JP2005350749A - Method for producing titanium and titanium alloy - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing titanium and a titanium alloy, by electrolyzing metallic oxide containing titanium oxide in a molten salt so as to reduce the titanium oxide. <P>SOLUTION: This production method comprises the steps of: charging a continuum made of a metallic oxide containing titanium oxide or further mixed with metallic titanium, into the molten salt including calcium chloride; passing an electric current between the continuum of a cathode and an anode immersed in the molten salt, to reduce the metallic oxide containing titanium oxide included in the continuum; and extracting the reduced continuum from the molten salt. When the production method employs the continuum comprising a conductor substrate and the metallic oxide containing titanium oxide deposited on the surface, it provides a layer of titanium or the titanium alloy on the surface of the substrate, which has been reduced from the metallic oxide containing titanium oxide. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing titanium and a titanium alloy by directly reducing a metal oxide containing titanium oxide by immersing it in a molten salt containing calcium chloride and energizing it.

  Metallic titanium and titanium alloys have excellent properties such as corrosion resistance, light weight and high strength (ie, high specific strength), and equipment materials for chemical plants including aircraft materials, petroleum refining, and petrochemistry. It is widely used in various industrial fields as materials for heat transfer tubes, heat exchanger materials, automobile parts, medical equipment, and sports equipment.

In the production of titanium metal, titanium oxide (TiO ₂ ) obtained by pretreatment of ores such as rutile (TiO ₂ ) and ilmenite (FeTiO ₃ ) is usually chlorinated to form titanium tetrachloride (TiCl ₄ ). A crawl method (Mg reduction method) is used in which a metal is reduced by reacting with magnesium to form sponge metal titanium.

However, in the process a batch method in which the titanium sponge titanium tetrachloride, it is difficult to continuously. In addition, for reuse of magnesium chloride produced by reduction of titanium tetrachloride (MgCl _2), molten salt MgCl ₂ When separating into Mg and Cl ₂ by the electrolytic method, a great amount of energy (electric power) is consumed. Therefore, development of the manufacturing method of the metal titanium which can be operated continuously and can reduce electric power consumption is calculated | required.

  One of such methods is expected to be a method of directly reducing titanium oxide to obtain titanium metal. As a technique related to this, Patent Document 1 discloses that in a molten chloride salt. A direct electrolysis method is disclosed in which oxygen is removed from oxides of metals such as Ti, Si, and Ge by electrolysis. In this method, for example, when a metal titanium containing oxygen is used as a cathode and current is supplied in the molten salt, oxygen in the titanium moves (dissolves) in the electrolyte rather than metal ions in the molten salt precipitate on the surface of the titanium. It utilizes the phenomenon that the reaction proceeds preferentially, and it is said that not only oxygen in titanium metal but also oxygen can be removed from titanium oxide by contacting titanium oxide with the cathode.

  If oxygen is removed from titanium oxide by the method described in Patent Document 1 and titanium metal is directly obtained, the process is simplified and energy is reduced compared to the conventional crawl method using titanium tetrachloride as an intermediate material. May be advantageous. However, it is difficult to immediately put it into practical use, and various problems need to be solved.

JP-T-2002-517613

  Under such circumstances, the present invention uses a method of reducing titanium oxide by electrolysis to form metal titanium, and uses a continuum of titanium oxide-containing metal oxide (a conductive substrate having titanium oxide attached to the surface). It is an object of the present invention to provide a method for producing titanium and a titanium alloy in which titanium oxide and the like are reduced by electrolysis in a molten salt containing calcium chloride.

In order to solve the above-mentioned problems, the present inventors have used a steel plate as a base material, a surface in which titanium oxide (TiO ₂ ) is adhered by thermal spraying as a cathode, a graphite (carbon) electrode as an anode, and chloride. As a result of electrolysis in a molten salt mainly composed of calcium, it was found that the attached titanium oxide was reduced to metal titanium and was coated on the steel sheet surface as a titanium layer. As a method of attaching titanium oxide to the substrate surface, in addition to thermal spraying, a method of pressure-bonding titanium oxide, a method of plasma-dissolving titanium oxide powder on the substrate surface, and the like can be applied.
Moreover, even if it used the mixture (sintered body) which mixed, shape | molded and sintered titanium oxide and metal titanium as a cathode, it confirmed that metal titanium was obtained similarly.

