WO2007026565A1 - METHOD FOR ELECTROLYSIS OF MOLTEN SALT, ELECTROLYTIC CELL, AND PROCESS FOR PRODUCING Ti USING SAID METHOD - Google Patents

METHOD FOR ELECTROLYSIS OF MOLTEN SALT, ELECTROLYTIC CELL, AND PROCESS FOR PRODUCING Ti USING SAID METHOD Download PDF

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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
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WIPO (PCT)
Prior art keywords
molten salt
electrolytic cell
metal
electrolysis
force sword
Prior art date
Application number
PCT/JP2006/316348
Other languages
French (fr)
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 EP06796611A priority Critical patent/EP1942210A1/en
Priority to EA200800718A priority patent/EA200800718A1/en
Priority to US11/991,072 priority patent/US20090152122A1/en
Priority to AU2006285971A priority patent/AU2006285971A1/en
Priority to CA002620402A priority patent/CA2620402A1/en
Publication of WO2007026565A1 publication Critical patent/WO2007026565A1/en
Priority to NO20080952A priority patent/NO20080952L/en

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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.

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Abstract

This invention provides a method for the electrolysis of a molten salt that can enhance metal fog formation metal concentration of the molten salt. In the method, electrolysis is carried out in such a state that a molten metal containing a chloride of a metal fog forming metal is supplied from one end of an electrolytic cell to a part between an anode and a cathode in a continuous or intermittent manner to provide a flow rate in one direction to the molten salt in its part near the surface of the cathode and thus to allow the molten salt to flow in one direction at the part near the surface of the cathode. In the method, while high current efficiency is maintained, only a molten salt enriched with a metal fog forming metal such as Ca can be effectively taken out. Further, this method can easily be carried out by the electrolytic cell according to the present invention. Furthermore, the application of the method for the electrolysis of a molten salt to the production of Ti by Ca reduction can realize the production of metal Ti with high efficiency. Thus, the method for the electrolysis of a molten salt, the electrolytic cell, and the process for producing Ti can be effectively utilized by the production of Ti by Ca reduction.

Description

明 細 書  Specification
溶融塩電解方法および電解槽並びにその方法を用いた Tiの製造方法 技術分野  Molten salt electrolysis method, electrolytic cell, and Ti production method using the method
[0001] 本発明は、メタルフォグ形成金属（例えば、 Ca、 Li、 Na、 A1等）の塩化物、特に Ca C1を含有する溶融塩を電気分解して、 Ca濃度が高められた溶融塩を得ることができ [0001] 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. Can get
2 2
る溶融塩電解方法、およびそれに用いる電解槽、並びにその方法を用いた Tiの製 造方法に関する。  The present invention relates to a molten salt electrolysis method, an electrolytic cell used therefor, and a Ti production method using the method.
背景技術  Background art
[0002] 金属 Tiの工業的な製法としては、 TiClを Mgにより還元するクロール法が一般的で  [0002] As an industrial production method of metal Ti, a crawl method in which TiCl is reduced with Mg is common.
4  Four
ある。このクロール法では、還元工程一真空分離工程を経て金属 Tiが製造される。 還元工程では、反応容器内で上方から供給される液体状の TiClが溶融 Mgにより  is there. In this crawl method, metal Ti is manufactured through a reduction process and a vacuum separation process. In the reduction process, liquid TiCl supplied from above in the reaction vessel is melted by molten Mg.
4  Four
還元され、粒子状の金属 Tiが生成し、逐次下方へ沈降してスポンジ状の金属 Tiが得 られる。真空分離工程では、反応容器内のスポンジ状金属 T 未反応の Mgおよ び副生物である MgClが除去される。  Reduced, particulate metal Ti is generated, and then sinks downward to obtain sponge-like metal Ti. In the vacuum separation process, sponge metal T unreacted Mg and by-product MgCl in the reaction vessel are removed.
2  2
[0003] クロール法による金属 Tiの製造では、高純度の製品を製造することが可能である。  [0003] In the production of metal Ti by the crawl method, it is possible to produce a high-purity product.
しかし、ノツチ式であるために製造コストが嵩み、製品価格が非常に高くなる。製造コ ストが嵩む原因の一つは、 TiClの供給速度を上げることが困難なことである。  However, since it is a Notch type, the manufacturing cost increases and the product price becomes very high. One reason for the increased manufacturing cost is that it is difficult to increase the supply rate of TiCl.
4  Four
[0004] その理由としては幾つか考えられる力 一つは、 TiClの供給速度を大きくしすぎる  [0004] There are several possible reasons for this. One is to increase the supply rate of TiCl too much
4  Four
と、沈降せず液面に残っている MgClに上方から TiClが供給されるようになるため、  Then, TiCl will be supplied from above to MgCl remaining on the liquid surface without settling,
2 4  twenty four
供給した TiClが未反応の TiClガスや還元が不十分な TiClガスなどとして反応容  The supplied TiCl reacts as unreacted TiCl gas or insufficiently reduced TiCl gas.
4 4 3 器外へ排出され、 TiClの利用効率が低下することである。  4 4 3 It is discharged to the outside of the vessel, and the utilization efficiency of TiCl decreases.
4  Four
[0005] また、クロール法では、反応容器内の溶融 Mg液の液面近傍だけで反応が行われ るため、発熱エリアが狭い。そのため、高速で TiClを供給すると冷却が間に合わなく  [0005] In the crawl method, 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.
4  Four
なることも、 TiClの供給速度が制限される大きな理由である。  This is also a major reason that the TiCl supply rate is limited.
4  Four
[0006] 更に、溶融 Mgの濡れ性 (粘着性)のため、生成した Ti粉が凝集した状態で沈降し、 沈降中にも高温の溶融液が有している熱により焼結して粒成長し、反応容器外へ回 収することが困難である。このため、金属 Tiの製造を連続的に行うことができず、生産 性が阻害される。 [0006] Further, due to the wettability (adhesiveness) of molten Mg, 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.
[0007] クロール法以外の Ti製造方法に関しては、米国特許第 2205854号明細書に、 Ti C1の還元剤として Mg以外に例えば Caの使用が可能なことが記載されている。そし Regarding the Ti production method other than the crawl method, 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. And
4 Four
て、 Caによる還元反応を用いた Tiの製造方法としては、米国特許第 4820339号明 細書 (以下、「文献 1」という）に、反応容器内に CaClの溶融塩を保持し、その溶融塩  As a method for producing Ti using a reduction reaction with Ca, US Pat. No. 4,820,339 (hereinafter referred to as “Literature 1”) holds a molten salt of CaCl in a reaction vessel and the molten salt.
