JP4510769B2 - Manufacturing method and apparatus for Ti or Ti alloy - Google Patents

Description

The present invention relates to a Ti or Ti alloy manufacturing method for manufacturing metal Ti or a Ti alloy by reducing metal chloride containing TiCl ₄ with Ca, and a manufacturing apparatus used therefor.

As an industrial method for producing metal Ti, a crawl method in which TiCl ₄ is reduced with Mg is generally used. In this crawl method, metal Ti is produced through a reduction process-vacuum separation process. In the reduction step, liquid TiCl ₄ supplied from above in the reaction vessel is reduced by molten Mg to form particulate metal Ti, which is successively settled downward to obtain sponge-like metal Ti. In the vacuum separation step, unreacted Mg and by-product MgCl ₂ are removed from the spongy metal Ti in the reaction vessel.

In the production of metal Ti by the crawl method, it is possible to produce a high-purity product. However, since it is a batch type, the manufacturing cost increases and the product price becomes very high. One of the causes of increased manufacturing cost is that it is difficult to increase the supply rate of TiCl ₄ .

There are several possible reasons for this, but one is that if the supply rate of TiCl ₄ is increased too much, TiCl ₄ is supplied from above to MgCl ₂ that does not settle and remains on the liquid surface. The supplied TiCl ₄ is discharged out of the reaction vessel as unreacted TiCl ₄ gas or TiCl ₃ gas with insufficient reduction, and the utilization efficiency of TiCl ₄ is lowered.

In the crawl method, the reaction is performed only in the vicinity of the liquid level of the molten Mg liquid in the reaction vessel, so that the heat generation area is narrow. For this reason, if TiCl ₄ is supplied at a high speed, cooling cannot be performed in time, which is a major reason that the supply speed of TiCl ₄ is limited.

  Furthermore, due to the wettability (adhesiveness) of the molten Mg, the Ti powder that has been formed settles in a coherent state, and during the sedimentation, particles are grown by sintering with the heat of the high-temperature melt. It is difficult to recover outside the container. For this reason, manufacture of metal Ti cannot be performed continuously but productivity is inhibited.

Regarding Ti production methods other than the crawl method, Patent Document 1 describes that, for example, Ca can be used as a reducing agent for TiCl ₄ in addition to Mg. And as a manufacturing method of Ti using the reduction reaction by Ca, in Patent Document 2, a molten salt of CaCl ₂ is held in a reaction vessel, and metallic Ca powder is supplied into the molten salt from above to melt A method is described in which Ca is dissolved in a salt and TiCl ₄ gas is supplied from below to react the dissolved Ca and TiCl ₄ in a molten salt of CaCl ₂ .

  However, in the method described in Patent Document 2, the metal Ca powder used as a reducing agent is extremely expensive, and if this is purchased and used, the manufacturing cost is higher than that of the crawl method. It cannot be established as a manufacturing method. In addition, highly reactive Ca is very difficult to handle, and this is also a major factor that hinders industrialization of the Ti production method by Ca reduction.

As another Ti production method, Patent Document 3 describes Olson's method in which TiO ₂ is directly reduced by Ca without passing through TiCl ₄ . This method is a kind of direct oxide reduction method. However, this method must use expensive high-purity TiO ₂ .

On the other hand, in order to industrially establish a Ti production method by Ca reduction, the present inventors must reduce TiCl ₄ with Ca, and economically reduce Ca in molten salt consumed in the reduction reaction. In consideration of the necessity of replenishment, a method of using Ca generated by electrolysis of molten CaCl ₂ and circulating this Ca, that is, “OYIK method (Oic method)” was proposed (Patent Document 4, Patent Document) 5). Patent Document 4 describes a method in which Ca is generated and replenished by electrolysis and Ca-rich molten CaCl ₂ is introduced into a reaction vessel and used to generate Ti particles by Ca reduction. Furthermore, a method of effectively suppressing back reaction accompanying electrolysis by using an alloy electrode (for example, Mg—Ca alloy electrode) as a cathode is shown.

US Pat. No. 2,205,854 U.S. Pat. No. 4,820,339 U.S. Pat. No. 2,845,386 JP 2005-133195 A JP 2005-133196 A

As described above, many researches and developments have been made on Ti production methods other than the crawl method. In particular, in the OYIK method proposed by the present inventors, Ca in the molten salt is consumed with the reduction reaction of TiCl ₄ , but when the molten salt is electrolyzed, Ca is generated in the molten salt, and thus obtained. If the produced Ca is reused in the reduction reaction, it is not necessary to replenish Ca from the outside, and there is no need to take out Ca alone, thereby improving the economic efficiency.

  Therefore, the inventors of the present invention are based on the OYIK method as a basic configuration, and further intend to develop a manufacturing process of metal Ti or Ti alloy that can be efficiently and stably operated on an industrial scale. The whole manufacturing process was examined.

The object of the present invention is to reduce TiCl ₄ and other metal chlorides in the production of metal Ti or Ti alloy by Ca reduction in which TiCl ₄ and other metal chlorides are reduced by Ca generated by electrolysis of molten CaCl _2. To provide a method for producing Ti or a Ti alloy capable of efficiently performing reaction, and further generating Ca by electrolysis of molten salt, and capable of stable operation on an industrial scale, and a production apparatus used therefor. is there.

In order to efficiently perform the reduction reaction of TiCl ₄ and other metal chlorides mentioned above as well as the production of Ca by electrolysis of molten salt, and to stabilize the operation, TiCl ₄ is reduced. Concentration of CaCl _{2 in the} molten salt contained in the reaction vessel to be introduced, suppression of concentration fluctuations, and removal of Ca in the molten salt drawn out of the reaction vessel and introduced into the electrolytic cell (recovery) )is important. Moreover, in order to enable production of Ti on an industrial scale, it is necessary to increase the supply rate of Ca to the reaction vessel (in other words, continuous treatment of a large amount of molten salt containing CaCl ₂ in the electrolysis process). is there.

When the Ca concentration of the molten salt charged into the reaction vessel is too low, unreacted TiCl ₄ gas is discharged out of the tank. Further, a gas of lower titanium chloride such as TiCl ₃ and TiCl ₂ is generated and dissolved in the molten salt, Ti is generated by reaction with Ca generated by electrolysis in the electrolytic cell, and is deposited on the cathode surface for operation. May cause trouble. In addition, the occurrence of TiC that causes C contamination of Ti is also a concern.

  On the other hand, when the Ca concentration of the molten salt is too high, a large amount of Ca is contained in the molten salt withdrawn from the reaction vessel, and Ca is evaporated in the separation step, resulting in a loss.

  In addition, when the molten salt after Ti is separated in the separation step is returned to the electrolytic cell, so-called back reaction occurs in which Ca in the molten salt reacts with chlorine generated by electrolysis, resulting in a decrease in current efficiency. However, when the Ca concentration in the molten salt is high, the current efficiency is greatly lowered due to the back reaction. Furthermore, the reaction heat accompanying the back reaction may disturb the temperature uniformity of the molten salt (bath salt) in the electrolytic cell, which may hinder the temperature control of the bath salt.

