EP1726689A1 - Verfahren zur herstellung von ti oder ti-legierung durch reduktion von ca - Google Patents

Verfahren zur herstellung von ti oder ti-legierung durch reduktion von ca Download PDF

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Publication number
EP1726689A1
EP1726689A1 EP05704329A EP05704329A EP1726689A1 EP 1726689 A1 EP1726689 A1 EP 1726689A1 EP 05704329 A EP05704329 A EP 05704329A EP 05704329 A EP05704329 A EP 05704329A EP 1726689 A1 EP1726689 A1 EP 1726689A1
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Prior art keywords
molten salt
reactor cell
alloys
generated
reduction
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French (fr)
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EP1726689A4 (de
Inventor
Tadashi Sumitomo titanium Corporation OGASAWARA
Makoto Sumitomo Titanium Corporation YAMAGUCHI
Masahiko Sumitomo Titanium Corporation HORI
Toru Sumitomo Titanium Corporation UENISHI
Katsunori Sumitomo Titanium Corporation DAKESHITA
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Osaka Titanium Technologies Co Ltd
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Osaka Titanium Technologies Co Ltd
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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
    • C25C3/26—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
    • 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
    • C22B34/129—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
    • 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

Definitions

  • the present invention relates to a method for producing Ti or Ti alloys through reduction by Ca, in which a metallic chloride containing titanium tetrachloride (TiCl 4 ) is reduced by Ca to produce Ti metals or Ti alloys.
  • a metallic chloride containing titanium tetrachloride TiCl 4
  • a Kroll method for reducing TiCl 4 by Mg is generally used as an industrial production method of the titanium metals.
  • the Ti metals are produced through a reduction step and a vacuum separation step.
  • the reduction step TiCl 4 which is of a raw material of Ti is reduced in a reactor vessel to produce the sponge metallic Ti.
  • the vacuum separation step unreacted Mg and magnesium chloride (MgCl 2 ) formed as by-products are removed from the sponge metallic Ti produced in the reactor vessel.
  • the reactor vessel is filled with the molten Mg, and the TiCl 4 liquid is supplied from above on a liquid surface of the molten Mg.
  • the generated Ti metals move sequentially downward.
  • the molten MgCl 2 which is of the by-product is generated near the liquid surface.
  • a specific gravity of molten MgCl 2 is larger than that of the molten Mg.
  • the molten MgCl 2 which is of the by-product moves downward due to the specific-gravity difference, and the molten Mg emerges in the liquid surface instead.
  • the molten Mg is continuously supplied to the liquid surface by the specific-gravity difference substitution, and the reducing reaction of TiCl 4 proceeds continuously.
  • the supplied TiCl 4 becomes lower grade chloride gases (referred to as "unreacted gas") such as an unreacted TiCl 4 gas and a TiCl 3 gas, and the unreacted gas is discharged outside the reactor vessel, which reduces utilization efficiency of TiCl 4 . It is necessary to avoid the generation of the unreacted gas, because a rapid increase in inner pressure of the reactor vessel is associated with the generation of the unreacted gas. Thus, there is a limit of the feed rate of TiCl 4 because of the above reasons.
  • Japanese Patent Application Publication No. 8-295955 proposes a method in which the reaction efficiency is enhanced by supplying liquid TiCl 4 in a dispersive manner to the liquid surface in which the molten Mg exists, and thereby the Ti precipitation is suppressed in the inner surface of the upper portion of the reactor vessel.
  • the method proposed in Japanese Patent Application Publication No. 8-295955 is not enough to suppress the Ti precipitation.
  • the Kroll method because the reaction is performed only near the liquid surface of the molten Mg in the reactor vessel, an exothermic area is narrowed and the temperature is locally elevated. Therefore, cooling becomes difficult, so that the feed rate of TiCl 4 is restricted.
  • Ti is generated in the particulate form near the liquid surface of the molten Mg liquid, and moves downward.
  • wetting properties adheresion properties
  • the generated Ti powder moves downward while aggregated, and the Ti particles are sintered to grow the Ti particles in size by the temperature condition of the molten liquid during moving downward, which makes it difficult to discharge the Ti particles outside the reactor vessel. Therefore, the continuous production is difficult to perform, and the improvement of the productivity is blocked. This is the reason why the Ti is produced in the batch manner in the form of the sponge titanium by the Kroll method.
