suppressed.
  • the electrolytic cell illustrated in FIG. 2 has the diaphragm 8, the effect of suppressing the knock reaction is further increased as compared with the case without the diaphragm.
  • the third embodiment of the molten salt electrolysis method of the present invention is an electrolysis method in which the Ca concentration of the molten salt in the electrolytic cell is controlled to be less than the saturation solubility. is there.
  • controlling the Ca concentration to be less than the saturation solubility means “electrolysis under the condition that the Ca concentration is close to the saturation solubility and does not precipitate”.
  • the shape of the electrolytic cell container and the electric power are set so that the "condition where the Ca concentration is close to the saturation solubility and does not precipitate" is satisfied at the site where the Ca concentration is highest in the electrolytic cell.
  • the optimum electrolysis conditions according to the pole shape, the distance between the poles, and the amount of molten salt extracted per unit time will be determined empirically.
  • the Ca concentration near the molten salt outlet on the force sword side is the highest, so the Ca concentration in this part is controlled to be less than the saturation solubility.
  • electrolysis can be performed without depositing metallic Ca in any part of the electrolytic cell.
  • the temperature of CaCl entering the electrolytic cell is set to 80.
  • the molten CaCl has a metallic Ca concentration of 0%.
  • the metal Ca concentration (A concentration) of 2 is 0 to less than 1%, and the molten CaCl metal Ca concentration from the electrolytic cell
  • the degree (B concentration) should be 0.1% or more.
  • the increase in metal Ca concentration (B–A concentration) in the electrolytic cell is 0.1% or more and 5.0% or less (supersaturation) in consideration of efficient use of Ca in the subsequent process. It is particularly desirable to set the concentration to include Ca. % Or more.
  • the molten salt electrolysis method of the present invention it is desirable to remove heat effectively because a large reaction heat is generated in the electrolytic cell. Specifically, it is desirable to install a cooler at the center of the force sword so as to extract the heat of reaction from the inside of the force sword, regardless of whether the aforementioned hollow force sword is used or not.
  • a cooler for example, a tubular heat exchanger is suitable.
  • cooler heat exchanger
  • the molten salt electrolysis method of the present invention the molten salt is electrolyzed while flowing in one direction near the surface of the force sword, so that a large amount of molten salt can be processed continuously.
  • the electrolytic cell of the present invention is an electrolytic cell used when the above-described molten salt electrolysis method is carried out.
  • An electrolytic cell container that is long in one direction for holding the molten salt contained therein, an anode and a force sword disposed along the longitudinal direction of the electrolytic cell container, and one end in the longitudinal direction of the electrolytic cell container
  • the molten salt supply port is provided in the section so that the molten salt can be supplied between the anode and the force sword, and the other end is electrolyzed with a molten salt having an increased ca concentration generated by electrolysis of the molten salt. It is characterized by an outlet for extracting molten salt to the outside of the tank.
  • the electrolytic cell illustrated in FIG. 1 is an embodiment of the electrolytic cell according to the present invention.
  • the anode surface and the force sword surface are opposed to each other in a substantially vertical direction, and between the anode and the force sword.
  • TiCl is added to Ca in a molten salt containing CaCl and dissolving Ca. Reaction to produce Ti particles in the molten salt, a separation step of separating the Ti particles formed in the molten salt from the molten salt, and the Ca concentration accompanying the generation of Ti particles.
  • the method is characterized in that the molten salt electrolysis method of the present invention is applied in the electrolysis step.
  • FIG. 3 is a diagram showing an example of steps when the Ti manufacturing method of the present invention is carried out. As shown in Fig. 3, this Ti manufacturing process involves the addition of TiCl to Ca in molten salt containing CaCl and dissolving Ca.
  • a reduction step 10 in which Ti particles are produced in the molten salt by reacting 2 4 a separation step 11 in which the Ti particles produced in the molten salt are separated from the molten salt, and accompanying the production of Ti particles And an electrolysis process for increasing the Ca concentration by electrolyzing the molten salt having a reduced Ca concentration.
  • the electrolytic cell 1 used for carrying out this electrolysis method is incorporated.
  • the electrolytic cell 1 used here has a cylindrical electrolytic cell container la that is long in the vertical direction, and an anode 2 and a force sword 3 that are arranged along the longitudinal direction of the electrolytic cell container la.
  • the electrolytic cell 1 has a molten salt supply port for supplying molten salt between the anode 2 and the force sword 3 at the upper end, and electrolysis of the molten salt at the lower end.
  • a molten salt extraction port is provided for extracting the molten salt with high Ca concentration to the outside of the electrolytic cell 1.
  • the electrolytic cell 1 Since the electrolytic cell 1 is a vertical type, it is easy to recover the chlorine gas generated on the anode side.
