WO2005035806A1 - Procede de production de ti ou d'alliage de ti par reduction par ca - Google Patents

Procede de production de ti ou d'alliage de ti par reduction par ca Download PDF

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Publication number
WO2005035806A1
WO2005035806A1 PCT/JP2004/014734 JP2004014734W WO2005035806A1 WO 2005035806 A1 WO2005035806 A1 WO 2005035806A1 JP 2004014734 W JP2004014734 W JP 2004014734W WO 2005035806 A1 WO2005035806 A1 WO 2005035806A1
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WIPO (PCT)
Prior art keywords
alloy
molten salt
molten
reaction vessel
reduction
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PCT/JP2004/014734
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English (en)
Japanese (ja)
Inventor
Tadashi Ogasawara
Makoto Yamaguchi
Masahiko Hori
Toru Uenishi
Yuko Urasaki
Kazuo Takemura
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Sumitomo Titanium Corporation
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Publication date
Priority claimed from JP2004044552A external-priority patent/JP2005133196A/ja
Priority claimed from JP2004074445A external-priority patent/JP2005264181A/ja
Application filed by Sumitomo Titanium Corporation filed Critical Sumitomo Titanium Corporation
Priority to US10/575,224 priority Critical patent/US20070131057A1/en
Priority to EP04792090A priority patent/EP1683877A4/fr
Priority to AU2004280401A priority patent/AU2004280401C1/en
Publication of WO2005035806A1 publication Critical patent/WO2005035806A1/fr

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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 metal chloride containing TiCl, which is treated with Ca to reduce metal Ti or a Ti alloy.
  • the present invention relates to a method for producing Ti or a Ti alloy by reducing Ca to be produced.
  • metal Ti is produced through a reduction step and a vacuum separation step.
  • TiCl which is the raw material of Ti, is reduced by Mg in the reaction vessel and sponge-like.
  • Metal Ti is produced.
  • sponge-like unreacted metal T produced in the reaction vessel and MgCl as a by-product are removed.
  • TiCl is reduced by Mg to form particulate metal Ti.
  • Generated metal Ti is successively below
  • the specific gravity of 22 is larger than the specific gravity of molten Mg. Due to this difference in specific gravity, the by-product molten MgCl
  • Ti is generated in the form of particles near the liquid surface and settles.
  • the generated Ti powder settles in an agglomerated state, and during the sedimentation, it sinters due to the temperature of the melt, grows grains, and is collected outside the reaction vessel. Is difficult. For this reason, continuous production is difficult and productivity is hindered. This is precisely the reason why Ti is produced as a titanium sponge in a batch in a reaction vessel.
  • Ca has a stronger affinity for C1 than Mg. In principle, it is a reducing agent for TiCl.
  • TiCl is supplied to the liquid level of the reducing agent in the reaction vessel,
  • the reaction field expands compared to the case where the reaction field is limited, and the heat generation area expands and cooling becomes easier.Thus, the supply rate of TiCl, which is the raw material for Ti, can be greatly increased, and the productivity is greatly improved.
  • Still another Ti production method is the Olson method described in US Patent No. 2,845,386. This is an oxide that directly reduces TiO with Ca without passing through TiCl
  • An object of the present invention is to provide a method for economically producing high-purity metal Ti or Ti alloy with high efficiency and without using an expensive reducing agent.
  • Ca dissolves about 1.5% in CaCl.
  • the supply rate of TiCl can be increased as described above.
  • the present inventors consider that in order to industrially establish a method for producing Ti by Ca reduction, it is necessary to economically replenish Ca in the molten salt consumed in the reduction reaction.
  • a method of using Ca generated by electrolysis of molten salt and a method of using and circulating Ca by this.
  • Ca in the molten salt is consumed during the reduction reaction, but when the molten salt is electrolyzed, Ca is generated in the molten salt. If the Ca thus obtained is reused for the reduction reaction, This eliminates the need for external Ca supplementation.
  • Ca is not required to be taken out by itself, so that the economic efficiency is improved. It is very difficult to extract Ca alone as a solid, but it is relatively easy to produce Ca in the molten salt.
  • the present invention has been made on the basis of a powerful idea, and is a method for producing Ti or a Ti alloy by the following Ca reduction (1), (2) or (3).
  • Ti and Ti alloy particles in the molten salt by reacting a metal chloride containing TiCl with Ca
  • a method for producing Ti by Ca reduction including a reducing step of generating and a separation step of separating Ti particles or Ti alloy particles generated in the molten salt from the molten salt (hereinafter referred to as a ⁇ first production method '' ).
  • the molten salt in which Ca is dissolved is held in the reaction vessel, and Ca in the molten salt contains TiCl.
  • the molten metal used for producing the Ti or Ti alloy and drawn out of the reaction vessel
  • a combination of a circulating electrolysis process in which salt is electrolyzed to generate and replenish Ca in the molten salt and return to the reaction vessel, and in the electrolysis process, an alloy electrode capable of forming a molten Ca alloy is used as a cathode in the electrolysis process Manufacturing method of Ti or Ti alloy by Ca reduction (hereinafter referred to as “second manufacturing method”).
  • the molten salt is electrolyzed using a molten Ca alloy as a cathode to increase the Ca content in the molten Ca alloy.
  • the molten Ca alloy is brought into contact with molten salt containing CaCl to dissolve Ca in the molten salt.