  • US Patent No. 2205854 describes that, in addition to Mg, for example, Ca can be used as the reducing agent of TiCl 4 .
  • US Patent No. 4820339 describes a method for producing Ti through the reducing reaction by Ca, in which the molten salt of CaCl 2 is held in the reactor vessel, the metallic Ca powder is 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 Ti metals are generated from TiCl 4 by the reaction of the following chemical formula (a), and CaCl 2 as the by-product is also generated at the same time.
  • Ca has a stronger affinity for Cl stronger than Mg has, and Ca is suitable for the reducing agent of TiCl 4 in principle.
  • An example of other Ti production methods includes an Olsen method described in US Patent No. 2845386 .
  • the Olsen method is a kind of oxide direct-reduction method for directly reducing TiO 2 by Ca, in which TiO 2 is directly reduced by Ca, not through TiCl 4 .
  • the oxide direct-reduction method is highly efficient, the oxide direct-reduction method is not suitable for the production of the high-purity Ti because it is necessary to use high-purity TiO 2 .
  • the present inventors consider that TiCl 4 be reduced by Ca, and the present inventors look into the method for utilizing Ca dissolved in the molten salt of CaCl 2 described in US Patent No. 4820339 .
  • Ca in the molten salt is consumed in the reducing reactor vessel as the reaction expressed by the chemical formula (a) proceeds, and it is necessary to continuously supply the metallic Ca powder to the reducing reactor vessel.
  • the present inventors focus on a method for controlling a dissolved Ca concentration in the molten salt by electrolysis in consideration of the fact that it is necessary that the Ca consumed in the reducing reaction is economically replenished into the molten salt.
  • the method for replenishing Ca consumed by the reduction of TiCl 4 with Ca generated by the electrolysis can also be achieved by respectively performing the reduction and the electrolysis in a reducing cell and an electrolytic cell to circulate the molten CaCl 2 between the cells.
  • the reactor cell can commonly be used as the reducing cell and the electrolytic cell. Therefore, because it is not necessary to separately provide the reducing cell and the electrolytic cell, there is a great advantage from a viewpoint of installation cost compared with the case in which the molten CaCl 2 is circulated between the reducing cell and the electrolytic cell.
  • the present invention is made based on the above consideration, and the summary of the present invention is a method for producing Ti or Ti alloys through reduction by Ca according to the following (1) to (7).
  • a method for producing Ti or Ti alloys through reduction by Ca including: a reduction electrolysis step in which a molten salt is held in a reactor cell to perform electrolysis using an electroconductive porous material as an cathode electrode in the molten salt of the reactor cell, the molten salt containing CaCl 2 while Ca being dissolved in the molten salt, and Ti or Ti alloys are generated in the molten salt by supplying a metallic chloride containing TiCl 4 into the molten salt through the cathode electrode in order to cause the metallic chloride containing TiCl 4 to react with Ca generated on a cathode electrode side by the electrolysis; and a Ti separation step of separating the Ti or Ti alloys from the molten salt inside the reactor cell or outside the reactor cell (hereinafter referred to as "production method described in (2)").
  • a method for producing Ti or Ti alloys through reduction by Ca including: a reduction electrolysis step in which a molten salt is held in a reactor cell to perform electrolysis in the molten salt of the reactor cell, the molten salt containing CaCl 2 while Ca being dissolved in the molten salt, and Ti or Ti alloys are generated in the molten salt by supplying a metallic chloride containing TiCl 4 into the molten salt in order to cause the metallic chloride containing TiCl 4 to react with Ca generated on a cathode electrode side by the electrolysis; a Ti separation step of separating the Ti or Ti alloys from the molten salt inside the reactor cell or outside the reactor cell; and a chlorination step of causing Cl 2 to react with TiO 2 to generate TiCl 4 , Cl 2 being generated on an anode electrode side in association with the electrolysis, in which TiCl 4 generated in the chlorination step is used for the Ti or Ti alloy generation reaction in the reactor cell (hereinafter referred to as "production method
  • a method for producing Ti or Ti alloys through reduction by Ca including: a reduction electrolysis step in which a molten salt is held in a reactor cell to perform electrolysis in the molten salt of the reactor cell, the molten salt containing CaCl 2 while Ca being dissolved in the molten salt, and Ti or Ti alloys are generated in the molten salt by supplying a metallic chloride containing TiCl 4 into the molten salt in order to cause the metallic chloride containing TiCl 4 to react with Ca generated on a cathode electrode side by the electrolysis; and a Ti separation step in which Ti or Ti alloys generated in the reactor cell are extracted to an outside of the reactor cell along with the molten salt and the Ti or Ti alloys are separated from the molten salt outside the reactor cell (hereinafter referred to as "production method described in (4)").
