WO2005080642A1 - Procédé pour la production du titane ou un alliage de titane reduction de ca - Google Patents

Procédé pour la production du titane ou un alliage de titane reduction de ca Download PDF

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Publication number
WO2005080642A1
WO2005080642A1 PCT/JP2005/001379 JP2005001379W WO2005080642A1 WO 2005080642 A1 WO2005080642 A1 WO 2005080642A1 JP 2005001379 W JP2005001379 W JP 2005001379W WO 2005080642 A1 WO2005080642 A1 WO 2005080642A1
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WIPO (PCT)
Prior art keywords
molten salt
alloy
reaction
reduction
electrolysis
Prior art date
Application number
PCT/JP2005/001379
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English (en)
Japanese (ja)
Inventor
Tadashi Ogasawara
Makoto Yamaguchi
Masahiko Hori
Toru Uenishi
Katsunori Dakeshita
Original Assignee
Sumitomo Titanium Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Titanium Corporation filed Critical Sumitomo Titanium Corporation
Priority to US10/589,949 priority Critical patent/US20070181435A1/en
Priority to EP05704329A priority patent/EP1726689A4/fr
Publication of WO2005080642A1 publication Critical patent/WO2005080642A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon

Definitions

  • the present invention provides a method for reducing a metal chloride containing titanium tetrachloride (TiCl 4) by using Ca
  • the present invention relates to a method for producing Ti or Ti alloy by Ca reduction for producing Ti or Ti alloy.
  • metal Ti is produced through a reduction step and a vacuum separation step.
  • TiCl a Ti raw material, is reduced by Mg in the reaction vessel,
  • Di-shaped metal Ti is produced.
  • unreacted Mg and by-product magnesium chloride (MgCl) are removed from the sponge-like metal Ti produced in the reaction vessel.
  • the molten Mg Since it is larger than the molten Mg, it sinks down and the molten Mg appears on the liquid surface. Due to the specific gravity difference substitution, the molten Mg is continuously supplied to the liquid surface, and the reduction reaction of TiCl proceeds continuously.
  • TiCl is an unreacted TiCl gas or a lower salt gas such as TiCl. ), And is discharged out of the reaction vessel, so that the use efficiency of TiCl decreases.
  • a method has been proposed in which the reaction efficiency is enhanced by dispersing and supplying the Ti on the surface, and the precipitation of Ti on the upper inner surface of the reaction vessel is suppressed.
  • the method proposed in the publication is not sufficient as a measure for suppressing the Ti precipitation.
  • the melting in the reaction vessel is not sufficient as a measure for suppressing the Ti precipitation.
  • the feed rate of 4 will be limited.
  • Ti is formed in the form of particles near the liquid surface and settles.
  • the generated Ti powder settles in an agglomerated state, and during the settling, it sinters under the temperature conditions of the melt, grows grains, and collects it outside the reaction vessel. It is difficult. For this reason, continuous production is difficult and productivity is hindered. This is exactly the reason that Ti by the Kroll method is produced as sponge titanium in the reaction vessel by the notch method.
  • metal Ti is generated from TiCl by the reaction of the following chemical formula (a), At the same time, CaCl is produced as a by-product.
  • Ca has a stronger affinity for C1 than Mg
  • the TiCl is supplied to the liquid surface of the reducing agent in the reaction vessel as in the
  • the reaction area is enlarged as compared with the limited case. As a result, the heat generation area expands and cooling becomes easier, so the supply rate of TiCl, which is the raw material for Ti, can be greatly increased, and productivity can be improved.
  • the oxide direct reduction method has high efficiency, it is not suitable for a method of producing high-purity Ti because expensive high-purity TiO must be used.
  • 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.
  • the Ca concentration in the molten salt can be increased. Therefore, if TiCl is supplied into molten CaCl so as to react with Ca generated on the cathode side, Ca consumed for Ti generation
  • Cathode Ca 2+ + 2e— ⁇ Ca ⁇ ⁇ ⁇ (c)
  • Electrolysis is carried out in a reduction tank and an electrolytic tank, respectively.
  • reaction tank functions as both a reduction tank and an electrolytic tank.
  • molten CaCl is circulated between the reduction tank and the electrolytic tank, which eliminates the need to provide both tanks.
  • the present invention has been made based on vigorous considerations, and the gist is a method for producing Ti or a Ti alloy by Ca reduction described in (1)-(7) below.
  • the molten salt containing CaCl and Ca dissolved therein is held in the reaction vessel, and the molten salt in the reaction vessel is melted.
  • a metal chloride containing TiCl is supplied into the molten salt so as to react with Ca generated on the cathode side in the electrolysis, and Ti or Ti is added to the molten salt.
  • the reaction tank partitions the inside of the tank into an anode side and a cathode side while allowing the flow of the molten salt in the tank. And a membrane for preventing Ca generated on the cathode side in the tank from moving to the anode side.
  • This is a method for producing Ti or a Ti alloy by Ca reduction (hereinafter referred to as “(1) Manufacturing method ”).