  Therefore, the present inventors suppress fluctuations in the Ca concentration of the molten salt charged into the reaction vessel and maintain it at a high concentration, and quickly recover the Ca in the molten salt sent to the electrolytic cell to obtain the Ca. Various studies were made to eliminate this and suppress back reaction.

As a result, while the molten salt sent to the electrolytic cell is brought into contact with a molten alloy containing Ca (molten Mg—Ca alloy), the electrode rod on the molten alloy side becomes the negative electrode and the electrode rod on the molten salt side becomes the positive electrode. It was found that by applying a voltage in this manner and making the applied voltage less than the decomposition voltage of CaCl ₂ , Ca dissolved in the molten salt can be quickly absorbed and recovered by the molten alloy. Thereby, the Ca concentration in the molten salt sent to the electrolytic cell can be reduced, the back reaction at the time of electrolysis of the molten salt can be suppressed, and Ca can be generated efficiently.

Also, when the polarity is reversed and a voltage lower than the decomposition voltage of CaCl ₂ is applied so that the electrode rod on the molten alloy side becomes a positive electrode and the electrode rod on the molten salt side becomes a negative electrode, Ca is released from the molten alloy side. Since it moves to the molten salt side, the molten alloy is integrated as a common component, and the molten salt is brought into contact with the molten alloy, while one molten salt side electrode rod becomes a positive electrode, and the other molten salt side electrode When a voltage (voltage less than the decomposition voltage of CaCl ₂ ) was applied so that the rod became a negative pole, absorption by the molten alloy of Ca dissolved in the one molten salt, and melting of the other from the molten alloy side It was found that Ca can be transferred to the salt side simultaneously. That is, removal of Ca dissolved in one molten salt and high concentration of Ca dissolved in the other molten salt can be simultaneously and rapidly advanced by applying a predetermined voltage.

  On the other hand, in order to suppress the fluctuation of the Ca concentration of the molten salt charged into the reaction vessel and maintain it at a high concentration, an adjustment vessel equipped with a Ca supply source is installed between the electrolytic vessel and the reaction vessel, and Ca is obtained by electrolysis. It was found that it is effective to use it for reduction after introducing molten salt with increased Ca concentration into the adjustment tank to make the Ca concentration constant. Thereby, Ca concentration of molten salt can always be maintained at a constant high concentration, and the reduction reaction can proceed efficiently. It has also been found that a molten alloy in which a voltage is applied to the molten salt to absorb Ca and the Ca concentration is increased can be used as a Ca supply source of the adjustment tank.

Furthermore, as a result of detailed investigations on the shape of the electrolytic cell container of the main electrolytic cell, the electrode shape, the electrolysis conditions, the distance between the electrodes, etc., the inventors have found that the molten salt flows in one direction near the cathode surface while flowing electricity. By recovering the molten salt that has decomposed and increased the Ca concentration on the outlet side of the electrolytic cell, the back reaction is suppressed and high current efficiency is maintained, and only the molten salt enriched in Ca is effectively taken out. In addition, it has been found that a large amount of CaCl ₂ -containing molten salt can be continuously processed, and the rate of Ca supply to the reaction vessel can be increased.

  The present invention has been made based on these findings, and the gist of the present invention is the following (1) or (2) Ti or Ti alloy production method and (3) or (4) production apparatus.

(1) A molten salt containing CaCl ₂ and dissolved in Ca is held in a reaction vessel, and a metal chloride containing TiCl ₄ is reacted with Ca in the molten salt to cause Ti particles or Ti alloy in the molten salt. A reduction step for generating particles, a separation step for separating the Ti particles or Ti alloy particles from the molten salt in the reaction vessel or outside the reaction vessel, and electrolyzing the molten salt extracted outside the reaction vessel. An electrolysis step for increasing the Ca concentration of the molten salt by generating Ca, a return step for introducing Ca generated by the electrolysis alone or together with the molten salt into the reaction vessel, and the separation step and the separation step. Less than the decomposition voltage of CaCl ₂ so that the molten salt sent to the electrolysis process is in contact with a molten alloy containing Ca and Mg, so that the electrode rod on the molten alloy side becomes the negative electrode and the electrode rod on the molten salt side becomes the positive electrode Apply a voltage of Method for producing Ti or Ti alloy of Ca dissolved in the molten salt is taken up in the molten alloy, containing Ca recovery step of sending a molten salt Ca concentration was reduced to electrolysis step by.

(2) A molten salt containing CaCl ₂ and dissolved in Ca is held in a reaction vessel, and a metal chloride containing TiCl ₄ is reacted with Ca in the molten salt to cause Ti particles or Ti alloy in the molten salt. A reduction step for generating particles, a separation step for separating the Ti particles or Ti alloy particles from the molten salt in the reaction vessel or outside the reaction vessel, and electrolyzing the molten salt extracted outside the reaction vessel. An electrolysis step for increasing the Ca concentration of the molten salt by generating Ca, a return step for introducing Ca generated by the electrolysis alone or together with the molten salt into the reaction vessel, and the separation step and the separation step. The molten salt side electrode plate in the Ca removal region in the Ca removal region holding the molten salt sent to the electrolysis step is separated from this region, and the molten salt side electrode in the Ca concentration region holding the molten salt sent to the reduction step + Against the plate By applying a voltage lower than the decomposition voltage of CaCl ₂ so as to be a pole, the molten salt in the Ca removal region where the Ca concentration is reduced is sent to the electrolysis process, and the Ca concentration in the Ca concentration region where the Ca concentration is increased A method for producing Ti or a Ti alloy including a Ca removal concentration step of sending molten salt to a reduction step.

Here, the “molten salt containing CaCl ₂ ” is a molten salt containing only molten CaCl ₂ or a molten salt obtained by adding CaF ₂ or the like to the molten CaCl ₂ in order to lower the melting point or adjust the viscosity. Hereinafter, it is also simply referred to as “molten salt” or “molten CaCl ₂ ”.

By "metal chloride containing TiCl _4", only TiCl _4, or, say TiCl _4, V, Al, Cr or the like, a mixture of chlorides of other metals to be added as an alloying element Ti. The other metal chlorides are also reduced by the simultaneous Ca and reduction of TiCl _4, by the use of metal chlorides comprising TiCl ₄ as raw materials, can be produced in Ti alloy.

  In addition, the electrode for applying a voltage is set to “−electrode” and “+ electrode” as described above, which is used on the premise of electrolysis of a bath salt (here, molten salt). ) "And" cathode (cathode) "to avoid confusion.

In the manufacturing method of Ti or Ti alloy of (1) or (2), if the applied voltage is less than 3.2 V (these embodiments are referred to as “embodiment 1a” and “embodiment 1b”, respectively). ), and manages the voltage applied by the specific numerical values, the Ca dissolved in CaCl ₂ without decomposing CaCl ₂ can be rapidly absorbed into the molten alloy.