  • the metal containing TiCl is added to the molten salt in which Ca is dissolved by the Ca replenishing process
  • a method for producing Ti or Ti alloy in a molten salt by supplying a salted sardine and producing Ti or Ti alloy in a molten salt. ).
  • the first production method includes a reduction step of generating Ti particles or Ti alloy particles in the molten salt, and a separation step of separating the generated Ti particles or Ti alloy particles from the molten salt.
  • a reduction step of generating Ti particles or Ti alloy particles in the molten salt and a separation step of separating the generated Ti particles or Ti alloy particles from the molten salt.
  • An embodiment may be adopted in which Ca is extracted to the outside and electrolyzed to generate Ca and used for a Ti or Ti alloy formation reaction (that is, a TiCl reduction reaction).
  • the second manufacturing method is
  • the feature of the dissolving step is that an alloy electrode that also has a molten Ca alloy force is used for the cathode.
  • a molten CaCl salt having an increased Ca concentration is circulated between the reduction step and the electrolysis step.
  • the third production method is similar to the second production method in that a molten Ca alloy electrode is used in the electrolysis step. However, when the Ca is circulated and used, the Ca content is increased. It is characterized in that molten Ca alloy is used as a Ca transport medium.
  • Ti particles are reduced by Ca reduction in a molten salt containing CaCl.
  • the vapor pressure at 850 ° C is very low, with 6.7 kPa (50 mmHg) for Mg and 0.3 kPa (2 mmHg) for Ca. Due to this difference in vapor pressure, the amount of Ti deposited on the inner surface of the upper part of the vessel is much smaller for Ca than for Mg. As a result, in the first to third manufacturing methods, the Ti C1 supply speed can be significantly increased.
  • Ca is inferior in wettability (adhesiveness) to Mg, and Ca adhering to precipitated Ti particles is CaC 1
  • the generated Ti can be taken out of the reaction vessel in a powder state, and continuous Ti production operation can be performed. Work is also possible.
  • a molten salt containing CaCl (hereinafter simply referred to as a molten salt or a molten salt)
  • TiCl Metal chloride containing TiCl in Ca dissolved in molten CaCl solution
  • the reduction reaction can be performed even in the molten Ca solution, and from this point, the reaction efficiency can be improved.
  • the direct supply of TiCl in the gaseous state to the molten CaCl solution is not suitable for Ca in the molten CaCl solution.
  • a TiCl liquid is supplied to the liquid surface of the molten Mg liquid.
  • TiCl gas could be supplied into the molten Mg solution to expand the reaction field.
  • the TiCl gas is supplied into the molten CaCl solution.
  • the reason may be that the vapor pressure of molten Ca is low.
  • the Ti generation step by the reduction reaction in the third production method corresponds to the reduction step
  • Ca is dissolved in the molten salt.
  • granular or Z or powdered Ti or Ti alloy hereinafter, also referred to as Ti particles or Ti alloy particles
  • the handling of Ti particles or Ti alloy particles generated in the molten salt it is also possible to separate the molten salt in the reaction vessel.
  • the operating capacity will be the S batch method.
  • it is preferable to take out the generated Ti in the form of particles withdraw the Ti together with the molten salt out of the reaction vessel, and separate the Ti particles from the molten salt outside the vessel.
  • Ti particles can be easily separated from the molten salt force by squeezing operation by mechanical compression.
  • the first manufacturing method includes the separation step, and the second and third manufacturing methods can also employ such an embodiment.
  • the extracting operation is performed in the second manufacturing method, and an embodiment in which the extracting operation is performed in the first manufacturing method can be adopted.
  • the third production method since the molten Ca alloy is used as a Ca transfer medium as described above, the extraction of the molten salt is not performed.
  • the second production method includes this circulation type electrolysis step, and the first production method also operates in an embodiment having this step.
  • the molten salt having the Ca concentration recovered in this way is returned to the reduction step, and this is repeated to produce Ti or a Ti alloy.
  • the phenomenon that occurs with respect to Ca is basically only an increase or decrease in the dissolved Ca concentration in the molten salt during the circulation process, and does not require an operation of extracting or supplementing Ca alone. Accordingly, high-purity metal Ti or Ti alloy can be produced economically with high efficiency and without using expensive reducing agents.
  • the third production method also includes a Ca generation step by electrolysis of a molten salt containing CaCl,
  • the first point is that the molten Ca alloy is used as a Ca transfer medium when replenishing the Ca of the molten salt. Or, it is different from the second manufacturing method.
  • the current efficiency in the electrolysis step has a large effect on economics, and furthermore, the success or failure of establishing industrial production technology.
  • One of the major causes of the reduction in current efficiency in this electrolysis process is the unreacted dissolved Ca in the molten salt sent to the electrolysis process in the reduction process.
  • the reduction reaction proceeds in the molten salt in the reaction vessel, and the dissolved Ca in the molten salt, which is the reducing agent, is consumed, but is not completely consumed. It cannot be avoided that unreacted dissolved Ca is contained in the molten salt obtained.
  • an alloy electrode made of a molten Ca alloy (hereinafter, referred to as a cathode) is used as a cathode in the electrolysis step.
  • a molten Ca alloy electrode or simply an alloy electrode.
