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US20080217184A1 - Method and Apparatus for Producing Ti Through Reduction by Ca - Google Patents

Method and Apparatus for Producing Ti Through Reduction by Ca Download PDF

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Publication number
US20080217184A1
US20080217184A1 US11/665,976 US66597605A US2008217184A1 US 20080217184 A1 US20080217184 A1 US 20080217184A1 US 66597605 A US66597605 A US 66597605A US 2008217184 A1 US2008217184 A1 US 2008217184A1
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Prior art keywords
molten salt
reaction tank
electrolytic cell
reduction
producing
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US11/665,976
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English (en)
Inventor
Masahiko Hori
Tadashi Ogasawara
Makoto Yamaguchi
Toru Uenishi
Masanori Yamaguchi
Yuichi Ono
Susumu Kosemura
Eiji Nishimura
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Osaka Titanium Technologies Co Ltd
Toho Titanium Co Ltd
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Osaka Titanium Technologies Co Ltd
Toho Titanium Co Ltd
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Assigned to OSAKA TITANIUM TECHNOLOGIES CO., LTD. reassignment OSAKA TITANIUM TECHNOLOGIES CO., LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SUMITOMO TITANIUM CORPORATION
Assigned to SUMITOMO TITANIUM CORPORATION, TOHO TITANIUM CO., LTD. reassignment SUMITOMO TITANIUM CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KOSEMURA, SUSUMU, NISHIMURA, EIJI, ONO, YUICHI, YAMAGUCHI, MASANORI, HORI, MASAHIKO, OGASAWARA, TADASHI, UENISHI, TORU, YAMAGUCHI, MAKOTO
Publication of US20080217184A1 publication Critical patent/US20080217184A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C22B34/1272—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
    • 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
    • C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode

Definitions

  • the present invention relates to a method and an apparatus for producing metallic Ti through reduction by Ca, in which titanium tetrachloride (TiCl 4 ) is reduced by Ca to produce the metallic Ti.
  • the Kroll method for reducing TiCl 4 by Mg is generally used as a method for industrially producing the metallic Ti.
  • TiCl 4 is obtained by chlorinating titanium oxide (TiO 2 ).
  • the metallic Ti is produced through a reduction step and a vacuum separation step.
  • the reduction step TiCl 4 is reduced by Mg in a reactor vessel.
  • the vacuum separation step unreacted Mg and magnesium chloride (MgCl 2 ) formed as a by-product are removed from the sponge metallic Ti produced in the reactor vessel.
  • the reactor vessel is filled with molten Mg, and the TiCl 4 liquid is supplied from above to a liquid surface of the molten Mg.
  • molten MgCl 2 which is of the by-product is generated near the liquid surface.
  • the generated metallic Ti sequentially moves downward. Because a specific gravity of the molten MgCl 2 is larger than that of the molten Mg, the molten MgCl 2 also moves downward, and the molten Mg comes up to the liquid surface instead.
  • the molten Mg is continuously supplied to the liquid surface by the specific-gravity difference substitution, and the reduction reaction of TiCl 4 proceeds continuously.
  • the supplied TiCl 4 becomes unreacted lower chloride gases (referred to as “unreacted gases”) such as an unreacted TiCl 4 gas and an unreacted TiCl 3 gas, and the unreacted gases are discharged outside the reactor vessel, which reduces utilization efficiency of TiCl 4 . It is necessary to avoid the generation of such unreacted gases, because a rapid increase in inner pressure of the reactor vessel is associated with the generation of the unreacted gases. Accordingly, there is a limit of the feed rate of TiCl 4 .
  • unreacted gases such as an unreacted TiCl 4 gas and an unreacted TiCl 3 gas
  • Japanese Patent Application Publication No. 0H8-295955 proposes a method in which the reaction efficiency is enhanced by supplying the liquid TiCl 4 in a dispersive manner to the liquid surface where the molten Mg exists, and thereby the Ti deposition is suppressed on the inner surface of the upper portion of the reactor vessel.
  • the method proposed in Japanese Patent Application Publication No. 08-295955 is not enough to suppress the Ti deposition.
  • U.S. Pat. No. 2,205,854 describes that, in addition to Mg, Ca can be used as the reducing agent of TiCl 4 .
  • U.S. Pat. No. 4,820,339 describes a method for producing Ti through the reduction reaction by Ca, wherein the molten salt of calcium chloride (CaCl 2 ) is held in a reactor vessel, metallic Ca powders are supplied into the molten salt from above, Ca is dissolved in the molten salt, and TiCl 4 gas is supplied from below to react the dissolved Ca with TiCl 4 in the molten salt of CaCl 2 .