  • a method for producing Ti or Ti alloys through reduction by Ca including: a reduction electrolysis step in which a multi-system molten salt is held in a reactor cell to perform electrolysis in the molten salt of the reactor cell, the multi-system molten salt containing at least one of NaCl, KCl, LiCl, and CaF 2 in addition to CaCl 2 , Ca being dissolved in the molten salt, and Ti or Ti alloys are generated in the molten salt by supplying a metallic chloride containing TiCl 4 into the molten salt in order to cause the metallic chloride containing TiCl 4 to react with Ca generated on a cathode electrode side by the electrolysis; and a Ti separation step of separating the Ti or Ti alloys from the molten salt inside the reactor cell or outside the reactor cell (hereinafter referred to as "production method described in (5)").
  • a method for producing Ti or Ti alloys through reduction by Ca including: a reduction electrolysis step in which a molten salt is held in a reactor cell to perform electrolysis in the molten salt in the reactor cell, the molten salt containing CaCl 2 while Ca being dissolved in the molten salt, and Ti or Ti alloys are generated in the molten salt by supplying a mixed gas containing TiCl 4 and another metallic chloride into the molten salt in order to cause the mixed gas to react with Ca generated on a cathode electrode side by the electrolysis; and a Ti separation step of separating the Ti or Ti alloys from the molten salt inside the reactor cell or outside the reactor cell (hereinafter referred to as "production method described in (6)").
  • a method for producing Ti or Ti alloys through reduction by Ca including: a reduction electrolysis step in which a molten salt is held in a reactor cell to perform electrolysis in the molten salt of the reactor cell, the molten salt containing CaCl 2 while Ca being dissolved in the molten salt, and Ti or Ti alloys are generated in the molten salt by supplying a metallic chloride containing TiCl 4 into the molten salt in order to cause the metallic chloride containing TiCl 4 to react with Ca generated on a cathode electrode side by the electrolysis, said Ti or Ti alloys being formed in powder whose average particle size ranging from 0.5 to 50 ⁇ m; and a Ti separation step of separating the Ti or Ti alloys from the molten salt inside the reactor cell or outside the reactor cell (hereinafter referred to as "production method described in (7)").
  • Fig. 1 is a view showing a relationship between a mixture ratio and a melting point in a binary-system mixed molten salt of CaCl 2 and NaCl;
  • Ti particles the particulate and/or powdery metallic Ti
  • Mg is produced by electrolyzing MgCl 2 , and the generated Mg can efficiently be recovered because Mg is hardly dissolved in MgCl 2 .
  • Na can efficiently be produced by electrolyzing NaCl.
  • Ca is produced by electrolyzing CaCl 2 , and the generated Ca is dissolved in CaCl 2 by about 1.5%.
  • the reducing reaction field is expanded and the heat generation area is simultaneously enlarged.
  • Mg has vapor pressure of 6.7 kPa (50 mmHg) at 850 °C while Ca has extremely small vapor pressure of 0.3 kPa (2 mmHg). Therefore, in the case where Ca is used for the reduction process, the Ti precipitation amount becomes dramatically lessened in the inner surface of the upper portion of the reactor cell when compared with the use of Mg. Accordingly, in the method for producing Ti or Ti alloys through the reduction by Ca according to the present invention, the TiCl 4 feed rate can be largely increased.
  • Ca is inferior in wetting properties (adhesion properties) to Mg, and Ca adhering to the precipitated Ti particles is dissolved in CaCl 2 , so that the particle growth caused by the aggregation and the sintering in the generated titanium particles are significantly lessened. Therefore, the generated Ti can be discharged in the form of particles from the reactor cell, and the Ti production can continuously be operated.
