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WO2007034645A1 - Procédé de production de titane et appareil correspondant - Google Patents

Procédé de production de titane et appareil correspondant Download PDF

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Publication number
WO2007034645A1
WO2007034645A1 PCT/JP2006/316355 JP2006316355W WO2007034645A1 WO 2007034645 A1 WO2007034645 A1 WO 2007034645A1 JP 2006316355 W JP2006316355 W JP 2006316355W WO 2007034645 A1 WO2007034645 A1 WO 2007034645A1
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WO
WIPO (PCT)
Prior art keywords
molten salt
concentration
electrolytic cell
molten
alloy
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2006/316355
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English (en)
Japanese (ja)
Inventor
Tadashi Ogasawara
Makoto Yamaguchi
Toru Uenishi
Masahiko Hori
Kazuo Takemura
Katsunori Dakeshita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Titanium Technologies Co Ltd
Original Assignee
Osaka Titanium Technologies Co Ltd
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 Osaka Titanium Technologies Co Ltd filed Critical Osaka Titanium Technologies Co Ltd
Priority to CA002623212A priority Critical patent/CA2623212A1/fr
Priority to AU2006293354A priority patent/AU2006293354A1/en
Priority to US11/992,162 priority patent/US20100089204A1/en
Priority to EP06782859A priority patent/EP1944383A4/fr
Priority to EA200800867A priority patent/EA200800867A1/ru
Publication of WO2007034645A1 publication Critical patent/WO2007034645A1/fr
Anticipated expiration legal-status Critical
Priority to NO20081519A priority patent/NO20081519L/no
Ceased legal-status Critical Current

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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
    • C22B34/1272—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing

Definitions

  • the present invention relates to a Ti production method for producing metal Ti by reducing TiCl with Ca, and
  • metal Ti is manufactured through a reduction process and a vacuum separation process.
  • the reduction process liquid TiCl supplied from above in the reaction vessel is melted by molten Mg.
  • Reduced, particulate metal Ti is generated, and then sinks downward to obtain sponge-like metal Ti.
  • sponge metal T unreacted Mg and by-product MgCl in the reaction vessel are removed.
  • the supplied TiCl reacts as unreacted TiCl gas or insufficiently reduced TiCl gas.
  • the reaction is performed only in the vicinity of the surface of the molten Mg liquid in the reaction vessel, so that the heat generation area is narrow. Therefore, if TiCl is supplied at high speed, the cooling will not be in time.
  • the upper force also supplies metallic Ca powder to dissolve Ca in the molten salt, and TiCl gas is supplied from below to react the dissolved Ca and TiCl in the molten CaCl salt.
  • the metal Ca powder used as the reducing agent is extremely expensive, and when purchased and used, the production cost is higher than that of the crawl method. Therefore, it cannot be established as an industrial Ti manufacturing method. It is difficult to handle Ca, which is highly reactive, and this is also a major factor that hinders the industrial process of Ti production by Ca reduction.
  • This method is a kind of direct oxide reduction method.
  • this method requires the use of expensive high-purity TiO.
  • JP-A-2005-133195 (hereinafter referred to as “Reference 3”) and JP-A-2005-133196 (hereinafter referred to as “Reference 4”),
  • the present inventors based on this OYIK method as a basic configuration, and further developed a metal Ti manufacturing process that can perform stable and efficient operation, and the entire manufacturing process. It was decided to add a study.
  • the OY or Ti alloy manufacturing method of the present invention which is a further evolution of the OYIK method, took the initials of four people who were deeply involved in the development and completion of the idea, “Ogasawara, Yamaguchi, Takahashi, Kanazawa”. The name of the law (Ouitsuku II method).
  • An object of the present invention is to reduce TiCl with Ca generated by electrolysis of molten CaCl.
  • TiCl reduction reaction In the production of Ti metal by Ca reduction, TiCl reduction reaction can be performed efficiently and industrial
  • the purpose is to provide a Ti manufacturing method capable of stable operation and a manufacturing equipment used therefor.
  • This molten salt was returned to the electrolytic cell that electrolyzes CaCl to produce Ca.
  • Ti is formed by the reaction between the generated Ca and lower salt titanium, and this Ti precipitates on the surface of the force sword, and depending on the shape of the electrolytic cell, the short circuit between the electrodes may occur in the cell. May cause blockage. There is also concern about the occurrence of TiC, which causes Ti contamination of C.