  • the molten salt in the electrolytic cell, and the interface between the molten Ca alloy and the molten salt constituting the alloy electrode are separated by a partition wall and divided into an anode side and an anti-anode side. It is desirable to introduce a salt to the anti-anode side.
  • the molten salt on the anode side contains no or little dissolved Ca, and the above-described back reaction and the accompanying decrease in current efficiency do not occur.
  • the molten salt on the anti-anode side is a molten salt fed to the reduction step, and contains unreacted dissolved Ca, though not so much.
  • Ca is released from the alloy electrode (cathode) to the molten salt on the opposite side of the anode. That is, only the anode side in the electrolytic cell is an electrolysis region, and on the anode side, Ca is efficiently generated by electrolysis of the molten salt in the absence of dissolved Ca, and the generated Ca causes the alloy electrode (cathode) to be generated.
  • Ca is replenished to the molten salt on the anti-anode side (that is, the used molten salt sent from the reduction process).
  • Ca is generated at the interface between the alloy electrode and the molten salt on the anode side, but there is a potential on the anode side (a potential difference occurs at the interface), so that the generated metal Ca is transferred to the alloy electrode as the cathode. It is captured. As a result, the Ca concentration in the alloy electrode increases. On the other hand, since there is no potential at the interface between the alloy electrode and the molten salt on the anti-anode side, Ca is dissolved into the molten salt due to the difference in Ca concentration between the alloy electrode and the molten salt. Since the Ca concentration in the molten salt on the anti-anode side is reduced by the reduction reaction, Ca can be dissolved in the molten salt. The same is true for the molten Ca alloy electrode used in the third manufacturing method described later.
  • the molten salt decreases with the electrolysis.
  • the molten salt that does not contain dissolved Ca may be newly replenished, or a part of the molten salt that is supplied with the power of the reduction process. May be used cyclically. Reduction process power If only a part of the molten salt sent is used, dissolved Ca to be mixed in is small, and knock reaction can be suppressed to a level that does not cause any problem.
  • the Ca alloy constituting the molten Ca alloy electrode an Mg-Ca alloy, an A1-Ca alloy, a Zn-Ca alloy or the like is desirable.
  • the melting point of these Ca alloys is relatively low, 500 ° C or higher for Mg-Ca alloy, 600 ° C or higher for A1-Ca alloy, and 420 ° C or higher for Zn-Ca alloy.
  • the Ca concentration is particularly preferably 45% or less for a Mg—Ca alloy, more preferably 15% or less. 20% or less is desirable for A1-Ca alloy.
  • Zn—Ca alloy it is desirable that the content be 40% or less, and more preferably 20% or less.
  • the lower limit of the Ca concentration is desirably 0.5%.
  • the two points are clearly different from the use of the molten alloy electrode in the first to third production methods.
  • a molten Ca alloy electrode is used as a cathode in the electrolysis step, and this is used as a Ca transfer medium. That is, in the second production method, Ca generated on the cathode side is dissolved in a molten Ca alloy constituting an electrode, and the Ca is converted from the molten Ca alloy into a used molten salt introduced into the reaction vessel by the reaction vessel. The Ca is recirculated and used by increasing the Ca concentration of the molten salt by leaching and circulating it. On the other hand, in the third production method, the molten Ca alloy with increased Ca content is transferred to the reaction vessel, and the molten salt containing CaCl To dissolve Ca in the molten salt to recycle Ca.
  • an electrolytic cell is required for performing a Ca generation step by electrolysis (that is, performing an operation in the Ca generation step), and Ti is generated by a reduction reaction.
  • a reaction vessel is required to perform the operation in the production process, but the electrolytic cell and the reaction vessel can be shared by one vessel (or vessel).
  • a temperature difference can be imparted to the molten salt between the electrolytic cell and the reaction vessel.
  • the temperature of the molten salt in the electrolytic cell is lower than the temperature of the molten salt in the reaction vessel. That is, a combination of high-temperature reduction and low-temperature electrolysis.
  • the reactivity of Ca is increased by the high-temperature reduction, the production efficiency of Ti or Ti alloy is improved, and the solubility of Ca in the molten salt is reduced by low-temperature electrolysis, and the transfer of Ca from the molten salt to the molten Ca alloy Is promoted.
  • the molten salt containing CaCl is held in the reaction vessel also serving as the electrolytic vessel, and the molten salt in the reaction vessel, This solution
  • the interface between the molten salt and the molten Ca alloy constituting the cathode is separated into an anode side and an anti-anode side by a partition wall, and electrolysis is performed. In the vicinity of the anode, C1 gas is generated, and the cathode (molten Ca alloy),
  • Ca is generated in the vicinity of the cathode separated on the anode side by the partition (Ca generation step). This Ca is taken into the molten Ca alloy. On the other hand, on the anti-anode side, a Ca replenishment process in which Ca dissolves from the molten Ca alloy into the molten salt proceeds.
  • the handling of the Ti particles or Ti alloy particles generated in the molten salt is as described above, and the third production method also includes a Ti separation step of separating the generated Ti or Ti alloy from the molten salt.
  • Embodiments can be employed.
  • the molten salt separated from Ti or Ti alloy in the Ti separation step is reacted with the molten Ca alloy in which Ca has been consumed in the Ti generation step, and the unreacted Ca in the molten salt causes the molten Ca It is possible to increase the Ca in the alloy and use the molten Ca alloy in the Ca replenishment process. In this way, Ca in the molten Ca alloy can be supplemented without using electrolysis.
