US20070131057A1 - Method for producing ti or ti alloy through reduction by ca - Google Patents

Method for producing ti or ti alloy through reduction by ca Download PDF

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US20070131057A1
US20070131057A1 US10/575,224 US57522404A US2007131057A1 US 20070131057 A1 US20070131057 A1 US 20070131057A1 US 57522404 A US57522404 A US 57522404A US 2007131057 A1 US2007131057 A1 US 2007131057A1
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molten salt
molten
alloys
reactor vessel
alloy
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Tadashi Ogasawara
Makoto Yamaguchi
Masahiko Hori
Toru Uenishi
Yuko Urasaki
Kazuo Takemura
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Osaka Titanium Technologies Co Ltd
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Osaka Titanium Technologies Co Ltd
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Priority claimed from JP2004044552A external-priority patent/JP2005133196A/ja
Priority claimed from JP2004074445A external-priority patent/JP2005264181A/ja
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Assigned to SUMITOMO TITANIUM CORPORATION reassignment SUMITOMO TITANIUM CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HORI, MASAHIKO, OGASAWARA, TADASHI, TAKEMURA, KAZUO, UENISHI, TORU, URASAKI, YUKO, YAMAGUCHI, MAKOTO
Publication of US20070131057A1 publication Critical patent/US20070131057A1/en
Assigned to OSAKA TITANIUM TECHNOLOGIES CO., LTD. reassignment OSAKA TITANIUM TECHNOLOGIES CO., LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SUMITOMO TITANIUM CORPORATION
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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
    • 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
    • C22B34/1295—Refining, melting, remelting, working up 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
    • 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

Definitions

  • the present invention relates to a method for producing Ti or Ti alloys through reduction by Ca (hereinafter, can be referred to as “by a Ca reduction”), in which a metallic chloride containing TiCl 4 is reduced by Ca to produce Ti metals or Ti alloys.
  • the Kroll method for reducing TiCl 4 by Mg is generally used as an industrial production method of Ti metals.
  • Ti metal is produced through a reduction step—vacuum separation step.
  • a reduction step TiCl 4 which is of a raw material of Ti is reduced by Mg in a reactor vessel to produce the sponge-like Ti metals.
  • a vacuum separation step unreacted Mg and MgCl 2 formed as a by-product are removed from the sponge-like Ti metals produced in the reactor vessel.
  • the reactor vessel is filled with the molten Mg, and TiCl 4 liquid is supplied from above the liquid surface of molten Mg.
  • TiCl 4 to be reduced by Mg in the vicinity of the liquid surface of molten Mg to generate Ti metals in a particulate form.
  • the generated Ti metal sequentially moves downward.
  • molten MgCl 2 is generated as a by-product in the vicinity of the liquid surface.
  • a specific gravity of molten MgCl 2 is larger than that of 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 reaction is continued.
  • the supplied raw material becomes an unreacted generated gas (referred to as an unreacted gas) such as an unreacted TiCl 4 gas and an unreacted TiCl 3 gas, and the unreacted gas is discharged outside the reactor vessel.
  • an unreacted gas such as an unreacted TiCl 4 gas and an unreacted TiCl 3 gas
  • the unreacted gas is discharged outside the reactor vessel. It is necessary to avoid the generation of unreacted gas, because a rapid increase in the inner pressure within the reactor vessel is associated with the generation of unreacted gas.
  • There is a limit of the feed rate of TiCl 4 which is of the raw material of Ti by reason of the above.
  • Ti is generated in a particulate form in the vicinity of the liquid surface of molten Mg liquid, and Ti moves downward.
  • wetting properties adheresion properties
  • the generated Ti particles moves downward and sinks to accumulate as sediment while aggregated, and the Ti particles are sintered to grow in particulate size to be the lump-like Ti at melting-temperature conditions during moving downward, which makes it difficult to discharge the Ti particles outside the reactor vessel. Therefore, in the Kroll method, the continuous production is difficult to be performed, and the improvement of productivity is blocked. This is why Ti is produced in the batch manner as well as in the form of sponge titanium by the Kroll method.
  • U.S. Pat. No. 2,205,854 describes that, besides 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 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 a TiCl 4 gas is supplied from below to react the dissolved Ca with TiCl 4 in the molten salt of CaCl 2 .
  • Ti metals are generated from TiCl 4 by the reaction of the following chemical formula (i), and CaCl 2 is also generated as the by-product at the same time.
  • Ca has a stronger affinity to Cl than Mg has, and Ca is suitable for the reducing agent of TiCl 4 in principle.
  • Ca is used while dissolved in the molten CaCl 2 .
  • the reducing reaction by Ca is utilized in the molten CaCl 2 , like the Kroll method, TiCl 4 is supplied to the liquid surface of reducing agent in the reactor vessel, which enlarges the reaction area compared with the case that the reaction area is restricted in the vicinity of liquid surface.
  • U.S. Pat. No. 2,845,386 describes the Olsen method as another Ti production method.
  • This method is a kind of oxide direct-reduction method for directly reducing TiO 2 by Ca.
  • the oxide direct-reduction method is highly efficient, it is not suitable for producing high-purity Ti. The reason is that this method entails to use expensive high-purity TiO 2 .
  • reducing TiCl 4 by Ca is indispensable and made an attempt to utilize Ca that dissolves in the molten salt of CaCl 2 as described in U.S. Pat. No. 4,820,339. Since Ca dissolves in CaCl 2 by about 1.5%, by utilizing the reducing reaction that Ca reduces TiCl 4 in this molten CaCl 2 , there is a possibility that the feed rate of TiCl 4 can be increased to thereby enhance the production efficiency dramatically, as afore-mentioned.
  • the present inventors consider that Ca in the molten salt, decreased by consumption during the reducing reaction, needs to be economically replenished in order to industrially establish the method for producing Ti by a Ca reduction, and came up with, as the replenishing means, the method of utilizing Ca being produced by an electrolysis of molten salt, as well as with the method of using this Ca in circulation. Namely, although Ca in the molten salt should be consumed in association with the reducing reaction, when electrolyzing this molten salt, Ca is generated in the molten salt. So by reusing Ca thus obtained for the reducing reaction, it becomes unnecessary to replenish Ca by outside source. Moreover, in this method, there is no need to strictly take out Ca only, which should be one factor to enhance the economic efficiency. If Ca should be independently extracted as a solid matter, a lot of difficulties are accompanied, while merely generating Ca in the molten salt is relatively easy to be done.
  • the present invention is completed based on such conception and pertains to a method for producing Ti or Ti alloys by a Ca reduction as described in the following (1), (2) or (3).
  • a method for producing Ti or Ti alloys by a Ca reduction includes: a reduction step in which a molten salt, containing CaCl 2 and having Ca dissolved therein, is held in a reactor vessel, and a metallic chloride containing TiCl 4 is reacted with Ca in the molten salt to generate Ti particles or Ti alloy particles in the molten salt; and a separation step in which Ti particles or Ti alloy particles, generated in the molten salt, are separated from the molten salt (hereinafter, referred to as a first production method).