  • the molten salt containing CaCl and Ca dissolved therein is held in the reaction vessel, and the molten salt in the reaction vessel is melted.
  • a salt electrolysis is performed using a conductive porous body as a cathode, and a metal salt containing TiCl is passed through the cathode so as to react with Ca generated on the cathode side in the electrolysis.
  • the molten salt containing CaCl and Ca dissolved therein is held in the reaction vessel, and the molten salt in the reaction vessel is melted.
  • a metal chloride containing TiCl is supplied into the molten salt so as to react with Ca generated on the cathode side in the electrolysis, and Ti or Ti is added to the molten salt.
  • the TiCl generated in the chlorination step is used for the Ti or Ti alloy formation reaction in the reaction tank.
  • the molten salt containing CaCl and Ca dissolved therein is held in the reaction vessel, and the molten salt in the reaction vessel is melted.
  • a metal chloride containing TiCl is supplied into the molten salt so as to react with Ca generated on the cathode side in the electrolysis, and Ti or Ti is added to the molten salt.
  • a reduction electrolysis step for producing an alloy Extracting the Ti or Ti alloy generated in the reaction tank together with the molten salt out of the reaction tank, and separating the Ti or Ti alloy from the molten salt outside the tank.
  • This is a method for producing Ti or a Ti alloy (hereinafter, referred to as “the production method described in (4)”).
  • a Ti separation step of separating the Ti or Ti alloy from the molten salt inside or outside the reaction tank a Ti separation step of separating the Ti or Ti alloy from the molten salt inside or outside the reaction tank.
  • a method for producing Ti or Ti alloy by Ca reduction hereinafter referred to as “(5) Method).
  • the molten salt containing CaCl and Ca dissolved therein is held in the reaction vessel, and the molten salt in the reaction vessel is melted.
  • Electrolysis is performed in a salt, and a mixed gas containing TiCl and other metal chlorides is supplied into the molten salt so as to react with Ca generated on the cathode side in the electrolysis, and
  • a Ti separation step of separating the Ti or Ti alloy from the molten salt inside or outside the reaction tank a Ti separation step of separating the Ti or Ti alloy from the molten salt inside or outside the reaction tank.
  • a method for producing Ti or Ti alloy by Ca reduction hereinafter referred to as “(6) Method).
  • the molten salt containing CaCl and Ca dissolved therein is held in the reaction vessel, and the molten salt in the reaction vessel is melted.
  • a metal chloride containing TiCl is supplied into the molten salt so as to react with Ca generated on the cathode side in the electrolysis, and Ti or Ti is added to the molten salt.
  • This is a method for producing Ti or a Ti alloy by Ca reduction (hereinafter, referred to as “the production method described in (7)”). Brief Description of Drawings
  • FIG. 1 shows the relationship between the mixing ratio and the melting point of a binary mixed molten salt of CaCl and NaCl.
  • FIG. 1 A first figure.
  • FIG. 2 is a configuration diagram of a metal Ti manufacturing apparatus to which the first embodiment of the method of the present invention can be applied.
  • FIG. 3 is a configuration diagram of a metal Ti manufacturing apparatus to which the second embodiment of the method of the present invention can be applied.
  • FIG. 1 is a configuration diagram of a metal Ti manufacturing apparatus to which a third embodiment of the present invention can be applied.
  • molten CaCl is held in a reaction tank, for example, as a molten salt. Supply TiCl to molten salt in the reaction tank.
  • the TiCl is reduced by Ca dissolved in the molten salt
  • Ti grains powdery metal Ti (hereinafter referred to as “Ti grains”) is generated.
  • Ti grains powdery metal Ti
  • the dissolved Ca in the molten salt is consumed with the formation of Ti particles, but the electricity of the molten CaCl
  • Mg is produced by electrolyzing MgCl.
  • the technology to increase the recovery rate of Ca is also used. Still, the production cost of Ca cannot be high Not get.
  • the area also expands.
  • the vapor pressure at 850 ° C is very small, 0.3 kPa (2 mmHg), whereas Mg is 6.7 kPa (50 mmHg).
  • the amount is much less when Ca is used for the reduction than for Mg. Therefore, in the method of the present invention for producing Ti or Ti alloy by Ca reduction,
  • Ca is less wettable (adhesive) than Mg, and Ca adhering to precipitated Ti particles is CaCl
  • the generated Ti particles can be taken out of the reaction tank in a powder state with much less agglomeration of the generated titanium particles and grain growth due to sintering, and a continuous Ti production operation is also possible.
  • Direct supply in a liquid state is a feature that increases the contact efficiency of TiCl with Ca in molten CaCl solution.
  • the TiCl liquid is supplied to the molten Ca liquid surface held on the molten CaCl liquid to perform a reduction reaction.
  • the molten Ca solution was kept thin enough to use Ca in the molten CaCl solution.
  • the method of the present invention for producing Ti or Ti alloy by Ca reduction is
  • the TiCl liquid is supplied to the liquid surface of the molten Mg liquid, but the reaction field is expanded.
  • the feeding mode can be implemented without any problem.