  • the Ca concentration of the molten salt charged into the reduction tank does not change and is always constant, and it is desirable that the concentration be high in order to allow the reduction reaction to proceed efficiently.
  • the present inventors have made various studies in order to suppress the fluctuation of the Ca concentration of the molten salt charged into the reduction tank and maintain it at a high concentration.
  • an adjustment tank equipped with a Ca supply source was installed between the electrolytic cell (hereinafter referred to as the “main electrolytic cell”) and the reduction tank, and molten salt with an increased Ca concentration was introduced into the adjustment cell in the main electrolytic cell. It was found that it is effective to use it for reduction after keeping the Ca concentration constant. It was also found that a molten Ca-Mg alloy is suitable as a Ca supply source.
  • the present invention has been made based on these findings, and the gist of the present invention is the following (1) Ti production method and (2) Ti production apparatus.
  • a reduction step of generating Ti grains in the salt, and melting the Ti grains generated in the molten salt A separation process for separating the salt force, and an electrolysis process for increasing the Ca concentration by electrolyzing the molten salt whose Ca concentration has decreased due to the formation of Ti grains.
  • the Ca concentration is increased using the main electrolytic cell.
  • the molten salt thus introduced is introduced into a regulating tank having a Ca supply source and brought into contact with the Ca supply source to make the Ca concentration of the molten salt constant, and then TiCl is reduced in the reduction step.
  • molten salt containing CaCl means only molten CaCl or molten CaC.
  • 1 is a molten salt containing KC1, CaF, etc. to adjust the melting point and viscosity. Less than
  • the Ca supply source is a molten Ca-Mg alloy
  • the Ca concentration in the molten Ca-Mg alloy is the same as that of the molten CaCl-containing alloy.
  • the molten salt from which the Ti grains have been separated in the separation step is once charged into the electrolytic cell for alloying, and the Ca concentration of the molten salt is reduced. If it is put into the main electrolytic cell, it is desirable because the residual Ca in the molten salt returned to the electrolysis process from the separation process can be removed and this residual Ca can be used effectively (hereinafter referred to as the first). 3).
  • the adjustment tank used in the production method of the present invention has a cooling function, an increase in the temperature in the tank based on an exothermic reaction can be mitigated in a later reduction tank, and the addition to the reduction tank Therefore, the Ca concentration of the molten salt can be kept constant at a constant and high concentration, and the reduction reaction can be performed efficiently, contributing to stable operation (hereinafter referred to as the fourth embodiment).
  • a reduction tank for reacting TiCl with the Ca to produce Ti grains and
  • an adjusting tank for introducing the molten salt into the reduction tank comprising an anode and a power sword, and performing electrolysis in the molten salt to form a cathode
  • the Ca supply source is a molten Ca-Mg alloy and includes an alloy electrolytic cell for increasing the Ca concentration of the molten Ca-Mg alloy
  • the first and It can be suitably used for implementing the Ti manufacturing method according to the second embodiment.
  • an electrolytic cell for an alloy is installed between the high-temperature decanter and the main electrolytic cell in the separation step, and the molten salt having a high Ca concentration in the alloy electrolytic cell can be introduced into the adjustment tank.
  • V is suitable for carrying out the Ti manufacturing method according to the third embodiment.
  • the molten salt with the Ca concentration increased in the main electrolytic cell is introduced into the adjustment tank equipped with the Ca supply source and the Ca concentration is made constant, and then used for the reduction of TiCl. Throw
  • Ti can be produced on an industrial scale by increasing the feed rate. This manufacturing method can be easily and suitably performed by the manufacturing apparatus of the present invention.
  • FIG. 1 is a diagram showing a schematic configuration example of the Ti manufacturing apparatus of the present invention.
  • FIG. 2 is a diagram showing another schematic configuration example of the Ti manufacturing apparatus of the present invention.
  • Fig. 3 is an explanatory diagram of the replenishment of Ca to the molten Ca-Mg alloy in the alloy electrolytic cell.
  • FIG. 4 is a diagram showing a schematic configuration example of the Ti manufacturing apparatus of the present invention in which an alloy electrolytic cell is incorporated.
  • FIG. 5 is a diagram showing a schematic configuration example of the Ti production apparatus of the present invention in which an alloy electrolytic cell is incorporated in the molten salt path returned from the separation step to the main electrolytic cell.
  • FIG. 6 is a longitudinal sectional view showing a configuration example of a main part of an electrolytic cell used when performing the molten salt electrolysis method used in the present invention.