  • a method for producing Ti or Ti alloys by a Ca reduction comprising a combined process of a reduction step and a circulation-type electrolysis step, wherein said reduction step includes the steps of holding a molten salt, containing CaCl 2 and having Ca dissolved therein, in a reactor vessel; and, reacting a metallic chloride containing TiCl 4 with Ca in the molten salt to generate Ti particles or Ti alloy particles in the molten salt, and wherein said circulation-type electrolysis is configured such that the molten salt, being used for producing said Ti or Ti alloys and discharged outside said reactor vessel, is electrolyzed to generate and replenish Ca in said molten salt which is returned to said reactor vessel, and wherein, in electrolyzing as above, an alloy electrode made of molten Ca alloy is employed for a cathode (hereinafter, referred to as a second production method).
  • a second production method an alloy electrode made of molten Ca alloy is employed for a cathode
  • a method for producing Ti or Ti alloys by a Ca reduction includes the steps of: generating Ca by an electrolysis in which a molten salt containing CaCl 2 is electrolyzed by employing a molten Ca alloy as a cathode to increase a Ca content ratio in said molten Ca alloy; replenishing Ca by dissolving Ca in relevant molten salt in which the molten Ca alloy, having Ca increased by the Ca generation step, get contacted with the molten salt containing CaCl 2 ; and, generating Ti by a reducing reaction such that a metallic chloride containing TiCl 4 is supplied into the molten salt having the dissolved Ca by the Ca replenishing step to thereby generate Ti or Ti alloys in the molten salt (hereinafter, referred to as a third production method).
  • a first production method as above is the method including: a reduction step in which Ti particles or Ti alloy particles are generated in the molten salt; and, a separation step in which Ti particles or Ti alloy particles thus generated are separated from the molten salt, but can adopt the embodiment mode, as described hereinbelow, such that CaCl 2 generated as a by-product in association with the generation of Ti or Ti alloys is discharged outside the reactor vessel to be electrolyzed for generating Ca that is to be utilized in the generation reaction (namely, the reducing reaction of TiCl 4 ) of Ti or Ti alloys.
  • a second production method has a feature in respect of using an alloy electrode made of molten Ca alloy for a cathode. Besides, in these methods i.e., a first and a second production method, in order to use Ca in circulation, the molten CaCl 2 salt with the enhanced Ca concentration is circulated between the reducing step and the electrolysis step.
  • a third production method appears to be similar to a second production method in respect of using an alloy Ca alloy electrode in the electrolysis step, but has a feature of making use of molten Ca alloy with the increased Ca content ratio as a carrier medium for transferring Ca, in using Ca circularly.
  • the method for producing Ti or the Ti alloys by a Ca reduction is named the “OYIK method” after initials of four persons of Ogasawara, Yamaguchi, Ichihasi, and Kanazawa who deeply engages in conception, development, and completion.
  • Ca is inferior in wetting properties (adhesion properties) to Mg, and the Ca adhering to precipitated Ti particles is dissolved in CaCl 2 , so that the aggregation of particles becomes less in the generated titanium particles and sintering is significantly lessened. Therefore, generated Ti can be discharged outside the reactor vessel in a particle state, and the Ti production can continuously be operated.
  • a metallic chloride containing TiCl 4 reacts with Ca dissolved in the molten salt containing CaCl 2 (hereinafter, may be referred to as a molten salt or molten CaCl 2 simply).
  • a molten salt or molten CaCl 2 simply it is not prohibited to hold the molten Ca liquid on the molten CaCl 2 liquid surface within the reactor vessel. Rather, by holding the molten Ca liquid on the molten CaCl 2 liquid surface, Ca can be supplied from the Ca liquid layer to the CaCl 2 liquid layer located below to thereby enable the reaction efficiency to be raised. Also, the reducing reaction even in the molten Ca liquid becomes possible, thus enabling the reaction efficiency to be raised too.
  • a supply mode of TiCl 4 to the molten CaCl 2 liquid although it is preferable for TiCl 4 in a gas state to be directly supplied into the molten CaCl 2 liquid since the contact efficiency of TiCl 4 with Ca in the molten CaCl 2 liquid is high, it is also possible for TiCl 4 in a liquid state or in a gas state to be supplied on the liquid surface of molten CaCl 2 liquid, or it is also possible for TiCl 4 in a liquid state or in a gas state to be supplied on the liquid surface of molten Ca liquid or deep into the liquid which is held on the liquid surface of molten CaCl 2 liquid.
  • the TiCl 4 liquid is supplied to the liquid surface of molten Mg liquid.
  • TiCl 4 gas is supplied into the molten Mg liquid in aiming the expansion of the reaction region.
  • Mg has the large vapor pressure
  • Mg vapor intrudes in a supply nozzle to react with TiCl 4 , and a supply pipe is clogged. The problem of nozzle clogging still remains even if TiCl 4 gas is supplied into the molten MgCl 2 liquid.
  • TiCl 4 in a first through a third production method in which TiCl 4 is reduced by Ca, it is particularly desirable that TiCl 4 be directly supplied in a gas state into the molten salt, and this supply mode can be applied with no problem in the actual operation. It is also possible that TiCl 4 is supplied on the liquid surface of molten salt, or it is also possible that liquid or gaseous TiCl 4 is supplied on the liquid surface or into the liquid of the molten Ca liquid held on the molten CaCl 2 liquid. These supply modes can also be applied with no problem in the actual operation.
  • the reduction step (Ti generation step by the reducing reaction in a third production method as above corresponds to the reduction step) is meant to undergo the reducing reaction by Ca dissolved in the molten salt to generate Ti or Ti alloys in a particulate form and/or powder form (hereinafter, may referred to as Ti particles or Ti alloy particles) within the reactor vessel.
  • Ti particles and the molten CaCl 2 liquid may be separated from each other outside the reactor vessel by utilizing the Ti generated in a particulate form to discharge the Ti particles outside the reactor vessel together with the molten CaCl 2 liquid.
  • the Ti particles can simply be separated from the molten CaCl 2 liquid by a squeezing operation such as a mechanical compression. In a first production method as above, this separation step is included, and a second and a third production method can also employ such an embodiment mode.
  • CaCl 2 is generated as the by-product at the same time when Ti is generated in the molten salt. Namely, the dissolved Ca concentration decreases, while CaCl 2 increases. Therefore, it is preferable for CaCl 2 within the vessel to be discharged toward the outside of the vessel according to the extent of the generation of CaCl 2 , and particularly preferable to discharge it at the later stage after Ca is used for generating Ti, i.e., at the stage in which Ca dissolved in CaCl 2 is consumed. In a second production method, this discharging operation is included, and a first production method can employ the embodiment mode to apply this discharging operation. However, in a third production method, the molten Ca alloy is utilized as a carrier medium for transferring Ca as afore-mentioned, so the molten salt is not discharged to the outside.