  • molten CaCl molten CaCl
  • the liquid level of the molten Ca liquid held on the two liquids and the form of supplying the TiCl liquid or gas into the liquid may be adopted.
  • TiCl is used as a raw material. It is also possible to produce a Ti alloy by mixing and using another metal salted product. Both TiCl and other metal chlorides are reduced by Ca at the same time.
  • TiCl and other metal chlorides may be used in a gaseous, liquid or slipped state.
  • the inside of the tank is divided into an anode side and a cathode side while permitting the flow of the molten salt in the tank.
  • the reaction can be effectively suppressed by using a reaction tank provided with a diaphragm for cutting and preventing Ca generated on the cathode side in the tank from moving to the anode side.
  • One or more of LiCl and CaF 2) may be mixed to form a multi-component molten salt.
  • the melting point of the salt is lowered, so that the temperature (bath temperature) of the molten salt can be lowered.
  • the temperature (bath temperature) of the molten salt can be lowered.
  • Figure 1 shows the relationship between the mixing ratio and melting point of binary mixed molten salts of CaCl and NaCl.
  • FIG. The melting point of CaCl alone is about 780 ° C, and the melting point of NaCl alone is about 800
  • the melting point is 600 ° C.
  • the temperature of the molten salt can be significantly reduced, which is rather desirable from the viewpoint of furnace material protection.
  • the characteristic phenomenon described above is the knock reaction, in particular, the back reaction that unreacted Ca binds to C1 generated on the anode side and returns to CaCl.
  • the Ti particles are taken out of the tank together with the used molten salt, and the Ti particles are extracted outside the tank. It is reasonable to work to separate the molten salt force from the operation. In this case, the molten salt separated from the Ti particles is usually returned to the anode side in the reaction tank, but the molten salt contains unreacted Ca although it has been used, and this is the back reaction. Cause.
  • unreacted Ca in the molten salt is replaced by Na by the reaction of the above formula (e).
  • Na unlike Ca, does not dissolve in the molten salt unlike Ca, so it is separated from the molten salt and separates and removes Na from the molten salt. It is possible to
  • Ca has a dissolving power in the molten salt.
  • the size of the generated Ti grains or Ti alloy grains is preferably 0.5 to 50 m on average. After the particles of Ti or Ti alloy are formed in the molten salt, the particles are withdrawn from the reaction tank together with the molten salt and separated from the molten salt, but the size of the particles is such that they flow together with the molten salt. If the size is not smaller than 50 m, it is difficult to extract the power of the reactor together with the molten salt. If the size is not more than 0.5 m, separation from the molten salt after the extraction becomes difficult.
  • FIG. 2 is a configuration diagram of a metal Ti manufacturing apparatus to which the first embodiment of the method of the present invention can be applied.
  • a reaction tank 1 for simultaneously performing a reduction reaction and an electrolytic reaction is used.
  • Reaction tank 1 contains Ca-rich molten CaCl
  • Hold 2 CaCl has a melting point of about 780 ° C, and its molten salt is heated above its melting point.
  • molten CaCl which is a molten salt, is energized between the anode 2 and the cathode 3 to supply electricity.
  • the partition wall 4 is a porous ceramic thin plate, and prevents Ca generated on the side of the cathode 3 from moving to the side of the anode 2 while allowing the movement of the molten salt. Then, in the reaction tank 1, in parallel with the electrolysis of the molten salt, gaseous TiCl is dispersed and injected into the molten salt on the cathode side in the tank. From this, the injected TiCl
  • the Ti particles collected at the bottom on the cathode side in reaction tank 1 are extracted from reaction tank 1 together with the molten salt present at the bottom, and sent to the Ti separation step.
  • Ti particles extracted together with the molten salt from the reaction tank 1 are subjected to molten salt force separation. Specifically, the Ti grains are compressed to squeeze out the molten salt.
  • the Ti particles obtained in the Ti separation step are melted to form a Ti ingot.
  • the molten salt separated by Ti particle force in the Ti separation step is a used molten salt, is consumed, and the Ca concentration is reduced. This molten salt is introduced to the anode side in the reaction tank 1 together with the used molten salt separately extracted from the reaction tank 1.
  • the molten salt used in the Ti separation process is sequentially introduced.
  • a unidirectional flow of the molten salt from the anode side to the cathode side is formed in the reaction tank 1, and Ca generated on the cathode side is prevented from flowing into the anode side.
  • a diaphragm 4 that partitions the inside of the reaction tank 1 into an anode side and a cathode side is provided, but if the installation of this diaphragm and the operation of forming the one-way flow are combined, knock reaction and This is more effective in suppressing the current efficiency from being lowered.
  • the generated TiCl is introduced into the reaction tank 1, and the Ti
