JP2019052350A - Metal titanium manufacturing device and method - Google Patents

Abstract

To provide a metal titanium manufacturing device and method capable of increasing titanium concentration of a recovery obtained in a previous process of a purification process compared to prior art.SOLUTION: A metal titanium manufacturing device has a reduction device for obtaining a liquid alloy consisting of titanium and bismuth by a reduction treatment of titanium tetrachloride in the presence of bismuth and magnesium, a concentration device for obtaining a concentrated intermetallic compound by depositing an intermetallic compound from the liquid alloy and separating bismuth included in the intermetallic compound, and a purification device for obtaining metal titanium by a purification treatment of the concentrated intermetallic compound, in which the concentration device makes only the intermetallic compound be a solid state selectively, and separates bismuth by applying inertia force.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a titanium metal production apparatus and method.

The following Patent Document 1 discloses a titanium production method that can efficiently obtain a titanium alloy and that can be produced continuously at low cost by refining the titanium alloy at a low cost. This manufacturing method includes step 1 (reduction step) in which titanium tetrachloride (TiCl ₄ ) is added to a mixture containing bismuth and magnesium to obtain a liquid alloy of bismuth and titanium, and components other than titanium are removed from the liquid alloy. Including a step 2 (refining step) for performing a refining treatment, and segregating a liquid alloy between step 1 and step 2 to form a liquid part, a solid-liquid coexisting part where a solid and a liquid coexist. The process of separating (segregation process) is included as an auxiliary process.

Japanese Patent No. 6095374

By the way, the segregated recovered material obtained in the segregation step is a precipitate (Ti ₈ Bi ₉ ) with bismuth (Bi) attached, and the titanium concentration is relatively low. In view of the large amount of energy consumed in the purification process, which is a subsequent process of the segregation process, it is necessary to increase the titanium concentration in the recovered product obtained in the segregation process or / and the reduction process, which is the previous process of the purification process, as much as possible. .

  This invention is made | formed in view of the situation mentioned above, It aims at provision of the metal titanium manufacturing apparatus and method which can raise the titanium concentration of the collection | recovery obtained by the pre-process of a refinement | purification process rather than before. To do.

  In order to achieve the above object, according to the present invention, as a first solution for a titanium metal production apparatus, titanium tetrachloride is reduced in the presence of bismuth and magnesium, whereby a liquid comprising titanium and the bismuth is obtained. A reduction device for obtaining an alloy, a concentration device for precipitating an intermetallic compound from the liquid alloy, and separating the bismuth incidental to the intermetallic compound to obtain a concentrated intermetallic compound, and a purification treatment of the concentrated intermetallic compound And a refining device for obtaining metallic titanium, and the concentrating device employs means for selectively bringing only the intermetallic compound into a solid state and separating the bismuth by applying an inertial force.

  In the present invention, as a second solving means related to the titanium metal production apparatus, in the first solving means, further comprising a segregation apparatus for obtaining a precipitate by performing a segregation treatment on the liquid alloy, A means of separating the bismuth by heating the precipitate and applying an inertial force to the precipitate is employed.

  In the present invention, as a third solving means relating to the titanium metal production apparatus, in the first or second solving means, a means is used in which the concentration device causes the inertial force to act as a centrifugal force.

  In the present invention, as a fourth solving means related to the titanium metal production apparatus, in the third solving means, the concentrating device has an internal atmosphere temperature set to a temperature at which only the intermetallic compound is selectively brought into a solid state. A set concentrating furnace, an inner container accommodated in the concentrating furnace and containing the precipitate obtained by the segregation apparatus, and a plurality of openings formed therein; a drive source for rotating the inner container at a predetermined speed; The means of providing is adopted.

  In the present invention, as a fifth solving means relating to the titanium metal production apparatus, in the first or second solving means, the concentration device is restrained in a state where the concentrating device is moved in a predetermined direction at a predetermined speed. Adopt a means of applying force.