  • CaCl 2 discharged as above is electrolyzed into Ca and Cl 2 , and the Ca thus produced replenishes the depleted Ca in the molten salt in which Ca concentration is lowered in association with the reducing reaction.
  • Ti particles or Ti alloy particles generated in the molten salt is extracted together with the molten salt outside the reactor vessel, and further, the remaining molten salt after Ti particles or Ti alloy particles are separated is similarly treated.
  • a second production method as above comprises this circulation-type electrolysis step, and a first production method can be operated with the embodiment mode including this step.
  • the molten salt in which the Ca concentration recovers like this is returned to the reduction step, and by repeating this operation over and over again, Ti or Ti alloys are produced.
  • the phenomenon that takes place here regarding Ca is basically an increase or decrease only in the dissolved Ca concentration in the molten salt in circulation process, and the operation such as discharging Ca independently and replenishing Ca is not required. Therefore, high-purity Ti metals or Ti alloys can be produced with high efficiency plus economically without using an expensive reducing agent.
  • a third production method also comprises a Ca generation step in which the molten salt containing CaCl 2 is electrolyzed, and a Ca replenishment step in which Ca in the molten salt whose Ca concentration is lowered is replenished, but differs from a first or a second production method in terms of utilizing the molten Ca alloy as a carrier medium for Ca.
  • an electric current efficiency in an electrolysis step should affect the economic efficiency, which influences on the success and failure of establishing a commercially viable production technology.
  • One of grave causes that lower the electric current efficiency in this electrolysis step is the presence of unreacted dissolved Ca in the molten salt being transferred from the reduction step to the electrolysis step.
  • the dissolved Ca i.e., a reducing agent
  • the dissolved Ca in the molten salt is consumed, but not necessarily consumed entirely, so that it cannot be avoided for the unreacted dissolved Ca to be retained more or less in the molten salt being transferred from the reduction step to the electrolysis step.
  • an alloy electrode made of molten Ca alloy (hereinafter, referred to as the molten Ca alloy electrode, or the alloy electrode simply) is employed for the cathode in the electrolysis step.
  • the molten Ca alloy electrode or the alloy electrode simply
  • the molten salt within the electrolytic cell, together with the interface between the molten Ca alloy constituting the above alloy electrode and the molten salt is divided into an anode side and a counter-anode side by installing a partition wall to thereby introduce the molten salt being supplied from the reactor vessel into the above counter-anode side.
  • the molten salt on the anode side when the molten salt on the anode side is electrolyzed while supposing that the dissolved Ca is essentially not contained, not only Cl 2 gas emerges on the surface of the anode but also Ca is generated at the interface between the molten Ca alloy constituting the cathode and the molten salt on the anode side, and the generated Ca is absorbed by the above molten Ca alloy electrode.
  • the molten salt on the anode side usually does not contain the dissolved Ca, and, if any, the amount is extremely small, so that neither the back reaction nor its accompanying effect like the drop of the electric current efficiency takes place.
  • the molten salt on the counter-anode side is the one transferred from the reduction step, which contains the unreacted dissolved Ca though the amount is not so much.
  • Ca is released from the alloy electrode (cathode) to the molten salt on the counter-anode side.
  • Ca is generated at the alloy electrode and at the interface on the anode side of the molten salt, but, as the anode side has an electric potential (the electric potential difference is generated), the generated Ca metals are taken into the alloy electrode in the cathode. Consequently, the Ca concentration in the alloy electrode rises. Meanwhile, as there is no electric potential at the alloy electrode and at the interface on the counter-anode side of the molten salt, Ca is driven to dissolve in the molten salt from the alloy electrode owing to the difference of Ca concentration between the alloy electrode and the molten salt. Since the Ca concentration in the molten salt on the counter-anode side becomes low due to the reducing reaction, Ca can readily dissolve in the molten salt. The above reason is applicable to the molten Ca alloy electrode to be employed in a third production method as described hereinbelow.
  • the amount of molten salt decreases as the electrolysis proceeds.
  • replenish it it can be done by either way: the molten salt that does not contain the dissolved Ca is newly replenished; or part of the molten salt transferred from the reduction step is circularly used. In the event that part of the molten salt transferred from the reduction step is used only, the amount of dissolved Ca to be brought in as the mixture is limitedly small, so that the back reaction can be controlled so as not to pose any harm.
  • the Ca alloy constituting a molten Ca alloy electrode Mg—Ca alloy, Al—Ca alloy, Zn—Ca alloy and the like are preferable. It is because the melting point of these Ca alloys is relatively low such that it is 500° C. or above in case of Mg—Ca alloy, 600° C. or above in case of Al—Ca alloy, and 420° C. or above in case of Zn—Ca alloy respectively. In order to ensure such a low melting point, it is preferable for the Ca concentration in Mg—Ca alloy to be 45% or less, more preferably 15% or less. In case of Al —Ca alloy, it is preferable to be 20% or less.
  • the lower limit of Ca concentration is preferably set to 0.5%. The reason is that the more the difference between the Ca concentration of molten salt on the counter-anode and the Ca concentration of molten Ca alloy is, the faster the dissolving rate of Ca into the molten salt becomes.
  • a first or a second production method as the means for the replenishment of Ca in the molten salt that is consumed in the reducing reaction, the molten salt whose Ca concentration is raised by the electrolysis of molten salt is circularly used.
  • this method entails circulating a large amount of molten salt between the reactor vessel and the electrolytic cell, thereby requiring a large scale of equipment.
  • the molten Ca alloy electrode is used for a cathode in the electrolysis step, and is utilized as a carrier medium for transferring Ca.
  • the generated Ca on the side of cathode gets dissolved in the molten Ca alloy constituting the electrode and this Ca elutes off from the above molten Ca alloy to the used molten salt, that is introduced from the reactor vessel, to thereby raise the Ca concentration of molten salt, which is circularly operated to end up in using Ca in circulation.
  • the molten Ca alloy with the increased Ca content ratio is transferred to the reactor vessel to get contacted with the molten salt containing CaCl 2 , and Ca gets dissolved into this molten salt, thus enabling Ca to be used circularly.
  • the electrolytic cell is necessary for proceeding the Ca generation step by the electrolysis (namely, to carry out the operation of the Ca generation step), and the reactor vessel is necessary for proceeding the Ti generation step by the reducing reaction.
  • the electrolytic cell and the reactor vessel can be one cell (or vessel) to be used in share.
  • the molten salt containing CaCl 2 is held in the electrolytic cell and in the reactor vessel, wherein the operation of Ca generation step by the electrolysis in the electrolytic cell is proceeded and, in parallel, the molten Ca alloy is transferred from the electrolytic cell to the reactor vessel to thereby proceed the Ca replenishment step along with the Ti generation step within the reactor vessel and transfer the molten Ca alloy salt whose Ca is consumed within the cell to the electrolytic cell reversely.