  • the generation of Ti particles by Ca reduction that is, the consumption of Ca
  • the replenishment of Ca by electrolysis are simultaneously performed in the reaction tank 1. For this reason, it is not necessary to replenish or remove Ca in the solid state. Manufactured economically and economically.
  • the reaction tank 1 also serves as a reduction tank and an electrolytic tank, and has a great economical advantage in terms of equipment. Furthermore, in the reaction tank 1, Ca generated on the cathode side is prevented from flowing into the positive electrode side, so that Ca reacts with the C1 gas generated on the anode side.
  • Action can also be prevented.
  • the temperature of the molten salt must be higher than the melting point of CaCl (about 780 ° C) in any process.
  • FIG. 3 is a configuration diagram of a metal Ti manufacturing apparatus to which the second embodiment of the present invention can be applied.
  • the second embodiment differs from the first embodiment in the following points. That is, as a molten salt, a mixture of CaCl and NaCl mixed at a ratio such that the melting point is 600 ° C or less is used, and the reaction tank 1
  • the mixed molten salt is kept at 600 ° C. or lower, and the mixed molten salt is kept at more than 600 ° C. in the separation tank 5 used in the Ti separation step.
  • the molten salt power is a mixed salt of SCaCl and NaCl.
  • Ca has higher reactivity than Mg.
  • mass production of Ti or Ti alloys by Ca reduction is an important technical issue
  • development of furnace materials that can withstand Ca for a long time is an important technical issue. Since the temperature of the molten salt can be lowered, the load on the furnace material is reduced, and significant progress can be expected toward solving this problem.
  • the molten salt is withdrawn from the reaction tank 1 together with the Ti particles and independently (that is, only the molten salt) is extracted into the separation tank 5.
  • the molten salt extracted from the reaction tank 1 is used and contains a small amount of unreacted Ca, although Ca is consumed. When this is returned to the anode 2 side in the reaction tank 1, it reacts with the C1 gas generated on the anode 2 side to back up.
  • the temperature of the molten salt in the separation tank 5 is different from that in the reaction tank 1, Since the temperature is kept above 600 ° C., unreacted Ca slightly contained in the molten salt is replaced by Na (see the above formula (e)). Unlike Ca, Na does not dissolve in the molten salt, separates and floats on the molten salt, and the molten salt is removed. The molten salt from which unreacted Ca (that is, the reducing agent metal) has been removed is sent to the anode 2 side in the reaction tank 1, where the temperature is controlled to 600 ° C or less. As described above, Na is removed. Therefore, the reaction of equation (d) does not occur, and Ca does not regenerate. Therefore, back reaction due to the incorporation of unreacted Ca and a decrease in current efficiency due to the back reaction are prevented.
  • unreacted Ca that is, the reducing agent metal
  • the Ti separation step in the second embodiment also serves as a Na separation step (reducing agent separation step), and the unreacted Ca in the molten salt returned to the reaction tank 1 is removed by replacing it with Na in advance. By doing so, it enables reasonable and economical operation.
  • the Na separated from the molten salt in the separation tank 5 is returned to the cathode 3 side in the reaction tank 1 and returned to Ca by controlling the temperature to 600 ° C or less (formula (d) above), Reused in the reduction reaction.
  • the temperature of the molten salt in the separation tank 5 can be naturally set to 600 ° C or lower, which is the same as that of the reaction tank 1. In this case, unreacted Ca cannot be removed, but the durability of the furnace material It is advantageous in terms of terms.
  • FIG. 4 is a configuration diagram of a metal Ti manufacturing apparatus to which the third embodiment of the present invention can be applied.
  • the third embodiment differs from the first embodiment in the structure of the cathode 3. That is, this is a configuration example of a metal Ti production apparatus capable of performing the production method described in (2) above.
  • the cathode 3 is a solid metal such as Fe or Ti.
  • the cathode 3 is a conductive porous body. Specifically, it is a porous conductive material such as a porous sintered body of Ti and a porous sintered body of Fe.
  • TiCl gas which is a raw material of Ti, passes through the porous cathode 3 (that is, passes through the inside of the porous body, and
  • carbon or graphite is used for the anode 2, and C1 is generated.
  • the feed rate can be increased, and high-purity Ti or Ti alloy can be produced continuously.
  • the reduction reaction and the electrolytic reaction proceed simultaneously in the reaction tank, and the Ca consumed by the reduction reaction can be supplemented by the electrolytic reaction, it is not necessary to handle Ca itself by itself. In addition, the back reaction due to Ca can be effectively suppressed.
  • the method of the present invention can be effectively used as a means for efficiently and economically producing high-purity metal Ti or Ti alloy, and is therefore widely applied as an industrial method for producing Ti or Ti alloy. It becomes possible.

