JPS5818142B2 - Equipment for supplying solid sublimable substances to high-temperature parts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention provides ZrCl, , HfC'A4 and A11C
This invention relates to an apparatus for supplying and adding a sublimable metal halide such as No. 13 in a solid state to a high-temperature container used industrially, such as a reduction reaction container or a sublimation purification container.

Conventionally, in order to supply a sublimable substance to a high-temperature container, it was first sublimated into a gaseous state using a sublimation device independent of the container, and then introduced into the container by pipe transfer. However, this conventional method has the following industrial drawbacks.

1) A sublimation device and heating energy for sublimation are required to once sublimate the sublimable substance into a gaseous state.

2. The conduit for transferring the gaseous sublimable substance from the above-mentioned sublimation device to the high-temperature container requires a temperature equal to or higher than the sublimation point of the sublimable substance over the entire area; If there is a low temperature area below the sublimation point, the sublimable substance will solidify and block the conduit.

For example, ZrCl3+ is a sublimable substance that is solid at room temperature and has a sublimation point of 331° C., and is used as a raw material for producing metallic zirconium sponge by reducing it with Mg in an inert gas atmosphere by the Kroll method.

The above reduction reaction by Mg proceeds according to the following formula.
generate.

Z r C14 (g) + 2Mg (1) - + Z r
(s) + 2 Mg C12 (1) (g): gas, (1
): liquid, (s) solid In order to carry out this reaction, conventionally, gasified ZrCl4 is introduced into a reaction vessel containing molten Mg and an inert gas atmosphere using a feeding device, and the Mg
The reaction was carried out by contacting with a sublimation device, but as mentioned above, a sublimation device and heating energy for that purpose are required.

In view of the above-mentioned shortcomings of conventional supply devices of this type, the inventors have conducted various studies on a device for supplying a sublimable substance in a solid state into a high-temperature container.

As an example, a method of inserting an electric heater into the conveyor shaft of a screw conveyor was proposed in a patent application filed in 1970 by the present applicant.
As disclosed in the specification and drawings of No. 17474, ``Method for manufacturing zirconium sponges and apparatus therefor'', even in this method, it is inevitable that ZrC114 adheres to the control wall surface of the supply means. , oj could not be supplied satisfactorily Regarding the points mentioned above, as a result of further research and experiments, it was found that gaseous ZrCl4 tends to solidify even when it comes into contact with the vessel wall in the temperature range of 250 to 280°C.

It has been found that when the same gaseous Z r C14 is rapidly cooled to about 150° C. or lower, it becomes a soft powder and does not solidify, and the present invention was completed based on this finding.

The present invention has been made in view of the above points, and it is an object of the present invention to provide a supply device in which the supply means does not become clogged when a sublimable substance is supplied to a high temperature section above its sublimation point. The purpose is to

That is, the present invention provides an apparatus for supplying a sublimable substance such as zirconium halide to a high temperature section such as a reduction reaction vessel or a sublimation purification vessel in the form of a solid, at least the portions of the two supply means that come into contact with the high temperature section. By cooling to a temperature below its sublimation point, the gaseous sublimable substance flowing from the high temperature section to the supply means is rapidly cooled and turned into powder, and the sublimable substance is transferred to the wall surface of the supply means. It is an object of the present invention to provide a device that prevents sticking and ensures smooth supply.

Next, the present invention will be explained with reference to a first embodiment shown in FIGS. 1 and 2.

The figure shows a zirconium sponge manufacturing apparatus having a supply device according to the present invention.

In Fig. 5, reference numeral 1 denotes a closed reaction vessel into which Mg is charged, which is placed in an electric furnace 3 having a heater 2, and whose upper opening is sealed by a sealing lid 5 having a pressure regulating valve 4. .

Reference numeral 6 denotes a storage tank 4 for storing purified powder Z r C114, and this storage tank 6 and the reaction vessel 1 are connected by the following automatic supply means 7 consisting of a closed screw feeder.

The transfer outer cylinder 8 of this supply means 7 has its inner end connected to the reaction vessel 1.
, and a portion of the lower end hopper of the storage tank 6 is opened at the upper surface near the outer end of the outer cylinder 8 .

A driven sprocket 10 is attached to the outer end of the screw shaft 9 that is rotatably supported in the outer cylinder 8 and protrudes from the outer end opening of the outer cylinder 8. The outer periphery of the shaft 9 is sealed.

A cooling water channel 13 is formed within the wall surface of the outer cylinder 8, which communicates from an inlet 11 opened at the upper surface near the inner end to an outlet 12 opened at the lower surface near the outer end. ing.

A cooling hole 15 having a drainage opening 14 on its outer end surface is formed in the screw shaft 9 in the shape of a bore, and inside this cooling hole 15 is a water flow pipe through which cooling water is supplied from the outer end opening side. 16 is loosely inserted.

In this way, the supply means 7 has a water-cooled structure.

Next, the operation of the above device will be explained.

First, check that the entire device is airtight, then exhaust the air and then inject Ar, an inert gas, to a pressure slightly higher than atmospheric pressure.

Mg in the reaction vessel 1 is melted by the electric furnace 3.

Heat to approximately 800°C.