  • Fig. 7 shows the hollow-force sword used in carrying out the molten salt electrolysis method used in the present invention. It is a figure which shows typically the structural example of a part of used electrolytic vessel.
  • FIG. 1 is a diagram showing a schematic configuration example of the Ti manufacturing apparatus of the present invention. As shown in FIG. 1, this apparatus holds a molten salt containing CaCl and dissolved in Ca and supplying the molten salt to the molten salt.
  • Separation means for separating the Ti grains formed in the salt from the molten salt, and the molten salt after the Ti grains are separated are held, and the anode 2 and the force sword 3 are provided.
  • a decanter type centrifugal sedimentator (high temperature decanter) 7 and a separation tank 8 are used as the separation means.
  • TiCl is added to Ca in a molten salt containing CaCl and dissolving Ca.
  • a reduction step of reacting to produce Ti particles in the molten salt a separation step of separating the Ti particles produced in the molten salt from the molten salt, and a Ca concentration accompanying the production of Ti particles.
  • the molten salt is made constant by bringing the molten salt into contact with the Ca supply source and then used for the reduction of TiCl in the reduction step.
  • the apparatus shown in FIG. 1 is used.
  • a molten salt in which Ca supplied from the adjustment tank 6 is dissolved at a constant concentration is reduced. Retained in tank 1 and reacted with TiCl supplied from TiCl supply port 9 to Ca in the molten salt,
  • Ti grains are formed in the molten salt.
  • the molten salt is not held in a stationary state in the reducing tank 1, but is held while gradually flowing down from above the reducing tank 1, while TiCl is added to the Ca in the molten salt. In Reduced to produce Ti grains.
  • Ti particles generated in the reduction step are separated from the molten salt in the "separation step".
  • Ti particles are first separated and recovered from the molten salt in a high-temperature decanter 7 and then separated in a separation tank 8.
  • the molten salt adhering to the Ti grains is removed.
  • the decanter type centrifugal settling machine is a type of centrifugal separator that spins down suspended matter by rotating a rotating cylinder at high speed. It can process at high speed and has high dehydration performance. Used in various processing plants. A type capable of high temperature treatment has also been developed and can be applied as a high temperature decanter 7 in this separation process.
  • the flow rate of the adhering molten salt is very small compared to the flow rate of the molten salt introduced into the reduction tank 1 after the Ca concentration is made constant in the adjustment tank 6, so that the flow from the adjustment tank 6 to the reduction tank 1 Variations in the Ca concentration of the molten salt introduced are negligible.
  • the molten salt having a reduced Ca concentration separated by the high-temperature decanter 7 is returned to the “electrolysis step”, and is introduced and held between the force sword 3 and the diaphragm 4 in the main electrolytic cell 5.
  • the configuration and operation of the main electrolytic cell 5 used in this step will be described in detail later.
  • the molten salt is not held in the main electrolytic cell 5 in a stationary state, but the main electrolytic cell 5 It is held while gradually flowing down from above, and is electrolyzed during that time, increasing the molten salt Ca concentration.
  • the molten salt in which the Ca concentration is increased using the main electrolytic cell 5 in the electrolysis step is introduced into the adjustment tank 6 having a Ca supply source, and the Ca supply source is introduced. After making the Ca concentration of the molten salt constant by bringing it into contact, it is used for the reduction of TiCl in the reduction step.
  • molten metal Ca or molten Ca—Mg alloy can be used as the Ca supply source.
  • molten metal Ca or molten Ca—Mg alloy is allowed to float on the molten salt with increased Ca concentration, and these Ca supply source and molten salt are brought into contact with each other.
  • the Ca supply source Ca can be supplied to the molten salt, and the Ca concentration can be maintained at a concentration close to the saturation solubility.
  • the Ca concentration of the metal is the saturation solubility, and precipitated metal Ca is also present, the metal Ca floats and separates due to the difference in specific gravity in the adjustment tank 6, and the Ca concentration is maintained at a concentration close to the saturation solubility. be able to. Furthermore, if the temperature of the molten salt at the time of extraction from the adjustment tank 6 is controlled to be constant, the Ca concentration can be controlled to a constant concentration near the saturation solubility at that temperature.
  • the adjusting tank 6 is installed, and the molten salt with an increased Ca concentration is introduced into the main electrolytic tank 5.
  • molten salt with a constant Ca concentration near its saturation solubility was charged into the reduction tank 1, and TiCl
  • the reduction reaction of 4 can be carried out efficiently and stable operation can be achieved.