2  2
中に上方力も金属 Ca粉末を供給して、溶融塩中に Caを溶け込ませると共に、下方 から TiClガスを供給して、 CaClの溶融塩中で溶解 Caと TiClを反応させる方法が  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.
4 2 4  4 2 4
記載されている。  Are listed.
[0008] し力しながら、上記文献 1に記載された方法は、還元剤として使用する金属 Caの粉 末が極めて高価で、これを購入して使用すると、製造コストはクロール法よりも高価と なるので、工業的な Ti製造法としては成立し得ない。カロえて、反応性が強い Caは取 り扱いが非常に難しぐこのことも、 Ca還元による Ti製造方法の工業ィ匕を阻害する大 きな要因になっている。  [0008] However, in the method described in the above-mentioned document 1, 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.
[0009] 更に別の Ti製造方法としては、米国特許第 2845386号明細書 (以下、「文献 2」と いう）に、 TiClを経由せず、 TiOを Caにより直接還元するオルソンの方法が記載さ  [0009] As yet another Ti production method, US Pat. No. 2,845,386 (hereinafter referred to as “Reference 2”) describes Olson's method in which TiO is directly reduced by Ca without passing through TiCl.
4 2  4 2
れている。この方法は、酸化物直接還元法の一種である。しかし、この方法では高価 な高純度の TiOを使用しなければならない。  It is. This method is a kind of direct oxide reduction method. However, this method requires the use of expensive high-purity TiO.
2  2
[0010] 一方、本発明者らは、 Ca還元による Ti製造方法を工業的に確立するためには、 Ti C1の Caによる還元が不可欠であり、還元反応で消費される溶融塩中の Caを経済的 [0010] On the other hand, in order to industrially establish a Ti production method by Ca reduction, the present inventors need to reduce Ti C1 with Ca, and the Ca in the molten salt consumed in the reduction reaction is reduced. Economic
4 Four
に補充する必要があると考え、特開 2005— 133195号公報（以下、「文献 3」という） および特開 2005— 133196号公報（以下、「文献 4」という）において、溶融 CaClの  In JP-A-2005-133195 (hereinafter referred to as “Reference 3”) and JP-A-2005-133196 (hereinafter referred to as “Reference 4”),
2 電気分解により生成する Caを利用すると共に、この Caを循環使用する方法、すなわ ち「OYIK法 (ォーイツク法)」を提案した。上記文献 3では、電気分解により Caが生成 、補充され、 Caリッチとなった溶融 CaClを反応容器に導入し、 Ca還元による Ti粒の  2 In addition to using Ca produced by electrolysis, we proposed a method of circulating this Ca, that is, the “OYIK method”. In Reference 3 above, Ca is generated and replenished by electrolysis, Ca-rich molten CaCl is introduced into the reaction vessel, and Ti particles are reduced by Ca reduction.
2  2
生成に使用する方法が記載され、上記文献 4では、更に、陰極として合金電極 (例え ば、 Mg— Ca合金電極)を用いることにより、電解に伴うバックリアクションを効果的に 抑制する方法が示されて ヽる。  The method used for generation is described, and the above-mentioned document 4 further shows a method of effectively suppressing back reaction accompanying electrolysis by using an alloy electrode (for example, Mg—Ca alloy electrode) as a cathode. Speak.
発明の開示 [0011] 前述のとおり、クロール法以外の Ti製造方法について、従来多くの研究開発が行 われてきた。特に本発明者らが提案した前記「OYIK法 (ォーイツク法)」では、 TiCl Disclosure of the invention [0011] As described above, much research and development has been conducted on Ti production methods other than the crawl method. In particular, in the “OYIK method” proposed by the present inventors, TiCl
4 の還元反応に伴 、溶融塩中の Caが消費される力 その溶融塩を電気分解すれば溶 融塩中に Caが生成し、こうして得られた Caを還元反応に再使用すれば、外部からの Ca補充が不要になり、し力も、 Caを単独で取り出す必要がないので、経済性が向上 する。  The power that Ca in the molten salt is consumed by the reduction reaction in (4) If the molten salt is electrolyzed, Ca is generated in the molten salt, and if the Ca thus obtained is reused in the reduction reaction, the external Since there is no need to replenish Ca, and there is no need to remove Ca alone, the economy is improved.
[0012] そこで、本発明者らは、基本的な構成はこの OYIK法に立脚し、更に、効率よぐ安 定した操業を行い得る金属 Ti製造プロセスの開発の一環として、溶融 CaClの電解  [0012] Therefore, 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
2 工程について検討を加えることとした。本発明の Tほたは Ti合金の製造方法は、そ の着想から開発、完成に深く関与した 4名「小笠原、山口、巿橋、金澤」のイニシャル をとり、「ΟΥΙΚ—Π法 (ォーイツクー II法）」と命名する。  It was decided to consider two processes. 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) ”.
[0013] 本発明の目的は、 Ca、 Li、 Na、 A1等のメタルフォグ形成金属の塩化物を含有する 溶融塩、特に CaClを含有する溶融塩を電気分解して、 Ca濃度が高められた溶融 [0013] 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. Melting
2  2
塩を得るに際し、高濃度 Ca含有溶融塩の回収を効率よく行うことが可能で、高電流 効率を維持でき、しカゝも大量の溶融 CaCl  When obtaining salt, it is possible to efficiently recover high-concentration Ca-containing molten salt, maintain high current efficiency, and large amounts of molten CaCl
2を連続して電解できる溶融塩電解方法、 およびそれに用いる電解槽、並びにその方法を適用した Tiの製造方法を提供するこ とにある。  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.
[0014] 前記の課題を解決するために、本発明者らは、溶融 CaClを使用し、電解槽容器  [0014] In order to solve the above problems, the present inventors use molten CaCl, and
2  2
の形状、電極形状、電解条件、極間距離等について詳細な検討を行い、本発明をな すに至った。  Detailed studies were made on the shape, electrode shape, electrolysis conditions, distance between electrodes, etc., and the present invention was achieved.
[0015] 本発明の要旨は、下記（1)の溶融塩電解方法、（2)の電解槽、およびその方法を 用いた（3)の Tiの製造方法にある。  [0015] 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.