  • TiCl 4 For a supply mode of TiCl 4 to the molten CaCl 2 liquid, it is particularly desirable that TiCl 4 be directly supplied in the gas state into the molten CaCl 2 liquid because of higher contact efficiency of TiCl 4 with Ca in the molten CaCl 2 liquid.
  • the TiCl 4 supply mode is not limited to the one in which TiCl 4 in the gas state is supplied.
  • the liquid or gaseous TiCl 4 is supplies to the liquid surface of the molten CaCl 2 liquid, or it is also possible that either the liquid or gaseous TiCl 4 is supplied to either the liquid surface or the inside of the molten Ca liquid held on the molten CaCl 2 liquid.
  • the reducing reaction is generated by supplying the TiCl 4 liquid to the surface of the molten Ca liquid held on the molten CaCl 2 liquid
  • the reaction can range from the molten Ca layer to the molten CaCl 2 layer to continue the Ti generation even if the specific-gravity difference substitution becomes unable to keep up with it due to the increase in the TiCl 4 feed rate.
  • the method for producing Ti or Ti alloys through the reduction by Ca according to the present invention has various advantages compared with the Kroll method. That is, in the Kroll method, the TiCl 4 liquid is supplied to the liquid surface of the molten Mg liquid, and it has been tried that the TiCl 4 gas is supplied into the molten Mg liquid in order to enlarge the reaction field. However, as described above, since the Mg has the large vapor pressure, the Mg vapor intrudes in a supply nozzle to react with TiCl 4 , and the supply nozzle is choked.
  • the nozzle choking is hardly generated, and the TiCl 4 gas can be supplied into the molten CaCl 2 liquid.
  • the reason why the nozzle choking is hardly generated is attributed to the fact that the molten Ca has the small vapor pressure. That is, the method for producing Ti or Ti alloys through the reduction by Ca according to the present invention, it is particularly desirable that TiCl 4 be directly supplied in the gas state to the molten CaCl 2 liquid, and this supply mode can be applied without any problem in the actual operation.
  • the Ti particles generated in the molten CaCl 2 liquid can be separated from the molten CaCl 2 liquid either in the reactor cell or outside the reactor cell.
  • the production mode becomes the batch manner.
  • the Ti particles and the molten CaCl 2 liquid can be separated from each other outside the reactor cell by utilizing the Ti generated in the particulate form to discharge the Ti particles outside the reactor cell along with the molten CaCl 2 liquid.
  • This step is included as the Ti separation step in the production method described in (4).
  • the Ti particles can simply be separated from the molten salt by a squeezing operation by means of mechanical compression.
  • Cl 2 is caused to react with TiO 2 to generate TiCl 4 , and the TiCl 4 is used for the Ti or Ti alloy generation reaction in the reactor cell.
  • TiCl 4 is used as the raw material.
  • the Ti alloy can also be produced by mixing TiCl 4 and other metallic chloride. Because TiCl 4 and other metallic chloride are simultaneously reduced by Ca, the Ti alloy particles can be produced by this method.
  • TiCl 4 and other metallic chloride may be used in either the gas state or the liquid state. However, as stipulated by the production method described in (6), because of higher contact efficiency of TiCl 4 with Ca in the molten CaCl 2 liquid, desirably TiCl 4 and other metallic chloride are used in the mixed gas containing TiCl 4 and other metallic chloride is used.
  • the back reaction problem particularly the back reaction in which Ca generated on the cathode electrode side is bonded to Cl 2 generated on the anode electrode side can effectively be suppressed by using a reactor cell including a membrane which partitions the electrolytic cell into the anode electrode side and the cathode electrode side.
  • the reactor cell holds the molten salt, and the membrane permits the molten salt to be circulated in the electrolytic cell while blocking the movement of Ca generated on the cathode electrode side to the anode electrode side in the reactor cell.
  • the molten salt is not formed by the single CaCl 2 but formed by a mixed salt so that a melting point of the molten salt is decreased to lower the molten salt temperature (namely bath temperature). That is, as stipulated by the production method described in (5), usually CaCl 2 having the melting point of 780 °C is used as the molten salt.