  In the present invention, as a means for solving the titanium metal production method, a reduction step of obtaining a liquid alloy comprising titanium and the bismuth by reducing titanium tetrachloride in the presence of bismuth and magnesium, and the liquid A concentration step of precipitating an intermetallic compound from the alloy and separating the bismuth incidental to the intermetallic compound to obtain a concentrated intermetallic compound; a purification step of purifying the concentrated intermetallic compound to obtain metallic titanium; In the concentration step, a means is adopted in which only the intermetallic compound is selectively brought into a solid state and the bismuth is separated by applying an inertial force.

  ADVANTAGE OF THE INVENTION According to this invention, the metal titanium manufacturing apparatus and method which can raise the titanium density | concentration of the collection | recovery obtained by the pre-process of a refinement | purification process conventionally can be provided.

1 is a system configuration diagram of a titanium metal manufacturing apparatus according to an embodiment of the present invention. It is a schematic diagram which shows the detailed structure of the concentration apparatus in one Embodiment of this invention. It is a Bi-Ti binary system phase diagram in one embodiment of the present invention.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1, the titanium metal production apparatus according to the present embodiment includes a reduction furnace 1, a Bi supply apparatus 2, a TiCl ₄ supply apparatus 3, an Mg supply apparatus 4, an MgCl ₂ recovery apparatus 5, a segregation apparatus 6, and a concentration apparatus 7. , A distillation device 8 and an exhaust device 9 are provided.

Among these components, the reduction furnace 1, the Bi supply device 2, the TiCl ₄ supply device 3, the Mg supply device 4, and the MgCl 2 recovery device 5 constitute the reduction device of this embodiment. That is, the reduction furnace 1, Bi supply device 2, TiCl ₄ supply device 3, Mg supply device 4 and MgCl 2 recovery device 5 have overall functions in the presence of bismuth (Bi) X 1 and magnesium (Mg) X 3. This is an apparatus for obtaining a liquid alloy (Bi—Ti liquid alloy X4) composed of titanium (Ti) and bismuth (Bi) by reducing titanium tetrachloride (TiCl ₄ ) X2.

The reduction furnace 1 performs reduction treatment of titanium tetrachloride in the presence of bismuth X1 and magnesium X3 at a temperature (reduction temperature) higher than the melting points of bismuth X1 and magnesium X3, whereby the Bi—Ti liquid alloy X4 and magnesium chloride are reduced. This is a heating furnace for generating (MgCl ₂ ) X 5. The reduction temperature is 900 ° C., for example. In the reduction furnace 1 set at such a reduction temperature, the liquid state Bi-Ti liquid alloy X4 and the liquid are obtained by adding the liquid state titanium tetrachloride X2 to the liquid state bismuth X1 and magnesium X3. The state of magnesium chloride X5 is produced. Such a reduction furnace 1 supplies Bi-Ti liquid alloy X4, which is one product, to the segregation device 6, and supplies magnesium chloride X5, which is the other product, to the MgCl2 recovery device 5.

The Bi supply device 2 is a bismuth supply source that supplies the reduction furnace 1 with bismuth X1, which is one of the raw materials for the reduction treatment. The TiCl ₄ supply device 3 is a titanium tetrachloride supply source that supplies titanium tetrachloride X2 that is one of the raw materials for the reduction treatment to the reduction furnace 1. The Mg supply device 4 is a magnesium supply source that supplies magnesium X3, which is one of the raw materials for the reduction treatment, to the reduction furnace 1. The MgCl ₂ recovery device 5 is a device that recovers magnesium chloride X5 that is one of the products from the reduction furnace 1.

The segregation apparatus 6 is an apparatus that obtains a solid-liquid mixture by subjecting the Bi—Ti liquid alloy X4 to segregation. That is, the segregation apparatus 6 maintains the Bi-Ti liquid alloy X4 at a predetermined segregation temperature, for example, 500 ° C., thereby providing a Bi—Ti liquid alloy (Ti ₈ Bi) having a higher titanium concentration than the Bi—Ti liquid alloy X4. ₉ liquid alloy) is selectively precipitated to form a solid-liquid mixture composed of Ti ₈ Bi ₉ intermetallic compound (solid phase) and bismuth X7 (liquid phase). The segregation device 6 provides the concentration device 7 with a mixture X6 containing a relatively large amount of Ti ₈ Bi ₉ among the solid-liquid mixture, and provides the bismuth X7 with the reduction furnace 1. The mixture X6 obtained by the segregation apparatus 6 is one in which bismuth (solid or liquid) is adhered or encapsulated between Ti ₈ Bi ₉ crystals (solid).