[0016] (1)メタルフォグ形成金属の塩化物を含有する溶融塩を電解槽の一端からアノード と力ソードの間に連続的または断続的に供給することにより、力ソード表面近傍の溶 融塩に一方向の流速を与え、溶融塩を力ソード表面近傍で一方向に流しつつ電気 分解することにより溶融塩のメタルフォグ形成金属濃度を高める溶融塩電解方法。  [0016] (1) Molten salt in the vicinity of the surface of the force sword by supplying a molten salt containing chloride of the metal fog forming metal continuously or intermittently from one end of the electrolytic cell between the anode and the force sword. A molten salt electrolysis method in which the metal fog forming metal concentration in the molten salt is increased by applying a flow rate in one direction and electrolyzing the molten salt in one direction near the surface of the force sword.
[0017] ここで言う「メタルフォグ形成金属」とは、例えば、 Ca、 Li、 Na、 A1等のように、金属 の塩ィ匕物にその金属自身が溶解する性質を備え (すなわち、 Caは CaClに、また Li は LiCl〖こ溶解する）、かつ TiClを還元する金属である。 [0017] 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.
4  Four
[0018] この溶融塩電解方法において、アノード表面および力ソード表面が対向して略垂直 方向に配置され、アノードと力ソードの間に隔膜または溶融塩の一部が流通可能に 構成された隔壁が設けられている電解槽を用いることとすれば、アノード側で発生す る塩素ガスを回収しやすい。また、電解により生成したメタルフォグ形成金属（例えば 、 Ca)と塩素（C1)とが反応して CaClに戻るバックリアクションを抑制することができる  [0018] In this molten salt electrolysis method, 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.
2  2
ので、望ましい (以下、第 1実施形態と記す)。  Therefore, it is desirable (hereinafter referred to as the first embodiment).
[0019] 力ソードが中空であり、力ソード表面力 力ソード内部に溶融塩が流入できる隙間ま たは穴を有し、力ソード内部に流入したメタルフォグ形成金属濃化溶融塩を電解槽 外へ抜き出すことができる実施形態を採用すれば、ノ ックリアクションを効果的に抑 制することができる（以下、第 2実施形態と記す)。 [0019] 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).
[0020] また、電解槽内の溶融塩のメタルフォグ形成金属濃度が飽和溶解度未満となるよう に制御することとすれば、 Ca濃度を高めて TiClの生成速度を増大させるとともに、 [0020] If 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,
4  Four
電解槽内部の閉塞などの弊害を抑制することができる（以下、第 3実施形態と記す)。  Defects such as blockage inside the electrolytic cell can be suppressed (hereinafter referred to as the third embodiment).
[0021] (2)メタルフォグ形成金属の塩化物を含有する溶融塩を保持する一方向に長い電 解槽容器と、前記電解槽容器の長手方向に沿って配置されたアノードおよびカソー ドを有し、前記電解槽容器の長手方向の一方の端部に、溶融塩供給口が前記ァノ 一ドとカソードの間に溶融塩を供給できるように設けられ、他方の端部に前記溶融塩 の電気分解により生成する Ca濃度が高められた溶融塩を電解槽外へ抜き出す溶融 塩抜き出し口が設けられて 、る電解槽。 [0021] (2) It has an electrolytic cell container that is long in one direction holding a molten salt containing a metal fog forming metal chloride, and an anode and a cathode that are arranged along the longitudinal direction of the electrolytic cell container. 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.
[0022] この電解槽が、アノード表面および力ソード表面が対向して略垂直方向に配置され 、更に、アノードと力ソードの間に隔膜または溶融塩の一部が流通可能に構成された 隔壁が設けられたものであれば、前記第 1実施形態の電解方法の実施に好適に使 用できる。 [0022] 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.
[0023] (3) CaClを含み且つ Caが溶解した溶融塩中の Caに TiClを反応させて前記溶融  [0023] (3) The above-mentioned molten TiCl is reacted with Ca in the molten salt containing CaCl and dissolved in Ca.
2 4  twenty four
塩中に Ti粒を生成させる還元工程と、前記溶融塩中に生成された Ti粒を前記溶融 塩力 分離する分離工程と、 Ti粒の生成に伴って Ca濃度が低下した溶融塩を電解 することにより Ca濃度を高める電解工程とを含み、電解工程で生成された Ca濃度が 高まった溶融塩を還元工程で TiClの還元に用いる Tiの製造方法であって、前記電 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:
4  Four
解工程で、前記（1)に記載の溶融塩電解方法を適用する Tiの製造方法。  A method for producing Ti, wherein the molten salt electrolysis method according to (1) is applied in the solution step.
[0024] 本発明の溶融塩電解方法は、溶融塩を力ソード表面近傍で一方向に流しつつ電 気分解して電解槽の出側でメタルフォグ形成金属濃度が高まった溶融塩を回収する 方法である。この電解方法によれば、ノ ックリアクションを抑制して高電流効率を維持 すると共に、 Caなどのメタルフォグ形成金属が濃化した溶融塩のみを効果的に取り 出すことができ、し力も、大量の溶融 CaClを連続電解することが可能である。この方 [0024] 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
2  2
法は本発明の電解槽により容易に実施することができる。  The method can be easily carried out by the electrolytic cell of the present invention.
[0025] また、本発明の溶融塩電解方法を Ca還元による Tiの製造に適用すれば、 Caが濃 化した溶融塩が比較的安定して得られるので、金属 Tiを効率よく製造することができ る。  [0025] Further, 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, so that metal Ti can be produced efficiently. it can.
図面の簡単な説明  Brief Description of Drawings
[0026] 図 1は、本発明の電解槽の要部の構成例を示す縦断面図である。 FIG. 1 is a longitudinal sectional view showing a configuration example of a main part of the electrolytic cell of the present invention.
図 2は、本発明の電解槽の他の構成例で、中空力ソードを用いた電解槽の一部の 構成を模式的に示す図である。  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.
図 3は、本発明の Tiの製造方法を実施する際の工程例を示す図である。 発明を実施するための最良の形態  FIG. 3 is a diagram showing a process example when the Ti manufacturing method of the present invention is carried out. BEST MODE FOR CARRYING OUT THE INVENTION
[0027] 以下に、本発明の溶融塩電解方法、電解槽およびその方法を用いる Tiの製造方 法を、図面を参照して具体的に説明する。なお、本発明の溶融塩電解方法において 、メタルフォグ形成金属は、 TiClを還元して Tiを生成させるに際しいずれも同様に [0027] Hereinafter, the molten salt electrolysis method, the electrolytic cell, and the Ti production method using the method of the present invention will be specifically described with reference to the drawings. In the molten salt electrolysis method of the present invention, the metal fog forming metal is the same when reducing TiCl to produce Ti.