  • the temperature difference of molten salt between in the electrolytic cell and in the reactor vessel there is a merit as below.
  • the temperature of molten salt in the electrolytic cell is set lower than that in the reactor vessel. Namely, it comes as a combination of a high-temperature reduction and a low-temperature electrolysis.
  • the Ca reactivity rises to enhance the efficiency of generating Ti or Ti alloys
  • the Ca solubility in the molten salt is reduced, thus resulting in promoting the transfer of Ca from the molten salt to the molten Ca alloy.
  • the molten salt containing CaCl 2 is held in the reactor vessel that serves as the electrolytic cell also, and the molten salt within the reactor vessel, together with the interface between this molten salt and the molten Ca alloy that constitutes the cathode is divided into an anode side and a counter-anode side by incorporating a partition wall, and thus, electrolyzing is proceeded.
  • Cl 2 gas is generated, and Ca is generated at the cathode (the molten Ca alloy) or in the neighboring region to the cathode, that is divided by the partition wall and disposed toward the anode side (Ca generation step).
  • the generated Ca is taken in the molten Ca alloy.
  • the replenishment step that Ca elutes off from the molten Ca alloy to the molten salt proceeds.
  • a third production method also can adopt an embodiment mode that includes the Ti separation step in which the generated Ti or Ti alloys is separated from the molten salt.
  • the molten salt separated from Ti or Ti alloys in the Ti separation step gets reacted with the molten Ca alloy whose Ca is consumed in the Ti generation step to increase Ca in the molten Ca alloy by the unreacted Ca in the molten salt and then this molten Ca alloy can be used in the Ca replenishment step.
  • Ca can be replenished into the molten Ca alloy without relying on the electrolysis.
  • the unreacted Ca can be removed from the molten salt that is separated from Ti or Ti alloys. Owing to this, when the molten salt separated from Ti or Ti alloys is introduced into the Ca generation step by the electrolysis, the back reaction can be prevented, which proves to be advantageous.
  • a mixed molten salt with NaCl, KCl or CaF 2 can be used also. If the mixed molten salt should be used, the melting point decreases to enable the temperature of molten salt to be lowered, thus increasing the durability of the vessel material to extend the service life thereof and suppressing the vaporization of Ca and salt from the liquid surface. For example, if it were the mixed salt with NaCl, the melting point of molten salt can be lowered down to about 500° C.
  • the merit for the vessel material by lowering the temperature of molten salt can be appreciated in all steps including the reduction step and the electrolysis step.
  • the electrolysis step by lowering the temperature of molten salt, the Ca solubility decreases, and the convection and the diffusion of molten salt are also suppressed, thereby resulting in suppressing the back reaction of Ca as described above. If the extent of reaction in the reduction step should be regarded as important, only the temperature of molten salt in the reduction step can be elevated.
  • the embodiment mode that the molten Ca liquid can be held on the molten salt in the reactor vessel could be employed, but in this case, it becomes impossible to lower the temperature of molten salt to the melting point of Ca (838° C.) or less. That said, by mixing Ca with other alkaline-earth metal or alkali metal, the melting point thereof can be lowered. For example, by mixing Ca with Mg, the melting point can be lowered down to 516° C.
  • the raw material of Ti basically TiCl 4 is adopted, but by using TiCl 4 as the mixture of other metallic chloride, Ti alloys can be produced also. Since TiCl 4 and other metallic chloride are reduced by Ca simultaneously, Ti alloy particles can be produced by this method. Meanwhile, the metallic chloride here in can be either gaseous state or liquid state.
  • the average particle diameter thereof is preferably set to 0.5-50 ⁇ m.
  • the proper size is preferably 50 ⁇ m or less.
  • the minimum proper size is set to 0.5 ⁇ m is that, when being lower than this, although possible to discharge it, it becomes difficult to separate from the molten salt.
  • Ca can be produced by electrolyzing CaCl 2 , but the generated Ca dissolves in CaCl 2 , thus making it difficult to efficiently produce Ca only, which is additionally compounded by the phenomenon that the generated Ca turns back to CaCl 2 due to the back reaction.
  • the productivity is poor, although the technique to enhance the recovery rate of Ca by the application of cooling the electrode in producing Ca by the electrolysis should be attempted, still leaving the production costs of Ca to be significantly high.
  • the molten salt with the dissolved Ca is proactively utilized, so that, even if Ca is mixed with the molten salt in the electrolysis step, it is not an issue at all by simply taking care of the back reaction, and there is no need to strictly separate Ca only. Namely, it is sufficient enough that the whole molten salt with Ca, or Ca that gets contained in the molten Ca alloy is charged from the electrolytic cell to the reactor vessel. Thus, the production costs of Ca by the electrolysis can be dramatically cut.
  • FIG. 1 is a view explaining a configuration of an apparatus for producing Ti metals that represents a first embodiment mode in a first production method
  • FIG. 2 is a view explaining a configuration of an apparatus for producing Ti metals that represents a second embodiment mode in a first production method
  • FIG. 3 is a view explaining a configuration of an apparatus for producing Ti metals that represents a third embodiment mode in a first production method
  • FIG. 4 is a view explaining a configuration of an apparatus for producing Ti metals that represents a first embodiment mode in a second production method
  • FIG. 5 is a view explaining a configuration of an apparatus for producing Ti metals that represents a second embodiment mode in a second production method
  • FIG. 6 is a view explaining a configuration of an apparatus for producing Ti metals that represents a third embodiment mode in a second production method
  • FIG. 7 is a view explaining a configuration of an apparatus for producing Ti metals that represents a first embodiment mode in a third production method
  • FIG. 8 is a view explaining a configuration of an apparatus for producing Ti metals that represents a second embodiment mode in a third production method.
  • FIG. 9 is a view explaining a configuration of an apparatus for producing Ti metals that represents a third embodiment mode in a third production method.
  • FIG. 1 is a view explaining a configuration of an apparatus for producing Ti metals that represents a first embodiment mode in a first production method.
  • a cylindrical reactor vessel 1 is employed.
  • the reactor vessel 1 is a closed vessel made of iron.
  • a reducing agent supply pipe 2 for supplying Ca which is a reducing agent is disposed at the ceiling portion of the reactor vessel 1 .
  • the bottom portion of reactor vessel 1 is made to have a tapered figuration with the opening diameter that gradually getting smaller downward so as to facilitate the discharge of the generated Ti particles, and, at the center part of the lower end part thereof, a Ti discharge pipe 3 for discharging the generated Ti is provided.
  • a cylindrical separating wall 4 with the embedded heat exchanger is disposed at the position with a predetermined space off from the inside surface of straight cylindrical vessel body.