  • Replenishment of Ca is also preferably performed at a low temperature without using this electrolysis. At low temperatures, the solubility of Ca in the molten salt decreases, the efficiency of removing unreacted Ca increases, and the transfer of Ca into the molten Ca alloy is promoted, and the Ca in the molten Ca alloy tends to increase .
  • CaCl having a melting point of 780 ° C. is used as a molten salt.
  • Mixed molten salts may be used.
  • the use of a mixed molten salt lowers the melting point and lowers the temperature of the molten salt, which increases the durability of the furnace material, prolongs the life of the furnace material, and reduces the evaporation of Ca and salts from the liquid surface. Is suppressed.
  • the melting point of the molten salt can be lowered to about 500 ° C.
  • the advantage in terms of the furnace material by lowering the temperature of the molten salt can be obtained in all steps including the reduction step and the electrolysis step.
  • the temperature of the molten salt is lowered, so that the solubility of Ca is lowered, and the convection and diffusion of the molten salt are suppressed, and the back reaction of Ca is also suppressed. If importance is placed on the reactivity in the reduction step, raise the temperature of the molten salt in the reduction step!
  • the temperature of the molten salt is set to the melting point of Ca (838 ° C.). C) It cannot be reduced below.
  • other alkaline earth metals and alkali metals are mixed with Ca By doing so, the melting point can be lowered. For example, by mixing Ca with Mg, the melting point can be lowered to 516 ° C. Force and the mixture force of Ca and Mg
  • TiCl is basically used as a raw material of Ti.
  • Ti alloy can be manufactured by mixing TiCl with other metal chlorides.
  • metal salted slag here may be used in the form of gas, liquid, or misaligned.
  • the average particle size is 0.5 to 50 ⁇ m. Because, after these grains are formed in the molten salt, the grains are removed by the molten salt force, but if they are not small enough to flow together with the molten salt, the removal becomes difficult . Therefore, an appropriate size is 50 m or less. In addition, the reason why the appropriate minimum diameter is set to 0.5 m is a force that makes it possible to remove even smaller objects, and that makes it difficult to separate from molten salt.
  • the strike can be reduced.
  • Mg is produced by electrolysis of MgCl, but Mg is Mg
  • the generated Ca dissolves in CaCl, making it difficult to produce only Ca efficiently.
  • a molten salt in which Ca is dissolved is positively used, so if caution is taken in knocking reaction, the molten salt is mixed with Ca in the electrolysis step. No problem It is not necessary to completely separate only Ca. That is, Ca may be introduced into the reaction vessel from the electrolytic bath together with the molten salt or contained in the molten Ca alloy. Therefore, the cost of electrolytic production of Ca can be significantly reduced.
  • FIG. 1 is a diagram illustrating a configuration of a metal Ti manufacturing apparatus showing a first embodiment of a first manufacturing method.
  • FIG. 2 is a diagram illustrating a configuration of a metal Ti manufacturing apparatus showing a second embodiment of the first manufacturing method.
  • FIG. 3 is a diagram illustrating a configuration of a metal Ti manufacturing apparatus showing a third embodiment of the first manufacturing method.
  • FIG. 4 is a diagram illustrating a configuration of a metal Ti manufacturing apparatus showing a first embodiment of the second manufacturing method.
  • FIG. 5 is a diagram illustrating a configuration of a metal Ti manufacturing apparatus showing a second embodiment of the second manufacturing method.
  • FIG. 6 is a view for explaining the configuration of a metal Ti manufacturing apparatus showing a third embodiment of the second manufacturing method.
  • FIG. 7 is a diagram illustrating a configuration of a metal Ti manufacturing apparatus showing a first embodiment of the third manufacturing method.
  • FIG. 8 is a diagram illustrating a configuration of a metal Ti manufacturing apparatus showing a second embodiment of the third manufacturing method.
  • FIG. 9 is a view for explaining the configuration of a metal Ti manufacturing apparatus showing a third embodiment of the third manufacturing method.
  • FIG. 1 is a view for explaining a configuration of a metal Ti manufacturing apparatus showing a first embodiment of a first manufacturing method.
  • reaction vessel 1 is an iron closed vessel.
  • a reducing agent supply pipe 2 for supplying Ca as a reducing agent is provided at the ceiling of the reaction vessel 1.
  • the bottom of the reaction vessel 1 has a tapered shape whose diameter is gradually reduced downward to promote the discharge of the generated Ti particles, and the generated Ti particles are discharged to the center of the lower end.
  • a Ti discharge pipe 3 is provided.
  • a cylindrical separation wall 4 containing heat exchange is disposed with a predetermined gap between the separation wall 4 and the inner surface of the same part in a straight month.
  • a molten salt discharge pipe 5 for discharging CaCl in the vessel to the side is provided.
  • the raw material supply pipe 6 for supplying TiCl through the separation wall 4 reaches the center of the container.
  • the liquid level is set to a level higher than the molten salt discharge pipe 5 and lower than the upper end of the separation wall 4. Inside the separation wall 4, the molten Ca
  • TiCl gas is supplied as a metal chloride containing C1.
  • the reaction efficiency is increased by ascending in the solution and promoting stirring with the molten CaCl solution.
