JPS6151615B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of metallic zirconium, in which a zirconium sponge is produced by reducing zirconium halide with a reducing agent made of an alkaline earth metal, such as reducing zirconium tetrachloride with metallic magnesium. It is about the method.

The present applicant had previously proposed a technology for producing zirconium sponges similar to Utility Application No. 129871/1987, but this proposed technology involves forming a reaction vessel and a condensation vessel into the same shape, An operating pipe is formed in the body of the reaction vessel, and the operating pipe of the vessel used as the reaction vessel is used as a pipe for charging the molten reducing agent and extracting the by-produced molten salt,
By using the operating pipe of the container used as the condensing container as the exhaust pipe, the work of converting the container to other uses is simplified and work efficiency is improved.

The present invention is a further development of the above-mentioned proposed technology, and an object of the present invention is to integrate the reaction vessel, condensation vessel, and partition stand after the reduction operation and separation operation are completed and before the dismantling operation. in a state
By rotating it 180 degrees, the joint between the container and the partition stand, which was previously used as a condensation container, can be used as a reaction container in the next operation without disassembling it, greatly reducing disassembly and assembly work. An object of the present invention is to provide a method for producing metal zirconium that can be used to produce metal zirconium.

In order to achieve the above object, the method for producing metallic zirconium of the present invention is such that after the separation operation is completed, the passage between the reaction vessel and the condensation vessel is closed by a damper, and the reaction vessel and the condensation vessel are integrated into a 180° angle. After the rotation, the condensation vessel is reused as a reaction vessel in the next step, that is, the method for producing metal zirconium of the present invention is characterized in that the lateral branch pipe communicating with the passage between the reaction vessel and the condensation vessel during reduction is After the reduction reaction is completed, a damper is inserted into the branch tube to close the branch tube and open and close the passage, and the damper is placed in the open state of the passage. After completing this separation operation, the passage is closed with the damper, and the reaction vessel and condensation vessel are rotated 180° as a unit, and the condensation vessel is reused as a reaction vessel in the next step. It is characterized by its use.

Hereinafter, the present invention will be specifically explained based on an illustrated embodiment.

First, the apparatus used to implement the method according to the present invention will be described.

The manufacturing apparatus of the embodiment includes a reaction vessel 20 and a condensation vessel 30 formed of equal-shaped vessels and facing each other vertically symmetrically, and an intermediate partition 1 interposed between both the vessels 20 and 30. , a heating furnace 17 surrounding the outer periphery and bottom of a reaction vessel 20, and the inner spaces of these vessels 20 and 30 form a reaction chamber 2 and a condensation chamber 3, respectively.

The partition 1 is formed of a substantially cylindrical heating furnace 4, and the partition 1 is formed with a central tube 5 serving as a passage that vertically communicates with the center. In this way, the sheathed heater 6 is embedded within the heating furnace 4. Further, in the center of the central cylinder 5, a branch cylinder 7 extending to the outside of the side of the partition table 1 is formed to protrude and communicate with the central cylinder 5, and this branch cylinder 7 is equipped with a feeder such as a screw conveyor. 8 or damper (valve body) 9
is detachably attached to the branch tube 7.
Small-diameter temperature and pressure detection tubes 16 and 16' are formed parallel to the branch tube 7 at positions near the top and bottom of the branch tube 7,
The temperature detection tubes 16, 16 are communicated with the central cylinder 5. Further, the upper and lower parts of the partition 1 are tapered with step portions 10a and 10b as boundaries, and relatively large-diameter recesses 11 and 11 are formed at the center of the upper and lower end surfaces of the partition 1. formed,
Upper and lower end portions 5a and 5b of the central cylinder 5 are positioned approximately in the middle of the internal space of the recess 11. The tips 5a and 5b have flanges 1
2 and 12 are formed, and a fusible melting plate 13 is placed and fixed on the upper flange 12 of the flanges 12 and 12 so as to close the inner space of the central cylinder 5. As the melting plate 13, a plate made of magnesium material is usually used. Further, one end of a temperature detection tube 15 is opened at the upper end surface and the lower end surface of the partition table 1, and this temperature detection tube 1
The other end of 5 projects outside of the partition stand 1. On the other hand, large-diameter dish-shaped flanges 21 and 31 are formed at the mutually opposing open ends of the containers 20 and 30 made of heat-resistant steel plates, and the dish-shaped flanges 2
Peripheral walls 21a, 31a protruding toward the respective containers 20, 30 are formed on the outer periphery of the containers 1, 31, and a drain pipe 22,
32 is fixedly installed, and a dish-shaped flange 21,
Packings 23, 33 are spread out on the sides of 31 from which the peripheral walls 21a, 31a protrude.