  • FIG. 2 is a diagram showing another schematic configuration example of the manufacturing apparatus of the present invention used when the Ti manufacturing method is carried out, similarly to the manufacturing apparatus shown in FIG.
  • the difference from the apparatus configuration shown in FIG. 1 is that a sedimentation separation tank (thickener) 13 using gravity is used instead of a high temperature decanter as a separation means, which is wider than the case where a high temperature decanter is used.
  • a sedimentation separation tank (thickener) 13 using gravity is used instead of a high temperature decanter as a separation means, which is wider than the case where a high temperature decanter is used.
  • the first embodiment of the production method of the present invention is a method in which the Ca supply source is a molten Ca-Mg alloy.
  • the Ca supply source is a molten Ca-Mg alloy
  • the molten Ca-Mg alloy power is also dissolved into the molten salt and it becomes necessary to replenish Ca in the alloy, it is easily replenished as described below. It is desirable because it can.
  • a second embodiment of the present invention is a method of increasing the Ca concentration in a molten Ca-Mg alloy by electrolyzing a molten salt containing CaCl in an alloy electrolytic cell in the first embodiment.
  • FIG. 3 is an explanatory diagram of the replenishment of Ca to the molten Ca—Mg alloy by the alloy electrolytic cell.
  • the electrolytic cell 14 for alloy hinders the movement of molten salt (molten CaCl).
  • the partition 15 is divided into an anode side and a force sword side by a partition 15 having an opening on the lower side.
  • An anode 2 is attached to the anode side, and the force sword side has a lower specific gravity than molten CaCl.
  • the molten Ca-Mg alloy 16 constitutes a power sword.
  • An electrode rod 17 is inserted into the molten Ca—Mg alloy 16.
  • a molten salt whose Ca concentration has been increased in the electrolysis process is introduced into the adjustment tank 6, and a molten Ca—Mg alloy 16 serving as a Ca supply source is held thereon.
  • the anode 2 has chlorine gas.
  • Ca is generated at the interface between molten Ca—Mg alloy 16 and molten CaCl, which is a force sword.
  • the Ca concentration of the Ca-Mg alloy 16 increases.
  • the molten Ca—Mg alloy 16 having an increased Ca concentration is transferred to the upper part of the molten Ca—Mg alloy 16 in the adjustment tank 6 (indicated as “MgZCa” in FIG. 3), and is moved to the lower part.
  • the existing Ca is supplied to the molten salt (ie, melted out), and the molten Ca—Mg alloy 16 having a reduced Ca concentration is returned to the molten Ca—Mg alloy 16 in the alloy electrolytic cell 14 (in FIG. 3, “Mg”).
  • the Ca generated by the electrolysis of the molten CaCl described above is molten Ca.
  • the replenishment of Ca to the molten Ca—Mg alloy used as the Ca supply source can be easily performed without affecting the Ca production process. Can be done.
  • FIG. 4 is a diagram showing a schematic configuration example of a manufacturing apparatus in which the alloy electrolytic cell shown in FIG. 3 is incorporated in order to carry out the manufacturing method of the present invention. If the first and second embodiments of the present invention are applied using this apparatus, Ca can be easily replenished to the molten Ca—Mg alloy used as the Ca supply source without affecting the operation. it can.
  • the molten salt after the Ti grains are separated in the separation step is once charged into the alloy electrolytic cell.
  • the Ca concentration of the molten salt is reduced and charged to the main electrolytic cell, and concerns such as a decrease in current efficiency due to the knock reaction can be eliminated.
  • FIG. 5 is a diagram showing a schematic configuration example of a manufacturing apparatus in which an alloy electrolytic cell is incorporated in the molten salt path returned from the separation step to the main electrolytic cell in the schematic configuration example shown in FIG.
  • an electrolytic cell 14 for the alloy is installed between the high-temperature decanter 7 and the main electrolytic cell 5 used in the separation process, and the molten salt after the Ti grains are separated and recovered is temporarily separated from this alloy.
  • the electrolytic cell 14 for use.
  • FIG. 5 shows a force illustrating an example in which an alloy electrolytic cell 14 is installed between the high-temperature decanter 7 and the main electrolytic cell 5.
  • the thickener 13 and the main electrolytic cell 5 An electrolytic cell 14 for alloy may be installed between them.
  • the fourth embodiment of the present invention is characterized in that the adjustment tank used in the production method of the present invention has a cooling function.