  • the Ti particles generated in the molten CaCl solution inside the separation wall 4 in the reaction vessel 1 Settles inside and accumulates on the bottom of the container.
  • the deposited Ti particles are appropriately extracted downward together with the molten CaC 1 liquid from the Ti discharge pipe 3 and sent to the separation step 7.
  • reaction vessel 1 Inside the separation wall 4, a molten CaCl solution in which Ca is dissolved is used, and the reduction reaction is performed by Ca in the molten CaCl solution.
  • the separation wall 4 is made of a molten CaCl solution containing a large amount of Ca before being used for the reduction of TiCl,
  • the separation step 7 the Ti particles extracted from the reaction vessel 1 together with the molten CaCl solution are dissolved.
  • the Ti particles are compressed to squeeze out the molten CaCl solution.
  • the electrolysis step 8 the molten CaCl solution introduced from the reaction vessel 1 and the separation step 7 is converted into electricity.
  • the easiness reduces the electrolytic production cost of Ca.
  • Oxygen is released in the form of CO.
  • the produced TiCl is reacted in
  • FIG. 2 is a configuration diagram of a metal Ti manufacturing apparatus showing a second embodiment of the first manufacturing method.
  • the second embodiment of the first manufacturing method differs from the first embodiment in that a reducing agent supply pipe 2a is provided at the lower part of the reaction vessel 1 and Ca is supplied from the lower part to the inside of the separation wall 4. I do.
  • the molten Ca liquid force as the reducing agent is determined by the specific gravity difference from the molten CaCl solution.
  • the inside of the separation wall 4 rises from bottom to top. Because Ca dissolves in CaCl during this floating process
  • FIG. 3 is a configuration diagram of a metal Ti manufacturing apparatus showing a third embodiment of the first manufacturing method.
  • the position of the raw material supply pipe 6a is different. That is, in the first or second embodiment, the raw material supply pipe 6 is configured to supply TiCl to the center of the container.
  • the configuration is such that TiCl is supplied to a position deviated from the center inside the separation wall 4.
  • FIG. 4 is a configuration diagram of a metal Ti manufacturing apparatus showing a first embodiment of the second manufacturing method.
  • a reaction vessel 1 for performing a reduction step and an electrolytic cell 10 for performing an electrolysis step are used.
  • the reaction vessel 1 holds Ca-rich molten CaCl in which Ca is dissolved in a relatively large amount as a molten salt.
  • CaCl has a melting point of about 780 ° C, and its molten salt is
  • the raw material supply pipe 6 is used to convert gaseous TiCl into molten salt in the reaction vessel 1.
  • the Ti particles collected at the bottom of the reaction vessel 1 are extracted from the reaction vessel 1 together with the molten salt present at the bottom, and sent to the Ti separation step 7.
  • the Ti particles extracted together with the molten salt from the reaction vessel 1 are separated by molten salt. Specifically, compress the Ti grains Squeeze out the molten salt.
  • the Ti particles obtained in the Ti separation step 7 are dissolved to form a Ti ingot.
  • the molten salt separated by Ti particle force in the Ti separation step 7 is a used molten salt, which consumes Ca and decreases the Ca concentration.
  • the molten salt is sent from the reaction vessel 1 to the electrolytic cell 10.
  • molten CaCl as a molten salt is electrolyzed between the anode 11 and the cathode 12.
  • An electrode rod 15 penetrated and inserted into the molten Ca alloy 14 and a partition wall 16 for partitioning the molten salt in the electrolytic cell 10 into an anode side and an anti-anode side are provided.
  • the molten Ca alloy 14 has a lower specific gravity than the molten salt here, for example, an Mg-Ca liquid or the like.
  • the heat-resistant and insulating partition wall 16 is located directly below the cathode 12 and divides the molten salt in the electrolytic cell 10 into an anode side and an anti-anode side together with an interface between the molten Ca alloy 14 and the molten salt.
  • the part is inserted into the molten Ca alloy 14, and the lower end is in close contact with the bottom plate of the electrolytic cell 10.
  • the molten salt sent from the reaction vessel 1 to the electrolytic cell 10 directly or via the Ti separation step 7 is introduced into the electrolytic cell 10 on the side opposite to the anode.
  • the molten salt on the anode side is molten CaCl containing substantially no dissolved Ca.
  • the molten salt on the anode side transfers electricity between anode 11 and cathode 12.
  • the Ca generated on the side melts into the molten Ca alloy.
  • the molten salt on the anti-anode side is a used molten salt introduced from the reaction vessel 1, and although dissolved Ca is consumed, unreacted dissolved Ca is included. Ca melts out of the molten Ca alloy 14 into this molten salt. As a result, dissolved Ca is replenished to the used molten salt introduced from the reaction vessel 1, and the Ca-rich molten salt is introduced into the reaction vessel 1 through the reducing agent supply pipe 2 to generate Ti particles by Ca reduction. Used for circulation.
  • TiCl which is a raw material of Ti, is generated by performing a salting treatment on TiO. Generated
  • TiCl is introduced into the reaction vessel 1 through the raw material supply pipe 6, and Ti particles are generated by Ca reduction.