  • the molten salt enriched in Ca thus obtained is extracted from the lower end portion of the electrolytic cell 1 and is then extracted and transferred to the reduction step 10. [0063] In the reduction step 10, when TiCl gas reacts with Ca in the molten salt enriched with Ca,
  • Particulate metal Ti is formed in the salt. As the reduction reaction proceeds in the molten salt, Ca in the molten salt is consumed, and Ti is generated and at the same time CaCl is produced as a by-product.
  • the Ti particles generated in the reduction step 10 are transferred to the separation step 11 together with the molten salt, and the Ti particles are separated from the molten salt.
  • solid-liquid separation operations such as a high-speed decanter (continuous centrifugation) method and a thickener one-way method can be applied.
  • the reaction vessel used in the reduction step 10 can discharge the molten salt containing CaCl produced as a by-product to the outside of the vessel.
  • the molten salt discharged from the reduction step 10 can be directly transferred to the electrolytic process (refer to References 3 and 4).
  • the Ti powder obtained by the crawl method is in an aggregated state, whereas the Ti particles obtained in the reduction process 10 are difficult to agglomerate and are difficult to adhere to the container. Ti grains can be transferred to the melting process as they are, and heated to melt to form Ti ingot 12.
  • the molten salt in which the Ca concentration remaining after separating and recovering Ti grains is sent to the electrolysis process, subjected to electrolytic treatment in the electrolytic cell 1 described above, and returned again as a molten salt in which Ca is concentrated. Used in the original process 10 to reduce TiCl.
  • molten salt in which Ca is concentrated to close to the saturation solubility in the electrolysis step can be obtained relatively stably, so that metal Ti can be produced efficiently and a large amount of Since Ca produced by continuous electrolysis of molten salt can be supplied to the reduction process, this method can also be applied to mass production.
  • the molten salt electrolysis method of the present invention is a method in which a molten salt is electrolyzed while flowing in one direction near the surface of a force sword. According to this electrolysis method, high current efficiency is maintained, and Ca and the like are maintained. Only the molten salt enriched in the metal fog forming metal can be taken out effectively. This electrolysis method can be easily carried out by the electrolytic cell of the present invention. Moreover, if the molten salt electrolysis method of the present invention is applied to the production of Ti by Ca reduction, a molten salt enriched with Ca can be obtained relatively stably, and metal Ti can be produced efficiently. Therefore, the molten salt electrolysis method of the present invention, the electrolytic cell, and the Ti production method to which this electrolysis method is applied are based on Ca reduction. It can be used effectively for the production of Ti.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé d’électrolyse d’un sel fondu susceptible d’améliorer la concentration métallique de la formation de vapeur métallique du sel fondu. Selon le procédé, l’électrolyse se déroule de telle sorte qu’un métal fondu contenant un chlorure d’un métal formant une vapeur métallique parvienne d’une extrémité d’une pile électrolytique à une partie située entre une anode et une cathode de manière continue ou intermittente pour assurer un débit dans une direction vers le sel fondu dans sa partie proche de la surface de la cathode et ainsi permettre au sel fondu de s’écouler dans une direction au niveau de la partie proche de la surface de la cathode. Selon le procédé, alors que l’on maintient une efficacité de courant élevée, seul un sel fondu enrichi d’un métal formant une vapeur métallique comme Ca peut effectivement être prélevé. De plus, ce procédé peut facilement être réalisé par la pile électrolytique selon la présente invention. Par ailleurs, l’application du procédé d’électrolyse d’un sel fondu à la production de Ti par réduction de Ca peut permettre de produire du métal Ti avec une grande efficacité. Ainsi, le procédé d’électrolyse d’un sel fondu, la pile électrolytique et le procédé de production de Ti peuvent servir efficacement à la production de Ti par réduction de Ca.
PCT/JP2006/316348 2005-08-30 2006-08-22 PROCÉDÉ D’ÉLECTROLYSE DE SEL FONDU, PILE ÉLECTROLYTIQUE, ET PROCÉDÉ DE PRODUCTION DE Ti À L’AIDE DUDIT PROCÉDÉ WO2007026565A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002620402A CA2620402A1 (fr) 2005-08-30 2006-08-22 Procede d'electrolyse de sel fondu, pile electrolytique, et procede de production de ti a l'aide dudit procede
US11/991,072 US20090152122A1 (en) 2005-08-30 2006-08-22 Method for electrolyzing molten salt, electrolytic cell, and process for producing ti using said method
AU2006285971A AU2006285971A1 (en) 2005-08-30 2006-08-22 Method for electrolysis of molten salt, electrolytic cell, and process for producing Ti using said method
EA200800718A EA200800718A1 (ru) 2005-08-30 2006-08-22 СПОСОБ ЭЛЕКТРОЛИЗА РАСПЛАВЛЕННОЙ СОЛИ, ЭЛЕКТРОЛИТИЧЕСКАЯ ЯЧЕЙКА И СПОСОБ ПОЛУЧЕНИЯ Ti С ИСПОЛЬЗОВАНИЕМ УКАЗАННОГО СПОСОБА
EP06796611A EP1942210A1 (fr) 2005-08-30 2006-08-22 PROCÉDÉ D ÉLECTROLYSE DE SEL FONDU, PILE ÉLECTROLYTIQUE, ET PROCÉDÉ DE PRODUCTION DE Ti À L AIDE DUDIT PROCÉDÉ
NO20080952A NO20080952L (no) 2005-08-30 2008-02-26 Fremgangsmate for elektrolyse av saltsmelte, elektrolytisk celle, og fremgangsmate for fremstilling av Ti ved anvendelse av nevnte fremgangsmate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-248603 2005-08-30
JP2005248603A JP2007063585A (ja) 2005-08-30 2005-08-30 溶融塩電解方法および電解槽並びにそれを用いたＴｉの製造方法