  In these (1) or (2) Ti or Ti alloy production methods (including Embodiments 1a and 1b, respectively), a molten salt whose Ca concentration has been increased in the electrolysis step is introduced into an adjustment tank having a Ca supply source. If the molten salt is brought into contact with the Ca supply source to make the Ca concentration of the molten salt constant and then sent to the reduction step (these are referred to as “embodiment 2a” and “embodiment 2b”, respectively) This is desirable because the Ca concentration of the molten salt introduced into the reaction vessel can always be maintained at a constant high concentration and the reduction reaction can proceed efficiently.

  In the manufacturing method of the embodiment 2a, if the molten alloy in which the Ca concentration is increased by absorbing Ca in the Ca recovery step is used as a Ca supply source or a part of the adjustment tank ( This is referred to as “Embodiment 3”, and it is desirable that Ca removed in order to suppress back reaction can be used effectively.

(3) To hold a molten salt containing CaCl ₂ and in which Ca is dissolved, and reacting a metal chloride containing TiCl ₄ supplied into the molten salt with the Ca to generate Ti grains or Ti alloy grains. Holding the molten salt after the Ti particles or Ti alloy particles are separated, the separation means for separating the Ti particles or Ti alloy particles generated in the molten salt from the molten salt, An electrolytic cell comprising an anode and a cathode, for electrolysis in the molten salt to generate Ca on the cathode side, and Ca produced by the electrolysis alone or together with the molten salt is introduced into the reaction vessel While the molten salt separated by the return means and sent to the electrolytic cell is brought into contact with the molten alloy containing Ca and Mg, the electrode rod on the molten alloy side is negative and the electrode rod on the molten salt side is + electrode and so as to lower than the decomposition voltage of CaCl ₂ Voltage is applied to thereby absorb the Ca dissolved in the molten salt in the molten alloy, apparatus for producing Ti or Ti alloy and a Ca recovery means for sending a molten salt Ca concentration was reduced to the electrolytic cell.

(4) To hold a molten salt containing CaCl ₂ and dissolved in Ca, and reacting a metal chloride containing TiCl ₄ supplied into the molten salt with the Ca to generate Ti grains or Ti alloy grains. Holding the molten salt after the Ti particles or Ti alloy particles are separated, the separation means for separating the Ti particles or Ti alloy particles generated in the molten salt from the molten salt, An electrolytic cell comprising an anode and a cathode, for electrolysis in the molten salt to generate Ca on the cathode side, and Ca produced by the electrolysis alone or together with the molten salt is introduced into the reaction vessel A return means, a Ca removal region that holds the molten salt separated in the separation step and sent to the electrolysis step, a Ca concentration region that is separated from this region and holds the molten salt sent to the reduction step, Molten salt in the Ca concentration region Melting in the Ca removal region where the concentration of Ca is reduced by applying a voltage less than the decomposition voltage of CaCl ₂ so that the molten salt side electrode plate in the Ca removal region becomes a positive electrode with respect to the electrode plate on the side. An apparatus for producing Ti or a Ti alloy having a Ca removing and concentrating device for sending salt to an electrolysis process and sending molten salt in a Ca concentration region where Ca is concentrated to the reduction process.

  These (3) or (4) Ti or Ti alloy production apparatus further includes a Ca supply source, and introduces the molten salt in the electrolytic cell to bring it into contact with the Ca supply source. If the concentration tank is made constant and an adjustment tank for introducing the molten salt into the reaction vessel is provided (these are referred to as “embodiment 4a” and “embodiment 4b”, respectively), the embodiment 2a , And can be suitably used for carrying out the production method of Embodiment 2b.

  Moreover, in the manufacturing apparatus of the said Embodiment 4a, if the molten alloy by which Ca density | concentration was raised by the said Ca collection | recovery means is used as a Ca supply source of the said adjustment tank, or its part (this is " Embodiment 5 ”) is suitable for carrying out the manufacturing method of Embodiment 3.

According to the method for producing Ti or Ti alloy of the present invention, Ca dissolved in the molten salt is quickly removed (recovered), and the back reaction at the time of electrolysis of the molten salt is suppressed, and the Ca generation is highly efficient. Can be achieved. Furthermore, at the same time that Ca is removed (recovered), the Ca concentration of the molten salt sent to the reduction step can be increased to contribute to the efficiency of the reduction reaction of TiCl ₄ in addition to the increase in the efficiency of Ca generation.

Further, to suppress the fluctuation of Ca concentration of molten salt charged to the reaction vessel using an adjusting tank having a Ca supply source and to maintain a high concentration, it is possible to perform efficiently the reduction reaction of TiCl _4, Furthermore, it is possible to continuously process a large amount of the CaCl ₂ -containing molten salt in the electrolysis process to increase the supply rate of Ca to the reaction vessel.

  Therefore, according to the method for producing Ti or Ti alloy of the present invention, efficient and stable operation is possible on an industrial scale. Moreover, this method can be easily and suitably implemented by the production apparatus of the present invention.

First, the Ti or Ti alloy manufacturing method described in (1) and the manufacturing apparatus described in (3) will be specifically described with reference to the drawings. In the description, the case where only TiCl ₄ is used as a raw material will be described.

  FIG. 1 is a diagram illustrating a schematic configuration example of an apparatus used when the Ti or Ti alloy manufacturing method described in (1) is performed.

As shown in FIG. 1, this apparatus holds a molten salt containing CaCl ₂ and dissolved in Ca, and reacts TiCl ₄ supplied in the molten salt with the Ca to generate Ti grains. Reaction vessel 1, separation means 2 for separating Ti particles generated in the molten salt from the molten salt, and electrolysis of the molten salt after the Ti particles are separated to generate Ca on the cathode side An electrolytic cell 3 to be dissolved, a return unit 4 for introducing Ca generated by electrolysis into the reaction vessel 1, and a Ca dissolved in a molten salt separated by the separating unit and sent to the electrolytic cell And Ca recovery means 5 for removing.

  The Ca recovery means 5 illustrated in FIG. 1 shows the main part thereof, and a molten salt 7 separated by the separation means 2 is introduced into a Ca recovery tank 6, and a molten alloy containing Ca and Mg thereon ( (Molten Mg—Ca alloy) or simply “molten alloy”) 8 is held. The electrode rod 9 inserted into the molten salt 7 constitutes a positive electrode, and the electrode rod 10 inserted into the molten Mg—Ca alloy 8 constitutes a negative electrode.

The electrolytic cell 3 is disposed in the vessel 3a along a longitudinal direction of the electrolytic cell vessel 3a, which is a pipe (cylindrical) shape that is long in one direction holding a molten salt containing CaCl ₂ . Similarly, a cylindrical anode 11 and a columnar cathode 12 are provided, and a molten salt supply port 14 is provided at one end (bottom plate 13) in the longitudinal direction of the electrolytic cell container 3a, and the other end (upper cover). 15) is provided with a molten salt outlet 16. The surface of the anode 11 and the surface of the cathode 12 face each other in a substantially vertical direction, and a diaphragm 17 is provided between the anode 11 and the cathode 12 for suppressing the passage of Ca generated by electrolysis of the molten salt. Yes. A cooler 18 is attached to the outer surface of the anode 11.