Thus, the flange 21 of the reaction vessel 20 is brought into close contact with the upwardly opening end surface of the heating furnace 17 via the packing 23, thereby sealing the inner hole 17a of the heating furnace 17. The lower part of the partition 1 is connected to the reaction vessel 20 so that the peripheral edge and the stepped portion 10b of the partition 1 are in close contact with each other.
It is fitted and fixed inside. Further, a condensation container 30 is placed over the top of the partition 1, and the inner peripheral edge of the flange 31 of the condensation container 30 and the partition 1
The drain pipe 32 of the flange 31 cooperates with a sprinkler pipe to be described later to perform a drainage function.

Further, on the circumferential wall of each of the containers 20, 30 near the bottom surface in the middle of the body, there are straight pipes 24, 34, and straight pipes 24, 34.
Operation pipes 26, 36, which are L-shaped pipes 25, 35 branched from 4, 34, are open.
The shaped tubes 25, 35 extend along the outer walls of the containers 20, 30 toward the openings of the containers 20, 30, and pass through the flanges 21, 31, respectively, with their outer ends 27, 37 extending to the outside. It is prominent. Therefore, the L-shaped tube outer end 27 of the reaction vessel 20 is not shown.
It is connected to a connecting pipe 18 that selectively communicates with the MgCl ₂ reservoir and the Mg melting furnace, and the condensation vessel 3
The straight pipe 34 of No. 0 is connected to an exhaust pipe 19 leading to a separate vacuum pump (not shown).

In addition, the exhaust pipe 19 is provided with an operation valve 50, and the straight pipe 24 of the reaction vessel 20 and the condensation vessel 30 are interposed in the exhaust pipe 19.
The outer end 37 of the L-shaped tube is closed with a blind lid.

In addition, the peripheral wall of the heating furnace 17 has a reaction vessel 2
For the purpose of preventing deformation due to internal pressure fluctuations in the furnace, an air passage pipe 5 is provided to make the internal pressure of the furnace inner hole 17a negative pressure.
1 is fixedly installed, but this passage pipe 51 is also used for cooling separately. Furthermore, a cooling water sprinkler pipe 53 and its cover are disposed close to the top of the condensation container 30 .

On the other hand, the damper 9 has a substantially cylindrical shape as shown in FIG.
It is said to be a semicircle that matches the curvature of the inner diameter of. Further, near the end on the side of the valve body 90, a tapered part 91 having a smaller diameter on the end side is formed, and this tapered part 9
1 is filled with a heat insulating material 92, and a heater 93 is placed inside the heat insulating material 92 near the valve body 90.
An operating handle 94 is formed at the other end of the damper 9, and a rotation positioning guide 94a is formed in a part of the handle 94.

Here, an embodiment of the manufacturing method according to the present invention using the embodiment manufacturing apparatus configured as described above will be described.

First, the airtightness of each part of the reaction vessel 20 and condensation vessel 30 in the combined state is confirmed by a pressure test, and then the reaction vessel 20 is connected to the heating furnace 17.
Next, the heating furnace 17 is energized to absorb and degas while preheating to 200°C to 300°C, and then enter the reaction chamber 2 from the regulating pipe 15 until atmospheric pressure is reached.
Ar is introduced into the furnace, and the temperature inside the furnace is raised to 750°C to 800°C.

Thereafter, 80 kg of molten Mg is charged into the reaction chamber 2 from the operation pipe 26, and then ZrCl ₄ is introduced from the feeder 8 and brought into contact with the molten Mg in the reaction chamber 2 to perform a reduction reaction.

When 700Kg of ZrCl ₄ has reacted, the Ar in the reaction chamber 2 is pressurized to 0.5Kg/cm ² , thereby the secondary MgCl ₂ is extracted from the operation pipe 26, and 80Kg of Mg is charged again. At the same time, ZrCl ₄ is introduced to continue the reaction. After charging 280Kg of ZrCl ₄ , 5MgCl ₂ is extracted. Note that during this operation, the heater 6 is not energized, so that the partition plate 13 located away from the reaction vessel 20 does not melt.

Next, the reaction operation cycle as described above is repeated 3 times ~
After repeating this five times, the feeder 8 is taken out from the branch tube 7, and a damper 9 is attached to the branch tube 7 in place of the feeder 8. At this time, the valve body 90 of the damper 9
is parallel to the axial direction of the central cylinder 5 as shown in FIG. let This melting of the partition plate 13 brings the reaction chamber 2 and condensation chamber 3 into communication, and the fact that the partition plate 13 has melted can be easily confirmed from the outside by measuring the pressure difference between the reaction chamber 2 and the condensation chamber 3. obtain.