  • the following two effects can be expected. One is to adjust the Ca concentration of the molten salt in the adjustment tank 6 and then use the TiCl Ca in the next reduction step.
  • the force that causes the reduction reaction by 4 The rise in the temperature in the reduction tank due to the heat generated by this reaction can be moderated to some extent by removing heat from the molten salt supplied to the reduction tank 1 in advance.
  • the saturated Ca solubility of the molten salt can be lowered by lowering the temperature of the molten salt in the adjusting tank 6.
  • the saturation solubility can be reached by lowering the temperature in the adjustment tank 6.
  • Ca precipitates due to cooling it floats and becomes a source of Ca.
  • the production apparatus of the present invention is a production apparatus used when the Ti production method described above is carried out, holds a molten salt containing CaCl and dissolved in Ca, and is supplied into the molten salt.
  • Separation means for separating the Ti grains generated from the molten salt, and the molten salt after the Ti grains are separated are retained, and an anode and a force sword are provided, and electrolysis is performed in the molten salt.
  • a main electrolytic cell for generating Ca on the cathode side and a Ca supply source are provided, and the molten salt in the main electrolytic cell is introduced and brought into contact with the Ca supply source to make the Ca concentration of the molten salt constant.
  • a regulating tank for charging the molten salt into the reducing tank are provided.
  • FIGS. 1 and 2 The apparatus configuration illustrated in FIGS. 1 and 2 is an embodiment of the manufacturing apparatus of the present invention.
  • the production method of the present invention can be suitably implemented using this production apparatus.
  • the apparatus configuration shown in FIG. 4 is another schematic configuration example of the manufacturing apparatus of the present invention.
  • the molten Ca—Mg alloy 16 is formed between the adjustment tank 6 and the alloy electrolytic tank 14. It is suitable for carrying out the Ti manufacturing method according to the first and second embodiments in which the molten Ca—Mg alloy used as a Ca supply source is replenished with Ca.
  • the apparatus configuration shown in FIG. 5 is still another schematic configuration example of the production apparatus of the present invention, and the alloy electrolytic cell 14 is interposed between the high-temperature decanter 7 and the main electrolytic cell 5 used in the separation process. In this way, the molten salt having a reduced Ca concentration in the alloy electrolytic cell 14 can be introduced into the main electrolytic cell 5.
  • the Ti manufacturing method according to the third embodiment can be easily performed.
  • reaction can be performed efficiently and stable operation can be performed.
  • the molten salt is electrolyzed while gradually flowing down from the upper side of the main electrolytic cell, so that a large amount of molten salt can be continuously processed.
  • the supply rate of Ca to the reduction tank is increased and Ti can be produced on an industrial scale.
  • FIG. 6 is a longitudinal sectional view showing a configuration example of a main part of an electrolytic cell used when the molten salt electrolysis method used in the present invention is carried out.
  • This electrolytic cell 5 has a pipe (cylindrical) shape that is long in one direction and holds a molten salt containing CaCl.
  • a molten salt supply port 20 is provided at one end (bottom plate 18) in the longitudinal direction of 5a, and a molten salt discharge port 21 is provided at the other end (upper cover 19).
  • the anode surface and the force sword surface are opposed to each other in a substantially vertical direction, and further, between the anode 2 and the force sword 3, the molten salt A diaphragm 4 is provided to suppress the passage of the Ca generated by the electrolysis of.
  • a cooler 22 is attached to the outer surface of the anode 2.
  • This electrolytic cell 5 is used as a main electrolytic cell in the production method of the present invention.
  • a molten salt containing a metal fog forming metal chloride is continuously or intermittently supplied between the one-end force anode and the force sword of the electrolytic cell.
  • the flow rate in one direction is given to the molten salt near the surface of the force sword, and the molten salt is electrolyzed while flowing in one direction near the surface of the force sword, thereby increasing the metal fog forming metal concentration of the molten salt.
  • metal fog forming metal has a property that the metal itself dissolves in a metal salt salt such as Ca, Li, Na, A1, etc. (ie, Ca is CaCl And again Li
  • molten salt containing a metal fog forming metal (Ca) chloride refers to molten CaCl alone or to molten CaCl to adjust the melting point, viscosity, etc.
  • molten salt electrolysis method first, a molten salt containing CaCl is added to the electrolytic cell 5.
  • One-end force is also supplied between the anode 2 and the force sword 3 continuously or intermittently.