  • the metallic Ti is generated from TiCl 4 by the reaction of the following chemical formula (i), and CaCl 2 which is of the by-product is also generated at the same time:
  • Ca has an affinity for Cl stronger than Mg has, and Ca is suitable for a reducing agent of TiCl 4 in principle.
  • Ca is used while dissolved in molten CaCl 2 .
  • an area (reaction field) where the reaction is created is enlarged, and the exothermic area is also enlarged, which facilitates the cooling. Accordingly, the feed rate of TiCl 4 can be largely enhanced, and the improvement of the productivity can be also expected.
  • U.S. Pat. No. 2,845,386 describes another Ti production method (Olsen method) in which TiO 2 is directly reduced by Ca not through TiCl 4 .
  • the method is a kind of oxide direct-reduction method. Although the method is highly efficient, the oxide direct-reduction method is not suitable to produce a high-purity Ti because it is necessary to use expensive high-purity TiO 2 .
  • An object of the present invention is to provide a method and an apparatus for economically producing a high-purity metallic Ti with high efficiency without using an expensive reducing agent.
  • the inventors proposes a method for generating Ca by electrolysis of the molten CaCl 2 liquid in an electrolytic cell to supply the CaCl 2 liquid containing Ca to the reaction tank in consideration of the fact that it is necessary that Ca consumed by the reduction reaction is economically replenished into the molten salt, i.e., it is necessary that Ca is replenished at low costs.
  • electrode reactions expressed by the following chemical formulas (ii) and (iii) proceed to generate a Cl 2 gas near the surface of an anode while Ca is generated near the surface of a cathode, which allows the Ca concentration to be increased in the electrolytic bath salt (molten CaCl 2 liquid) near the cathode.
  • the molten CaCl 2 liquid containing the high-concentration Ca near the cathode is deposited on and adheres to a metal plate, net, or wire having a temperature lower than a bath temperature, and the molten CaCl 2 liquid is transported into the reaction tank, which allows Ca consumed for the reduction of TiCl 4 to be replenished as needed. Therefore, the replenishment of the metallic Ca from the outside or the extraction of the metallic Ca is not required, which allows the metallic Ti to be economically produced.
  • Cathode Ca 2+ +2e ⁇ Ca (iii)
  • the present invention is made based on the above consideration, and the summary of the present invention resides in (1) a Ti production method and (2) a production apparatus in which the Ti production method is implemented.
  • a first aspect of the present invention provides a method for producing Ti through reduction by Ca, the method including: a Ti generation step wherein TiCl 4 is supplied to a reaction tank to generate Ti in a molten salt while the molten salt is retained in the reaction tank, the molten salt containing CaCl 2 , the Ca being dissolved in the molten salt; an electrolytic step wherein a molten salt is electrolyzed in an electrolytic cell to generate Ca on an cathode side while the molten salt is retained in the electrolytic cell, the molten salt containing CaCl 2 ; and a Ca transportation step wherein the Ca generated in the electrolytic step is transported to the reaction tank while the Ca is deposited on and adheres to a continuum body in the electrolytic cell, the continuum body being movably constructed while part of the continuum body is immersed in the molten salt either within the reaction tank or electrolytic cell, and the transported Ca is caused to dissolve in the molten salt retained in the reaction tank.
  • the continuum body is caused to function as a cathode. Therefore, Ca can directly, electrolytically be deposited on the surface of the continuum body.
  • a cathode is provided near part of the continuum body, the part of the continuum body being immersed in the molten salt.
  • the molten salt or the cathode in the electrolytic cell is kept at a temperature of a melting point of Ca or less. Therefore, Ca can surely electrolytically be deposited on the surface of the cathode.
  • Ti generated in the Ti generation step is extracted to the outside of the reaction tank along with the molten salt, Ti is separated, and the molten salt is transported to the electrolytic cell. Therefore, Ti can continuously be produced.