4  Four
作用するので、以下、メタルフォグ形成金属が Caの場合について説明する。  In the following, the case where the metal fog forming metal is Ca will be described.
[0028] 図 1は、本発明の溶融塩電解方法を実施する際に用いられる電解槽の要部の構成 例を示す縦断面図である。 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.
[0029] この電解槽 1は、 CaClを含有する溶融塩を保持する一方向に長い配管（円筒)形 [0029] This electrolytic cell 1 has a pipe (cylindrical) shape that is long in one direction and holds a molten salt containing CaCl.
2  2
状の電解槽容器 laと、前記電解槽容器 laの長手方向に沿って当該容器 la内に配 置された同じく円筒形状のアノード 2、および円柱状の力ソード 3を有し、前記電解槽 容器 laの長手方向の一方の端部 (底盤 4)に溶融塩供給口 6が設けられ、他方の端 部（上蓋 5)には溶融塩抜き出し口 7が設けられている。アノード表面と力ソード表面が 対向して略垂直方向に配置され、更に、アノード 2と力ソード 3の間に、溶融塩の電解 で生成した Caの通過を抑制するための隔膜 8が設けられている。また、アノード 2の 外面には冷却器 9が取り付けられている。 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.
[0030] 本発明の溶融塩電解方法は、メタルフォグ形成金属（Ca)の塩化物（CaCl )を含 [0030] The molten salt electrolysis method of the present invention includes a metal fog forming metal (Ca) chloride (CaCl 3).
2 有する溶融塩を電解槽の一端力 アノードと力ソードの間に連続的または断続的に 供給することによって力ソード表面近傍の溶融塩に一方向の流速を与え、溶融塩を 力ソード表面近傍で一方向に流しつつ電気分解することにより溶融塩の Ca濃度を高 めることを特徴として 、る。  2 By supplying the molten salt having one end force of the electrolytic cell continuously or intermittently between the anode and the force sword, a flow rate in one direction is given to the molten salt near the surface of the force sword, and the molten salt is placed near the surface of the force sword. It is characterized by increasing the Ca concentration of the molten salt by electrolysis while flowing in one direction.
[0031] すなわち、本発明の溶融塩電解方法においては、先ず、 CaClを含有する溶融塩 That is, in the molten salt electrolysis method of the present invention, first, a molten salt containing CaCl is used.
2  2
を電解槽 1の一端力もアノード 2と力ソード 3の間に連続的または断続的に供給する。 なお、ここで、「CaClを含有する溶融塩」とは、溶融 CaClのみ、または、溶融 CaCl  The one end force of the electrolytic cell 1 is also supplied continuously or intermittently between the anode 2 and the force sword 3. Here, the “molten salt containing CaCl” means only molten CaCl or molten CaCl.
2 2 2 に、融点の低下、粘性等の調整のために KC1、 CaF等をカ卩えた溶融塩である。以下  2 2 2 is a molten salt containing KC1, CaF, etc. for adjusting the melting point and viscosity. Less than
2  2
、単に「溶融塩」という。  This is simply called “molten salt”.
[0032] 電解槽 1は一方向に長!、形状（図示した例では、垂直方向に細長!/、配管（円筒）形 状)を有しているので、溶融塩を電解槽 1の一端力 アノード 2と力ソード 3の間に連続 的または断続的に供給することにより、力ソード 3表面近傍の溶融塩に一方向の流速 を与え、溶融塩を力ソード 3表面近傍で一方向に流すことが可能となる。この場合、少 なくとも力ソード 3表面近傍の溶融塩が一方向に流れる状態が現出されればよぐァノ ード 2と力ソード 3間の溶融塩全体が一方向に流れてもよい。なお、前記の「力ソード 表面近傍」とは、力ソード表面で生成した Caが存在している力ソード表面に隣接する 領域をいう。  [0032] 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. By supplying continuously or intermittently between the anode 2 and the force sword 3, 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. Is possible. In this case, it is sufficient that the molten salt near the surface of the force sword 3 flows in one direction. 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.
[0033] 溶融塩の供給は、通常は連続的に行うが、後工程等との関係で、断続的に、つまり 溶融塩の供給を一次停止しても、再度供給を続けてもよい。溶融塩の供給を一次停 止した場合は、力ソード表面近傍における溶融塩の流れも停止する。従って、前記の 「力ソード表面近傍の溶融塩に一方向の流速を与える」際の「流速」には、厳密に言 えば、流れのない流速 0の状態も含まれる。  [0033] Although 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. When the supply of molten salt is temporarily stopped, 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.
[0034] 続ヽて、溶融塩を電気分解する。すなわち、溶融塩を力ソード表面近傍で一方向 に流しつつ電気分解して力ソード表面で Caを生成させるのである力 電解槽 1は一 方向に長い形状を有しており、更に、図 1に示した例では、電解電圧を低く抑えるた めにアノード 2と力ソード 3間の距離を比較的狭くして 、るので、 Ca濃度が低 、溶融 塩供給口 6付近の溶融塩と電解により Ca濃度が高まった溶融塩抜き出し口 7付近の 溶融塩との混合を防止して、 Caが濃化した溶融塩のみを効果的に抜き出すことがで きる。 [0034] Subsequently, the molten salt is electrolyzed. In other words, 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. In addition, in the example shown in FIG. 1, the distance between the anode 2 and the force sword 3 is made relatively small in order to keep the electrolysis voltage low. 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.
[0035] 前記文献 2に記載の技術は、還元に Caを使用する力 TiClではなぐ TiOを直接  [0035] The technique described in Document 2 described above is based on the ability to use Ca for reduction.
4 2 4 2
Caで還元して Tiとする直接還元法であり、本発明の電解方法とは異なるものである。 更に、前記文献 2に記載の直接還元法では、アノードである炭素電極が COとなって This is a direct reduction method that reduces to Ca to Ti, and is different from the electrolysis method of the present invention. Furthermore, in the direct reduction method described in Document 2, the carbon electrode serving as the anode becomes CO.
2 消耗するほか、溶融塩中に炭化チタン (TiC)が生成するため、得られる Tiには C汚 染が生じた Tiが混入し、加工性が劣化するので、この Tiを展伸材として用いる際に 問題となる。  2 In addition to being consumed, titanium carbide (TiC) is generated in the molten salt, so the Ti that is obtained is contaminated with C-contaminated Ti, which degrades workability. When it comes to problems.