  The concentration device 7 is a device that obtains the concentrated intermetallic compound X9 by separating bismuth incidental to the mixture X6 from the mixture X6. As shown in FIG. 1, the concentrating device 7 includes at least a concentrating furnace 7a, an Ar gas supply device 7b, and a drive source 7c. The concentrating furnace 7a is a bottomed cylindrical container that contains the mixture X6 and holds it in a predetermined atmosphere, and is installed in a posture in which the axis is in the vertical direction. That is, the concentrating furnace 7a includes an annular peripheral surface having a predetermined diameter and a predetermined cylinder length, a disk-shaped bottom surface that closes one end of the peripheral surface, and a disk-shaped surface that closes the other end of the peripheral surface. An upper surface.

  Such a concentration furnace 7a is configured, for example, as shown in FIG. That is, the concentration furnace 7a includes a heater 7d, a heat insulating member 7e, a receiving container 7f, a perforated drum 7g, and a shaft 7h. The heater 7d is an electric heater provided on the peripheral surface of the concentration furnace 7a, and heats the inside of the concentration furnace 7a to a predetermined concentration temperature (for example, 500 ° C.). The heat insulating member 7e is provided on the bottom surface of the concentration furnace 7a, and suppresses heat dissipation from the bottom surface of the concentration furnace 7a. In the configuration of FIG. 2, the heat insulating member 7e is not provided on the upper surface and the side surface of the concentration furnace 7a, but the heat insulating member 7e may be provided on the upper surface and the side surface.

  The receiving container 7f is a cylindrical container provided concentrically in the concentration furnace 7a. The receiving container 7f includes a bottom portion that closes the lower end, but the upper end is released. The perforated drum 7g is an inner container that is concentrically accommodated in the receiving container 7f of the concentrating furnace 7, accommodates the mixture X6, and has a plurality of holes (openings) formed discretely. This perforated drum 7g is provided with a lower portion that closes the lower end similarly to the receiving container 7f, but the upper end is released.

  A shaft 7h is fixed to the upper part of the perforated drum 7g so as to be coaxial with the axial center. That is, the shaft 7h is a rod-like member extending along the axial center of the perforated drum 7g, one end (lower end) is fixed to the upper part of the perforated drum 7g, and the other end (upper end) is the output of the power source 7c. It is connected to the shaft.

  Subsequently, the Ar gas supply device 7b is a device that supplies the Ar gas X8 to the concentration furnace 7a. When the Ar gas supply device 7b supplies the Ar gas X8 to the concentration furnace 7a, the inside of the concentration furnace 7a becomes an Ar gas atmosphere (inert gas atmosphere). The drive source 7c is a rotational power source that rotates the mixture X6 in the concentration furnace 7a. That is, the drive source 7c rotates the mixture X6 accommodated in the perforated drum 7g by rotationally driving the perforated drum 7g accommodated in the concentration furnace 7a.

The concentrating device 7 configured as described above heats the mixture X6 accommodated in the perforated drum 7g in an Ar gas atmosphere, and causes the centrifugal force to act on the mixture X6 by rotating the perforated drum 7g. Such a concentrator 7 functions as a kind of centrifuge, and separates liquid-phase bismuth from solid-phase Ti ₈ Bi ₉ crystals by applying centrifugal force to the mixture X6. . The concentration device 7 removes most of the liquid phase bismuth by such centrifugation, and supplies the alloy having a titanium concentration higher than the mixture X6, that is, the concentrated intermetallic compound X9, to the distillation device 8. The centrifugal force is a kind of inertial force as is well known.