  • a second aspect of the present invention provides an apparatus for producing Ti through reduction by Ca, the apparatus comprising: a reaction tank in which TiCl 4 supplied to a molten salt is caused to react with Ca to generate Ti while the molten salt is retained, the molten salt containing CaCl 2 , the Ca being dissolved in the molten salt; an electrolytic cell which retains a molten salt containing CaCl 2 , the electrolytic cell including an anode and a cathode, the electrolytic cell performing electrolysis in the molten salt to generate Ca on the cathode side; and a continuum body which is movably constructed while part of the continuum body is immersed in the molten salt either in the reaction tank or electrolytic cell, the continuum body transporting the generated Ca to the reaction tank while Ca is deposited on and adheres to the part immersed in the electrolytic cell, the continuums body causing the transported Ca to dissolve in the molten salt retained in the reaction tank.
  • the continuum body constitutes a cathode. Therefore, Ca can directly electrolytically be deposited on the surface of the continuum body.
  • a cathode is provided near part of the continuum body, the part of the continuum body being immersed in the molten salt.
  • the molten salt or the cathode in the electrolytic cell is kept at a temperature of a melting point of Ca or less. Therefore, Ca can surely electrolytically be deposited on the surface of the cathode.
  • the Ti production apparatus includes means for separating Ti from the molten salt to transport the molten salt to the electrolytic cell after the Ti separation, the Ti being generated in the reaction tank and extracted to the outside of the reaction tank along with the molten salt. Therefore, Ti can continuously be produced.
  • the method for producing Ti through reduction by Ca according to the present invention is directed to a method for reducing TiCl 4 in which the high purity material is easily obtained, so that the high-purity metallic Ti can be produced.
  • Ca is used as a reducing agent, and TiCl 4 is caused to react with Ca in the molten salt containing CaCl 2 , so that the feed rate of TiCl 4 can be enhanced.
  • Ca to be consumed in the reduction reaction can be replenished by the electrolysis of the molten CaCl 2 liquid, so that the present invention has the economical advantage.
  • Ca is inferior to Mg in wetting properties (adhesion properties), and the Ti granules are generated in the molten CaCl 2 liquid, so that the aggregation in the generated Ti granules and the grain growth by the sintering are significantly lessened. Therefore, the Ti granules can be taken out to the outside of the reactor vessel, and the Ti production can continuously be operated.
  • the Ti production method of the present invention can preferably implemented with the Ti production apparatus of the present invention.
  • FIG. 1 is a view showing a configuration example of an apparatus in which a Ti production method of the present invention can be implemented.
  • FIG. 2 is a view showing another configuration example of the apparatus in which the Ti production method of the present invention can be implemented
  • FIG. 1 is a view showing a configuration example of an apparatus (Ti production apparatus of the present invention) in which a Ti production method of the present invention can be implemented.
  • the apparatus comprises a reaction tank 1 , an electrolytic cell 2 , and a continuum body 5 .
  • TiCl 4 supplied into a molten salt 3 a is caused to react with Ca to generate Ti.
  • the electrolytic cell 2 retains a molten salt 3 b containing CaCl 2
  • the electrolytic cell 2 includes an anode 4 and a cathode (in the example, the continuum body 5 constitutes the cathode).
  • the electrolysis is performed in the molten salt 3 b to generate Ca on the cathode side.
  • the continuum body 5 is movably constructed while part of the continuum body 5 is immersed in the molten salt 3 a, 3 b either within the reaction tank 1 and electrolytic cell 2 .
  • the continuum body 5 serves to transport the generated Ca into the reaction tank 1 while Ca is deposited on and adheres to the immersed part of the continuum body 5 in the electrolytic cell 2 , and the transported Ca is dissolved in the molten salt 3 a retained in the reaction tank 1 .
  • the continuum body 5 is a so-called endless belt, and the continuum body 5 is moved in an arrow direction of FIG. 1 while part of the continuum body 5 is immersed in the molten salt 3 a in the reaction tank 1 as well as another part thereof being immersed in the molten salt 3 b in the electrolytic cell 2 .
  • the continuum body 5 is rotatably constructed.
  • the portion when attention is focused on the movement of a particular portion in the surface of the continuum body 5 , the portion can be deemed to be moved (i.e., the portion is moved in the rotating direction of the continuum body), so that the expression of “the continuum body 5 is movably constructed” is adopted here according to the function in which Ca is transported into the reaction tank 1 while Ca generated in the electrolytic cell 2 is deposited and adheres to the continuum body 5 in the electrolytic cell 2 .
  • a barrier membrane 6 b is provided in the electrolytic cell 2 , and a partition wall 6 a is attached in the reaction tank 1 .
  • the barrier membrane 6 b blocks the movement of Ca generated on the cathode side to the anode side.
  • a lower portion of the partition wall 6 a is opened.