  • the electrolytic cell 5 Since the electrolytic cell 5 is long in one direction and has a shape (in the example shown in the figure, it is elongated in the vertical direction! / Pipe (cylindrical) shape), the molten salt is applied to one end force of the electrolytic cell 5 Anode
  • the molten salt is applied to one end force of the electrolytic cell 5 Anode
  • the entire molten salt between the anode 2 and the force sword 3 may flow in one direction.
  • the term “near the force sword surface” refers to a region adjacent to the force sword surface where Ca generated on the force sword surface is present.
  • the supply of the molten salt is usually performed continuously, the supply of the molten salt may be continued intermittently, that is, even if the supply of the molten salt is temporarily stopped in relation to the post-process or the like. Temporary stop of molten salt supply When stopped, the flow of the molten salt near the surface of the force sword is also stopped. Therefore, strictly speaking, the “flow velocity” when “giving a one-way flow velocity to the molten salt near the surface of the force sword” includes a state where the flow velocity is zero without any flow.
  • the molten salt is electrolyzed.
  • the force electrolysis cell 5 in which molten salt is electrolyzed while flowing in the vicinity of the surface of the force sword to generate Ca on the surface of the force sword has a long shape in one direction.
  • the distance between the anode 2 and the force sword 3 is made relatively small in order to keep the electrolysis voltage low, so the Ca concentration is low and the molten salt near the molten salt supply port 20 is electrolyzed with the molten salt. Mixing with the molten salt in the vicinity of the molten salt extraction port 21 having an increased concentration can be prevented, and only the molten salt enriched with Ca can be effectively extracted.
  • the document 2 describes a technique of "forming a molten salt flow in the vicinity of a force sword in the production of Ti by Ca reduction in a molten salt".
  • the anode and the force sword are placed facing each other along the longitudinal direction in the electrolytic cell, it is formed near the force sword surface or between the force sword surface and the diaphragm when a diaphragm is provided.
  • a unidirectional molten salt flow is formed along the surface of the force sword, and the molten salt with increased Ca concentration is recovered on the outlet side of the electrolytic cell by electrolysis in that state.
  • N / A and the description that suggests it is not shown! /.
  • the anode surface and the force sword surface face each other and are arranged in a substantially vertical direction, and a partition wall configured to allow a part of the diaphragm or the molten salt to flow between the anode and the force sword. If the electrolytic cell provided is used, it will be generated on the anode side. It is easy to collect the chlorine gas. Also, Ca and chlorine generated by electrolysis react with CaCl
  • substantially vertical direction means “substantially” and “substantially”, and “substantially vertical direction” means the vertical direction or its directional force also in the horizontal direction. A slightly inclined direction.
  • the molten salt electrolysis method using the electrolytic cell in which both electrodes are arranged opposite to each other in a substantially vertical direction can be preferably carried out by using the electrolytic cell illustrated in FIG.
  • the electrolytic cell illustrated in Fig. 6 CaCl is supplied into the lower force tank 5 of the electrolytic cell 5 and extracted from above.
  • the anode surface and the force sword surface are arranged in a substantially vertical direction, and the unidirectional flow rate is also applied to the molten salt near the force sword surface. Therefore, the flow direction of the molten salt is vertical, and the chlorine gas generated on the anode side floats easily, so it can be easily recovered.
  • Examples of the diaphragm provided between the anode and the force sword include, for example, many containing yttria (Y 2 O 3).
  • a porous ceramic body can be used.
  • a porous ceramic body made by firing yttria has a selective permeability that allows Ca and chlorine ions to pass through but does not allow metal Ca to pass through. It also reduces by Ca, which has strong reducing power. It has an excellent resistance to calcium reduction that is not possible, and is suitable as a diaphragm in the molten salt electrolysis method used in the present invention.
  • Electrolysis can be carried out with high current efficiency at which knock reaction is unlikely to occur.
  • a partition configured to allow a part of the molten salt to flow therethrough may be used.
  • the partition wall does not allow molten salts such as Ca and chlorine ions as well as metallic Ca, but by providing slits or holes through which molten salt can pass in a part of the partition wall, electrolysis can be achieved, while metal Ca It is possible to limit knock reaction by restricting the passage to some extent.
  • the force sword is hollow, has a gap or a hole through which the molten salt can flow from the surface of the force sword to the inside of the force sword, and the Ca concentrated molten salt flowing into the force sword is removed.
  • An electrolytic cell with a force sword that can be pulled out of the electrolytic cell shall be used. If so, knock reaction can be effectively suppressed.