This reaction vessel 1 weighs 0.1 to 0.2 kg more than the storage tank 6.
/cr! Since the pressure is high, powdered refined ZrC114 is pumped into the reaction vessel 1 while being pushed by the screw of the supply means 7.
Supply and add inside.

The above powdered ZrcIj4 was supplied into the reaction vessel 1.

The heat inside the container 1 is absorbed to gasify it, and it reacts with Mg to form Zr.
and at the same time produce MgCl2 as a by-product.

Here, the supply means 7 is a cooling water channel 13 in the outer cylinder 8.
The screw shaft 9 is constantly water-cooled from the inside and outside by cooling water that flows from the inner end opening of the water flow pipe 16 through the cooling hole 15 to the drainage opening 14.

Therefore, even if the gaseous ZrC14 enters the supply means 7, it is rapidly cooled to about 150°C and heated to 250-280°C.
Since the temperature range of 0.degree. C. is extremely narrow, ZrCl does not solidify on the wall surface, becomes a powder, and is directly transported back into the reaction vessel 1, so there is no risk of clogging the passage.

The operation of the device according to the present invention will be explained in more detail in comparison with the prior art.

The reaction vessel 1 is made of heat-resistant steel, but since Fe and Zr forming the vessel 1 form a eutectic and become alloyed at 935°C, in the case of the conventional reaction by introducing the gaseous ZrCl4, the temperature due to the exothermic reaction Although it was not possible to accelerate the reaction rate due to the increase in
In the four-supply system, part of the heat of one reaction is transferred to solid ZrC.
The rise in reaction temperature is suppressed because it is taken over by the gasification of l14.

The reaction speed will be accelerated by that proportion.

Furthermore, if solid Z and rcA4 are supplied by a supply means such as a simple screw feeder,
The temperature at the junction between the supply means and the reaction vessel is approximately 700° C., whereas the temperature at the side of the storage tank of solid ZrCl 14 is approximately room temperature.

Therefore, a gaseous Z
r There is a temperature range in which C14 tends to solidify, and gaseous ZrCA'4 from the reaction vessel enters the supply means and gradually adheres to the screw feeder blades, which thickens and eventually forms the supply passage. There is a risk of blockage.

In contrast, according to the apparatus according to the present invention.

As mentioned above, there is no risk of supply passage blockage;
Compared to the conventional gaseous ZrCl4 supply method, tests have shown that zirconium sponge can be produced with approximately twice the efficiency.

FIG. 3 shows a second embodiment of the present invention, in which solid ZrCA4 similar to the above is added and supplied from a storage tank 6 to a reaction vessel 1 via a supply means 7 consisting of a rotary feeder. It is a device that does

Even in the case of such an apparatus, there is a risk that ZrCl4 solidifies in the chute pipe 17 connecting the supply means 7 and the reaction vessel 1 and blocks the supply passage. By attaching a cooling jacket 18 having the same structure as the outer cylinder 8 in Example 1 and rapidly cooling it by passing cooling water, the gaseous Zrcl 14 entering from the side of the reaction vessel 1 becomes powder, and clogging of the passage is prevented. Ru.

In the second embodiment, parts corresponding to those in the first embodiment are given the same reference numerals as in the first embodiment, and detailed explanation thereof is omitted.

Note that the apparatus according to the present invention is not limited to supplying powdered Z r C14 to a reaction vessel, but can also be used to supply Hf (J?4 and) kl
The present invention can also be applied to a device that supplies a sublimable substance such as a metal halide such as C13 to a high temperature section, and similar effects can be obtained.

As explained above, in this invention, the gaseous sublimable substance that enters the supply means from the high temperature section is rapidly cooled in the supply means, so that it is re-supplied in the form of powder. This has the effect of efficiently supplying the solid sublimable substance to a high temperature section above its sublimation point without causing blockage of the supply passage.

9 Brief Description of the Drawings FIG. 1 is a partial cross-sectional view of a zirconium sponge manufacturing apparatus having a supply device according to the first embodiment of the present invention, FIG. 2 is an enlarged cross-sectional view of the same essential parts, and FIG. The figure is a sectional view of a zirconium sponge manufacturing apparatus 5 having a supply device according to a second embodiment of the present invention.

1... Reaction vessel as a high temperature section, 7...
・Supply means, 13... Cooling water channel, 15...
...Cooling hole, 16...Water pipe, 18...
...cooling jacket.

Claims (1)

[Claims] 1. Transferring a solid sublimable substance to a high abyss below its sublimation point,
A device for supplying a solid substance by a supply means, characterized in that at least a portion of the supply means that comes into contact with the high temperature part is cooled to a temperature below the sublimation point of the sublimable substance. Device for feeding substances to high temperatures. 2. In an apparatus for supplying solid zirconium halides as a solid sublimable substance into a high-temperature container such as a reduction reaction container or a sublimation purification container at a high temperature higher than the sublimation point thereof, as a solid by a supply means, at least The part of the supply means connected to the inside of the high-temperature container is rapidly cooled to a temperature below the sublimation point of the zirconium halides, thereby controlling the gaseous zirconium halides flowing out from the high-temperature container side to the supply means side. Supplying the solid sublimable substance to the high temperature section according to claim 1, characterized in that the solid sublimable substance is condensed into powder in the cooling section of the supply means and sent back into the container. Bag too