  • the molten salt (molten CaCl 2 in which Ca is dissolved) is subjected to the reduction step (reaction vessel 1), the separation step 7, and the electrolysis step (electrolysis tank 10). Circulate and reduce
  • reaction vessel 1 By repeating the operation of replenishing Ca consumed in the step (reaction vessel 1) in the electrolysis step (electrolysis tank 10), production of Ti is continued in the reduction step (reaction vessel 1).
  • high-quality Ti grains are continuously produced by Ca reduction simply by manipulating the Ca concentration in the molten salt without performing supplementation and removal of solid Ca.
  • the used molten salt containing unreacted dissolved Ca is introduced into the electrolysis step, and the unreacted dissolved Ca is removed from the non- Since it is introduced on the anti-anode side, which is the region, and is not directly involved in electrolysis, back reaction due to dissolved Ca is prevented. Therefore, the current efficiency in the electrolysis process increases. On the anode side, which is an electrolysis area in the electrolysis tank 10, molten CaCl is consumed as electrolysis proceeds. Make up for this
  • molten CaCl containing substantially no dissolved Ca is externally supplemented.
  • a small amount of spent molten salt is introduced into the anode side separately from or together with the replenishment (according to the route shown by the broken line in FIG. 4).
  • the temperature of the molten salt is higher than the melting point of CaCl (about 780 ° C) in any process.
  • FIG. 5 is a configuration diagram of a metal Ti manufacturing apparatus showing a second embodiment of the second manufacturing method.
  • the reaction vessel 1 used here is a cylindrical closed vessel made of iron.
  • a reducing agent supply pipe 2 for supplying Ca as a reducing agent is provided at the ceiling of the reaction vessel 1.
  • the bottom of the reaction vessel 1 has a tapered shape whose diameter is gradually reduced downward in order to promote the discharge of the generated Ti particles.
  • a discharge pipe 3 is provided.
  • a cylindrical separation wall 4 containing heat exchange is arranged with a predetermined gap between the separation wall 4 and the inner surface of the same part.
  • a molten salt discharge pipe 5 for discharging CaCl in the vessel to the side is provided.
  • the liquid level is set to a level higher than the molten salt discharge pipe 5 and lower than the upper end of the separation wall 4.
  • TiCl gas is supplied as a metal chloride containing C1.
  • the TiCl is reduced by Ca in the molten CaCl solution
  • the reaction efficiency is increased by ascending in the solution and promoting stirring with the molten CaCl solution.
  • reaction vessel 1 Inside the separation wall 4, a molten CaCl solution in which Ca is dissolved is used, and the reduction reaction is performed by Ca in the molten CaCl solution.
  • the separation wall 4 is made of a molten CaCl solution containing a large amount of Ca before being used for the reduction of TiCl,
  • the Ti particles are compressed to squeeze out the molten CaCl solution.
  • the molten CaCl solution obtained in the separation step 7 is the molten CaCl
  • the electrolysis step 8 as described above, the molten CaCl liquid introduced from the reaction vessel 1 and the separation step 7 is separated into Ca and C1 gas by electrolysis using the molten Ca alloy electrode as a cathode.
  • the Ca is returned into the reaction vessel 1 through the reducing agent supply pipe 2.
  • Ca is from CaCl
  • the by-product oxygen is emitted in the form of CO.
  • the produced TiCl is supplied through the raw material supply pipe 6.
  • FIG. 6 is a configuration diagram of a metal Ti manufacturing apparatus showing a third embodiment of the second manufacturing method.
  • the position of the raw material supply pipe 6a is different from that in the second embodiment.
  • the raw material supply pipe 6 supplies TiCl to the center of the container.
  • TiCl is placed at a position where the central force inside the separation wall 4 is biased.
  • the temperature of the molten salt can be reduced by using the mixed molten salt also in the embodiment of V and deviation.
  • FIG. 7 is a configuration diagram of a metal Ti manufacturing apparatus showing a first embodiment of the third manufacturing method.
  • a reaction vessel 1 for performing a Ti generation step by a reduction reaction and an electrolytic cell 10 for performing a Ca replenishment step by electrolysis are used.
  • the reaction vessel 1 holds Ca-rich molten CaCl in which Ca is dissolved in a relatively large amount as a molten salt.
  • the inside of the reaction vessel 1 is divided into two parts except for a bottom part by a heat-resistant partition wall 17, one of which is a reduction chamber 18, and the other of which is a molten Ca alloy, which will be described later, is brought into contact with a molten salt to form a molten salt.
  • This is the Ca replenishing chamber 19 where Ca is dissolved in the molten salt. Both chambers communicate at the lower part of the reaction vessel 1, Guarantee the free flow of molten salt.
  • gaseous TiCl is dispersed and injected into the molten salt in the reaction vessel 1.
  • the Ti particles collected at the bottom of the reduction chamber 18 are extracted from the reduction chamber 18 together with the molten salt present at the bottom, and sent to the Ti separation step 7.
  • the Ti particles extracted together with the molten salt from the reduction chamber 18 are separated by molten salt power. Specifically, the Ti particles are compressed to squeeze out the molten salt.
  • the Ti particles obtained in the Ti separation step 7 are dissolved to form a Ti ingot.
  • the molten salt that has been subjected to Ti particle separation in the Ti separation step 7 is a used molten salt, Ca is consumed, and the Ca concentration is reduced. This molten salt is sent to the above-mentioned electrolytic cell 10.