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Abstract

Procédé pour la production du titane ou un alliage de titane de haute pureté avec rétention du sel fondu contenant du CaCl2 et ayant le Ca coulé dans un récipient de réaction (1), l'électrolysation du récipient de réaction et alimentation du chlorure de métal contenant le TiCl4 dans le sel fondu de manière à réagir avec le Ca généré sur le côté de l'électrode négative par électrolyse pour produire du granulé de Ti ou d'alliage Ti dans le sel fondu. En outre, quand le récipient de réaction est ajusté avec un diaphragme adapté (4) tout en permettant la circulation du sel fondu dans le récipient de réaction, la division de l'intérieur du récipient de réaction en côté d'électrode (2) et côté d'électrode négative (3) et le blocage du transfert de Ca formé sur le côté d'électrode négative du récipient de réaction au côté d'électrode positive, toute contre-réaction au CA peut être supprimée de manière efficace. En outre, quand un matériau conducteur poreux est utilisé comme électrode négative, une productivité accrue peut être atteinte.
PCT/JP2005/001379 2004-02-20 2005-02-01 Procédé pour la production du titane ou un alliage de titane reduction de ca WO2005080642A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/589,949 US20070181435A1 (en) 2004-02-20 2005-02-01 Method for producing ti or ti alloy through reduction by ca (as amended)
EP05704329A EP1726689A4 (fr) 2004-02-20 2005-02-01 Proc d pour la production du titane ou un alliage de titane reduction de ca

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2004-044827 2004-02-20
JP2004044827 2004-02-20
JP2004-318075 2004-11-01
JP2004318075A JP2005264320A (ja) 2004-02-20 2004-11-01 Ｃａ還元によるＴｉ又はＴｉ合金の製造方法

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WO (1) WO2005080642A1 (fr)

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JP2012533685A (ja) 2009-07-17 2012-12-27 ボストン・エレクトロニツク・マテリアルズ・エルエルシー 金属粉末および合金の製造および用途
EP2709784A4 (fr) * 2011-05-16 2015-11-18 Boston Electronic Materials Llc Fabrication et applications de poudres et alliages métalliques
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US9856569B2 (en) 2012-07-03 2018-01-02 Field Upgrading Limited Apparatus and method of producing metal in a nasicon electrolytic cell
CN103290433B (zh) * 2013-06-26 2016-01-20 石嘴山市天和铁合金有限公司 一种双电解槽熔盐电解制备纯钛的装置及其工艺
JP2015098626A (ja) * 2013-11-19 2015-05-28 住友電気工業株式会社 精製金属の製造方法
CA3047102C (fr) 2016-09-14 2023-12-05 Universal Achemetal Titanium, Llc Procede de production d'alliage de titane-aluminium-vanadium
CA3049769C (fr) 2017-01-13 2023-11-21 Universal Achemetal Titanium, Llc Alliage-mere de titane pour alliages a base de titane-aluminium
KR101966257B1 (ko) * 2017-11-27 2019-04-05 한국원자력연구원 전해환원 장치에 사용되는 양극 모듈, 이를 포함하는 전해환원 장치 및 그 방법

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EP1808513A4 (fr) * 2004-10-12 2009-07-29 Toho Titanium Co Ltd Méthode de production d un métal par électrolyse en milieu sel fondu et méthode de production de titane métallique

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EP1726689A1 (fr) 2006-11-29
EP1726689A4 (fr) 2007-07-25
US20070181435A1 (en) 2007-08-09
JP2005264320A (ja) 2005-09-29

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