The present invention has been made based on such knowledge, and the gist thereof is in the following method for producing titanium and titanium alloy. That is,
“Oxidation contained in a continuum by introducing a continuum containing a metal oxide containing titanium oxide into a molten salt containing calcium chloride, using the continuum as a cathode, and energizing the anode immersed in the molten salt. “Method for producing titanium and titanium alloy by reducing titanium-containing metal oxide and extracting from molten salt”.

  Here, “continuum containing titanium oxide-containing metal oxide” means that titanium oxide alone or titanium oxide as a main component, for example, vanadium oxide, aluminum oxide, chromium oxide or the like is added to titanium as an alloy component. It contains elemental oxides and has a continuous form in the length direction. For example, titanium oxide and titanium metal are mixed, molded, and sintered (sintered body), or titanium oxide on the surface. An attached conductor base material.

In addition, “molten salt containing calcium chloride” means only calcium chloride (CaCl ₂ ), or in addition to calcium chloride, potassium chloride (KCl), calcium fluoride for adjusting the melting point, viscosity, etc. A molten salt containing (CaF ₂ ) and the like. When a mixed salt is used for the molten salt, if the concentration of calcium compound such as calcium chloride or calcium fluoride is too low, the calcium ion in the molten salt is insufficient and the reaction rate decreases, so the concentration of the calcium compound is 10 mass. % Or more is desirable.

  In the method for producing titanium and titanium alloy according to the present invention, “introduction of the continuum into the molten salt, reduction of the metal oxide containing titanium oxide, and extraction of the continuum after the reduction treatment from the molten salt are performed continuously. It is desirable to adopt the method of “performing” (this is referred to as the method of “Embodiment 1”), because the operation can be continued and the production efficiency can be improved.

  In the production method of the present invention (including the method of “Embodiment 1”), the “continuous body is a continuous body in which titanium oxide-containing metal oxide and titanium metal are mixed” (this is referred to as “embodiment 2”). If the method is adopted, good electrical conductivity can be secured, and the production can be performed efficiently.

  In the production method of the present invention (including the methods of “Embodiments 1 and 2”), “the continuum is obtained by attaching a titanium oxide-containing metal oxide to the surface of a continuous conductor base material; The titanium or titanium alloy obtained by reducing the titanium oxide-containing metal oxide contained in the continuum is formed as a titanium or titanium alloy layer on the substrate surface ”(this is referred to as“ embodiment 3 ”). If the method is adopted, it can be used for applications such as coating the surface of a steel sheet with titanium or a titanium alloy to make the material excellent in corrosion resistance, and the use of titanium and titanium alloys can be diversified.

  Here, the “conductor base material” is a material having a high electrical conductivity, and is generally a ferrous metal such as carbon steel, alloy steel or stainless steel, or a non-ferrous metal such as nickel or titanium. However, any material can be used as a base material as long as it is a semiconductor or a material exhibiting conductivity necessary for electrolysis at a high temperature.

  In the production method of the present invention (including the methods of “Embodiments 1 to 3”), if the method of “using the anode as a graphite electrode” (this is referred to as the method of “Embodiment 4”), high-temperature calcium chloride is converted. The electrode is not eroded even in the molten salt contained, and is excellent in thermal shock resistance.

  In the production method of the present invention (including the methods of “Embodiments 1 to 4”), a method of “making the continuous body or substrate into a plate shape, a linear shape, a square shape or a tubular shape” (referred to as “Embodiment 5”). By adopting the method, it is possible to produce various shapes of titanium or titanium alloys, and to form (coat) titanium or titanium alloy layers on the substrate surfaces of various shapes.

  In the method of “Embodiments 3 to 5”, if the method of “performing current supply to the substrate from the side of the substrate extracted from the molten salt” (this is referred to as the method of “Embodiment 6”) is adopted. Since the titanium oxide-containing metal oxide is reduced and the surface of the base material is coated with titanium or a titanium alloy, the conductivity to the base material is good and the production can be performed efficiently.