  • FIG. 7 is a diagram schematically showing a configuration example of a part of an electrolytic cell using a hollow force sword.
  • the anode 2 and the hollow force sword 3a face each other in the substantially vertical direction along the longitudinal direction in the electrolytic cell 5, and between the anode 2 and the force sword 3a.
  • the force sword 3a is provided with a gap or a hole through which the molten salt can flow into the cathode as well as the force sword surface force.
  • the electrolytic cell constructed in this way is used, the molten salt is extracted from above the hollow portion of the force sword 3a, so that the inner side of the force sword from the outer side as shown by the white arrow in the figure. A molten salt flow to the (hollow part) is formed, and Ca generated on the outer surface of the force sword 3a is immediately taken into the force sword 3a without diffusing and moving to the anode side. Thereby, back reaction can be effectively suppressed. Since the electrolytic cell illustrated in FIG. 7 has the diaphragm 4, the knock reaction suppressing effect is further increased as compared with the case without the diaphragm.
  • controlling the Ca concentration to be less than the saturation solubility means “electrolysis under conditions where the Ca concentration is close to the saturation solubility and does not precipitate”.
  • the shape of the electrolytic cell container and the electric power are set so that the "condition where the Ca concentration is close to the saturation solubility and does not precipitate" is satisfied at the site where the Ca concentration is highest in the electrolytic cell.
  • the optimum electrolysis conditions according to the pole shape, the distance between the poles, and the amount of molten salt extracted per unit time will be determined empirically.
  • the Ca concentration near the molten salt outlet on the force sword side is the highest, so the Ca concentration in this part is controlled to be less than the saturation solubility.
  • electrolytic operation becomes possible.
  • the molten salt with the increased Ca concentration in the electrolysis step is adjusted to have a Ca supply source.
  • the molten salt is introduced into a tank and brought into contact with the Ca supply source, and the Ca concentration of the molten salt is kept high and constant.
  • the optimum electrolysis conditions, the amount of molten salt withdrawn, etc. are determined empirically. Even so, a certain degree of control is possible.
  • the molten salt electrolysis method used in the present invention When the molten salt electrolysis method used in the present invention is carried out, a large heat of reaction is generated in the electrolytic cell, so it is desirable to effectively remove the heat. Specifically, it is desirable to install a cooler at the center of the force sword to remove the reaction heat from the internal force of the force sword, regardless of whether or not the hollow force sword is used.
  • a cooler for example, a tubular heat exchanger is suitable.
  • cooler heat exchanger
  • the energized surface area needs to be increased in order to increase the energization amount and increase the amount of Ca generation.
  • a groove process for forming a groove on the electrode surface can be applied.
  • molten salt electrolysis method it is possible to relatively stably obtain a molten salt in which Ca is concentrated to near the saturation solubility while suppressing adverse effects such as clogging inside the electrolytic cell. Can be manufactured efficiently.
  • the molten salt is electrolyzed while flowing in one direction near the surface of the force sword, a large amount of molten salt can be processed continuously.
  • the electrolytic cell used for carrying out this molten salt electrolysis method retains a molten salt containing CaCl.
  • the electrolytic cell container has an anode and a force sword disposed along the longitudinal direction of the electrolytic cell container, and is melted at one end in the longitudinal direction of the electrolytic cell container.
  • a salt supply port is provided so that the molten salt can be supplied between the anode and the power sword, and the molten salt having an increased Ca concentration generated by electrolysis of the molten salt at the other end is provided outside the electrolytic cell.
  • the electrolytic cell illustrated in Fig. 6 is an embodiment thereof, and the anode surface and the cathode surface are arranged to face each other in a substantially vertical direction, and a diaphragm is provided between the anode and the force sword. It has an electrolytic cell. Instead of the diaphragm, a partition wall configured to allow a part of the molten salt to flow therethrough may be provided.
  • the molten salt whose Ca concentration has been increased in the electrolysis step is introduced into an adjustment tank equipped with a Ca supply source to make the Ca concentration constant, and then used for the reduction of TiCl.
  • Reduction tank equipped with a Ca supply source to make the Ca concentration constant, and then used for the reduction of TiCl.
  • the reduction reaction of 4 can be performed efficiently, stable operation is possible, and Ti can be manufactured on an industrial scale. Therefore, the production method of the present invention and the production apparatus of the present invention capable of easily and suitably carrying out this method can be effectively used for the production of Ti by Ca reduction.