[0036] また、前記文献 2には、「溶融塩中での Ca還元による Tiの生成において、力ソード 付近に溶融塩の流れを形成する」技術が記載されている。しかし、アノードと力ソード を電解槽内の長手方向に沿って対向させて配置し、力ソード表面近傍において、ま たは隔膜等が設けられている場合には力ソード表面と隔膜の間に形成される力ソード 室において、力ソード表面に沿った一方向の溶融塩の流れを形成させ、その状態で 電解することにより電解槽の出側で Ca濃度が高まった溶融塩を回収するという本発 明の技術思想な ヽしはそれを示唆する記述は示されては!ヽな ヽ。  [0036] Further, 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". However, when 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. In this force sword chamber, 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!
[0037] 従って、電解槽内で溶融塩に一方向の流れを形成させる点では共通しても、本発 明の溶融塩電解方法と前記文献 2に記載される技術は全く相違している。  [0037] Therefore, 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.
[0038] 本発明の溶融塩電解方法における第 1実施形態は、アノード表面および力ソード表 面が対向して略垂直方向に配置され、アノードと力ソードの間に隔膜または溶融塩の 一部が流通可能に構成された隔壁が設けられている電解槽を用いる方法である。前 記の「略垂直方向」の「略」とは、「ほぼ」、「概ね」という意味であり、「略垂直方向」とは 、垂直方向、またはその方向力 水平方向へ向けて若干傾いた方向をいう。  [0038] In the first embodiment of the molten salt electrolysis method of the present invention, 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.
[0039] この第 1実施形態に係る電解方法は、前記図 1に例示した電解槽を用いることによ り好適に実施できる。なお、図 1に例示した電解槽では、電解槽 1の下方カゝら CaCl  [0039] 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.
2 を電解槽 1内に供給し、上方カゝら抜き出す方式を採っているが、逆に、電解槽 1の上 方から供給し、下方力 抜き出す方式を採用することも可能である。 2 is supplied to the electrolytic cell 1 and is taken out from the upper side. It is also possible to adopt a method of supplying from the side and extracting the downward force.
[0040] この電解方法で用いる電解槽では、アノード表面および力ソード表面が対向して略 垂直方向に配置されており、一方、力ソード表面近傍の溶融塩には一方向の流速が 与えられているので、その溶融塩の流れ方向は縦方向であり、アノード側で発生する 塩素ガスは容易に浮上するので回収しやす 、。  [0040] In the electrolytic cell used in this electrolysis method, 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.
[0041] アノードと力ソードの間に設ける隔膜としては、例えば、イットリア (Y O )を含む多  [0041] Examples of the diaphragm provided between the anode and the force sword include, for example, many kinds including yttria (Y 2 O 3).
2 3 孔質セラミックス体を使用することができる。イットリアを焼成して多孔質セラミックス体 としたものは、 Caや塩素のイオンは通すが金属 Caを通過させな 、と 、う選択透過性 を備え、また、強力な還元力をもつ Caによっても還元されない優れた耐カルシウム還 元性を有しており、本発明の溶融塩電解方法における隔膜として好適である。  2 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.
[0042] このような隔膜がアノードと力ソードの間に設けられた電解槽を用いれば、力ソード 側に生成する Caがアノード（黒鉛)側に生成する塩素とすぐに反応して CaClに戻る [0042] If an electrolytic cell in which such a diaphragm is provided between the anode and the force sword is used, Ca generated on the force sword side reacts immediately with chlorine generated on the anode (graphite) side and returns to CaCl.
2 ノ ックリアクションが起こり難ぐ高い電流効率で電解することができる。  2 Electrolysis can be carried out with high current efficiency at which knock reaction is unlikely to occur.
[0043] 隔膜の代わりに溶融塩の一部が流通可能に構成された隔壁を用いてもよい。隔壁 は金属 Caはもとより Caや塩素のイオンなど溶融塩も通さないが、隔壁の一部に溶融 塩が通過できるスリットや穴などを設けておくことにより、電解を可能とし、一方、金属 Caの通過をある程度制限して、ノ ックリアクションを抑制することが可能となる。 [0043] Instead of the diaphragm, 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.
[0044] 本発明の溶融塩電解方法 (第 1実施形態を含む）における第 2実施形態は、カソー ドが中空であり、力ソード表面力 力ソード内部（すなわち、中空部）に溶融塩が流入 できる隙間または穴を有し、力ソード内部に流入した Ca濃化溶融塩を電解槽外へ抜 き出すことができる方法である。 [0044] In the second embodiment of the molten salt electrolysis method of the present invention (including the first embodiment), 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.
[0045] 図 2は、中空力ソードを用いた電解槽の一部の構成例を模式的に示す図である。図 2に示すように、この電解槽 1では、電解槽 1内の長手方向に沿ってアノード 2と中空 力ソード 3aが対向して略垂直方向に配置されており、アノード 2と力ソード 3aの間に は隔膜 8が設けられている。図示していないが、力ソード 3aには、力ソード表面から力 ソード内部に溶融塩が流入できる隙間または穴が設けられている。  FIG. 2 is a diagram schematically showing a configuration example of a part of an electrolytic cell using a hollow force sword. As shown in FIG. 2, in this electrolytic cell 1, 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. Although not shown, 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.
[0046] このように構成された電解槽を用いれば、溶融塩を力ソード 3aの中空部上方から抜 き出すことにより、同図中に白抜き矢印で示すように、力ソード外面側から内部（中空 部）への溶融塩流が形成され、力ソード 3aの外表面で生成した Caはアノード側へ拡 散移動することなぐ直ちに力ソード 3aの内部へ取り込まれる。これにより、バックリア クシヨンを効果的に抑制することができる。図 2に例示した電解槽は隔膜 8を有してい るので、隔膜がない場合に比べて、ノ ックリアクション抑制効果はより一層大きくなる。 [0046] By using 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. (Hollow 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. Since 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.
[0047] 中空力ソードに設ける隙間や穴の大きさ、位置等は特に限定しない。アノード面 (隔 膜が設けられている場合には、隔膜表面)と力ソード外面との距離、溶融塩の抜き出 し量 (溶融塩の供給量)等を勘案し、効果的な力ソード内面側への溶融塩流が形成さ れるように適宜定めるのがよい。  [0047] There are no particular restrictions on the size and position of the gaps and holes provided in the hollow force sword. Considering the distance between the anode surface (diaphragm surface if a diaphragm is provided) and the outer surface of the force sword, the amount of molten salt extracted (the amount of molten salt supplied), etc. It is advisable to determine appropriately so that a molten salt flow to the side is formed.