Publications (1)

Publication Number Publication Date
WO2007026565A1 true WO2007026565A1 (fr) 2007-03-08

Family

ID=37808663

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/316348 WO2007026565A1 (fr) 2005-08-30 2006-08-22 PROCÉDÉ D’ÉLECTROLYSE DE SEL FONDU, PILE ÉLECTROLYTIQUE, ET PROCÉDÉ DE PRODUCTION DE Ti À L’AIDE DUDIT PROCÉDÉ

Country Status (9)

Country Link
US (1) US20090152122A1 (fr)
EP (1) EP1942210A1 (fr)
JP (1) JP2007063585A (fr)
CN (1) CN101248217A (fr)
AU (1) AU2006285971A1 (fr)
CA (1) CA2620402A1 (fr)
EA (1) EA200800718A1 (fr)
NO (1) NO20080952L (fr)
WO (1) WO2007026565A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009144176A (ja) * 2007-12-11 2009-07-02 Toho Titanium Co Ltd 金属カルシウムの製造方法および溶融塩電解装置
JP2009287045A (ja) * 2008-05-27 2009-12-10 Toho Titanium Co Ltd 金属カルシウムの製造方法および製造装置

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009048022A1 (fr) * 2007-10-09 2009-04-16 Osaka Titanium Technologies Co., Ltd. Pompe de type à ailettes rotatives
JPWO2009122705A1 (ja) * 2008-03-31 2011-07-28 株式会社キノテック・ソーラーエナジー 電解槽
AR076863A1 (es) 2009-05-12 2011-07-13 Metalysis Ltd Aparato y metodo para reduccion de materia prima solida.
AU2011330970B2 (en) 2010-11-18 2016-10-20 Metalysis Limited Electrolysis apparatus
CN103290433B (zh) * 2013-06-26 2016-01-20 石嘴山市天和铁合金有限公司 一种双电解槽熔盐电解制备纯钛的装置及其工艺
CN104611732B (zh) * 2015-02-15 2017-03-22 攀钢集团攀枝花钢铁研究院有限公司 气冷阴极、熔盐电解装置及电解方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5985880A (ja) * 1982-08-31 1984-05-17 ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク 溶融した塩類の混合物の中で塩化リチウムを電解してリチウムを連続的に製造する方法および装置
JPS6059089A (ja) * 1983-09-13 1985-04-05 Agency Of Ind Science & Technol 共融塩電解装置
JPS60190587A (ja) * 1984-02-24 1985-09-28 ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク リチウムの連続製造法及び装置
JP2005068539A (ja) * 2003-08-28 2005-03-17 Sumitomo Titanium Corp 金属製造方法及び装置
JP2005133195A (ja) * 2003-10-10 2005-05-26 Sumitomo Titanium Corp Ｃａ源の循環によるＴｉ又はＴｉ合金の製造方法
JP2006111895A (ja) * 2004-10-12 2006-04-27 Toho Titanium Co Ltd 溶融塩電解による金属の製造方法および製造装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2205854A (en) * 1937-07-10 1940-06-25 Kroll Wilhelm Method for manufacturing titanium and alloys thereof
US2845386A (en) * 1954-03-16 1958-07-29 Du Pont Production of metals
US4617098A (en) * 1982-08-31 1986-10-14 Rhone-Poulenc Specialites Chimiques Continuous electrolysis of lithium chloride into lithium metal
FR2582019B1 (fr) * 1985-05-17 1987-06-26 Extramet Sa Procede pour la production de metaux par reduction de sels metalliques, metaux ainsi obtenus et dispositif pour sa mise en oeuvre