  Further, in the apparatus shown in FIG. 1, a decanter type centrifugal sedimentator (high temperature decanter) 19 and a separation tank 20 are used as the separation means 2.

In order to carry out the method for producing Ti or Ti alloy described in the above (1) using the apparatus shown in FIG. 1, first, the molten salt supplied from the electrolytic cell 3 through the return means 4 is reacted. held in the container 1, the Ca in the molten salt, by reacting TiCl ₄ was supplied from the TiCl ₄ feed port 21, to produce the Ti particles in the molten salt. That is, the “reduction process”.

In this reduction step, the molten salt is not held in the reaction vessel 1 in a stationary state, but is held while gradually flowing down from the upper side of the reaction vessel 1, while TiCl _{4 as} a raw material is melted. Ti particles are produced by reduction by Ca in the salt. When metal chlorides containing TiCl ₄ (for example, chlorides of V, Al, Cr, etc.) are used as raw materials, these metal chlorides are also reduced by Ca as described above, so TiCl ₄ Ti alloy grains can be produced by adding a predetermined amount of metal chloride in advance to finally produce a Ti alloy.

  Ti particles generated in the reduction step are separated from the molten salt in a “separation step”.

  Separation of the Ti particles from the molten salt can be performed in the reaction vessel by using an appropriate reaction vessel, but in that case, a batch system is used. Therefore, in order to increase the productivity, for example, a molten salt in which Ca is dissolved is continuously supplied using the reaction vessel of the type shown in FIG. 1, and the generated Ti particles are extracted out of the reaction vessel. Separation from the molten salt is preferably performed outside.

  In the separation step, when the apparatus shown in FIG. 1 is used, first, the Ti particles are separated and recovered from the molten salt by the high-temperature decanter 19, and then the molten salt adhering to the Ti particles is removed by the separation tank 20.

  The decanter type centrifugal settling machine is a type of centrifugal separator in which suspended substances are centrifuged by rotating a rotating cylinder at a high speed, which enables high speed processing and high dehydration performance. A type capable of high temperature treatment has also been developed, and can be applied as a high temperature decanter 19 in this separation step.

  The Ti particles extracted from the high-temperature decanter 19 are heated and melted by the plasma irradiated from the plasma torch 22 in the separation tank 20, poured into the mold 23, and become a Ti ingot 24.

  On the other hand, there is a possibility that fine particles of Ti are mixed in the molten salt separated from the Ti particles (this is referred to as “adhesive molten salt”). For this reason, there is a possibility that a problem may occur when the adhering molten salt is returned to the electrolysis process. Therefore, as shown in FIG. In addition, since Ca remains in the adhering molten salt to some extent, it is reasonable to return it to the reaction vessel 1 from the viewpoint of effective utilization of Ca.

The molten salt having a reduced Ca concentration separated by the high temperature decanter 19 is sent to the “Ca recovery step”. That is, while the molten salt is introduced into the Ca recovery tank 6 and brought into contact with the molten Mg—Ca alloy 8, the voltage is set so that the electrode rod on the molten alloy side becomes the negative electrode and the electrode rod on the molten salt side becomes the positive electrode. Apply. The applied voltage at this time is less than the decomposition voltage of CaCl ₂ . Thus, without disassembling the CaCl _2, to absorb the Ca dissolved in CaCl ₂ promptly molten alloy, Ca concentration becomes possible to send to the rapid electrolysis step the molten salt decreased. Since the Ca concentration in the molten salt is reduced, back reaction is suppressed.

  As an electrode for applying the voltage, it is preferable to use a metal such as iron for the negative electrode and an insoluble electrode such as a graphite electrode for the positive electrode.

FIG. 2 is a diagram schematically showing the relationship between the voltage applied between the molten alloy and the molten salt and the current flowing between the two electrodes, as a result of examination by the inventors. (A) is a case where Ca is not contained in CaCl ₂ (before addition of Ca), and (b) is a case where Ca is contained (after addition of Ca).

As shown in the figure, when Ca is not included, no current flows even when the applied voltage is increased (see FIG. 2A). However, when Ca is added, a minute current starts to flow even if a slight voltage is applied, and a substantially constant current (this is expressed as “a” which is applied until the applied voltage reaches near the decomposition voltage Vb (3.2 V) of CaCl _2. Current)). When the voltage is further increased, the current value increases rapidly because CaCl ₂ is electrolyzed (FIG. 2B).

The limit current is due to the transition of Ca from the molten salt side (+ pole side) to the molten alloy side (− pole side) (that is, Ca dissolved in CaCl ₂ is absorbed by the molten alloy). The magnitude depends on the concentration of Ca dissolved in CaCl ₂ , and the limit current decreases as the Ca concentration decreases.

According to the examination results of the present inventors, when the limiting current density was 0.14 A / cm ² , the Ca concentration was about 0.01% by mass.

  As described above, the limit current decreases as the Ca concentration of the molten salt decreases, so in order to rapidly decrease the Ca concentration and increase the Ca removal (recovery) efficiency, the Ca recovery tank is enlarged and melted. It is desirable to increase the contact area between the salt 7 and the molten Mg—Ca alloy 8.

The manufacturing method of the embodiment 1a is the same as the manufacturing method of the Ti or Ti alloy of the present invention described in the above (1), wherein “the applied voltage is less than 3.2 V (that is, a voltage lower than the decomposition voltage of CaCl ₂ ). )] Is a method of removing Ca. The applied voltage is managed with specific numerical values, and without causing decomposition of CaCl ₂ , a potential difference is applied between the molten salt side electrode rod and the molten alloy side electrode rod to quickly absorb Ca into the molten alloy. it can. Even if the applied voltage is small, there is an effect of removing Ca, so the lower limit is not limited. However, in order to effectively remove Ca, it is desirable that the applied voltage be 0.01 V or more.

  The molten salt in which the Ca concentration is reduced in the Ca recovery step is sent to the “electrolysis step”, electrolyzed to generate Ca, and the Ca concentration of the molten salt is increased.

  That is, as shown in FIG. 1, first, molten salt is put between the cathode 12 and the diaphragm 17 of the electrolytic cell 3 and held. Since the electrolytic cell 3 has a shape that is long in one direction (in the illustrated example, a vertically elongated pipe (cylindrical shape)), the molten salt is continuously provided between the anode 11 and the cathode 12 from one end of the electrolytic cell 3. By supplying periodically or intermittently, a flow rate in one direction is given to the molten salt near the surface of the cathode 12, and the molten salt can flow in one direction near the surface of the cathode 12. Although the supply of the molten salt is normally performed continuously, the supply of the molten salt may be intermittently stopped, that is, the supply of the molten salt may be temporarily stopped or continued again.

  Subsequently, the molten salt is electrolyzed. The molten salt is electrolyzed while flowing in the vicinity of the surface of the cathode 12 to generate Ca on the surface of the cathode. The electrolytic cell 3 has a long shape in one direction, and is further shown in FIG. In the example, since the distance between the anode 11 and the cathode 12 is made relatively small in order to keep the electrolysis voltage low, the molten salt in the vicinity of the molten salt supply port 14 with a low Ca concentration and the molten salt with an increased Ca concentration by electrolysis are used. Mixing with the molten salt in the vicinity of the extraction port 16 can be prevented, and only the molten salt enriched with Ca can be effectively extracted.