  • At least one of other salts can be mixed into CaCl 2 to form a multi-system molten salt.
  • other salts for example, NaCl, KCl, LiCl, and CaF 2
  • the melting point of the salt can be decreased to lower the molten salt temperature.
  • a life of the reactor material can be lengthened, the reactor material cost can be reduced, and the Ca or salt vaporization from the liquid surface can also be suppressed.
  • Fig. 1 shows a relationship between a mixture ratio and a melting point in the binary molten salt of CaCl 2 and NaCl.
  • the melting point of CaCl 2 is singly about 780 °C, while the melting point of NaCl is singly about 800 °C.
  • the melting point of the mixed salt becomes not more than 600 °C when the mixture ratio of NaCl ranges from about 20% to about 45%.
  • the critical phenomenon is desirable from the viewpoint of reactor material protection because the large decrease in molten salt temperature can be realized.
  • the critical phenomenon effectively suppresses the back reaction, particularly the back reaction in which the unreacted Ca is bonded to Cl 2 generated on the anode electrode side and Ca returns to CaCl 2 .
  • the Ti particles generated on the cathode electrode side in the reactor cell is separated from the molten salt, as described above, form the view point of operation, it is rational that the Ti particles are extracted to the outside of the cell along with the molten salt after use and the Ti particles are separated from the molten salt outside the cell.
  • the molten salt separated from the Ti particles is returned onto the anode electrode side in the reactor cell, the molten salt contains the unreacted Ca although the molten salt is already used, which results in the back reaction.
  • the unreacted Ca in the molten salt is replaced by Na through the reaction of the chemical formula (e), when the molten salt having the temperature not more than 600 °C extracted from the cathode electrode side in the reactor cell is temporarily heated more than 600 °C outside the reactor cell before the molten salt is returned to the anode electrode side in the reactor cell.
  • Na is not dissolved in the molten salt but Na is separated from the molten salt, so that Na can be separated and removed from the molten salt.
  • the multi-system molten salt containing CaCl 2 and NaCl Ca is dissolved in the molten salt while Na is not dissolved in the molten salt.
  • the molten salt temperature exceeds 600 °C, Na is generated instead of Ca.
  • the unreacted Ca contained in the molten salt after use can be decreased to effectively suppress the back reaction caused by the unreacted Ca and the decrease in current efficiency.
  • the average size of the generated Ti particles of Ti alloy particles ranges from 0.5 to 50 ⁇ m.
  • the Ti or Ti alloy particles are extracted from the reactor cell along with the molten salt, and the Ti or Ti alloy particles are separated from the molten salt.
  • the Ti or Ti alloy particles having the sizes not more than 50 ⁇ m can be fluidized along with the molten salt.
  • the particle size is more than 50 ⁇ m, it is difficult that the Ti or Ti alloy particles are extracted from the reactor cell along with the molten salt.
  • the Ti or Ti alloy particles are not less than 0.5 ⁇ m, it is difficult that the Ti or Ti alloy particles are separated from the molten salt after the extraction.
  • Fig. 2 is a block diagram showing a Ti metal production apparatus to which a first embodiment mode of the present invention can be applied.
  • a reactor cell 1 in which the reducing reaction and the electrolytic reaction concurrently occur is used in the first embodiment mode.
  • the reactor cell 1 holds the Ca-rich molten CaCl 2 in which the relatively large amount of Ca is dissolved as the molten salt.
  • CaCl 2 has the melting point of about 780 °C, and the molten salt of CaCl 2 is heated to at least the melting point thereof.
  • the molten CaCl 2 which is of the molten salt is electrolyzed by passing the current between an anode electrode 2 and a cathode electrode 3, the Cl 2 gas is generated on the side of anode electrode 2, and Ca is generated on the side of cathode electrode 3.
  • the inside of the reactor cell 1 is divided into the anode electrode side and the cathode electrode side by a membrane 4.
  • the membrane 4 is formed by a porous ceramic thin plate, and the membrane 4 blocks the movement of Ca generated on the side of the cathode electrode 3 toward the side of the anode electrode 2 while permitting the molten salt to be moved.