  • a molten salt discharge pipe 5 for discharging sideways CaCl 2 in the reactor vessel is provided, and, at the lower area thereof, a raw material supply pipe 6 for supplying TiCl 4 that is a raw material of Ti is provided to penetrate the separating wall 4 to reach the central part of the plenum in the vessel.
  • the molten CaCl 2 liquid, as the molten salt, where Ca dissolves is held in the reactor vessel 1 .
  • the liquid surface thereof is set to the height level that is lower than the upper end of the separating wall 4 but higher than the molten salt discharge pipe 5 .
  • the molten Ca liquid as the molten metal containing Ca is held on the molten CaCl 2 liquid surface.
  • TiCl 4 gas as a metallic chloride containing TiCl 4 is supplied to the molten CaCl 2 at the inner side from the separating wall 4 by means of the raw material supply pipe 6 .
  • TiCl 4 is reduced by Ca in the molten CaCl 2 liquid to thereby generate Ti metals in a particulate form within the molten CaCl 2 liquid.
  • TiCl 4 gas that is supplied into the molten CaCl 2 liquid turns to numerous bubbles which buoy and move upward in the molten CaCl 2 liquid and promote stirring the molten CaCl 2 liquid, thus enhancing the reaction efficiency.
  • the molten CaCl 2 liquid in which Ca is consumed by the reducing reaction on the inner side from the separating wall 4 within the reactor vessel 1 moves, via the lower part of separating wall 4 , upward on the outer side of separating wall 4 , and gets discharged through the molten salt discharge pipe 5 .
  • the discharged molten CaCl 2 liquid is to be transferred to an electrolysis step 8 .
  • Ca On the inner side from the separating wall 4 , Ca elutes in the molten CaCl 2 liquid from the molten Ca liquid held on the liquid surface of molten CaCl 2 liquid to thereby get replenished. Along with this, on the molten CaCl 2 liquid at the inner side from the separating wall 4 , Ca is replenished through the reducing agent supply pipe 2 .
  • the Ti metals can be continuously produced within the reactor vessel 1 .
  • the reaction region expands to the almost all area on the inner side from the separating wall 4 , thus enabling the feed rate of TiCl 4 to be increased.
  • the separating wall 4 blocks the molten CaCl 2 liquid containing Ca abundantly prior to be used in reducing TiCl 4 to mix with the molten CaCl 2 liquid with few Ca after use to thereby enhance the reaction efficiency.
  • the separation step 7 the Ti particles discharged together with the molten CaCl 2 liquid from the reactor vessel 1 are separated from the molten CaCl 2 liquid. To be concrete, said Ti particles are compressed to squeeze out the molten CaCl 2 liquid. Then, Ti particles are cleaned. The molten CaCl 2 liquid that is obtained in the separation step 7 is transferred together with the molten CaCl 2 liquid discharged from the reactor vessel 1 to the electrolysis step 8 .
  • the electrolysis step 8 the molten CaCl 2 liquid from the reactor vessel 1 as well as the separation step 7 is electrolyzed into Ca and Cl 2 gas. Ca returns to the inside of reactor vessel 1 .
  • Ca does not need to be separated strictly from CaCl 2 , and can return to the inside of reactor vessel 1 together with CaCl 2 without causing any problem. It is because CaCl 2 with the dissolved Ca is used in the reactor vessel 1 . Owing to this ease in the separation operation, the production costs of Ca by the electrolysis is lowered.
  • Cl 2 gas generated in the electrolysis step 8 is transferred to a chlorination step 9 .
  • TiO 2 is subjected to a chlorination process to yield TiCl 4 .
  • oxygen generated as a by-product is discharged in the form of CO 2 .
  • TiCl 4 thus made is introduced into the inside of reactor vessel 1 through the raw material supply pipe 6 .
  • the way things are, by circulating CaCl 2 , Ca as the reducing agent and Cl 2 gas are cycled. That is, essentially by only supplementing TiO 2 and C, Ti metals are continuously produced.
  • FIG. 2 is a view explaining a configuration of an apparatus for producing the Ti metals that represents a second embodiment mode in a first production method.
  • a second embodiment mode in a first production method here differs from a first embodiment mode with respect to that the reducing agent supply pipe 2 a is provided at the lower part of reactor vessel 1 and from its lower part, Ca is supplied on the inner side of separating wall 4 .
  • the molten Ca liquid as the reducing agent comes up from below to float on the inner side of separating wall 4 due to the specific gravity difference from the molten CaCl 2 liquid.
  • Ca gets dissolved in CaCl 2 to enhance the efficiency of Ca dissolution.
  • the molten Ca thus floated remains to lie on the surface of molten CaCl 2 liquid to get Ca dissolved in the molten CaCl 2 located below.
  • FIG. 3 is a view explaining a configuration of an apparatus for producing Ti metals that represents a third embodiment mode in a first production method
  • This third embodiment mode differs in terms of the location of the raw material supply pipe 6 a .
  • the raw material supply pipe 6 a is configured to supply TiCl 4 into the central part of the inside of vessel, while in a third embodiment mode, it is configured to supply TiCl 4 into the off-set position from the centerline, being located on the inner side from the separating wall 4 .
  • the convection due to the gas lift of TiCl 4 gas takes place within the molten CaCl 2 liquid on the inner side of separating wall 4 . Owing to this convection in CaCl 2 , the dissolution of Ca into CaCl 2 is promoted to thereby enhance the dissolution efficiency.
  • FIG. 4 is a view explaining a configuration of an apparatus for producing Ti metals that represents a first embodiment mode in a second production method.
  • the reactor vessel 1 in which the reduction step is carried out and the electrolytic cell 10 in which the electrolysis step is carried out are employed.
  • the reactor vessel 1 holds the Ca-rich molten CaCl 2 , as the molten salt, in which comparatively abundant Ca dissolves.
  • the melting point of CaCl 2 is about 780° C., and this molten salt is heated to the melting point or above.
  • the gaseous TiCl 4 is injected into the molten salt within the reactor vessel 1 in a randomly-dispersed manner, and is reduced by the dissolved Ca in the molten salt to generate Ti metals in a particulate form.
  • the generated Ti particles incrementally accumulate at the bottom of reactor vessel 1 due to the specific gravity difference.
  • Ti particles accumulated at the bottom of reactor vessel 1 are discharged, together with the molten salt lying at the said bottom, from the reactor vessel 1 and transferred to the separation step 7 .
  • Ti particles that are discharged together with the molten salt from the reactor vessel 1 are separated from the molten salt. To be concrete, said Ti particles are compressed to squeeze out the molten salt. Ti particles obtained in the Ti separation step 7 are to be melted to yield Ti ingots.
  • the molten salt separated from Ti particles in the Ti separation step 7 is the used molten salt where Ca is consumed and the Ca concentration is lowered. This molten salt is transferred from the reactor vessel 1 to the electrolytic cell 10 .