  • the apparatus also includes means for transporting only the molten salt 3 a into the electrolytic cell 2 after recovering Ti by the extraction of Ti generated in the reaction tank 1 to the outside of the reaction tank 1 along with the molten salt 3 a.
  • the apparatus is configured so as to perform an operation in which chlorine (Cl 2 ) generated by the anode 4 in the electrolytic cell 2 is recovered and caused to react with titanium oxide (TiO 2 ) to generate TiCl 4 supplied into the reaction tank 1 .
  • the molten salt 3 a in which CaCl 2 is includes while Ca is dissolved is retained in the reaction tank 1 , and TiCl 4 is supplied into the reaction tank 1 to generate Ti in the molten salt 3 a. That is, a “Ti generation step” is performed.
  • the molten CaCl 2 having a melting point of 780° C. is used as the molten salt 3 a.
  • the temperature of the molten salt 3 a is lowered because a lifetime of the reaction tank 1 is extended while the vaporization of Ca or the molten salt from the liquid surface is suppressed, when the temperature of the molten salt 3 a is lowered. Therefore, desirably a mixed salt of CaCl 2 and another salt is used as the molten salt 3 a.
  • the melting point of the molten salt 3 a can be lowered to about 500° C. at the lowest temperature.
  • TiCl 4 is supplied in a gas state to the molten salt 3 a in the reaction tank 1 in consideration of contact efficiency between TiCl 4 and Ca in the molten salt.
  • the present invention is not limited to the gaseous TiCl 4 , but the liquid TiCl 4 can be supplied on the liquid surface of the molten salt 3 a or into the molten salt 3 a. In the example of FIGS. 1 or 2 , the liquid TiCl 4 is supplied to the neighborhood of a bottom portion of the reaction tank 1 through a supply pipe 7 .
  • the supply of TiCl 4 into the reaction tank 1 causes the reaction of the chemical formula (i) to proceed to generate the metallic Ti.
  • Ca in the molten salt 3 a is consumed in association with the generation of Ti, Ca transported from the electrolytic cell 2 to the continuum body 5 is dissolved, and the molten salt whose Ca concentration is increased is supplied to the neighborhood of a front end of the TiCl 4 supply pipe 7 through the opening in the lower portion of the partition wall 6 a. Therefore, the reaction of the chemical formula (i) proceeds effectively.
  • Ti is generated in the form of granule or powder.
  • the Ca is much inferior to Mg in wetting properties (adhesion properties), and Ca adhering to the deposited Ti granule is dissolved in CaCl 2 . Therefore, the aggregation of the generated Ti granules or the grain growth by sintering is hardly generated compared with the case of Mg.
  • Ti generated in the molten salt 3 a can be separated from the molten salt 3 a either inside the reaction tank 1 or outside the reaction tank 1 .
  • the operation becomes a batch manner.
  • Ti is extracted to the outside of the reaction tank 1 along with the molten salt 3 a, and Ti is separated from the molten salt 3 a outside the reaction tank 1 .
  • the operation becomes a batch manner because CaCl 2 is continuously increased in the reaction tank 1 .
  • the apparatus of FIG. 1 includes means for extracting the generated Ti to the outside of the reaction tank along with the molten salt 3 a. Because the generated Ti takes the granular or powder form, the generated Ti can easily separated from the molten salt by a squeezing operation such as mechanical compression, and the operation can continuously be performed. The separated Ti is conveyed to a melting step.
  • the molten salt 3 b containing CaCl 2 is also retained in the electrolytic cell 2 , and the molten salt 3 b is electrolyzed to generate Ca on the cathode side. That is, an “electrolytic step” is performed.
  • the molten CaCl 2 liquid is electrolyzed, Ca is generated near the surface of the cathode by the electrode reactions of the chemical formulas (ii) and (iii).
  • the molten salt in which Ca is consumed by the reaction of the chemical formula (i) in the reaction tank 1 to lower the Ca concentration can also be used as the molten CaCl 2 liquid.
  • the apparatus of FIG. 1 includes the means for transporting only the molten salt into the electrolytic cell 2 after recovering Ti by the extraction of Ti generated in the reaction tank 1 to the outside of the reaction tank 1 along with the molten salt 3 a, which allows the formation of the cycle, in which the molten salt is delivered to the electrolytic cell 2 after Ti is recovered and Ca generated by the electrolysis is deposited on and adheres to the continuum body 5 is returned to the reaction tank 1 . Therefore, Ti can continuously be produced.