  • the gaseous TiCl 4 is injected in the dispersive manner into the molten salt on the cathode electrode side in the cell in parallel with the electrolysis of the molten salt. Therefore, the injected TiCl 4 is reduced to generate the particulate metallic Ti by the Ca dissolved in the molten salt. The generated Ti particles move downward by the specific gravity difference and accumulate at the bottom on the cathode electrode side in the reactor cell 1.
  • the Ti particles accumulating at the bottom on the cathode electrode side of the reactor cell 1 are extracted from the reactor cell 1 along with the molten salt existing at the bottom of the reactor cell 1, and the Ti particles and the molten salt are sent to a Ti separation step.
  • the Ti separation step the Ti particles and molten salt discharged from the reactor cell 1 are separated from the molten salt. Specifically the Ti particles are compressed to squeeze the molten salt.
  • the Ti particles obtained in the Ti separation step is melted and formed in a Ti ingot.
  • the molten salt separated from the Ti particles in the Ti separation step is designated as the molten salt after use in which Ca is consumed to decrease the Ca concentration.
  • the molten salt separated in the Ti separation step, along with other molten salt after use separately extracted from the reactor cell 1, is introduced to the anode electrode side in the reactor cell 1.
  • Ca in the molten salt is consumed on the cathode electrode side in the reactor cell 1 as the Ti particles are generated by the reducing reaction.
  • Ca is generated near the surface of the cathode electrode 3 in the cell by the electrolysis which proceeds concurrently in the cell, and the consumed amount of Ca is replenished by Ca generated though the electrolysis. That is, TiCl 4 supplied into the molten salt is sequentially reduced in a direct manner by Ca generated near the surface of the cathode electrode 3.
  • the molten salt after use is sequentially introduced from the Ti separation step on the anode electrode side in the reactor cell 1.
  • a unidirectional flow of the molten salt is formed from the anode electrode side toward the cathode electrode side in the reactor cell 1 to avoid the flow of Ca generated on the cathode electrode side into the anode electrode side.
  • the membrane 4 is provided to divide the inside of the reactor cell 1 into the anode electrode side and the cathode electrode side. The combination of the provision of the membrane and the operation creating the unidirectional flow further effectively suppresses the back reaction and the decrease in the current efficiency caused thereby.
  • the Cl 2 gas generated on the side of the anode electrode 2 in the reactor cell 1 is sent to a chlorination step.
  • the Cl 2 gas is caused to react with TiO 2 and carbon (C) (chlorination) to generate TiCl 4 which is of the Ti raw material.
  • C TiO 2 and carbon
  • the generated TiCl 4 is introduced to the reactor cell 1, and TiCl 4 is used in a circulating manner to generate the Ti particles by the Ca reduction.
  • the Ti particle generation by the Ca reduction i.e., the Ca consumption and the Ca replenishment by the electrolysis are concurrently performed in the reactor cell 1.
  • the reactor cell 1 is used as both the reducing cell and the electrolytic cell, so that there is an economical advantage in the facilities.
  • the flow of Ca generated on the cathode electrode side into the anode electrode side is avoided in the reactor cell 1, so that the back reaction in which Ca reacts with the Cl 2 gas generated on the anode electrode side can be prevented.
  • the molten salt temperature is managed to be more than the melting point (about 780 °C) of CaCl 2 in each step.
  • Fig. 3 is a block diagram showing a Ti metal production apparatus to which a second embodiment mode of the present invention can be applied.
  • the second embodiment mode differs from the first embodiment mode in the following points. That is, a mixture of CaCl 2 and NaCl is used as the molten salt. In the mixture, CaCl 2 and NaCl are mixed together at a mixture ratio in which the melting point of the mixture becomes not more than 600 °C. The mixed molten salt is held at temperatures of not more than 600 °C in the reactor cell 1, and the mixed molten salt is held at temperatures of more than 600 °C in a separation cell 5 used in the Ti separation step.
  • the molten salt is held at temperatures of not more than 600 °C the reactor cell 1 in which the reducing reaction and the electrolytic reaction concurrently occur (namely, low-temperature reduction and low-temperature electrolysis are performed)
  • Ca which is of the reducing agent exists in the molten salt (see chemical formula (d))
  • the reducing reaction by Ca and the Ca generation and replenishment by the electrolysis are concurrently performed.