In addition, in the electrolytic cell illustrated in FIG. 1, CaCl ₂ is supplied into the tank 3 from below the electrolytic cell 3 and extracted from above, but conversely, it is supplied from above the electrolytic cell 3 and below. It is also possible to adopt a method of extracting from the.

  In the electrolytic cell used in this method, the anode surface and the cathode surface face each other in a substantially vertical direction, while the molten salt in the vicinity of the cathode surface is given a flow rate in one direction. The flow direction is vertical, and the chlorine gas generated on the anode side floats easily and is easy to recover.

  When electrolyzing the molten salt using this electrolytic cell, a large amount of molten salt is continuously processed, so it is desirable to effectively remove heat in the electrolytic cell. Specifically, for example, it is desirable to install a cooler in the center of the cathode and extract the reaction heat from the inside of the cathode. As the cooler, for example, a tubular heat exchanger is suitable.

  If a cooler (heat exchanger) is also installed on the anode side, the heat removal efficiency is further increased. In the electrolytic cell shown in FIG. 1, the cooler 18 installed so as to surround the anode 11 is this example.

  Ca produced by electrolysis in the electrolysis step is introduced into the reaction vessel alone or together with the molten salt through a “returning step”.

  When the apparatus shown in FIG. 1 is used, a molten salt with an increased Ca concentration is obtained in the electrolytic cell, so Ca is introduced into the reaction vessel through a returning step together with the molten salt.

  However, an electrolytic cell having a configuration capable of recovering Ca generated by electrolyzing the molten salt as it is, that is, including Ca alone (including a state where a very small amount of molten salt is mixed in Ca) is used. For example, in the method for producing Ti or Ti alloy of (1), it is possible to adopt an embodiment in which Ca generated by electrolysis is dissolved in a molten salt and introduced into a reaction vessel. That is, in the returning step, without using molten salt as a Ca transfer medium, the generated Ca is transferred as it is to the vicinity of the reaction vessel, and is then dissolved in a separately prepared molten salt and introduced into the reaction vessel. Therefore, reduction of the cost required for transfer can be expected.

Furthermore, if a reaction vessel capable of allowing the produced Ca to enter the reaction vessel as it is and reacting with TiCl ₄ is used, an embodiment in which Ca is introduced into the reaction vessel alone can be employed. is there.

  FIG. 3 is a diagram illustrating a schematic configuration example of an apparatus used when performing the method of Embodiment 2a or Embodiment 3 in the method of manufacturing Ti or Ti alloy described in (1).

  In this apparatus shown in FIG. 1, the molten salt in the electrolytic cell 3 is further introduced and brought into contact with a Ca supply source to make the Ca concentration of the molten salt constant. It is an apparatus provided with an adjustment tank 25 for charging into the reaction vessel 1.

  The manufacturing method of Embodiment 2a is the same as the manufacturing method of Ti or Ti alloy according to the present invention described in (1) (including Embodiment 1a). The molten salt is introduced into an adjustment tank having a source and brought into contact with the Ca supply source to make the Ca concentration of the molten salt constant and then sent to the reduction step.

  If the apparatus shown in FIG. 3 is used, the molten salt enriched in Ca extracted from the electrolytic cell 3 is introduced into the adjusting tank 25 and brought into contact with the Ca supply source 26, whereby the Ca of the molten salt 27 is obtained. After making the concentration constant, the reaction vessel 1 can be charged. That is, it is a method in which the processing in the adjustment tank 25 is incorporated in the return process.

The Ca concentration of the molten salt in which Ca is concentrated in the electrolysis process varies with slight variations in the electrolysis conditions in the electrolytic cell 3. For this reason, when the molten salt subjected to the electrolytic treatment in the electrolytic cell 3 is directly charged into the reaction vessel 1, the Ca concentration is not always kept constant. Therefore, as described above, the current efficiency due to the generation of lower titanium chloride and the back reaction. May occur, and the efficiency of the reduction reaction of TiCl ₄ may be reduced, making it difficult to perform stable operation.

Therefore, by introducing the molten salt whose Ca concentration is increased using the electrolytic cell 3 in the electrolysis step into the adjustment tank 25 having the Ca supply source 26 and bringing it into contact with the Ca supply source 26, the Ca concentration of the molten salt Then, it is used for the reduction of TiCl _{4 in} the reduction step.

  In addition, since the adhesion molten salt separated from the Ti particles in the separation tank 20 is very small compared to the flow rate of the molten salt introduced from the electrolytic tank 3 to the reaction vessel 1 through the adjustment tank 25, the above-mentioned As described above, the reaction vessel 1 may be directly returned. However, as shown in FIG. 3, it is desirable to introduce the reaction vessel 1 after introducing it into the adjustment tank 25 to make the Ca concentration constant.

  As the Ca supply source 26, a molten alloy containing a relatively high content of Ca such as molten metal Ca or molten Mg-Ca alloy can be used.

  That is, the Ca concentration is increased, and molten metal Ca or molten Mg—Ca alloy or the like is suspended on the molten salt 27 introduced into the adjustment tank 25, and the Ca supply source 26 and the molten salt 27 are brought into contact with each other. Keep it. Thereby, if the Ca concentration of the molten salt 27 is less than its saturation solubility, Ca can be supplied from the Ca supply source 26 to the molten salt 27 and the Ca concentration can be maintained at a concentration near the saturation solubility. Further, when the Ca concentration of the molten salt 27 is the saturation solubility and the precipitated metal Ca is also present, the metal Ca floats and separates due to the specific gravity difference in the adjustment tank 25, and the Ca concentration is near the saturation solubility. The concentration can be kept. Furthermore, if the temperature of the molten salt 27 at the time of extracting from the adjustment tank 25 is controlled to be constant, the Ca concentration can be controlled to a constant concentration near the saturation solubility at that temperature.

Therefore, regardless of whether the Ca concentration of the molten salt in which Ca is concentrated in the electrolytic cell 3 is the saturation solubility or less, the molten salt extracted from the electrolytic cell 3 by installing the adjusting tank 25. By introducing the molten salt, a molten salt having a Ca concentration in the vicinity of its saturation solubility is charged into the reaction vessel 1 so that the reduction reaction of TiCl ₄ can be performed efficiently and stable operation can be performed.

  However, if electrolysis is performed in the electrolytic cell 3 until the Ca concentration exceeds the saturation solubility, the metallic Ca is deposited inside the electrolytic cell 3 and may cause troubles such as blockage of the electrolytic cell. Therefore, when increasing the Ca concentration in the electrolytic cell 3, electrolysis is performed while controlling to increase the Ca concentration until immediately before the saturation solubility, and a molten salt having a high concentration of Ca but less than the saturation solubility is adjusted. It is desirable to perform an operation that is introduced into the tank 25 and brought into contact with the Ca supply source 26 so that the Ca concentration is a constant concentration in the vicinity of the saturation solubility.