  • the electrolytic cell 10 contains molten CaCl as a molten salt, and the molten CaCl is
  • the cathode 12 is a molten Ca alloy electrode.
  • the cathode 12 is an insulating heat-resistant container 13 that is inserted into the molten salt in the electrolytic bath 10 and has an open bottom, and is housed in the heat-resistant container 13.
  • the molten Ca alloy 14 and the electrode rod 15 inserted through the top plate of the heat-resistant container 13 and inserted into the molten Ca alloy 14 are provided.
  • the Ca generated on the side of the cathode 12 is taken into the molten Ca alloy 14 in the heat-resistant container 13 in the form of an alloy or solid solution. Thereby, the Ca concentration of the molten Ca alloy 14 in the heat-resistant container 13 increases.
  • the molten Ca alloy 14 in the heat-resistant container 13 reaches a predetermined concentration (for example, 15%)
  • the molten Ca alloy 14 having the high Ca concentration is transferred to the Ca in the reaction container 1 by the first transport pipe 20. Inject into refill chamber 19 from above.
  • the molten Ca alloy 14 'injected previously floats on the molten salt in the Ca replenishing chamber 19.
  • This molten Ca alloy 14 ⁇ has a high Ca concentration at the time of injection, and has a low Ca concentration (for example, several%) by releasing and dissolving Ca in a molten salt below. Therefore, in parallel with the transport of the molten Ca alloy 14 having a high Ca concentration from the inside of the heat-resistant container 13 to the Ca replenishing chamber 19, the used molten Ca alloy having a low Ca concentration that floats on the molten salt in the Ca replenishing chamber 19 14 ′ is transported into the heat-resistant container 13 by the second transport pipe 21.
  • Ca in the molten salt is consumed by the Ca reduction reaction in the reaction vessel 1, and the Ca is melted in the electrolytic cell 10. It is produced by electrolysis of salt and is recycled to produce Ti particles by reduction. In addition, it is not necessary to circulate the molten salt between the reaction vessel 1 and the electrolytic cell 10 when circulating Ca.
  • the molten Ca alloy 14 is used as the cathode in the electrolytic cell 10, and Ca is supplied to the molten salt in the reaction vessel 1 simply by reciprocating between the reaction vessel 1 and the electrolytic cell 10 using this as a Ca transfer medium. And Ti production continues.
  • FIG. 8 is a configuration diagram of a metal Ti manufacturing apparatus showing a second embodiment of the third manufacturing method.
  • the second embodiment differs from the first embodiment in the following points.
  • molten salt a multi-component molten salt having a low melting point obtained by mixing CaCl and another salted product is used.
  • the molten salt is introduced into the Ca removing tank 22. If the melting point of the molten salt is, for example, about 650 ° C., the reaction vessel 1 performs a high-temperature operation in which the temperature of the molten salt is increased to about 850 ° C. On the other hand, in the electrolytic cell 10 and the Ca removing tank 22, low-temperature operation is performed with the temperature of the molten salt lowered to about 700 ° C.
  • the molten salt sent from the reaction vessel 1 to the electrolytic cell 10 through the Ti separation step 7 is used molten salt, and although dissolved Ca is consumed, unreacted Contains dissolved Ca. If unreacted Ca enters the electrolysis process, C1 gas generated on the anode 11 side
  • the molten salt (containing unreacted Ca) introduced from the Ti separation step 7 is transported from the Ca replenishment chamber 19 in the reaction vessel 1 to the heat-resistant vessel 13 in the electrolysis vessel 10. It is mixed with a part of the used low Ca concentration molten Ca alloy 14 '(indicated as Mg in Fig. 9). As a result, the unreacted Ca in the molten salt is taken into the molten Ca alloy 14 ′ having a low Ca concentration, the unreacted Ca is removed, and the molten Ca alloy 14 having a high Ca concentration is generated.
  • the molten salt from which unreacted Ca has been removed in this way is circulated and used without waste, and the force is also increased by the back reaction due to the unreacted Ca in the molten salt and the current caused by the back reaction. A decrease in efficiency is suppressed.
  • the high Ca concentration molten Ca alloy 14 (indicated as Mg—Ca in FIG. 9) by-produced in the Ca removal tank 22 is introduced into the Ca replenishing chamber 19 in the reaction vessel 1.
  • the solubility of Ca in the molten salt is reduced, the convection and diffusion of the molten salt are also suppressed, and the back reaction is also suppressed at these point forces.
  • Ca solubility is reduced, Ca ⁇ precipitates, and the precipitated Ca is absorbed by the alloy.
  • FIG. 9 is a configuration diagram of a metal Ti manufacturing apparatus showing a third embodiment of the third manufacturing method.
  • the third embodiment differs from the first embodiment and the second embodiment in the following points.
  • the reaction vessel 1 also serves as an electrolytic cell, and includes a reduction chamber 23 having a deep bottom and an electrolysis chamber 24 having a shallow bottom.
  • the anode 11 is disposed on the anti-reduction chamber side in the electrolysis chamber 24,
  • the heat vessel 13 is disposed at a boundary between the reduction chamber 23 and the electrolysis chamber 24 so as to straddle both chambers.
  • the molten salt in the reaction vessel 1 is supplied to the anode 16 together with the interface between the molten Ca alloy 14 and the molten salt in the heat-resistant vessel 13 by a partition wall 16 provided at the boundary between the reduction chamber 23 and the electrolysis chamber 24.