  • the barrier membrane 6 b is provided to block the movement of Ca generated on the cathode side to the side of the anode 4 (however, the barrier membrane 6 b cannot block the movements of Ca 2+ and Cl ⁇ ), there is no risk of generating the back reaction.
  • a partition wall whose lower portion is opened can be used in place of the barrier membrane 6 b.
  • the continuum body 5 is used in the Ti production method of the present invention.
  • the continuum body 5 is movably constructed while part of the continuum body 5 is immersed in the molten salt either in the reaction tank 1 or electrolytic cell 2 .
  • the generated Ca is deposited on and adheres to the continuum body 5 in the electrolytic cell 2 , Ca is transported into the reaction tank 1 , and Ca is dissolved in the molten salt 3 a retained in the reaction tank 1 . That is, a “Ca transportation step” is performed.
  • a broken line shown in part of the continuum body 5 indicates the deposited and adhered Ca.
  • the continuum body 5 is slowly moved in the arrow direction by drive rollers 8 a and 8 b. Focusing attention on a portion of the continuum body 5 (or example, the portion designated by the letter A in FIG. 1 where the continuum body 5 is pulled up in air from the molten salt 3 a ), the temperature of the portion A in motion is lowered while moving from the position, where the portion A is currently shown in FIG. 1 (at this point, Ca is completely dissolved without adhering to the continuum body 5 ), through the drive roller 8 a until the portion A is immersed in the molten salt 3 b in the electrolytic cell 2 .
  • the dissolved Ca near the portion A is deposited on and adheres to the portion A (i.e., the surface of the continuum body 5 ) along with CaCl 2 soon after the portion A is immersed in the molten salt 3 b in the electrolytic cell 2 .
  • the continuum body 5 constitutes the cathode, and Ca is directly deposited on the surface of the continuum body 5 , so that the deposition and adhesion of Ca are generated more rapidly.
  • the temperature of the molten salt is lowered to about 500° C. which is much lower than the melting point (839° C.) of Ca.
  • the melting point (839° C.) of Ca As the result, Ca can be deposited efficiently and securely on the cathode.
  • portion A Because the continuum body 5 (portion A) reaches the reaction tank 1 through the drive roller 8 b while Ca and CaCl 2 are deposited and adhere to the surface of the continuum body 5 (portion A), Ca is transported from the electrolytic cell 2 to the reaction tank 1 in association with the movement of the continuum body 5 .
  • the deposited and adhered Ca comes into contact with the molten salt 3 a in the reaction tank 1 , Ca is gradually dissolved to increase the Ca concentration of the molten salt 3 a in the reaction tank 1 .
  • the metal plate, and the metal net or wire can be used as the continuum body 5 .
  • Molybdenum, tantalum, and titanium are suitable for the continuum body 5 because of excellent durability in the molten salts 3 a and 3 b.
  • the continuum body is made of metal, as shown in FIG. 1 , the continuum body can function as the cathode to directly electrolytically deposit Ca on the surface of the continuum body. Therefore, desirably the continuum body is made of metal.
  • the moving speed of the continuum body 5 can appropriately be adjusted as long as Ca generated in the electrolytic cell 2 is deposited on and adheres to the continuum body 5 without troubles, as long as Ca is transported into the reaction tank 1 without troubles, and as long as the transported Ca is dissolved in the molten salt 3 a in the reaction tank 1 without trouble.
  • the molten salt 3 a in the reaction tank 1 is kept at the temperature equal to or higher than the temperature of the molten salt 3 b in the electrolytic cell 2 . Therefore, solubility of Ca is enhanced to increase the Ca concentration of the molten salt 3 a, and the TiCl 4 reduction reaction of the chemical formula (i) can efficiently be performed. Additionally, Ca which is deposited on and adheres to the continuum body 5 can be dissolved in the molten salt 3 a at a higher rate.
  • the apparatus of FIG. 1 is configured to perform the operation in which Cl 2 generated by the anode 4 in the electrolytic cell 2 is recovered to cause Cl 2 to react with TiO 2 and carbon (C) and thereby TiCl 4 supplied to the reaction tank 1 is generated. That is, the Cl 2 gas generated in the electrolytic step is recovered, the Cl 2 gas is caused to react with TiO 2 at a high temperature to generate TiCl 4 , and TiCl 4 is used as TiCl 4 supplied to the reaction tank 1 .