  • the molten CaCl 2 as the molten salt is electrolyzed between an anode 11 and a cathode 12 to generate Cl 2 gas on the side of anode 11 and to generate Ca on the side of cathode 12 .
  • the cathode 12 denotes a molten Ca alloy electrode 14 , comprising: a heat resistant vessel 13 with an open bottom part to be inserted into the molten salt in the electrolytic cell 10 ; a molten Ca alloy 14 contained within the heat resistant vessel 13 ; an electrode rod 15 penetrating the ceiling part of heat resistant vessel 13 to be inserted into said molten Ca alloy 14 ; and a partition wall 16 dividing the molten salt within the electrolytic cell 10 into an anode side and a counter-anode side.
  • the molten Ca alloy 14 here is represented by, for example, Mg —Ca liquid whose specific gravity is smaller than that of the molten salt.
  • the partition wall 16 which is heat resistant and has an insulation capability is provided just beneath the cathode 12 , wherein the upper end part of said wall is inserted into the molten Ca alloy 14 and the lower end part is closely attached to the bottom plate part of electrolytic cell 10 so as to bisect the molten salt within the electrolytic cell 10 together with the interface between the molten Ca alloy 14 and the molten salt located below into the anode side and the counter-anode side.
  • the molten salt transferred to the electrolytic cell 10 directly from the reactor vessel 1 or via the Ti separation step 7 is introduced on the counter-anode side within the electrolytic cell 10 .
  • the molten salt on the anode side essentially consists of the molten CaCl 2 without containing the dissolved Ca.
  • This molten salt on the anode side is electrolyzed between the anode 11 and the cathode 12 to generate Cl 2 gas on the side of anode 11 and Ca on the side of cathode 12 .
  • the generated Ca on the side of cathode 12 elutes into the molten Ca alloy.
  • the molten salt on the counter-anode side is the used molten salt which is introduced from the reactor vessel 1 , and contains unreacted and dissolved Ca, while dissolved Ca therein is consumed. Ca elutes into this molten salt from the molten Ca alloy 14 .
  • dissolved Ca is replenished to the used molten salt which is introduced from the reactor vessel 1 , and the molten salt that became Ca-rich is introduced to the reactor vessel 1 through the reducing agent supply pipe 2 , thus being circularly used in generating Ti particles by the Ca reduction.
  • the Cl 2 gas generated in the vicinity of the surface of anode 11 is transferred to a chlorination step 9 .
  • TiO 2 is chlorinated to yield TiCl 4 as a raw material of Ti.
  • TiCl 4 thus made is introduced into the reactor vessel 1 through the raw material supply pipe 6 to be used circularly for producing Ti particles by the Ca reduction.
  • the molten salt (the molten CaCl 2 in which Ca dissolved) circulates among the reduction step (reactor vessel 1 ), the separation step 7 and the electrolysis step (electrolytic cell 10 ), and by repeating the operation that the Ca consumed in the reduction step (reactor vessel 1 ) is replenished in the electrolysis step (electrolytic cell 10 ), the production of Ti continues in the reduction step (reactor vessel 1 ). Namely, without replenishing nor discharging the solid Ca, by simply controlling the Ca concentration in the molten salt, high-quality Ti particles are continuously produced by the Ca reduction.
  • the unreacted dissolved Ca is introduced to the counter-anode side that is a non-electrolyzing region within the electrolytic cell 10 and is kept indifferent with the electrolysis to thereby block the back reaction by said dissolved Ca. Therefore, the electric current efficiency in the electrolysis step is enhanced.
  • the molten CaCl 2 is consumed. To replenish it, the molten CaCl 2 that does not contain the dissolved Ca essentially is supplemented from the outside source. Or, a small amount of used molten salt is introduced on the anode side, independently from or in combination with the above supplementing (route shown by the broken line in FIG. 4 ).
  • the temperature of molten salt in either step is controlled to be higher than the melting point of CaCl 2 (about 780° C.).
  • FIG. 5 is a view explaining a configuration of an apparatus for producing Ti metals that represents a second embodiment mode in a second production method.
  • reactor vessel 1 In this second embodiment mode, the structure of reactor vessel 1 is concretely defined.
  • the reactor vessel 1 that is employed here is a closed vessel with a cylindrical form that is made of iron.
  • a reducing agent supply pipe 2 for supplying Ca which is a reducing agent is disposed at the ceiling portion of the reactor vessel 1 .
  • the bottom portion of reactor vessel 1 is made to have a tapered figuration with the opening diameter that gradually getting smaller downward so as to facilitate the discharge of the generated Ti particles, and, at the center part of the lower end part thereof, a Ti discharge pipe 3 for discharging the generated Ti is provided.
  • a cylindrical separating wall 4 with the embedded heat exchanger is disposed at the position with a predetermined space off from the inside surface of straight cylindrical vessel body.
  • a molten salt discharge pipe 5 for discharging sideways CaCl 2 in the reactor vessel is provided, and, at the lower area thereof, a raw material supply pipe 6 for supplying TiCl 4 that is a raw material of Ti is provided to penetrate the separating wall 4 to reach the central part of the plenum in the vessel.
  • the molten CaCl 2 liquid for example as the molten salt, where Ca dissolves is held in the reactor vessel 1 .
  • the liquid surface thereof is set to the height level that is lower than the upper end of the separating wall 4 but higher than the molten salt discharge pipe 5 .
  • TiCl 4 gas as a metallic chloride containing TiCl 4 is supplied to the molten CaCl 2 at the inner side from the separating wall 4 by means of the raw material supply pipe 6 .
  • TiCl 4 is reduced by Ca in the molten CaCl 2 liquid to thereby generate Ti metals in a particulate form within the molten CaCl 2 liquid.
  • TiCl 4 gas that is supplied into the molten CaCl 2 liquid turns to numerous bubbles which buoy and move upward in the molten CaCl 2 liquid and promote stirring the molten CaCl 2 liquid, thus enhancing the reaction efficiency.
  • the generated Ti particles in the molten CaCl 2 liquid on the inner side from the separating wall 4 within the reactor vessel 1 move downward in this liquid to accumulate as sediment at the bottom area within the vessel.
  • the accumulated Ti particles are discharged downward together with the molten CaCl 2 liquid through the Ti discharge pipe 3 and transferred to a separation step 7 .
  • the molten CaCl 2 liquid in which Ca is consumed by the reducing reaction on the inner side from the separating wall 4 within the reactor vessel 1 moves, via the lower part of separating wall 4 , upward on the outer side of separating wall 4 , and gets discharged through the molten salt discharge pipe 5 .
  • the discharged molten CaCl 2 liquid is to be transferred to an electrolysis step 8 .
  • the Ti metals can be continuously produced within the reactor vessel 1 .
  • the reaction region expands to the almost all area on the inner side from the separating wall 4 , thus enabling the feed rate of TiCl 4 to be increased.