  In the method of “Embodiments 3 to 6”, the method of “when the substrate is plate-shaped, the thickness is 0.1 to 3.5 mm” (this is referred to as the method of “Embodiment 7”) is adopted. Is desirable.

  Further, in the method of “Embodiments 3 to 7”, the method of “making the thickness of the metal oxide containing titanium oxide to be adhered to the substrate surface 0.1 to 1.5 mm” (this is the same as that of “Embodiment 8”). Method).

  In the method of “Embodiment 3”, a method of “the substrate is titanium and the titanium oxide-containing metal oxide to be attached to the substrate surface is titanium oxide” (this is referred to as the method of “Embodiment 9”) is adopted. For example, titanium used as a base material can be thickened or thickened, and it can be dissolved as it is to form an ingot.

  According to the method for producing titanium and titanium alloy of the present invention, titanium and titanium alloy can be produced by electrolysis and reduction of a continuous body of titanium oxide-containing metal oxide. It is also possible to use iron or another metal as a base material, to form a titanium or titanium alloy layer on the surface thereof, and to give excellent corrosion resistance.

  Below, the manufacturing method of the titanium and titanium alloy of this invention is demonstrated in detail including the embodiment.

  FIG. 1 is a diagram showing a schematic configuration example of an apparatus capable of performing the method of the present invention. As shown in the figure, this apparatus includes an electrolytic cell 6 containing a molten salt 5 containing calcium chloride, and an anode 7 immersed in the molten salt 5. The continuum 1a unwound from the coil 2 is introduced into the molten salt 5 and is configured to be energized from the pinch roll 8 on the exit side of the electrolytic cell 6 with the continuum 1a as a cathode. After the electrolysis, the continuous body 1a extracted from the molten salt 5 is wound around the coil 9.

  In the production method of the present invention, first, “a continuum containing a titanium oxide-containing metal oxide is introduced into a molten salt containing calcium chloride”.

  The reason for using a continuous body, that is, a sintered body or conductor base material having a continuous form in the length direction is to continuously manufacture titanium or a titanium alloy. If the method of the above “Embodiment 1” is employed, continuous operation can be realized.

  If a continuum in which a titanium oxide-containing metal oxide and metal titanium are mixed is used as the continuum, good conductivity can be ensured, so that the production can be performed efficiently (method of “Embodiment 2”). As a method for producing such a continuum, any method can be used as long as it is a mixture of a titanium oxide-containing metal oxide and a metal titanium and has a continuous form in the length direction. It is not limited to a specific method.

  For example, a method in which a mixture of metal titanium and titanium oxide is made into a continuous mixture by plasma melting, a method in which metal titanium and titanium oxide are mixed and formed into a sintered body, and a binder is added to titanium oxide to form a paste. In addition, a method of mixing and forming metal titanium into this to form a sintered body can be applied.

  As the continuous body, a continuous conductor base material surface with a titanium oxide-containing metal oxide adhered can be used (the method of “Embodiment 3”). For example, it is possible to use iron as a base material and to form a titanium or titanium alloy layer on the surface thereof, thereby significantly improving the corrosion resistance.

  Subsequently, “reducing the titanium oxide-containing metal oxide contained in the continuum by applying current between the continuum as the cathode and the anode immersed in the molten salt”.

  As a result, titanium oxide or a metal oxide mainly containing titanium oxide and containing an oxide of a titanium alloy component such as vanadium oxide is reduced to produce a titanium alloy containing metal titanium or vanadium.

  Then, “(The continuum after the reduction treatment) is extracted from the molten salt”. Thereby, titanium metal or a titanium alloy can be obtained.

  Furthermore, the method of “Embodiment 3” using a continuous conductor base material surface with a titanium oxide-containing metal oxide adhered will be described with reference to the drawings.