  • FIG. 2 is a view showing another configuration example of the apparatus (Ti production apparatus of the present invention) in which the Ti production method of the present invention can be implemented.
  • a cathode 9 is provided near a portion where the continuum body 5 is immersed in the molten salt 3 b, while all other configurations of the apparatus of FIG. 2 are similar to those of FIG. 1 .
  • the temperature of the continuum body 5 immersed in the molten salt 3 b in the electrolytic cell 2 is considerably lowered compared with the temperature of the molten salt 3 b. Therefore, in the apparatus of FIG. 2 , Ca generated near the surface of the cathode 9 can be transported from the electrolytic cell 2 to the reaction tank 1 while deposited on and adheres to the surface of the continuum body 5 .
  • an electrode made of a metal such as Fe and Ti can be used, and particularly a porous electrode is desirably used. Because a surface area per unit mass is increased, the electrolytic current can be enhanced to increase the amount of generated Ca.
  • the porous electrode is made of the metal such as Fe and Ti.
  • the titanium oxide sintered material can also be used because the titanium oxide sintered material exhibits good conductivity at high temperatures.
  • the cathode 9 When the cathode 9 is arranged near the continuum body 5 (i.e., near the portion where the continuum body 5 is immersed in the molten salt 3 b ), Ca generated near the surface of the cathode 9 is easily deposited on and adheres to the surface of the continuum body 5 , which allows Ca to be transported from the electrolytic cell 2 to the reaction tank 1 .
  • the feed rate of TiCl 4 which is of the raw material can be enhanced, and the continuous production can be performed. Furthermore, the method of the present invention has an economical advantage because Ca consumed in a reduction reaction of TiCl 4 can be replenished by the electrolysis of CaCl 2 . Therefore, the Ti production method of the present invention can efficiently be utilized as means for economically producing the high-purity metallic Ti, and the Ti production apparatus of the present invention can suitably be used for the Ti production method of the present invention.

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US11/665,976 2004-11-01 2005-10-26 Method and Apparatus for Producing Ti Through Reduction by Ca Abandoned US20080217184A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2004317842A JP2006124813A (ja) 2004-11-01 2004-11-01 Ｃａ還元によるＴｉの製造方法及び装置
JP2004-317842 2004-11-01
PCT/JP2005/019655 WO2006049050A1 (fr) 2004-11-01 2005-10-26 PROCÉDÉ SERVANT À PRODUIRE DU Ti VIA LA RÉDUCTION PAR DU Ca ET APPAREIL POUR CELA

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US20060219053A1 (en) * 2003-08-28 2006-10-05 Tadashi Ogasawara Method and apparatus for producing metal
CN110983378A (zh) * 2019-11-15 2020-04-10 北京理工大学 可溶阳极在熔盐中制备金属铝和四氯化钛的装置及方法

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WO2009008121A1 (fr) * 2007-07-12 2009-01-15 Toho Titanium Co., Ltd. Procédé pour produire du calcium métallique de pureté élevée, procédé pour produire du titane métallique avec l'utilisation du calcium, et appareil de production de calcium métallique de pureté élevée
MY180279A (en) 2010-11-18 2020-11-26 Metalysis Ltd Electrolysis apparatus
UA114395C2 (uk) * 2010-11-18 2017-06-12 Метелесіс Лімітед Спосіб електролітичного відновлення твердої сировини
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
CN108546964B (zh) * 2018-05-29 2019-12-24 钢研晟华科技股份有限公司 一种金属钛的制备装置以及制备方法
CN109763148B (zh) 2019-01-14 2020-11-03 浙江海虹控股集团有限公司 一种连续电解制备高纯金属钛粉的装置和方法

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Publication number Priority date Publication date Assignee Title
US20060219053A1 (en) * 2003-08-28 2006-10-05 Tadashi Ogasawara Method and apparatus for producing metal
CN110983378A (zh) * 2019-11-15 2020-04-10 北京理工大学 可溶阳极在熔盐中制备金属铝和四氯化钛的装置及方法

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CA2585454A1 (fr) 2006-05-11
EA200700988A1 (ru) 2007-10-26
AU2005301828A1 (en) 2006-05-11
WO2006049050A1 (fr) 2006-05-11
AU2005301828B2 (en) 2008-07-24
JP2006124813A (ja) 2006-05-18
NO20072710L (no) 2007-06-26
CN101048518A (zh) 2007-10-03
EP1816221A1 (fr) 2007-08-08
UA84095C2 (ru) 2008-09-10

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