[0048] 本発明の溶融塩電解方法 (第 1および第 2実施形態を含む）における第 3実施形態 は、電解槽内の溶融塩の Ca濃度が飽和溶解度未満となるように制御する電解方法 である。なお、前記の「Ca濃度が飽和溶解度未満となるように制御する」とは、「Ca濃 度が飽和溶解度に近く、且つ析出しな 、条件で」電解することを意味する。  [0048] The third embodiment of the molten salt electrolysis method of the present invention (including the first and second embodiments) 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. The above-mentioned “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”.
[0049] 具体的には、電解槽内の Ca濃度が最も高くなつている部位において「Ca濃度が飽 和溶解度に近ぐ且つ析出しない条件」が満たされるように、電解槽容器の形状、電 極形状、極間距離等に応じた最適の電解条件、溶融塩の単位時間当たりの抜き出し 量等を経験的に定めることになる。特に、アノードと力ソード間に隔膜や隔壁を用いる 場合は、力ソード側の溶融塩抜き出し口近傍の Ca濃度が最も高くなるので、この部 分の Ca濃度が飽和溶解度未満となるように制御することにより、電解槽のどの部位に お!ヽても金属 Caを析出させな 、電解操業が可能となる。  [0049] Specifically, 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. In particular, when a diaphragm or partition wall is used between the anode and the force sword, 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. As a result, electrolysis can be performed without depositing metallic Ca in any part of the electrolytic cell.
[0050] このような電解方法を採用すれば、電解槽内部の閉塞などの弊害を抑制しつつ、 C aが飽和溶解度近くまで濃化した溶融塩を比較的安定して得ることができる。  [0050] By adopting such an electrolysis method, it is possible to relatively stably obtain a molten salt in which Ca is concentrated to near the saturation solubility while suppressing adverse effects such as clogging inside the electrolytic cell.
[0051] 本発明の Ca濃化に関する実施形態の一例では、電解槽に入る CaClの温度を 80  [0051] In an example of an embodiment of the present invention relating to Ca concentration, the temperature of CaCl entering the electrolytic cell is set to 80.
2  2
0°Cとして、その溶融 CaClの金属 Ca濃度が 0%から、電解槽から出る溶融 CaClの  At 0 ° C, the molten CaCl has a metallic Ca concentration of 0%.
2 2 金属 Ca濃度を 1%にまで増カロさせることができる。そして、電解槽に入る溶融 CaCl  2 2 Metal Ca concentration can be increased to 1%. And the molten CaCl entering the electrolytic cell
2 の金属 Ca濃度 (A濃度）を 0〜1%未満とし、電解槽から出る溶融 CaClの金属 Ca濃  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
2  2
度 (B濃度）を 0. 1%以上とするのが望ましい。また、電解槽での金属 Ca濃度の増加 分 (B— A濃度）は、後工程での Caが効率よく利用されることを考慮すると、 0. 1%以 上、 5. 0%以下 (過飽和の Caを含めた濃度）とするのが望ましぐ特に望ましくは 1. 0 %以上である。 The degree (B concentration) should be 0.1% or more. In addition, 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.
[0052] 本発明の溶融塩電解方法の実施に際しては、電解槽では大きな反応熱が発生す るので、抜熱を効果的に行うことが望ましい。具体的には、前述の中空力ソードを用 いない場合でも、用いる場合でも、力ソードの中心部に冷却器を設置して、反応熱を 力ソード内部から抜熱することが望ましい。冷却器としては、例えばチューブ状の熱 交換器が好適である。  [0052] When the molten salt electrolysis method of the present invention is carried out, 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. As the cooler, for example, a tubular heat exchanger is suitable.
[0053] アノード側にも冷却器 (熱交換器)を設置すると抜熱効率は更に高くなる。前記図 1 に示した、アノード 2を取り巻くように設置した冷却器 9はこの例である。  [0053] If a cooler (heat exchanger) is also installed on the anode side, the heat removal efficiency is further increased. The cooler 9 installed so as to surround the anode 2 shown in FIG. 1 is an example of this.
[0054] 電解に際し、通電量を高めて Ca生成量の増大を図るには、通電表面積を大きくす る必要がある。アノード 2の内面、すなわち、図 1に例示した電解槽 1において、カソ ード表面と対向する面については、大きい通電表面積を確保するために内面に微細 な凹凸を設けることが望ましい。そのための方法としては、例えば、電極表面に溝を 形成するみぞ加工などが適用できる。  [0054] During electrolysis, in order to increase the amount of energization and increase the amount of Ca generation, it is necessary to increase the surface area of energization. Regarding the inner surface of the anode 2, that is, the surface facing the cathode surface in the electrolytic cell 1 illustrated in FIG. 1, it is desirable to provide fine irregularities on the inner surface in order to ensure a large current-carrying surface area. As a method for that purpose, for example, groove processing for forming a groove on the electrode surface can be applied.
[0055] 本発明の溶融塩電解方法によれば、溶融塩を力ソード表面近傍で一方向に流しつ つ電気分解するので、大量の溶融塩を連続して処理することが可能である。  [0055] According to 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.
[0056] 本発明の電解槽は、前述した溶融塩電解方法を実施する際に用いられる電解槽で あり、 CaCl  [0056] The electrolytic cell of the present invention is an electrolytic cell used when the above-described molten salt electrolysis method is carried out.
2含有する溶融塩を保持する一方向に長い電解槽容器と、前記電解槽容 器の長手方向に沿って配置されたアノードおよび力ソードを有し、前記電解槽容器 の長手方向の一方の端部に、溶融塩供給口が前記アノードと力ソードの間に溶融塩 を供給できるように設けられ、他方の端部に前記溶融塩の電気分解により生成する c a濃度が高められた溶融塩を電解槽外へ抜き出す溶融塩抜き出し口が設けられてい ることを特徴としている。  (2) 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.
[0057] 前記図 1に例示した電解槽は、この本発明の電解槽の一実施形態で、アノード表 面および力ソード表面が対向して略垂直方向に配置され、アノードと力ソードの間に 隔膜が設けられている電解槽である。隔膜の代わりに、溶融塩の一部が流通可能に 構成された隔壁が設けられたものであってもよ ヽ。前記図 1に示した電解槽を用いれ ば、前述したように、本発明の溶融塩電解方法を好適に実施することができる。  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. An electrolytic cell provided with a diaphragm. Instead of the diaphragm, a partition wall configured to allow a part of the molten salt to flow therethrough may be provided. If the electrolytic cell shown in FIG. 1 is used, as described above, the molten salt electrolysis method of the present invention can be suitably carried out.