  • the low-temperature reduction and the low-temperature electrolysis are performed in the reactor cell 1, so that the reactor material life can be lengthened to decrease the reactor material cost.
  • the molten salt temperature is decreased to reduce the impact on the reactor material during the operation by the low-temperature reduction and the low-temperature electrolysis, so that the present invention largely contributes to solve the problem of the reactor material life.
  • the molten salt and the Ti particles are extracted from the reactor cell 1 into the separation cell 5, or the molten salt is independently extracted from the reactor cell 1 into the separation cell 5.
  • the molten salt extracted from the reactor cell 1 is already used, and the molten salt contains the slight amount of unreacted Ca although Ca is consumed.
  • the molten salt containing the unreacted Ca is returned to the side of the anode electrode 2 in the reactor cell 1, the unreacted Ca reacts with the Cl 2 gas generated on the side of the anode electrode 2 to generate the back reaction.
  • the molten salt is held at temperatures of more than 600 °C in the separation cell 5, so that the unreacted Ca slightly contained in the molten salt is replaced by Na (see chemical formula (e)).
  • Ca is not dissolved in the molten salt, Ca is separated to float on the molten salt, and Ca is removed from the molten salt.
  • the molten salt in which the unreacted Ca (namely, reducing agent metal) is removed is sent to the side of the anode electrode 2 in the reactor cell 1, and the molten salt temperature is managed to br not more than 600 °C. Because Na is removed as described above, the reaction of the chemical formula (d) does not occur, and Ca is not regenerated. Therefore, the back reaction caused by the mixture of the unreacted Ca and the decrease in current efficiency caused by the back reaction are blocked.
  • the Ti separation step in the second embodiment mode also functions as the Na separation step (reducing agent separation step), and the unreacted Ca in the molten salt returned to the reactor cell 1 is removed by previously replacing the unreacted Ca with Na, which enables the rational and economical operation to be realized.
  • Na separated from the molten salt in the separation cell 5 is sent back to the side of the cathode electrode 3 in the reactor cell 1, Na returns to Ca (see chemical formula (d)) by managing the melt at temperatures of not more than 600 °C, and Na is reused for the reducing reaction.
  • the molten salt temperature in the separation cell 5 can obviously be set at the same temperature as the reactor cell 1 whose temperature is not more than 600 °C. In this case, there is an advantage from the viewpoint of reactor material durability while the unreacted Ca cannot be removed.
  • Fig. 4 is a block diagram showing a Ti metal production apparatus to which a third embodiment mode of the present invention can be applied.
  • the third embodiment mode differs from the first embodiment mode in a structure of the cathode electrode 3. That is, the third embodiment mode is a configuration example of the Ti metal production apparatus in which the production method described in (2) can be performed.
  • the cathode electrode 3 is made of an electroconductive porous material in the third embodiment mode while the cathode electrode 3 is made of the solid metals such as Fe and Ti in the first embodiment mode.
  • the cathode electrode 3 is made of the electroconductive porous material such as a Ti sintered porous material and a Fe sintered porous material.
  • the TiCl 4 gas which is of the Ti raw material is supplied into the molten salt on the side of the cathode electrode 3 in the reactor cell 1 through the porous cathode electrode 3 (namely, flows through the inside of the porous material).
  • TiCl 4 is supplied into the molten salt on the cathode electrode side in the reactor cell 1, it is necessary that TiCl 4 is supplied to a portion near the surface of the cathode electrode 3 as much as possible. Because the Ca generation by the electrolysis is performed near the surface of the cathode electrode 3, the reaction efficiency is increased when TiCl 4 is supplied to the portion near the surface of the cathode electrode 3. The productivity of the Ti particles is further improved by adopting the third embodiment mode.
  • the mixed molten salt of CaCl 2 and NaCl can be used, the low-temperature reduction and low-temperature electrolysis can be performed with the mixed molten salt of CaCl 2 and NaCl, and the unreacted Ca (reducing agent) can be separated at high temperatures.
  • carbon or graphite is used as the anode electrode 2 to generate the Cl 2 gas.
  • the feed rate of TiCl 4 which is of the raw material can be enhanced, and the high-purity Ti or Ti alloys can continuously be produced.