  The distillation apparatus 8 is an apparatus that obtains titanium metal by subjecting the concentrated intermetallic compound X9 to a distillation process, which is a kind of purification process. That is, the distillation apparatus 8 heats the concentrated intermetallic compound X9 to a predetermined distillation temperature under a reduced pressure atmosphere, thereby selectively vaporizing bismuth forming the concentrated intermetallic compound X9 to obtain titanium metal. The distillation temperature is 1000 ° C., for example. Moreover, such a distillation apparatus 8 is a kind of purification apparatus.

  The exhaust device 9 is a vacuum pump that exhausts the internal gas of the distillation device 8 to the outside. The exhaust device 9 supplies bismuth X10 obtained by the exhaust process of the exhaust device 9 to the reduction furnace 1. In addition, the inside of the distillation apparatus 8 becomes a decompression atmosphere by the action | operation of the exhaust apparatus 9. FIG.

Here, the titanium metal manufacturing apparatus configured as described above is controlled in an integrated manner by a control device (not shown). That is, the operations of the Bi supply device 2, the TiCl ₄ supply device 3, the Mg supply device 4, the MgCl 2 recovery device 5, the segregation device 6, the concentration device 7, the distillation device 8 and the exhaust device 9 described above are appropriately controlled by the control device. As a result, a series of manufacturing steps as described below is performed.

  Next, the operation of the titanium metal production apparatus according to this embodiment, that is, the metal titanium production method using the metal titanium production apparatus will be described in detail with reference to FIG.

In this titanium metal production apparatus, a reduction process (reduction process) is first performed by a reduction device. That is, in the reduction apparatus, the atmospheric temperature of the reduction furnace 1 is set to a predetermined reduction temperature, the Bi supply apparatus 2 supplies bismuth X1 to the reduction furnace 1, and the TiCl ₄ supply apparatus 3 supplies titanium tetrachloride X2 to the reduction furnace. 1 and the Mg supply device 4 supplies magnesium X3 to the reduction furnace 1.

As a result, in the reduction furnace 1, the chemical reaction (reduction reaction) of the following formula (1) proceeds, and Bi—Ti liquid alloy X4 and magnesium chloride X5 made of titanium and bismuth are generated.
TiCl ₄ + Bi + 2Mg → Bi-Ti + 2MgCl ₂ (1)

  In the formula (1), “Bi—Ti” indicates a Bi—Ti liquid alloy X4 made of titanium and bismuth. The supply amount of each raw material supplied to the reduction furnace 1, that is, the supply amount of bismuth X1, titanium tetrachloride X2 and magnesium X3 to the reduction furnace 1 is the mole of each raw material in the reduction reaction represented by the above formula (1). It is set as appropriate based on the ratio.

Here, the Bi—Ti liquid alloy X4 and the magnesium chloride X5 exist as liquids in the reduction furnace 1, but both are phase-separated into two layers due to the difference in specific gravity. That is, the Bi—Ti liquid alloy X4 has a relatively large specific gravity, and thus becomes a lower layer liquid product in the reduction furnace 1. On the other hand, since magnesium chloride X5 has a relatively small specific gravity, it becomes an upper liquid product in the reduction furnace 1. The lower Bi—Ti liquid alloy X4 is taken out from the bottom of the reduction furnace 1 and supplied to the segregation device 6, and the upper magnesium chloride X5 is taken out from the middle part of the reduction furnace 1 and recovered in the MgCl ₂ recovery device 5. Is done.

This titanium metal production apparatus is subsequently subjected to a segregation process (segregation process) by the segregation apparatus 6. That is, the segregation apparatus 6 performs a segregation process on the Bi—Ti liquid alloy X4. As shown in the phase diagram of FIG. 3, the Bi—Ti liquid alloy X4 has a predetermined segregation temperature (eg, 500 ° C.) and a Ti ₈ Bi ₉ when the titanium concentration in the Bi—Ti liquid alloy X4 is 47 at% or less. Intermetallic compounds are deposited.