  The manufacturing method of the third embodiment is a method of defining the Ca supply source of the adjustment tank used in the method of the second embodiment, and “a molten alloy in which the Ca concentration is increased by absorbing Ca in the Ca recovery step. , Used as a Ca supply source of the adjustment tank or a part thereof.

  That is, as shown in FIG. 3, the molten alloy 8 in which the Ca concentration is increased by absorbing Ca in the Ca recovery step (Ca recovery means 5) is transferred to the adjustment tank 25 and used as the Ca supply source 26. The whole of the Ca supply source 26 may be a molten alloy transferred from the Ca recovery process, or may be used as a part of the Ca supply source 26 when the amount is small. In any case, the Ca removed from the molten salt separated by the high-temperature decanter 19 and sent to the electrolysis process to suppress back reaction can be used effectively.

  In the production methods of Embodiment 2a and Embodiment 3 as well, an embodiment in which Ca generated by the above-described electrolysis is dissolved in a molten salt and introduced into the reaction vessel, or Ca alone is introduced into the reaction vessel. The embodiment to introduce can be taken.

  The Ti or Ti alloy manufacturing apparatus described in (3) is an apparatus used when the Ti or Ti alloy manufacturing method described in (1) is performed, and the schematic configuration thereof is shown in FIG. As shown. The operation of each part is also as described above, and if this apparatus is used, the Ti or Ti alloy manufacturing method (including Embodiment 1a) described in (1) above can be suitably implemented.

  The manufacturing apparatus of the said Embodiment 4a and Embodiment 5 is another embodiment of the manufacturing apparatus as described in said (3), and is an apparatus provided with the adjustment tank in the return process, as shown in FIG. As described above, this apparatus is suitable for carrying out the Ti or Ti alloy manufacturing method according to Embodiments 2a and 3.

Next, the Ti or Ti alloy manufacturing method described in (2) and the manufacturing apparatus described in (4) will be described. Here, the case where only TiCl ₄ is used as a raw material will be described.

  FIG. 4 is a diagram showing a schematic configuration of an apparatus used when the Ti or Ti alloy manufacturing method described in (2) is performed.

  This apparatus is an apparatus in which a Ca removal and concentration apparatus is installed in place of the Ca recovery means in the apparatus shown in FIG. 1, and the transfer path of the molten salt is changed accordingly.

That is, as shown in FIG. 4, a reaction vessel for holding a molten salt containing CaCl ₂ and dissolving Ca and reacting TiCl ₄ supplied into the molten salt with the Ca to produce Ti particles. 1, separation means 2 for separating Ti particles generated in the molten salt from the molten salt, and electrolysis of the molten salt after the Ti particles are separated to generate Ca on the cathode side The electrolytic cell 3, the return means 4 for introducing Ca generated by electrolysis into the reaction vessel 1, and the molten salt separated by the separating means (high temperature decanter) and sent to the electrolytic cell 3 And a Ca removing and concentrating device 28 for increasing the concentration of Ca dissolved in the molten salt separated by a separating means (separating tank) and introduced into the reaction vessel 1 at the same time. Yes.

The Ca removal / concentration device 28 is shown in its main part, and has a Ca removal / concentration tank 28a. In this tank 28a, molten CaCl ₂ is divided into a Ca concentration area 29 and a Ca removal area 30 by a partition wall 31. The molten Mg—Ca alloy 32 is held in contact with the molten salt held in the Ca concentration region 29 and the Ca removal region 30.

Furthermore, an electrode plate 33 for applying a voltage lower than the decomposition voltage of CaCl ₂ is a positive electrode at the bottom of the Ca removal region 30 with respect to the molten salt side electrode plate 34 in the Ca concentration region 29. Is provided. In the illustrated example, the Ca enrichment region 29 and the Ca removal region 30 are separated by the partition wall 31, but are not necessarily limited thereto. For example, both regions may be separated by separate tanks that can be individually removed.

When performing the manufacturing method of Ti or Ti alloy according to (2) using the apparatus shown in FIG. 4, operations in the “reduction process”, “separation process”, “electrolysis process”, and “return process” Is basically the same as the case where the manufacturing method described in (1) above is carried out using the apparatus shown in FIG. The same applies to the fact that if a metal chloride containing TiCl ₄ is used as a raw material, a Ti alloy can be finally produced.

  What is different from the case of using the apparatus shown in FIG. 1 is the destination of the molten salt separated from the Ti grains in the separation step and the treatment there. That is, as shown in FIG. 4, the molten salt having a reduced Ca concentration separated by the high temperature decanter 19 passes through the route La, and the Ca removal region 30 of the Ca removal concentration tank 28a provided in the Ca removal concentration tank 28 is provided. On the other hand, the adhering molten salt separated from the Ti grains in the separation tank 22 is sent to the Ca concentration region 29 of the Ca removal concentration tank 28a via the path Lb.

Here, the electrode plate 33 is arranged so that the electrode plate 33 provided on the molten salt side in the Ca removal region 30 becomes a positive electrode with respect to the electrode plate 34 provided on the molten salt side in the Ca concentration region 29. A voltage lower than the decomposition voltage of CaCl ₂ is applied through the electrode plate 34.

  By applying this voltage, the molten Mg—Ca alloy 32 existing in the vicinity of the contact portion with the molten salt in the Ca removal region 30 is relatively in relation to the molten salt side (+ polar side) in the Ca removal region 30. -Since it functions as a pole, dissolved Ca moves to the molten Mg-Ca alloy 32 side and is absorbed as indicated by an arrow in the Ca removal and concentration tank 28a of FIG. As a result, the dissolved Ca in the Ca removal region 30 is removed, and the Ca concentration of the Mg—Ca alloy 32 increases.

  On the other hand, the molten Mg—Ca alloy 32 in the vicinity of the contact portion with the molten salt in the Ca concentrated region 29 functions as a positive electrode relative to the molten salt side (−polar side) in the Ca concentrated region 29. Therefore, Ca in the molten Mg—Ca alloy 32 moves to the molten salt side in the Ca concentrated region 29 and the Ca concentration in the Ca concentrated region 29 increases.

Thus, by applying a voltage lower than the decomposition voltage of CaCl ₂ to the electrode plate 33 in the Ca removal and concentration tank 28a, the dissolved Ca in the Ca removal region 30 is removed and at the same time, the dissolved Ca in the Ca concentration region 29 is removed. The concentration of can be increased. In addition, if the Ca removing and concentrating device 28 having the main configuration shown in FIG. 4 is used, this simultaneous processing can be easily performed using a very simple device with respect to any shape and configuration.

The reason why the applied voltage is less than the decomposition voltage of CaCl ₂ is to avoid the generation of Ca due to decomposition of CaCl ₂ .

  As the electrode for applying the voltage, as in the case of the electrode rod attached to the Ca recovery tank 6 (FIGS. 1 and 3) described above, the negative electrode is a metal such as iron, and the positive electrode is a graphite electrode or the like. It is preferable to use an insoluble electrode.