  • the reducing reaction and the electrolytic reaction can concurrently be caused to proceed, and Ca consumed in the reducing reaction can be replenished by the electrolytic reaction, so that it is not necessary to singly handle Ca.
  • the back reaction caused by Ca can also effectively be suppressed. Accordingly, the method according to the present invention can effectively be utilized as means for efficiently and economically producing the high-purity Ti metals or Ti alloys, and the method according to the present invention can widely applied to the industrial Ti or Ti alloy production method.

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EP05704329A 2004-02-20 2005-02-01 Verfahren zur herstellung von ti oder ti-legierung durch reduktion von ca Withdrawn EP1726689A4 (de)

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JP2004044827 2004-02-20
JP2004318075A JP2005264320A (ja) 2004-02-20 2004-11-01 Ｃａ還元によるＴｉ又はＴｉ合金の製造方法
PCT/JP2005/001379 WO2005080642A1 (ja) 2004-02-20 2005-02-01 Ｃａ還元によるＴｉ又はＴｉ合金の製造方法

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EP1808513A4 (de) * 2004-10-12 2009-07-29 Toho Titanium Co Ltd Verfahren zur herstellung von metall durch schmelzflusselektrolyse und verfahren zur herstellung von metallischem titan
CN103290433A (zh) * 2013-06-26 2013-09-11 石嘴山市天合铁合金有限公司 一种双电解槽熔盐电解制备纯钛的装置及其工艺
WO2014008410A1 (en) * 2012-07-03 2014-01-09 Ceramatec, Inc. Apparatus and method of producing metal in a nasicon electrolytic cell

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JP4193984B2 (ja) * 2003-08-28 2008-12-10 株式会社大阪チタニウムテクノロジーズ 金属製造装置
WO2008038405A1 (fr) * 2006-09-28 2008-04-03 Toho Titanium Co., Ltd. Récipient d'électrolyse de sel fondu pour la fabrication de métal et procédé de fabrication de métal à l'aide de celui-ci
EP2109691B1 (de) * 2007-01-22 2016-07-13 Materials And Electrochemical Research Corporation Metallothermische reduktion von in-situ erzeugtem titanchlorid
JP2012533685A (ja) * 2009-07-17 2012-12-27 ボストン・エレクトロニツク・マテリアルズ・エルエルシー 金属粉末および合金の製造および用途
CN103687685A (zh) * 2011-05-16 2014-03-26 波士顿电子材料有限公司 金属粉末和合金的制造和应用
US9816192B2 (en) 2011-12-22 2017-11-14 Universal Technical Resource Services, Inc. System and method for extraction and refining of titanium
JP2015098626A (ja) * 2013-11-19 2015-05-28 住友電気工業株式会社 精製金属の製造方法
BR112019005038B1 (pt) 2016-09-14 2022-12-20 Universal Achemetal Titanium, Llc Um método para produzir liga de titânio-alumínio-vanádio
AU2018249909B2 (en) 2017-01-13 2023-04-06 Universal Achemetal Titanium, Llc Titanium master alloy for titanium-aluminum based alloys
KR101966257B1 (ko) * 2017-11-27 2019-04-05 한국원자력연구원 전해환원 장치에 사용되는 양극 모듈, 이를 포함하는 전해환원 장치 및 그 방법

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JP3718691B2 (ja) * 2002-04-18 2005-11-24 財団法人生産技術研究奨励会 チタンの製造方法、純金属の製造方法、及び純金属の製造装置

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1808513A4 (de) * 2004-10-12 2009-07-29 Toho Titanium Co Ltd Verfahren zur herstellung von metall durch schmelzflusselektrolyse und verfahren zur herstellung von metallischem titan
WO2014008410A1 (en) * 2012-07-03 2014-01-09 Ceramatec, Inc. Apparatus and method of producing metal in a nasicon electrolytic cell
US9856569B2 (en) 2012-07-03 2018-01-02 Field Upgrading Limited Apparatus and method of producing metal in a nasicon electrolytic cell
CN103290433A (zh) * 2013-06-26 2013-09-11 石嘴山市天合铁合金有限公司 一种双电解槽熔盐电解制备纯钛的装置及其工艺
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

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