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  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
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Abstract

La présente invention concerne un procédé de production de titane, comprenant l'étape de réduction consistant à fournir un sel en fusion contenant CaCl2 et ayant du calcium dissout dans celui-ci et à faire réagir TiCl4 avec le calcium de façon à former de ce fait des particules de titane, l'étape de séparation consistant à séparer les particules de titane formées dans le sel en fusion de celui-ci et l'étape d'électrolyse consistant à électrolyser le sel en fusion de façon à augmenter la concentration en calcium, le sel en fusion ayant la concentration en calcium augmentée dans l'étape d'électrolyse étant introduit dans un récipient de régulation de façon à rendre constante de ce fait la concentration en calcium dans le sel en fusion et étant ensuite utilisé dans la réduction de TiCl4 lors de l'étape de réduction. Dans ce procédé, on peut non seulement supprimer toute fluctuation de la concentration en calcium du sel en fusion chargé dans un récipient de réduction mais on peut également maintenir une concentration élevée de celui-ci. En outre, le traitement continu d'un grand volume de sel en fusion devient réalisable. Par conséquent, la réaction de réduction de TiCl4 peut être effectuée de manière efficace, et en tant que procédé de réalisation de la production de titane à une échelle industrielle, le procédé peut être utilisé de manière efficace dans la production de titane par la réduction de calcium.
PCT/JP2006/316355 2005-09-20 2006-08-22 Procédé de production de titane et appareil correspondant Ceased WO2007034645A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002623212A CA2623212A1 (fr) 2005-09-20 2006-08-22 Procede de production de titane et appareil correspondant
AU2006293354A AU2006293354A1 (en) 2005-09-20 2006-08-22 Process for producing Ti and apparatus therefor
US11/992,162 US20100089204A1 (en) 2005-09-20 2006-08-22 Process for Producing Ti and Apparatus Therefor
EP06782859A EP1944383A4 (fr) 2005-09-20 2006-08-22 Procédé de production de titane et appareil correspondant
EA200800867A EA200800867A1 (ru) 2005-09-20 2006-08-22 СПОСОБ ПОЛУЧЕНИЯ Ti И УСТРОЙСТВО ДЛЯ ЭТОГО
NO20081519A NO20081519L (no) 2005-09-20 2008-03-28 Fremgangsmate og apparatur for fremstilling av Ti

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JP2005-271995 2005-09-20
JP2005271995A JP2007084847A (ja) 2005-09-20 2005-09-20 Ｔｉの製造方法および装置

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AU (1) AU2006293354A1 (fr)
CA (1) CA2623212A1 (fr)
EA (1) EA200800867A1 (fr)
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WO2009011190A1 (fr) * 2007-07-13 2009-01-22 Osaka Titanium Technologies Co., Ltd. Procédé pour produire du métal et appareil pour produire du métal
JP2013170290A (ja) * 2012-02-20 2013-09-02 Toshiba Corp 溶融塩電解装置および溶融塩電解方法
CN101925427B (zh) * 2008-01-23 2014-06-18 特拉迪姆有限公司 减敏金属或合金粉末及其制造的方法和/或反应釜

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CN103898555A (zh) * 2012-12-25 2014-07-02 攀钢集团攀枝花钢铁研究院有限公司 一种生产金属钛的方法
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
JP6997617B2 (ja) * 2017-12-27 2022-02-04 東邦チタニウム株式会社 溶融塩電解方法、溶融金属の製造方法および、溶融塩電解槽

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WO2009011190A1 (fr) * 2007-07-13 2009-01-22 Osaka Titanium Technologies Co., Ltd. Procédé pour produire du métal et appareil pour produire du métal
CN101925427B (zh) * 2008-01-23 2014-06-18 特拉迪姆有限公司 减敏金属或合金粉末及其制造的方法和/或反应釜
JP2013170290A (ja) * 2012-02-20 2013-09-02 Toshiba Corp 溶融塩電解装置および溶融塩電解方法

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US20100089204A1 (en) 2010-04-15
CN101268204A (zh) 2008-09-17
AU2006293354A1 (en) 2007-03-29
EA200800867A1 (ru) 2008-10-30
EP1944383A1 (fr) 2008-07-16
EP1944383A4 (fr) 2009-12-02
CA2623212A1 (fr) 2007-03-29
JP2007084847A (ja) 2007-04-05
NO20081519L (no) 2008-04-02

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