  2 to 4 are schematic configuration examples of an apparatus that can carry out the method of “Embodiment 3” of the present invention. FIG. 2 shows a case where titanium oxide is attached to the surface of a substrate by pressure bonding. FIG. 4 also shows the case of plasma spraying. In the examples of FIGS. 2 to 4, the base material has a plate (band) shape.

In FIG. 2, after supplying powdered titanium oxide (TiO ₂ ) 3 to the surface of the conductor base material 1 b unwound from the coil 2, the titanium oxide is adhered to the surface of the base material by pressing with a roll 4. The base material 1b is introduced into the molten salt 5 containing calcium chloride in the electrolytic cell 6. An anode 7 is immersed in the molten salt 5, and the substrate 1 b is used as a cathode to conduct electricity between the anode and the cathode for electrolysis. After the electrolysis, the substrate 1b is extracted from the molten salt 5 and wound around the coil 9.

FIG. 3 shows a case where titanium oxide (TiO ₂ ) is adhered to the surface of the conductor base 1b by thermal spraying, and the subsequent steps are the same as those in FIG. Thermal spraying may be performed by a normal method of spraying fine powder of titanium oxide in a semi-molten state with compressed air. Although the figure shows the example which sprays from the upper direction of the base material 1b, and receives a splash with the saucer 10, if the base material 1b is arrange | positioned vertically and the system sprayed from the side is taken, the base material 1b will be shown. It is also possible to deposit titanium oxide on both sides.

FIG. 4 shows a case where titanium oxide (TiO ₂ ) is attached to the surface of the conductor base 1b by plasma dissolution, and the subsequent steps are the same as those in FIG. Plasma melting means that a thin layer of titanium oxide powder is spread on the surface of the base material, and the titanium oxide is melted by irradiating it with a method such as scanning weak plasma to form a titanium oxide layer on the surface of the base material. It is a method to do.

  When plasma melting is applied, a plasma current supply function and a cooling function are required on the substrate side. For example, when a water-cooled roller electrode is used and a plate-shaped substrate passes over the roller electrode, A method of supplying titanium oxide powder and immediately irradiating with plasma can be employed. Since the lower surface of the plate-like substrate is in contact with the water-cooled roller electrode, current can be supplied and heat can be removed.

  In the method of “Embodiment 3” of the present invention, first, “titanium oxide-containing metal oxide is attached to the continuous conductor base material surface”.

  As the “continuous conductor base material”, in the example shown in FIGS. 2 to 4, a belt-like base material unwound from the coil 2 is used. The reason why such a continuous base material is used is that it is assumed that the operation is continuously performed. If the method of the above “Embodiment 1” is employed, continuous operation can be realized.

  The shape of the substrate is not limited to this, and may be linear (including a thicker than the concept of “line” such as a round bar), square, or tubular. The same applies to the continuum used in the production method of the present invention described above (the method of “Embodiment 5”). The method of attaching titanium oxide to the surface of the base material needs to be selected as appropriate according to the shape of the base material, but various surfaces of the base material should be coated with titanium to make the material excellent in corrosion resistance. Is possible.

  In the example shown in FIGS. 2 to 4, titanium oxide is used as the titanium oxide-containing metal oxide to be attached to the substrate surface. For example, titanium oxide containing vanadium oxide, aluminum oxide, chromium oxide, or the like is used. It may be used. The same applies to the continuum used in the production method of the present invention described above.

  Vanadium oxide, aluminum oxide, chromium oxide and the like are reduced in the same manner as titanium oxide, and are in a solid solution state in titanium as vanadium, aluminum, chromium, etc., and are coated on the substrate surface as an alloy layer, so vanadium oxide, The mixing amount of aluminum oxide, chromium oxide, or the like may be set in accordance with the alloy composition.

  Subsequently, “This substrate is introduced into a molten salt containing calcium chloride, the substrate is used as a cathode, and the titanium oxide-containing metal oxide on the substrate surface is reduced by energizing between the anode immersed in the molten salt. ].

In this way, when the base material to which titanium oxide (TiO ₂ ) is attached is used as a cathode, electricity is passed between the anode and electrolysis, an electrode reaction of the following formula (1) occurs at the cathode, and ( 2) The chemical reaction of the formula proceeds, and titanium oxide (TiO ₂ ) is reduced by the Ca generated by the reaction of the formula (1) to produce metal Ti.