  • Side and anti-anode side corresponds to the electrolysis chamber 24 having a shallow bottom
  • the anti-anode side corresponds to the reduction chamber 23 having a deep bottom.
  • the feature of the third embodiment is, firstly, that the reactor structure is simple because the reaction container 1 also serves as an electrolytic cell. Second, the efficiency of operation is increased because the molten Ca alloy 14 is not transported between the electrolytic cell and the reaction vessel. In addition, equipment for carrying out the transportation between the tank and the container is not required, and the equipment is also simplified from this point. However, it is difficult to give a temperature difference to the molten salt in the reduction zone and the electrolysis zone.
  • the method for producing Ti or a Ti alloy by the first to third Ca reductions is a method for reducing TiCl.
  • Ca is used as the reducing agent, and in particular, the molten salt containing CaCl and in which Ca is dissolved is held in a reaction vessel,
  • the supply rate of TiCl which is a raw material of Ti, can be increased, and the force is increased.
  • the second manufacturing method a decrease in current efficiency due to mixing of unreacted Ca, which is a problem in the electrolysis step, can be effectively suppressed by using a molten Ca alloy electrode.
  • the molten Ca alloy electrode used in the electrolysis step is used as a Ca transfer medium, so that a powerful circulation of the molten salt is not required.
  • the method for producing Ti or Ti alloy of the present invention can be effectively used as a means for efficiently and economically producing high-purity metal Ti.

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Abstract

Procédé de production de Ti ou d'un alliage de Ti à l'aide de la réduction par Ca, qui comporte une étape de réduction consistant à introduire du sel fondu contenant CaCl2 et dans lequel est dissous Ca dans une cuve de réaction (1) et à faire réagir Ca dans le sel fondu avec un chlorure métallique contenant TiCl4, pour produire des particules de Ti ou des particules d'alliage de Ti dans le sel fondu, et une étape de séparation (7) consistant à séparer les particules de Ti ou les particules d'alliage de Ti formées dans le sel fondu dudit sel fondu. Il est préférable d'ajouter une étape d'électrolyse (8) destinée à électrolyser le CaCl2 extrait de la cuve de réaction (1) en Ca et en Cl2, le Ca formé étant utilisé pour la réaction dans la cuve de réaction (1) en vue de la formation de Ti ou d'un alliage de Ti. Dans l'étape d'électrolyse (8), l'utilisation d'une électrode en alliage comportant de l'alliage de Ca fondu en tant que cathode améliore l'efficacité du courant électrique et l'alliage de Ca fondu peut également être utilisé efficacement en tant que milieu de transport de Ca afin d'augmenter la concentration en Ca. Ledit procédé permet la production d'un Ti métallique de grande pureté, avec un bon rendement et à faible coût.
PCT/JP2004/014734 2003-10-10 2004-10-06 Procede de production de ti ou d'alliage de ti par reduction par ca WO2005035806A1 (fr)

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US10/575,224 US20070131057A1 (en) 2003-10-10 2004-10-06 Method for producing ti or ti alloy through reduction by ca
EP04792090A EP1683877A4 (fr) 2003-10-10 2004-10-06 Procede de production de ti ou d'alliage de ti par reduction par ca
AU2004280401A AU2004280401C1 (en) 2003-10-10 2004-10-06 Method for producing Ti or Ti alloy through reduction by Ca

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JP2003352661 2003-10-10
JP2003-352661 2003-10-10
JP2004-044552 2004-02-20
JP2004044552A JP2005133196A (ja) 2003-10-10 2004-02-20 溶融塩の循環によるＴｉ又はＴｉ合金の製造方法
JP2004074445A JP2005264181A (ja) 2004-03-16 2004-03-16 溶融Ｃａ合金をＣａ移送媒体とするＴｉ又はＴｉ合金の製造方法
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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
PL2109691T3 (pl) * 2007-01-22 2017-02-28 Materials And Electrochemical Research Corporation Redukcja metalotermiczna chlorku tytanu generowanego in situ
US9157730B2 (en) * 2012-10-26 2015-10-13 Applied Materials, Inc. PECVD process
CN104313645B (zh) * 2014-10-28 2017-08-08 苏州萨伯工业设计有限公司 含钪铝合金材料的制备装置及制备工艺
WO2017027915A1 (fr) 2015-08-14 2017-02-23 Coogee Titanium Pty Ltd Procédé pour la production d'un matériau composite à l'aide d'un oxydant excédentaire
NO20220517A1 (en) * 2022-05-05 2023-11-06 Norsk Hydro As A process and apparatus for production of aluminium

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WO2007034645A1 (fr) * 2005-09-20 2007-03-29 Osaka Titanium Technologies Co., Ltd. Procédé de production de titane et appareil correspondant
JP2007084847A (ja) * 2005-09-20 2007-04-05 Sumitomo Titanium Corp Ｔｉの製造方法および装置
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EP1944383A4 (fr) * 2005-09-20 2009-12-02 Osaka Titanium Technologies Co Procédé de production de titane et appareil correspondant

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US20070131057A1 (en) 2007-06-14
EP1683877A4 (fr) 2008-06-25
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EP1683877A1 (fr) 2006-07-26
AU2004280401A1 (en) 2005-04-21

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