  • the separating wall 4 blocks the molten CaCl 2 liquid containing Ca abundantly prior to be used in reducing TiCl 4 to mix with the molten CaCl 2 liquid with few Ca after use to thereby enhance the reaction efficiency.
  • the separation step 7 the Ti particles discharged together with the molten CaCl 2 liquid from the reactor vessel 1 are separated from the molten CaCl 2 liquid. To be concrete, said Ti particles are compressed to squeeze out the molten CaCl 2 . Then, Ti particles are cleaned. The molten CaCl 2 liquid that is obtained in the separation step 7 is transferred together with the molten CaCl 2 liquid discharged from the reactor vessel 1 to the electrolysis step 8 .
  • the electrolysis step 8 the molten CaCl 2 liquid from the reactor vessel 1 as well as the separation step 7 is electrolyzed into Ca and Cl 2 gas. Ca returns to the inside of reactor vessel 1 .
  • Ca does not need to be separated strictly from CaCl 2 , and can return to the inside of reactor vessel 1 together with CaCl 2 without causing any problem. It is because CaCl 2 with the dissolved Ca is used in the reactor vessel 1 . Owing to this ease in the separation operation, the production costs of Ca by the electrolysis is lowered.
  • Cl 2 gas generated in the electrolysis step 8 is transferred to a chlorination step 9 .
  • TiO 2 is subjected to a chlorination process to yield TiCl 4 .
  • oxygen generated as a by-product is discharged in the form of CO 2 .
  • TiCl 4 thus made is introduced into the inside of reactor vessel 1 through the raw material supply pipe 6 .
  • the way things are, by circulating CaCl 2 , Ca as the reducing agent and Cl 2 gas are cycled. That is, essentially by only supplementing TiO 2 and C, Ti metals are continuously produced.
  • FIG. 6 is a view explaining a configuration of an apparatus for producing Ti metals that represents a third embodiment mode in a second production method.
  • the position of the raw material supply pipe 6 a is different in comparison with a second embodiment mode. Namely, in a second embodiment mode, the raw material supply pipe 6 a is configured to supply TiCl 4 into the central part of the inside of vessel, while in a third embodiment mode, it is configured to supply TiCl 4 into the off-set position from the centerline, being located on the inner side from the separating wall 4 .
  • FIG. 7 is a view explaining a configuration of an apparatus for producing Ti metals that represents a first embodiment mode in a third production method.
  • the reactor vessel 1 in which the Ti generation step by the reducing reaction is carried out and the electrolytic cell 10 in which the Ca replenishment step by electrolyzing is carried out are employed.
  • the reactor vessel 1 holds the Ca-rich molten CaCl 2 , as the molten salt, in which comparatively abundant Ca dissolves.
  • the melting point of CaCl 2 is about 780° C., and this molten salt is heated to the melting point or above.
  • the inside cavity except the bottom part in the reactor vessel 1 is bisected by the heat resistant partition wall 17 , wherein one is a reduction compartment 18 and the other is a Ca replenishment compartment 19 in which the molten Ca alloy gets in contact with the molten salt so as to make Ca in the molten Ca alloy to dissolve in the molten salt. Both compartments are in flow communication at the under part of reactor vessel 1 where to allow the molten salt to freely flow back and forth.
  • the gaseous TiCl 4 is injected into the molten salt within the reactor vessel 1 in a randomly-dispersed manner, and is reduced by the dissolved Ca in the molten salt to generate Ti metals in a particulate form.
  • the generated Ti particles incrementally accumulate at the bottom of reactor vessel 1 due to the specific gravity difference.
  • Ti particles accumulated at the bottom of reduction compartment 18 are discharged, together with the molten salt lying at the said bottom, from the reduction compartment 18 and transferred to the Ti separation step 7 .
  • Ti separation step 7 Ti particles that are discharged together with the molten salt from the reduction compartment 18 are separated from the molten salt. To be concrete, said Ti particles are compressed to squeeze out the molten salt. Ti particles obtained in the Ti separation step 7 are to be melted to yield Ti ingots.
  • the molten salt separated from Ti particles in the Ti separation step 7 is the used molten salt where Ca is consumed and the Ca concentration is lowered. This molten salt is transferred to said electrolytic cell 10 .
  • molten CaCl 2 as the molten salt is held and the electrolysis of said molten CaCl 2 is carried out by means of an anode 11 and a cathode 12 .
  • Cl 2 gas is generated on the side of anode 11 and Ca is generated on the side of cathode 12 .
  • the cathode 12 denotes a molten Ca alloy electrode, to be concrete, comprising: a heat resistant vessel 13 having insulation capability and an open bottom part to be inserted into the molten salt in the electrolytic cell 10 ; a molten Ca alloy 14 contained within the heat resistant vessel 13 ; and, an electrode rod 15 penetrating the ceiling part of heat resistant vessel 13 to be inserted into said molten Ca alloy 14 .
  • the generated Ca on the side of cathode 12 is taken into the molten Ca alloy 14 within the heat resistant vessel 13 as an alloy or in the liquid state.
  • the Ca concentration in the molten Ca alloy 14 within the heat resistant vessel 13 rises.
  • this molten Ca alloy 14 with the high Ca concentration is charged to the Ca replenishment compartment 19 within the reactor vessel 1 from above through a first transport pipe 20 .
  • the molten Ca alloy 14 ′ that was charged previously floats.
  • This molten Ca alloy 14 ′ has the high Ca concentration when charged, but, by releasing Ca toward the molten salt located below to have it dissolved, it becomes to have a low Ca concentration (for example, a few %).
  • the used molten Ca alloy 14 ′ with the low Ca content that floats above the molten salt in the Ca replenishment compartment 19 is transported to the inside of heat resistant vessel 13 through a second transport pipe 21 .
  • the Ca replenishment by dissolving from the molten Ca alloy 14 to the below molten salt can be continued in the Ca replenishment compartment 19 .
  • Ca that is consumed in association with the generation of Ti particles in the reduction compartment 18 can be replenished to thereby sustain said generation reaction.
  • the Cl 2 gas generated in the vicinity of the surface of anode 11 is transferred to a chlorination step 9 .
  • TiO 2 and C are chlorinated to yield TiCl 4 as a raw material of Ti and to release CO 2 gas also.
  • TiCl 4 thus made is introduced into the reactor vessel 1 through the raw material supply pipe 6 to be used circularly for producing Ti particles by the Ca reduction.
  • the way things are, in a first embodiment mode in a third production method, Ca in the molten salt is consumed by the Ca reducing reaction in the reactor vessel 1 , an then, this Ca is generated by the electrolysis of molten salt in the electrolytic cell 10 to be used circularly for generating Ti particles by the reducing reaction. Moreover, there is no need to circulate the molten salt between the reactor vessel 1 and the electrolytic cell 10 for using Ca in circulation.