Cathode: 2Ca ²⁺ + 4e ⁻ → 2Ca (1)
TiO ₂ + 2Ca → Ti + 2CaO (2)
On the other hand, in the anode, if it is a graphite electrode, an electrode reaction of the following formula (3) occurs, and carbon dioxide (CO ₂ ) is generated from the anode surface.

Anode: 2CaO + C → CO ₂ + 2Ca ²⁺ + 4e ⁻ (3)
The total reaction caused by electrolysis is represented by the following formula (4). Formally, titanium oxide (TiO ₂ ) is reduced with carbon (C), and a metal titanium layer is formed on the surface of the substrate.

TiO ₂ + C → Ti + CO ₂ (4)
The material of the anode is not particularly limited as long as it is a conductor, but the graphite (carbon) electrode is a good electrical conductor and excellent in chemical resistance and thermal shock resistance, and it is desirable to use this (“Embodiment 4”). the method of).

  If the apparatus illustrated in FIGS. 2 to 4 is used, the introduction of the base material into the molten salt, the reduction of the titanium oxide-containing metal oxide, and the extraction of the base material after the reduction treatment from the molten salt are continuously performed. It is possible to carry out, and it is possible to continuously form (coat) a titanium or titanium alloy layer on the surface of the substrate.

  In the apparatus illustrated in FIG. 2 to FIG. 4, current is supplied from the pinch roll 8 on the outlet side of the electrolytic cell 6 to the base material 1 b. It is desirable to carry out from the side of the base material extracted from 5 (the method of “Embodiment 6”). In the illustrated example, the titanium oxide is attached to only one side of the base material, but it may be attached to both sides, and it is difficult to ensure conductivity. On the base side extracted from the molten salt 5, the titanium oxide is attached. This is because the substrate surface is coated with titanium and the substrate can be reliably energized.

  Then, “(removed base material after reduction treatment) from the molten salt”. Thereby, a titanium or titanium alloy layer can be formed on the substrate surface.

  When the substrate is plate-like, the thickness is preferably 0.1 to 3.5 mm (the method of “Embodiment 7”). If the plate thickness is less than 0.1 mm, the strength is low, and rarely, the substrate may be broken during production. In addition, if the plate thickness exceeds 3.5 mm, the substrate is bent by a roll for guiding the substrate, so that the titanium oxide-containing metal oxide layer attached to the surface and the reduced titanium or titanium alloy layer are also bent. In that case, peeling of the base material from the titanium oxide-containing metal oxide layer or titanium or titanium alloy layer may occur.

  The thickness of the titanium oxide-containing metal oxide is desirably 0.1 to 1.5 mm (the method of “Embodiment 8”). When the thickness is less than 0.1 mm, for example, when a titanium oxide layer is formed by thermal spraying, it becomes difficult to form a uniform titanium oxide layer, and the titanium layer formed by reduction is also nonuniform due to this. There is a case.

  According to the method of “Embodiment 3” described above, the titanium oxide-containing metal oxide can be continuously reduced to titanium metal or a titanium alloy, and titanium or titanium alloy is applied to the surface of the substrate having various shapes. The material can be coated to have excellent corrosion resistance.

  In the method of “Embodiment 3”, for example, by selecting a suitable plate-like base material, the obtained titanium or titanium alloy layer is peeled off, whereby a titanium or titanium alloy thin plate is formed. It is also possible to obtain. In this case, the substrate can be reused any number of times.

  The method of the above “Embodiment 9” is a method of “a substrate is titanium and a titanium oxide-containing metal oxide to be attached to the substrate surface is titanium oxide”. For example, a titanium plate is used as a substrate. If titanium oxide is attached to the surface of the substrate and electrolyzed and reduced in a molten salt containing calcium chloride, the layer (coating layer) formed on the surface of the substrate is also metallic titanium. Is obtained. By using this as a base material and performing the same treatment a plurality of times, the thickness of the titanium base material can be further increased.