[0058] 本発明の Ti製造方法は、 CaClを含み且つ Caが溶解した溶融塩中の Caに TiCl を反応させて前記溶融塩中に Ti粒を生成させる還元工程と、前記溶融塩中に生成さ れた Ti粒を前記溶融塩から分離する分離工程と、 Ti粒の生成に伴って Ca濃度が低 下した溶融塩を電解することにより Ca濃度を高める電解工程とを含み、電解工程で 生成された Ca濃度が高まった溶融塩を還元工程で TiClの還元に用いる Tiの製造 [0058] In the Ti production method of the present invention, 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 production of Ti using the molten salt with increased Ca concentration produced in the electrolysis process for the reduction of TiCl in the reduction process.
4  Four
方法であって、前記電解工程で、本発明の溶融塩電解方法を適用することを特徴と している。  The method is characterized in that the molten salt electrolysis method of the present invention is applied in the electrolysis step.
[0059] 図 3は、本発明の Ti製造方法を実施する際の工程例を示す図である。図 3に示す ように、この Ti製造工程は、 CaClを含み且つ Caが溶解した溶融塩中の Caに TiCl  [0059] 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.
2 4 を反応させて前記溶融塩中に Ti粒を生成させる還元工程 10と、前記溶融塩中に生 成した Ti粒を前記溶融塩から分離する分離工程 11と、 Ti粒の生成に伴って Ca濃度 が低下した溶融塩を電解することにより Ca濃度を高める電解工程とを含んでいる。本 発明の Ti製造方法では、この電解工程で、前述の溶融塩電解方法を適用するので 、この電解方法の実施に用いる電解槽 1が組み込まれて 、る。  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. In the Ti production method of the present invention, since the molten salt electrolysis method is applied in this electrolysis step, the electrolytic cell 1 used for carrying out this electrolysis method is incorporated.
[0060] ここで用いられている電解槽 1は、垂直方向に長い円筒形状の電解槽容器 laと、 前記電解槽容器 laの長手方向に沿って配置されたアノード 2および力ソード 3を有し 、アノード 2と力ソード 3の間に隔膜 8が設けられた電解槽 1である。前記電解槽 1には 、図示していないが、上端部に、アノード 2と力ソード 3の間に溶融塩を供給するため の溶融塩供給口が、また下端部に、溶融塩の電気分解により生成する Ca濃度が高 められた溶融塩を電解槽 1外へ抜き出す溶融塩抜き出し口が設けられている。  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. An electrolytic cell 1 in which a diaphragm 8 is provided between an anode 2 and a force sword 3. Although not shown, 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.
[0061] 電解槽 1の上端部力 供給された CaClを含有する溶融塩は電解槽 1内を下方へ  [0061] Force at upper end of electrolytic cell 1 The supplied molten salt containing CaCl moves downward in electrolytic cell 1
2  2
移行しつつ電気分解され、 Caが生成する。溶融塩中の Ca濃度は下方へ行くほど高 められる。その間、アノード 2と力ソード 3の間に設けられた隔膜 8によりバックリアクショ ンが抑制され、高い電流効率が維持される。また、操業時には、溶融塩の Ca濃度が 飽和溶解度未満、すなわち、 Ca濃度が飽和溶解度に近ぐ且つ析出しないように制 御される。なお、電解槽 1が縦型なので、アノード側で発生する塩素ガスの回収が容 易である。  It undergoes electrolysis while migrating to produce Ca. The Ca concentration in the molten salt increases as it goes downward. Meanwhile, the back reaction is suppressed by the diaphragm 8 provided between the anode 2 and the force sword 3, and high current efficiency is maintained. In operation, the molten salt is controlled so that the Ca concentration of the molten salt is less than the saturation solubility, that is, the Ca concentration is close to the saturation solubility and does not precipitate. Since the electrolytic cell 1 is a vertical type, it is easy to recover the chlorine gas generated on the anode side.
[0062] このようにして得られた Caが濃化した溶融塩が電解槽 1の下端部の溶融塩抜き出 しロカ 抜き出され、還元工程 10へ移送される。 [0063] 還元工程 10で、 Caが濃化した溶融塩中の Caに TiClのガスを反応させると、溶融 [0062] 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,
4  Four
塩中に粒子状の金属 Tiが生成する。溶融塩中での還元反応が進行すると、溶融塩 中の Caが消費され、 Tiを生成すると同時に CaClが副生される。  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.
2  2
[0064] 還元工程 10で生成した Ti粒は溶融塩と共に分離工程 11へ移送され、 Ti粒は溶融 塩から分離される。分離には、高速デカンター (連続遠心分離)方式、シックナ一方 式等の固液分離操作が適用できる。なお、図示していないが、この還元工程 10で使 用される反応容器が前記副生する CaClを含有する溶融塩を該容器外へ排出でき  [0064] 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. For the separation, solid-liquid separation operations such as a high-speed decanter (continuous centrifugation) method and a thickener one-way method can be applied. Although not shown, 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.
2  2
るように構成されて 、るものであれば、この還元工程 10からの排出溶融塩を電解ェ 程へ直接移送することもできる (前記文献 3、文献 4参照)。  As long as it is configured as described above, the molten salt discharged from the reduction step 10 can be directly transferred to the electrolytic process (refer to References 3 and 4).
[0065] クロール法で得られる Ti粉が凝集した状態であるのに対し、還元工程 10で得られ る Ti粒は凝集しにくぐかつ容器に固着しにくいので、容器力も取り出しやすぐ回収 後の Ti粒をそのまま溶解工程へ移送し、加熱溶解して Tiインゴット 12とすることが可 能である。 [0065] 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.
[0066] 一方、 Ti粒を分離回収した後に残留する Ca濃度が低下した溶融塩は、電解工程 へ送られ、前述した電解槽 1で電解処理を受け、 Caが濃化した溶融塩として再度還 元工程 10で TiClの還元に使用される。  [0066] On the other hand, 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.
4  Four
[0067] 本発明の Ti製造方法では、電解工程で Caが飽和溶解度近くまで濃化した溶融塩 が比較的安定して得られるので、金属 Tiを効率よく製造することができ、また、大量の 溶融塩を連続電解して生成する Caを還元工程へ供給できるので、量産にも対応し 得る方法である。  [0067] In the Ti production method of the present invention, a 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.