This Ti ₈ Bi ₉ intermetallic compound is a precipitate of the Bi—Ti liquid alloy X4, and is a solid substance whose titanium concentration is higher than that of the Bi—Ti liquid alloy X4. Further, since this Ti ₈ Bi ₉ intermetallic compound has a lower density than the Bi—Ti liquid alloy X4, it floats in the Bi—Ti liquid alloy X4 and becomes a floating body. That is, in the segregation apparatus 6, when the Bi—Ti liquid alloy X4 is exposed to a predetermined segregation temperature, a solid-liquid mixture composed of Ti ₈ Bi ₉ intermetallic compound (solid phase) and bismuth (liquid phase) is generated. .

Here, the mixture X6 is a solid material in which bismuth (solid) is attached to or included in Ti ₈ Bi ₉ crystals (solid). Further, Ti ₈ Bi ₉ crystals forming the mixture X6 and bismuth have different melting points.

The concentration apparatus 7 performs a concentration step (concentration process) on such a mixture X6. That is, the concentrating device 7 sets the inside of the concentrating furnace 7a to a predetermined concentrating temperature (for example, 500 ° C.) and an argon gas atmosphere, and Ti ₈ Bi ₉ intermetallic compound Ti ₈ Bi ₉ crystals housed in the perforated drum 7g. The bismuth adhered or encapsulated in (solid) is selectively maintained in a liquid state. As a result, the perforated drum 7g is in a state in which the mixture X6 made of Ti ₈ Bi ₉ crystal (solid) and bismuth (liquid) is stored.

In the concentrating device 7, the driving source 7c rotates the perforated drum 7g in this state. As a result, centrifugal force (inertial force) acts on the mixture X6 in the perforated drum 7g, so that bismuth (liquid) is separated from the Ti ₈ Bi ₉ crystal (solid) and adheres to the inner surface of the perforated drum 7g. It scatters toward the receiving container 7f from a plurality of holes formed in the perforated drum 7g.

That is, in the concentrating device 7, bismuth (solid or liquid) incidental to the Ti ₈ Bi ₉ crystal (solid) of the mixture X6 is maintained in a liquid state, and is received from the Ti ₈ Bi ₉ crystal (solid) by the action of centrifugal force. It adheres to the inner surface of 7f. As a result of such solid-liquid separation, in the concentrating device 7, an intermetallic compound having a titanium concentration higher than that of the mixture X6, that is, a concentrated intermetallic compound X9 that is a concentrate of the mixture X6 is obtained.

  The titanium metal production apparatus subsequently performs a distillation process (distillation process) using the distillation apparatus 8. That is, the distillation apparatus 8 selectively vaporizes bismuth forming the concentrated intermetallic compound X9 by placing the concentrated intermetallic compound X9 under a predetermined distillation temperature and a reduced-pressure atmosphere, thereby obtaining metallic titanium.

  And the bismuth (gas phase) which the exhaust apparatus 9 acquired from the distillation apparatus 8 is supplied to the reduction furnace 1 as FIG. 1 shows. Also, bismuth (liquid phase) contained in the solid-liquid mixture of the segregation apparatus 6 is supplied to the reduction furnace 1 as shown in FIG. Therefore, since bismuth is not supplied from the exhaust device 9 and the segregation device 6 to the reduction furnace 1 at the initial stage of operation of the titanium metal production apparatus, it is necessary to supply bismuth from the Bi supply apparatus 2, but after the operation, Bi supply is required. The amount of bismuth supplied from the apparatus 2 to the reduction furnace 1 can be reduced.

  Thus, in this embodiment, since the concentration process is performed between the segregation process and the distillation process (purification process), the recovered material (concentrated metal) having a higher titanium concentration than the recovered material (mixture X6) obtained in the segregation process. A distillation step (purification step) is performed using intercalation compound X9). That is, according to the present embodiment, since the titanium concentration of the recovered product obtained in the previous step of the purification step can be increased as compared with the conventional case, the energy consumption in the distillation step (purification step) which is the subsequent step is reduced as compared with the conventional case. Can be reduced.

In addition, this invention is not limited to the said embodiment, For example, the following modifications can be considered.
(1) In the above embodiment, the concentrating device 7 that applies the centrifugal force (inertial force) to the mixture X6 is used, but the present invention is not limited to this. As another device configuration for applying a dynamic inertia force to the mixture X6, for example, it is conceivable to stop (stop) the mixture X6 while moving the mixture X6 in a predetermined direction at a predetermined speed.