  FIG. 5 is a diagram showing a schematic process example of an apparatus capable of carrying out the method of “Embodiment 9”.

  In FIG. 5, a titanium plate is used as a base material, and titanium oxide is attached to the surface of a titanium plate 12 unwound from the seed coil 11. As the adhesion method, the methods illustrated in FIGS. 2 to 4 can be applied. The titanium plate 12 is introduced into a molten salt 13 containing calcium chloride, the titanium plate 12 is used as a cathode, an anode 14 (using a graphite electrode) is immersed in the molten salt, and the electrolysis is performed. Reduce titanium oxide. It is desirable to supply current to the titanium plate 12 from the side where the titanium plate 12 is extracted from the molten salt 13. In the illustrated example, the current is supplied through the pinch roll 15. The titanium plate 12 after completion of electrolysis is extracted from the molten salt 13 and wound up as an electrolysis end coil 16. Using the electrolysis termination coil 16 as the seed coil 11, the same process can be performed a plurality of times.

  The thus-obtained “titanium substrate with increased thickness” is made of metallic titanium in both the substrate part and the coating part.

  Titanium oxide powder and metallic titanium powder (particle size of about 200 μm or less) are mixed and plasma-dissolved, and the oxygen concentration is 2 to 32% by mass (hereinafter simply referred to as “%”), and the thickness is 1 to 2.5 mm. A plate-like continuum in the range of was formed. This plate-like continuum was electrolytically reduced using the apparatus shown in FIG. 1, and the oxygen concentration of the continuum after electrolysis was investigated.

Table 1 shows the mixing ratio of titanium oxide (TiO ₂ ) powder and metal titanium powder used as raw materials, the plate thickness and oxygen concentration of the obtained plate-like continuum, and the oxygen concentration and evaluation results of the continuum after electrolysis. Show. If the oxygen concentration after electrolysis was 1% or less, it was evaluated as “pass”.

  As is clear from the results shown in Table 1, in any of Examples 1 to 5, the reduction of titanium oxide can be advanced to reduce the oxygen concentration of the continuum after electrolysis to 0.7% or less. Met.

Next, using iron (carbon steel) or metal titanium having a thickness of 0.05 to 5 mm as a base material, the method of “Embodiment 3” is applied to form a metal titanium layer on the surface of the base material. The quality was investigated. Titanium oxide (TiO ₂ ) was used as a metal oxide to be attached to the substrate surface, and was attached by thermal spraying. Part of the adhesion was also attempted by pressure bonding and plasma melting.

  Table 2 shows the base material used and its thickness, the method of attaching titanium oxide to the base material, and the thickness of the titanium oxide layer. Furthermore, the evaluation result of the titanium metal layer is also shown. The evaluation of the metal titanium layer is based on the appearance and the cut surface when the substrate on which the metal titanium layer is formed is shear-cut from the substrate side to the metal titanium layer side perpendicular to the length direction. When the peeling of the metal titanium layer was not observed, or the peeling ratio was 10% or less with respect to the observation length, it was determined as acceptable. The observation length was 50 mm or more in total length.

In Table 2, Examples 6 to 10 are cases in which the base material thickness is made constant at 0.8 mm, and the thickness of the titanium oxide layer attached to the surface is changed within the range of 0.05 to 2 mm. . In any case, a good metal titanium layer could be formed. However, when the thickness of the titanium oxide layer is 2 mm (Example 8), it takes a long time for electrolysis (that is, reduction of TiO ₂ to Ti), and the thickness of the titanium oxide layer is 0.05 mm. In the case (Example 10), some unevenness occurred on the surface after coating. Judging from this result, the thickness of the titanium oxide-containing metal oxide deposited on the substrate surface is preferably 0.1 to 1.5 mm.

  Examples 11 to 14 are cases in which the thickness of the titanium oxide layer to be attached to the surface of the base material is constant at 0.5 mm and the base material thickness is changed within a range of 0.05 to 3.5 mm. Also in this case, a good metal titanium layer was obtained. However, when the substrate thickness is 5 mm (Example 12), the titanium layer may be peeled off rarely. Further, when the substrate thickness was as thin as 0.05 mm (Example 14), the substrate was sometimes torn, although rare. From this result, when the substrate is plate-shaped, the thickness is preferably 0.1 to 3.5 mm.