  • the molten Ca alloy 14 is used for the cathode in the electrolytic cell 10 , and by utilizing it as a carrier medium for transferring Ca to merely reciprocate between the reactor vessel 1 and the electrolytic cell 10 , it becomes possible to keep supplying Ca to the molten salt in the reactor vessel 1 to sustain the Ti production.
  • the temperature of molten salt in either step is controlled to be higher (for example, 800-850° C.) than the melting point of CaCl 2 (about 780° C.).
  • FIG. 8 is a view explaining a configuration of an apparatus for producing Ti metals that represents a second embodiment mode in a third production method.
  • the molten salt As the molten salt, a multi-element system molten salt having the low melting point where CaCl 2 is mixed with other chloride is employed. Before introducing the molten salt, being separated from Ti particles in the Ti separation step 7 , to the electrolytic cell 10 , said molten salt is introduced to the Ca removal cell 22 .
  • the melting point of molten salt be set to, for example, 650° C.
  • the high-temperature operation such that the temperature of molten salt is heightened to 850° C. or so is applied in the reactor vessel 1 .
  • the low-temperature operation such that the temperature of molten salt is lowered down to 700° C. or so is applied in the electrolytic cell 10 and in the Ca removal cell 22 .
  • the molten salt transferred from the reactor vessel 1 to the electrolytic cell 10 via the Ti separation step 7 is the used one which still retains the unreacted dissolved Ca, while the majority of the dissolved Ca is consumed.
  • the unreacted Ca happens to be brought in to the electrolytic cell 10 , it reacts with Cl 2 gas generated on the side of anode 11 to turn back to CaCl 2 , i.e., the so-called back reaction takes place, where the electrolytic current is consumed, thus lowering the electric current efficiency.
  • the molten salt introduced from the Ti separation step 7 (retains the unreacted Ca) is mixed with part of the used molten Ca alloy 14 ′ (designated by Mg in FIG. 8 ) having the low Ca concentration and being transferred from the Ca replenishment compartment 19 to the heat resistant vessel 13 in the electrolytic cell 10 .
  • the unreacted Ca in the molten salt is taken into the molten Ca alloy 14 ′ with the low Ca concentration, so that the unreacted Ca is removed and the molten Ca alloy 14 with the high Ca concentration is generated.
  • the molten salt By introducing the molten salt without the unreacted Ca to the electrolytic cell 10 in this way, the molten salt can be circularly used without any waste, and the back reaction, attributable to the unreacted Ca in the molten salt, as well as the resultant drop of electric current efficiency can be suppressed.
  • the molten Ca alloy 14 (designated by Mg—Ca in FIG. 8 ) with the high Ca concentration, being regenerated in the Ca removal cell 22 , is introduced to the Ca replenishment compartment 19 in the reactor vessel 1 .
  • the Ca solubility in the molten salt decreases, and also, the convection and diffusion of molten salt are suppressed. From this aspect also, the back reaction can be suppressed. Besides, by carrying out the low-temperature operation in the Ca removal cell 22 , the Ca solubility decreases to precipitate Ca, and then, the precipitated Ca is absorbed by the alloy.
  • FIG. 9 is a view explaining a configuration of an apparatus for producing Ti metals that represents a third embodiment mode in a third production method. This third embodiment mode differs from a first embodiment mode and a second embodiment mode over the following aspects.
  • the reactor vessel 1 doubles as the electrolytic cell, comprising a reduction compartment 24 with a deep bottom and an electrolysis compartment 24 with a shallow bottom.
  • An anode 11 is disposed within the electrolysis compartment 24 but on the counter side as opposed to the reduction compartment side, whereas the heat resistant vessel 13 constituting a cathode 12 is disposed so as to ride over the interface between the reduction compartment 23 and the electrolysis compartment 24 .
  • the molten salt in the reactor vessel 1 together with the interface between the molten Ca alloy 14 and the molten salt within the heat resistant vessel 13 , is divided into an anode side and a counter-anode side by a partition wall 16 that is disposed at the interface between the reduction compartment 23 and the electrolysis compartment 24 .
  • the anode side corresponds to the electrolysis compartment 24 with the shallow bottom
  • the counter-anode side corresponds to the reduction compartment 23 with the deep bottom.
  • TiCl 4 as a raw material of Ti is introduced in the molten salt therein to be reduced by Ca in the molten salt to thereby generate Ti particles.
  • the electrolysis of molten salt by means of the anode 11 and cathode 12 proceeds to generate Ca.
  • the generated Ca is taken in the molten Ca alloy 14 within the heat resistant vessel 13 .
  • the Ca taken in the molten Ca alloy 14 is released and dissolves in the molten salt on the counter-anode side, i.e., in the reduction compartment 23 within the reactor vessel 1 .
  • the Ca consumed in association with the generation of Ti particles is replenished.
  • Ca in the molten salt to be introduced to the electrolysis compartment 24 can be removed beforehand like the case in a second embodiment mode.
  • the drop of electric current efficiency due to the mixture of unreacted Ca can be effectively suppressed by employing the molten Ca alloy electrode.
  • the molten Ca alloy electrode employed in the electrolysis step is utilized as a carrier medium for transferring Ca, so that the circulation of molten salt in a large scale becomes unnecessary.
  • the method for producing Ti or Ti alloys by the present invention can be widely applied as means for producing high-purity Ti metals with high efficiency and economically.

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CN104313645A (zh) * 2014-10-28 2015-01-28 南京萨伯工业设计研究院有限公司 含钪铝合金材料的制备装置及制备工艺
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WO2023214031A1 (fr) * 2022-05-05 2023-11-09 Norsk Hydro Asa Procédé et appareil pour la production d'aluminium et procédé et appareil pour la production d'une charge d'alimentation contenant du chlorure d'aluminium

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EP3334847A4 (fr) 2015-08-14 2018-06-27 Coogee Titanium Pty Ltd Procédé pour la production d'un matériau composite à l'aide d'un oxydant excédentaire

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US20060219053A1 (en) * 2003-08-28 2006-10-05 Tadashi Ogasawara Method and apparatus for producing metal
KR20210149208A (ko) * 2012-10-26 2021-12-08 어플라이드 머티어리얼스, 인코포레이티드 Ｐｅｃｖｄ 장치 및 프로세스
KR102460527B1 (ko) 2012-10-26 2022-10-27 어플라이드 머티어리얼스, 인코포레이티드 Ｐｅｃｖｄ 장치 및 프로세스
CN104313645A (zh) * 2014-10-28 2015-01-28 南京萨伯工业设计研究院有限公司 含钪铝合金材料的制备装置及制备工艺
WO2023214031A1 (fr) * 2022-05-05 2023-11-09 Norsk Hydro Asa Procédé et appareil pour la production d'aluminium et procédé et appareil pour la production d'une charge d'alimentation contenant du chlorure d'aluminium

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EP1683877A1 (fr) 2006-07-26
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EP1683877A4 (fr) 2008-06-25
WO2005035806A1 (fr) 2005-04-21

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