  In the Ca removal and concentration device 28, the Ca removal and concentration process is performed in this manner, Ca dissolved in the molten salt in the Ca removal region 30 is removed, and the Ca concentration of the molten salt in the Ca concentration region 29 is removed. Rises.

  The path Lc provided between the path La and the path Lb is a path for achieving a quantitative balance between the molten salt in the Ca removal region 30 and the molten salt in the Ca concentration region 29. That is, the amount of the molten salt separated by the high-temperature decanter 19 is overwhelmingly larger than the amount of the adhered molten salt separated by the separation tank 22, so that the melting in the Ca removal region 30 is performed only by the route La and the route Lb. The balance between the amount of salt and the amount of molten salt in the Ca concentration region 29 cannot be achieved, and the Ca removal and concentration apparatus 1 cannot continuously perform the removal and concentration of Ca. Therefore, a part of the molten salt separated by the high temperature decanter 19 is sent to the Ca concentration region 29 through the path Lc, and the process is continuously performed.

  The molten salt from which Ca has been removed by the Ca removing and concentrating device 1 is sent to the “electrolysis step”. However, since Ca has been removed, so-called back reaction occurs in which Ca in the molten salt reacts with chlorine generated by electrolysis. It is suppressed and Ca can be generated efficiently by electrolysis.

In addition, the molten salt in the Ca concentration region 29 is returned to the reduction process, but the Ca remaining in the adhered molten salt is increased in concentration and the Ca concentration is increased, so that the efficiency of the TiCl ₄ reduction reaction is increased. It is effective for.

  Ca produced by electrolysis in the electrolysis step is introduced into the reaction vessel alone or together with the molten salt through a “returning step”.

The manufacturing method of the embodiment 1b is the same as the manufacturing method of Ti or Ti alloy described in (2), except that the applied voltage is less than 3.2 V (that is, the decomposition voltage of CaCl ₂ ). This is a method of increasing the concentration of dissolved Ca in the Ca enriched region 29 at the same time as removing dissolved Ca in the Ca removed region 30. As in the case of the manufacturing method of Embodiment 1a, the lower limit of the applied voltage is not limited. However, in order to effectively remove Ca, it is desirable that the applied voltage be 0.01 V or more.

  FIG. 5 is a diagram showing a schematic configuration example of an apparatus used when performing the method of Embodiment 2b in the method of manufacturing Ti or Ti alloy described in (2).

  In this apparatus shown in FIG. 4, the molten salt in the electrolytic cell 3 is further introduced and brought into contact with a Ca supply source to make the Ca concentration of the molten salt constant. It is an apparatus provided with an adjustment tank 25 for charging into the reaction vessel 1.

  The manufacturing method of Embodiment 2b is the same as the manufacturing method of Ti or Ti alloy described in (2) (including Embodiment 1b), “The molten salt having a Ca concentration increased in the electrolysis step has a Ca supply source. This is a method in which the molten salt is brought into contact with a Ca supply source after being introduced into a regulating tank, and the Ca concentration of the molten salt is made constant and then sent to the reduction step.

  The manufacturing method of Embodiment 2b can be easily implemented by using the apparatus shown in FIG. 5 as described with reference to FIG. 3 for the manufacturing method of Embodiment 2a.

  In addition, in the manufacturing method of Ti or Ti alloy described in (2) (including Embodiment 1b) and the manufacturing method of Embodiment 2b, as in the case of the manufacturing method described in (1) above, An embodiment in which Ca produced by decomposition is dissolved in a molten salt and introduced into the reaction vessel, or an embodiment in which Ca is introduced alone into the reaction vessel can be employed.

  The Ti or Ti alloy production apparatus described in (4) above is an apparatus used when the Ti or Ti alloy production method described in (2) above is carried out. This is as shown in FIG. If this apparatus is used, the manufacturing method (including Embodiment 1b) of Ti or Ti alloy described in the above (2) can be suitably carried out.

  The manufacturing apparatus of the embodiment 4b is another embodiment of the manufacturing apparatus described in (4), and includes an adjustment tank in the return process as shown in FIG. As described above, this apparatus is suitable for implementing the Ti or Ti alloy manufacturing method according to Embodiment 2b.

When the Ti or Ti alloy production method described above (including Embodiments 1a, 1b, 2a, 2b and 3) is carried out, a chlorination step is added, and TiCl ₄ produced in the reaction vessel is used as a raw material. The embodiment used for the production reaction of can be taken.

That is, in the electrolysis process described above, chlorine (Cl ₂ ) is by-produced on the anode side as the molten salt is electrolyzed, but this Cl ₂ reacts with titanium oxide (TiO ₂ ) to produce TiCl ₄ . , (1) or in the method for producing Ti or Ti alloy (2), the Cl ₂ to generate the anode side with the electrolysis of the molten salt by reacting a titaniferous ore to produce a TiCl _4, after purification by distillation This TiCl ₄ is used as a raw material. When manufacturing a Ti alloy, in the chlorination step, and TiO _2, and a Cl ₂ to generate the anode side to a mixture of oxides of the metal to be added as an alloying element reacted Ti to TiCl ₄ What is necessary is just to produce | generate the metal chloride containing and use this as a raw material.

By adopting such an embodiment, by effectively utilizing the Cl ₂ formed as a by-product with the electrolysis of the molten salt, in the manufacturing process, it is possible to circulate the use of Cl _2.

According to the manufacturing method of Ti or Ti alloy of the present invention, Ca dissolved in the molten salt sent to the electrolytic cell is quickly removed (recovered), and Ca generation at the time of electrolysis of the molten salt is improved. Can be achieved. Moreover, the Ca concentration of the molten salt sent to the reaction vessel is increased simultaneously with the removal (recovery) of Ca, and in addition to the high efficiency of the Ca generation, it can contribute to the efficiency of the TiCl ₄ reduction reaction, Can suppress the fluctuation | variation of Ca density | concentration of molten salt thrown into reaction container, and can maintain it at high concentration. Furthermore, it is possible to continuously process a large amount of CaCl ₂ -containing molten salt in the electrolysis process to increase the supply rate of Ca to the reaction vessel, thereby generating Ca during electrolysis of the molten salt and reducing TiCl ₄ . Can be performed efficiently, and stable operation on an industrial scale becomes possible.

  Therefore, the manufacturing method of Ti or Ti alloy of the present invention and the manufacturing apparatus of the present invention capable of easily and suitably carrying out this method can be effectively used for manufacturing Ti or Ti alloy by Ca reduction. it can.