After confirming the above, open the operating valve 50 to start the exhaust, and sprinkle water from the water pipe 53 to the condensation container 3.
During this vacuum separation operation, the temperature of the reaction chamber 2 is maintained at 900°C to 1000°C.

During this period, as shown in Figure 4a, MgCl ₂ and Mg evaporated from the reaction chamber 2 are transferred to the condensation chamber 3.
The zirconium sponge is absorbed by heat and adheres to the inner wall of the same chamber 3. This separation operation is completed in about 10 hours, and the above operation can produce about 800 kg of zirconium sponge. During the separation operation, the central cylinder 5 is heated by the sheathed heater 6 and the vicinity of the valve body 90 of the damper 9 is heated by the heater 93, so that the inside of the central cylinder 5 is heated by the heater 93.
MgCl ₂ and Mg are reliably sent into the condensation chamber 3 without being condensed.

Therefore, after the separation operation is completed, the reaction vessel 20
is extracted from the heating furnace 17, the damper 9 is rotated 90 degrees, and the reaction vessel 2 is removed as shown in FIG.
0, the condensation container 30, and the intermediate partition stand 1 are rotated 180 degrees in an integrated state. The operation of extracting the reaction container 20 is carried out by lifting the container 20 with a crane or the like, or by lowering or disassembling the heating furnace 17. Such a partition stand 1
The inside of the central cylinder 5 has been used as a reaction vessel 20 in a closed state, and the vessel in which the zirconium sponge is produced is positioned above, and has been used as a condensation vessel 30 until now.
A container with MgCl ₂ and Mg adhered to the inner wall is positioned below. Next, as shown in FIG. 4c, the reaction vessel 2 is placed above the
The container used as a container is separated from the partition table 1, and an empty container is placed and fixed on the partition table 1 in place of this container. During the container separation and assembly operations, the container located below containing MgCl ₂ and Mg is sealed with the outside air by the damper 9 and the crust is prevented from falling.

Next, as shown in FIG. 4d, the damper 9 and feeder 8 can be replaced again to prepare for the next operation of the apparatus.

As explained above, according to the method of the present invention, after the completion of the evaporative separation operation of zirconium halide,
After closing the passage between the reaction vessel and the condensation vessel using a damper and rotating the two vessels together by 180 degrees, the condensation vessel is reused as the reaction vessel in the next process, so it is not necessary to dismantle and disassemble both vessels. Assembly work is greatly streamlined, allowing for efficient manufacturing.

Furthermore, since the large amount of Mg remaining in the condensation vessel acts as a new reducing agent in the reaction vessel, the amount of reducing agent can be reduced accordingly, and the ignitable Mg in the vessel is isolated from the outside air by a damper. The effect is that there is no risk of combustion.

Furthermore, according to the method of the present invention, the attachment/detachment and opening/closing operations of the damper are performed using a branch pipe for attaching the feeder for supplying zirconium halide, so the operations are facilitated and the manufacturing equipment used This also has the effect of simplifying the process.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view showing an example of a metal zirconium production apparatus used for carrying out the method of the present invention, and FIG.
The figure is a perspective view of the damper, FIG. 3 is an explanatory diagram showing the joint state of the branch pipe and the feeder, and the branch pipe and the damper, and FIG. 4 is an explanatory diagram showing the operating state of the reaction vessel and the condensing vessel. 5... Central tube as a passage, 7... Branch tube, 8
...Feeder, 9...Damper, 20...Reaction vessel, 30...Condensation vessel.

Claims (1)

[Scope of Claims] 1. A method for producing metallic zirconium in which zirconium halide is reduced and separated by evaporation using a reaction vessel and a condensation vessel communicating with the reaction vessel, comprising:
During reduction, zirconium halide is supplied from a side branch tube communicating with the passage between the reaction vessel and the condensation vessel to perform reduction, and after the reduction reaction is completed, the branch tube is closed in the branch tube. and inserting a damper for opening and closing the passage, performing an evaporative separation operation with the damper in the open state of the passage, and after completing this separation operation, closing the passage with the damper,
A method for producing metal zirconium, characterized in that the reaction vessel and the condensation vessel are rotated 180° as a unit, and then the condensation vessel is reused as a reaction vessel in the next step. 2. The method for producing metallic zirconium according to claim 1, wherein zirconium halide is reduced with magnesium. 3. The method for producing metallic zirconium according to claim 1 or 2, wherein after the completion of the reduction reaction, the magnesium and magnesium chloride remaining in the zirconium are heated to evaporate, condensed in a condensation vessel, and separated. 4. Production of metal zirconium according to claim 1, 2, or 3, in which the damper is removed during reduction of zirconium halide and replaced with a feeder for supplying zirconium halide. Method.