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5985880A (ja) * 1982-08-31 1984-05-17 ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク 溶融した塩類の混合物の中で塩化リチウムを電解してリチウムを連続的に製造する方法および装置
JPS6059089A (ja) * 1983-09-13 1985-04-05 Agency Of Ind Science & Technol 共融塩電解装置
JPS60190587A (ja) * 1984-02-24 1985-09-28 ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク リチウムの連続製造法及び装置
JP2005068539A (ja) * 2003-08-28 2005-03-17 Sumitomo Titanium Corp 金属製造方法及び装置
JP2005133195A (ja) * 2003-10-10 2005-05-26 Sumitomo Titanium Corp Ｃａ源の循環によるＴｉ又はＴｉ合金の製造方法
JP2006111895A (ja) * 2004-10-12 2006-04-27 Toho Titanium Co Ltd 溶融塩電解による金属の製造方法および製造装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009144176A (ja) * 2007-12-11 2009-07-02 Toho Titanium Co Ltd 金属カルシウムの製造方法および溶融塩電解装置
JP2009287045A (ja) * 2008-05-27 2009-12-10 Toho Titanium Co Ltd 金属カルシウムの製造方法および製造装置

Also Published As

Publication number Publication date
US20090152122A1 (en) 2009-06-18
EP1942210A1 (fr) 2008-07-09
JP2007063585A (ja) 2007-03-15
CA2620402A1 (fr) 2007-03-08
AU2006285971A1 (en) 2007-03-08
CN101248217A (zh) 2008-08-20
NO20080952L (no) 2008-02-29
EA200800718A1 (ru) 2008-08-29

Similar Documents

Publication Publication Date Title
JP4602986B2 (ja) 溶融塩電解による金属カルシウムの製造方法
WO2007026565A1 (fr) PROCÉDÉ D’ÉLECTROLYSE DE SEL FONDU, PILE ÉLECTROLYTIQUE, ET PROCÉDÉ DE PRODUCTION DE Ti À L’AIDE DUDIT PROCÉDÉ
WO2005080642A1 (fr) Procédé pour la production du titane ou un alliage de titane reduction de ca
WO2005080643A1 (fr) PROCÉDÉ DE FABRICATION DE Ti OU D’UN ALLIAGE DE Ti PAR RÉDUCTION DE Ca
WO2005103338A1 (fr) Production d'alliages de fer/titane
WO2007034645A1 (fr) Procédé de production de titane et appareil correspondant
JP4395386B2 (ja) Ｃａ源の循環によるＴｉ又はＴｉ合金の製造方法
JP4347089B2 (ja) Ｃａ還元によるＴｉ又はＴｉ合金の製造方法
JP4510769B2 (ja) Ｔｉ又はＴｉ合金の製造方法及び装置
JP2009019250A (ja) 金属製造方法および装置
EP1995353A1 (fr) PROCEDE D'EXTRACTION / DE CONCENTRATION DE METAL FORMANT UN BROUILLARD METALLIQUE PRESENT DANS UN SEL FONDU, APPAREIL CORRESPONDANT, PROCEDE ET APPAREIL DE PRODUCTION DE Ti OU D'ALLIAGE DE Ti AU MOYEN DE CEUX-CI
JP2006124813A (ja) Ｃａ還元によるＴｉの製造方法及び装置
WO2005035806A1 (fr) Procede de production de ti ou d'alliage de ti par reduction par ca
JP2006274340A (ja) Ｔｉ又はＴｉ合金の製造方法
JP4249685B2 (ja) Ｃａ還元によるＴｉの製造方法
JP2005133196A (ja) 溶融塩の循環によるＴｉ又はＴｉ合金の製造方法
JP4227113B2 (ja) 引上げ電解方法
WO2008038405A1 (fr) Récipient d'électrolyse de sel fondu pour la fabrication de métal et procédé de fabrication de métal à l'aide de celui-ci
JP2005264181A (ja) 溶融Ｃａ合金をＣａ移送媒体とするＴｉ又はＴｉ合金の製造方法
JP2007239073A (ja) 溶融塩中メタルフォグ形成金属の除去及び高濃度化方法と装置
JP2009041089A (ja) 電解槽及びそれを用いる金属の製造方法
JP2009133010A (ja) Ｃａ還元によるＴｉ又はＴｉ合金の製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680031084.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2620402

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 11991072

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2006285971

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2006796611

Country of ref document: EP

Ref document number: 200800718

Country of ref document: EA

ENP Entry into the national phase

Ref document number: 2006285971

Country of ref document: AU

Date of ref document: 20060822

Kind code of ref document: A