It is a figure which shows the example of schematic structure of the manufacturing apparatus of Ti or Ti alloy of this invention. It is a figure which shows typically the relationship between the voltage applied between the molten alloy and molten salt of the Ca collection | recovery tank used by this invention, and the electric current which flows between both poles then. It is a figure which shows the other schematic structural example of the manufacturing apparatus of Ti or Ti alloy of this invention. It is a figure which shows the further another schematic structural example of the manufacturing apparatus of Ti or Ti alloy of this invention. It is a figure which shows the further another schematic structural example of the manufacturing apparatus of Ti or Ti alloy of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1: Reaction container 2: Separation means 3: Electrolysis tank 3a: Electrolysis tank container 4: Return means 5: Ca collection means 6: Ca collection tank 7: Molten salt 8: Molten alloy containing Ca and Mg (molten Mg-Ca alloy) )
9, 10: electrode rod 11: anode 12: cathode
13: Bottom plate 14: Molten salt supply port 15: Upper lid 16: Molten salt outlet
17: Diaphragm 18: Cooler 19: Decanter type centrifugal sedimentator (high temperature decanter)
20: Separation tank 21: TiCl ₄ supply port 22: Plasma torch 23: Mold 24: Ti ingot 25: Adjustment tank 26: Ca supply source 27: Molten salt 28: Ca removal concentration apparatus 28a: Ca removal concentration tank 29: Ca concentration Region 30: Ca removal region 31: Partition 32: Molten Mg-Ca alloy 33, 34: Electrode plate

Claims (9)

A molten salt containing CaCl ₂ and dissolved in Ca is held in a reaction vessel, and a metal chloride containing TiCl ₄ is reacted with Ca in the molten salt to produce Ti grains or Ti alloy grains in the molten salt. Reducing step, separating step of separating the Ti particles or Ti alloy particles from the molten salt in the reaction vessel or outside of the reaction vessel, and electrolyzing the molten salt drawn out of the reaction vessel to produce Ca By performing an electrolysis step for increasing the Ca concentration of the molten salt, a return step for introducing Ca generated by the electrolysis alone or together with the molten salt into the reaction vessel, and the separation step to the electrolysis step. While the molten salt to be fed is brought into contact with a molten alloy containing Ca and Mg, a voltage lower than the decomposition voltage of CaCl ₂ is applied so that the electrode rod on the molten alloy side becomes the negative electrode and the electrode rod on the molten salt side becomes the positive electrode. By applying The Ca dissolved in the molten salt is taken up in the molten alloy, a manufacturing method of the Ti or Ti alloy, characterized in that it comprises a Ca recovery step of sending a molten salt Ca concentration was reduced to electrolysis step. A molten salt containing CaCl ₂ and dissolved in Ca is held in a reaction vessel, and a metal chloride containing TiCl ₄ is reacted with Ca in the molten salt to produce Ti grains or Ti alloy grains in the molten salt. Reducing step, separating step of separating the Ti particles or Ti alloy particles from the molten salt in the reaction vessel or outside of the reaction vessel, and electrolyzing the molten salt drawn out of the reaction vessel to produce Ca By performing an electrolysis step for increasing the Ca concentration of the molten salt, a return step for introducing Ca generated by the electrolysis alone or together with the molten salt into the reaction vessel, and the separation step to the electrolysis step. The molten salt side electrode plate in the Ca removal region holding the molten salt to be sent is separated from this region, and the molten salt side electrode plate in the Ca concentration region holding the molten salt sent to the reduction step + Thus, by applying a voltage lower than the decomposition voltage of CaCl ₂ , the molten salt in the Ca removal region where the Ca concentration is reduced is sent to the electrolysis process, and the molten salt in the Ca concentration region where the Ca concentration is increased. The manufacturing method of Ti or Ti alloy characterized by including the Ca removal concentration process which sends A to a reduction process.   The method for producing Ti or a Ti alloy according to claim 1 or 2, wherein the applied voltage is less than 3.2V.   The molten salt whose Ca concentration has been increased in the electrolysis step is introduced into an adjustment tank having a Ca supply source, and the molten salt is brought into contact with the Ca supply source to make the Ca concentration of the molten salt constant, and then sent to the reduction step. The manufacturing method of Ti or Ti alloy in any one of Claims 1-3 characterized by the above-mentioned.   The molten alloy in which the Ca concentration is increased by absorbing Ca in the Ca recovery step is provided with a Ca supply source, and the molten salt in the electrolytic cell is introduced and brought into contact with the Ca supply source. 2. The method for producing Ti or Ti alloy according to claim 1, wherein the molten salt is used as a Ca supply source or a part thereof in an adjustment tank for charging the molten salt into the reaction vessel after the Ca concentration is constant. . A reaction vessel for holding a molten salt containing CaCl ₂ and dissolving Ca, and reacting a metal chloride containing TiCl ₄ supplied into the molten salt with the Ca to produce Ti particles or Ti alloy particles Separating means for separating the Ti particles or Ti alloy particles generated in the molten salt from the molten salt; and holding the molten salt after the Ti particles or Ti alloy particles are separated; An electrolytic cell for performing electrolysis in the molten salt to generate Ca on the cathode side, and a return means for introducing Ca generated by the electrolysis alone or together with the molten salt into the reaction vessel While the molten salt separated by the separating means and sent to the electrolytic cell is brought into contact with a molten alloy containing Ca and Mg, the electrode rod on the molten alloy side becomes the negative electrode, and the electrode rod on the molten salt side becomes the positive electrode. CaCl ₂ decomposition voltage lower than the voltage so Applying the Ca dissolved in the molten salt is taken into the molten alloy, apparatus for producing Ti or Ti alloy and having a Ca recovery means for sending a molten salt Ca concentration was reduced to the electrolytic cell. A reaction vessel for holding a molten salt containing CaCl ₂ and dissolving Ca, and reacting a metal chloride containing TiCl ₄ supplied into the molten salt with the Ca to produce Ti particles or Ti alloy particles Separating means for separating the Ti particles or Ti alloy particles generated in the molten salt from the molten salt; and holding the molten salt after the Ti particles or Ti alloy particles are separated; An electrolytic cell for performing electrolysis in the molten salt to generate Ca on the cathode side, and a return means for introducing Ca generated by the electrolysis alone or together with the molten salt into the reaction vessel A Ca removal region that holds the molten salt separated in the separation step and sent to the electrolysis step, and a Ca concentration region that is separated from this region and holds the molten salt sent to the reduction step, and is a Ca concentration region Electricity on the molten salt side The molten salt in the Ca removal region having a reduced Ca concentration by applying a voltage lower than the decomposition voltage of CaCl ₂ so that the electrode plate on the molten salt side in the Ca removal region becomes a positive electrode with respect to the electrode plate. An apparatus for producing Ti or a Ti alloy, characterized in that it has a Ca removal and concentration apparatus that sends the molten salt in the Ca concentration region where Ca is concentrated to the reduction process.   Further, a Ca supply source is provided, and the molten salt in the electrolytic cell is introduced and brought into contact with the Ca supply source to make the Ca concentration of the molten salt constant, and then the molten salt is charged into the reaction vessel. An apparatus for producing Ti or a Ti alloy according to claim 6 or 7, characterized in that said adjustment tank is provided. Further, a Ca supply source is provided, and the molten salt in the electrolytic cell is introduced and brought into contact with the Ca supply source to make the Ca concentration of the molten salt constant, and then the molten salt is charged into the reaction vessel. The molten alloy having a Ca concentration increased by the Ca recovery means is used as a Ca supply source or a part thereof in the adjustment tank. Ti alloy production equipment.

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