産業上の利用の可能性  Industrial applicability
[0068] 本発明の溶融塩電解方法は、溶融塩を力ソード表面近傍で一方向に流しつつ電 気分解する方法であり、この電解方法によれば、高電流効率を維持し、 Caなどのメタ ルフォグ形成金属が濃化した溶融塩のみを効果的に取り出すことができる。この電解 方法は本発明の電解槽により容易に実施することができる。また、本発明の溶融塩 電解方法を Ca還元による Tiの製造に適用すれば、 Caが濃化した溶融塩が比較的 安定して得られ、金属 Tiを効率よく製造することができる。従って、本発明の溶融塩 電解方法、電解槽、およびこの電解方法を適用する Tiの製造方法は、 Ca還元による Tiの製造に有効に利用することができる。 [0068] 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.

Claims

請求の範囲 The scope of the claims
[1] メタルフォグ形成金属の塩化物を含有する溶融塩を電解槽の一端からアノードと力 ソードの間に連続的または断続的に供給することにより、力ソード表面近傍の溶融塩 に一方向の流速を与え、溶融塩を力ソード表面近傍で一方向に流しつつ電気分解 することにより溶融塩のメタルフォグ形成金属濃度を高めることを特徴とする溶融塩電 解方法。  [1] By supplying a molten salt containing metal fog forming metal chloride from one end of the electrolytic cell between the anode and the force sword continuously or intermittently, the molten salt near the force sword surface is unidirectionally supplied. A molten salt electrolysis method characterized by increasing the concentration of metal fog forming metal in the molten salt by applying a flow rate and electrolyzing the molten salt in one direction near the surface of the force sword.
[2] アノード表面および力ソード表面が対向して略垂直方向に配置され、アノードとカソ ードの間に隔膜または溶融塩の一部が流通可能に構成された隔壁が設けられてい る電解槽を用いることを特徴とする請求項 1に記載の溶融塩電解方法。  [2] An electrolytic cell in which an anode surface and a force sword surface are opposed to each other and arranged in a substantially vertical direction, and a partition wall configured to allow a part of a diaphragm or a molten salt to flow between the anode and the cathode is provided. The molten salt electrolysis method according to claim 1, wherein:
[3] 力ソードが中空であり、力ソード表面力も力ソード内部に溶融塩が流入できる隙間ま たは穴を有し、力ソード内部に流入したメタルフォグ形成金属濃化溶融塩を電解槽 外へ抜き出すことを特徴とする請求項 1または 2に記載の溶融塩電解方法。  [3] The force sword is hollow, and the force sword surface force has a gap or a hole into which the molten salt can flow into the force sword, and the metal fog forming metal concentrated molten salt flowing into the force sword is removed from the electrolytic cell. The molten salt electrolysis method according to claim 1, wherein the molten salt electrolysis method is extracted.
[4] 電解槽内の溶融塩のメタルフォグ形成金属濃度が飽和溶解度未満となるように制 御することを特徴とする請求項 1〜3のいずれかに記載の溶融塩電解方法。  [4] The molten salt electrolysis method according to any one of [1] to [3], wherein the metal fog forming metal concentration of the molten salt in the electrolytic cell is controlled to be less than the saturation solubility.
[5] メタルフォグ形成金属の塩化物を含有する溶融塩を保持する一方向に長!ヽ電解槽 容器と、  [5] Metal fogging metal that is long in one direction to hold molten salt containing chloride of metal!
前記電解槽容器の長手方向に沿って配置されたアノードおよび力ソードを有し、 前記電解槽容器の長手方向の一方の端部に、溶融塩供給口が前記アノードとカソ ードの間に溶融塩を供給できるように設けられ、  An anode and a force sword are disposed along the longitudinal direction of the electrolytic cell container, and a molten salt supply port is melted between the anode and the cathode at one end of the electrolytic cell container in the longitudinal direction. Provided to supply salt,
他方の端部に前記溶融塩の電気分解により生成する Ca濃度が高められた溶融塩 を電解槽外へ抜き出す溶融塩抜き出し口が設けられていることを特徴とする電解槽。  An electrolytic cell characterized in that a molten salt extraction port is provided at the other end for extracting the molten salt generated by electrolysis of the molten salt and having an increased Ca concentration to the outside of the electrolytic cell.
[6] アノード表面および力ソード表面が対向して略垂直方向に配置され、更に、ァノー ドとカソードの間に隔膜または溶融塩の一部が流通可能に構成された隔壁が設けら れて 、ることを特徴とする請求項 5に記載の電解槽。 [6] The anode surface and the force sword surface are arranged to face each other in a substantially vertical direction, and further, a partition wall is provided between the anode and the cathode so that a part of the diaphragm or molten salt can flow. 6. The electrolytic cell according to claim 5, wherein:
[7] CaClを含み且つ Caが溶解した溶融塩中の Caに TiClを反応させて前記溶融塩 [7] By reacting TiCl with Ca in the molten salt containing CaCl and dissolving Ca, the molten salt
2 4  twenty four
中に Ti粒を生成させる還元工程と、前記溶融塩中に生成された Ti粒を前記溶融塩 力 分離する分離工程と、 Ti粒の生成に伴って Ca濃度が低下した溶融塩を電解す ることにより Ca濃度を高める電解工程とを含み、電解工程で生成された Ca濃度が高 まった溶融塩を還元工程で TiClの還元に用いる Tiの製造方法であって、 A reduction step for generating Ti grains therein, a separation step for separating the Ti grains generated in the molten salt by the molten salt force, and electrolyzing the molten salt in which the Ca concentration is reduced as the Ti grains are generated. In the process of increasing the Ca concentration, and the Ca concentration generated in the electrolysis process is high. A method for producing Ti in which the molten salt is used to reduce TiCl in the reduction process,
4  Four
前記電解工程で、請求項 1〜4のいずれかに記載の溶融塩電解方法を適用するこ とを特徴とする Tiの製造方法。  A method for producing Ti, wherein the molten salt electrolysis method according to any one of claims 1 to 4 is applied in the electrolysis step.
PCT/JP2006/316348 2005-08-30 2006-08-22 METHOD FOR ELECTROLYSIS OF MOLTEN SALT, ELECTROLYTIC CELL, AND PROCESS FOR PRODUCING Ti USING SAID METHOD WO2007026565A1 (en)

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EP1942210A1 (en) 2008-07-09
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