  Example 15 is a case where the material of the base material in Example 6 was changed from iron to metal titanium, but a good metal titanium layer was obtained.

  In Example 16, the titanium oxide was adhered to the surface of the substrate by pressure bonding with a roll, but good results were obtained as in the case of adhesion by thermal spraying.

  Example 17 is a case where titanium oxide was adhered to the substrate surface by plasma melting. The plasma melting was performed by the method using the water-cooled roller electrode described above. In this case as well, a good metal titanium layer was obtained, as in the case of being deposited by thermal spraying.

  According to the method for producing titanium and titanium alloy of the present invention, titanium or titanium alloy can be produced by continuously electrolyzing and reducing titanium oxide-containing metal oxide, and iron or other metal as a base material. And a titanium or titanium alloy layer can be formed (ie, coated) on the surface. Therefore, the manufacturing method of the present invention can be effectively used as a means for providing materials used in devices and parts that require the corrosion resistance of titanium or titanium alloys, particularly in various industrial fields. it can.

It is a figure which shows the example of schematic structure of the apparatus which can implement the method of this invention. It is a figure which shows the schematic structural example of the apparatus which can implement the method of the "embodiment 3" of this invention. It is a figure which shows the other schematic structural example of the apparatus which can implement the method of the "embodiment 3" of this invention. It is a figure which shows the further another schematic structural example of the apparatus which can implement the method of the "embodiment 3" of this invention. It is a figure which shows the example of a schematic process of the apparatus which can implement the method of "Embodiment 9" of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a: Continuous body 1b: Conductive base material 2: Coil 3: Titanium oxide 4: Roll 5: Molten salt 6: Electrolysis tank 7: Anode 8: Pinch roll 9: Coil 10: Sauce 11: Seed coil 12: Titanium plate 13: Molten salt 14: Anode 15: Pinch roll 16: Electrolysis finished coil

Claims (10)

  A continuum containing a titanium oxide-containing metal oxide is introduced into a molten salt containing calcium chloride, and the continuum is used as a cathode and energized between an anode immersed in the molten salt and contained in the continuum. A method for producing titanium and a titanium alloy, wherein the metal oxide is reduced and extracted from the molten salt.   The introduction of the continuum into the molten salt, the reduction of the titanium oxide-containing metal oxide, and the extraction of the continuum after the reduction treatment from the molten salt are continuously performed. A method for producing titanium and titanium alloys.   3. The method for producing titanium and a titanium alloy according to claim 1, wherein the continuum is a continuum in which a titanium oxide-containing metal oxide and metal titanium are mixed.   The continuum is obtained by attaching a titanium oxide-containing metal oxide to the surface of a continuous conductor base material. The continuum is energized between the anode and the titanium oxide-containing metal oxide contained in the continuum. The titanium or titanium alloy obtained as described above is formed as a titanium or titanium alloy layer on a substrate surface.   The method for producing titanium and a titanium alloy according to any one of claims 1 to 4, wherein the anode is a graphite electrode.   The method for producing titanium and a titanium alloy according to any one of claims 1 to 5, wherein the continuous body or the substrate is plate-shaped, linear, rectangular or tubular.   The method for producing titanium and a titanium alloy according to any one of claims 4 to 6, wherein a current is supplied to the substrate from the side of the substrate extracted from the molten salt.   The method for producing titanium and a titanium alloy according to any one of claims 4 to 7, wherein the substrate is plate-shaped and has a thickness of 0.1 to 3.5 mm.   The method for producing titanium and a titanium alloy according to any one of claims 4 to 8, wherein the thickness of the titanium oxide-containing metal oxide adhered to the substrate surface is 0.1 to 1.5 mm. 5. The method for producing titanium according to claim 4, wherein the base material is titanium, and the titanium oxide-containing metal oxide to be adhered to the surface of the base material is titanium oxide.

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