  More specifically, for example, the inertial force different from the centrifugal force can be applied to the mixture X6 by linearly moving the perforated drum 7g containing the mixture X6 in a direction perpendicular to the peripheral surface and causing a sudden stop. In order to cause such inertial force to act on the mixture X6, it is preferable to employ a concentrator having a configuration optimized for the inertial force instead of the concentrator 7.

(2) Although the concentrating device 7 in the above embodiment is a kind of centrifugal separator, it is conceivable to optimize each component based on the properties of the mixture X6. For example, the perforated drum 7g may be replaced with a cylindrical shape to have another shape, for example, a cubic shape.

(3) In the above embodiment, the concentration temperature is, for example, 500 ° C., but the present invention is not limited to this. According to the state diagram shown in FIG. 3, the concentration temperature may be in the range of 425 to 930 ° C. as the maximum width, and more preferably in the range of 425 to 700 ° C.

(4) In the said embodiment, although the distillation process was employ | adopted as a refinement | purification process, this invention is not limited to this. Other purification steps may be employed in place of the distillation step. As another purification process, for example, an electrolytic purification process described in Patent Document 1 may be employed.

(5) In the said embodiment, although the concentration process was performed with respect to the recovered material (mixture X6) obtained by a segregation process, the case where a segregation process is abbreviate | omitted as needed is considered. In such a case, the concentration step may be performed on the recovered material (Bi-Ti liquid metal X4) obtained in the reduction step.

1 reduction furnace 2 Bi feeder 3 TiCl ₄ feed device 4 Mg supply device 5 MgCl ₂ recovery device 6 segregation device 7 concentrator 7a concentration furnace 7b Ar gas supply apparatus 7c driving source 7d heater 7e insulating member 7f receptacle 7g perforated drum (Inner container)
7h Shaft 8 Distillation equipment (purification equipment)
9 Exhaust device

Claims (6)

A reduction device for obtaining a liquid alloy comprising titanium and the bismuth by reducing titanium tetrachloride in the presence of bismuth and magnesium;
A concentrating device for obtaining a concentrated intermetallic compound by precipitating an intermetallic compound from the liquid alloy and separating the bismuth incidental to the intermetallic compound;
A purification apparatus for purifying the concentrated intermetallic compound to obtain metallic titanium,
The concentration apparatus separates the bismuth by selectively solidifying only the intermetallic compound and applying an inertial force. A segregation device for obtaining a precipitate by performing a segregation treatment on the liquid alloy;
The said concentration apparatus isolate | separates the said bismuth by heating the said deposit and making an inertial force act on the said deposit, The metal titanium manufacturing apparatus of Claim 1 characterized by the above-mentioned.   The titanium metal production apparatus according to claim 1 or 2, wherein the concentrating device causes the inertial force to act as a centrifugal force. The concentrator is
A concentration furnace in which the internal atmospheric temperature is set to a temperature at which only the intermetallic compound is selectively brought into a solid state;
An inner container accommodated in the concentrating furnace, containing the precipitate obtained by the segregation apparatus and having a plurality of openings formed therein;
The metal titanium manufacturing apparatus according to claim 3, further comprising: a drive source that rotates the inner container at a predetermined speed.   3. The titanium metal production apparatus according to claim 1, wherein the concentration device causes the inertial force to act by stopping in a state where the concentration device is moved in a predetermined direction at a predetermined speed. A reduction step of obtaining a liquid alloy comprising titanium and the bismuth by reducing titanium tetrachloride in the presence of bismuth and magnesium;
A concentration step of precipitating an intermetallic compound from the liquid alloy and obtaining a concentrated intermetallic compound by separating the bismuth incidental to the intermetallic compound;
A purification step of purifying the concentrated intermetallic compound to obtain metallic titanium,
In the concentration step, only the intermetallic compound is selectively solidified, and the bismuth is separated by applying an inertial force.

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