JPH0270009A - Container for producing high-purity fine powder of active metal - Google Patents

Abstract

PURPOSE:To allow the pulverization of active metals to the high-purity powder by frosting the moisture in hermetic containers provided with rubber gloves for operation and further converting the moisture to hydroxyl groups by metal Na, than pulverizing the same in an inert gaseous atmosphers at the time of producing the powder of specific active metal which easily forms hydroxide thereof. CONSTITUTION:The plural hermetic containers 2a, 2b, 2c respectively provided with the rubber gloves 3 for operation are connected and the inside of the containers 2a to 2c are evacuated to a vacuum by a discharge system 11 provided to the central container 2b at the time of pulverizing the active metal such as Sr, Ba, Y and Hf which easily forms hydroxide by reacting with water in a high purity state. An inert gas such as Ar is introduced from a gas connecting pipe 28 into the containers. The pressures in and out of the rubber gloves 3 are uniformized by a pressure equalizing means 7 provided to the rubber gloves 3. The residual moisture in the containers is cooled down to <=-150 deg.C by a cryogenic frosting device 29 porovided in the containers 2a to 2c and is thereby frosted. The metal Na is brought into contact with the frost to remove the moisture in the form of NaOH. The inert gaseous atmosphere contg. no moisture is generated in the hermetic containers and the active metals such as Sr are ground in the high-purity state without forming the hydroxide with the moisture.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a container for producing high-purity fine powder of active metal,
In particular, strontium (
High purity fine powder of active metals (I[a, I[
This relates to a container for producing high-purity fine powder of active metals (Group A, IVa, IVb metals). The active metals (IIa, II
The production of high-purity fine powders of [Group a, IVa, IVb metals] is attracting attention9 The surface area of the active metals that generate these hydroxide compounds increases as they are pulverized1, resulting in gas adsorption, occlusion, and surface It causes oxidation, and there is a problem that especially active group I [a metals] react rapidly with moisture and produce pentahydroxide compounds, and these problems have not yet been solved and it is difficult to produce high-purity fine powder. Conventional technology has passed 9 Conventionally, superconducting materials are S), rontium (Sr-), barium (Ba), yttrium (Y), lanthanum (La,
), copper (C, u ), etc., and conventionally, compounds such as single metal salts and oxides have been used as raw materials to produce composite oxides9. Super heat-resistant hafnium (11,f) fine powder undergoes hydrogen reduction of Hf salts to generate and carbonize Hf.

However, since these manufacturing methods use metal compounds, the reaction system is more complex than that of pure metal fine powder, resulting in a decrease in purity, which causes a decline in the performance of characteristic values depending on the application. There was also the problem that elements and groups that are not needed in the final product, especially those contained in salts, decomposed and escaped during the manufacturing process, forming vacancies and causing disorder in the crystals.9 Furthermore, there was a problem that the reaction system Since it is complex, it requires multiple steps, and there is a problem in that the cost due to the installation Li cost during mass production is large.

Therefore, the present applicant has developed active metals (I[a, I[Ia, , IVa, IVb group metals) that generate such hydroxide compounds.
[Problems to be Solved by the Invention] However, conventionally, the above-mentioned method for producing high-purity fine powder of active metals has been filed separately. Since the powder manufacturing method J had not been established, there was no equipment that could effectively carry out this manufacturing method.9 Therefore, in view of these problems, the present invention has developed a method for producing active metals that produce hydroxide compounds. na,,I[Ia,IV a
The object of the present invention is to provide a container for producing high-purity fine powder of active metals, which can produce high-purity fine powder of active metals (Group IV b metals).

[Means for Solving the Problems] In order to achieve the purpose of the upper rudder, the present invention cJ provides one side wall of a hermetically sealed container in which rubber gloves are worn while facing the interior in order to perform internal work in an inert gas atmosphere. The container is equipped with a cryogenic cooling means for condensing moisture remaining in the container, and is also equipped with a diagonal arbor that makes the internal pressure equal to atmospheric pressure.

In addition, a plurality of sealed containers with the above-mentioned rubber gloves attached are installed in communication with each other. 1. This opening/closing door is equipped with a single pressure equalizing stage for communicating the inside of the glove covered with the opening/closing door so as to maintain the same atmosphere as the inside of the container.

``Function) - 1 A series of IJ'' is constructed, and a cryogenic cooling means is provided on one side wall of the sealed container to which rubber gloves are attached facing the inside in order to perform internal work in an inert gas atmosphere.
When the ultra-low temperature chiller is brought into contact with the airtight container using this cooling means, the residual moisture in the atmospheric gas (dew condenses on the inner wall of the container). This method uses the moisture trap technology disclosed in ``Removal Method''9.
~ Liumium lumps are brought into contact with each other to form sodium hydroxide by acting as a so-called solid phase getter, and the residual moisture is decomposed and removed as hydroxyl groups. Further, the atmospheric gas still contains a residual trace amount of moisture without dew condensation L7. Regarding this, metal helium is heated in an atmospheric gas containing this residual trace amount of water using the device disclosed in "S1-Lium Steam Generator", which has not been filed separately. ~ Generating and dispersing lithium vapor 9 Then, the sodium~lium vapor comes into dispersion contact with the residual W contained in the atmospheric gas L and the amount of water, acting as a so-called gas phase getter, and producing sodium hydroxide. The residual trace water that could not be removed by the solid-phase getter is reduced to an extremely low concentration (to 10-, 1. OOW, /Vp p b
) The active metal that produces the hydroxide compound is pulverized in the inert gas atmosphere from which residual moisture has been removed.
This pulverization is performed by mechanically pulverizing the active metal using the cryogenic cooling device to reduce its ductility and using a detailed crushing method.

The finely powdered powder is then sealed and stored in a storage container under an atmosphere described in 2 above to maintain its high purity during storage.

The series of internal operations described in step 2 must be carried out safely by using rubber gloves attached to the container, or by having the container equipped with an accumulator to equalize its internal pressure to atmospheric pressure. Furthermore, since a plurality of closed containers to which the rubber gloves are attached are provided in communication with each other, different tasks can be performed individually within each container, making it possible to perform assembly line work.

Furthermore, in order to install the rubber gloves in item 1, an opening/closing door is provided at the opening so as to cover it from the outside, and since this opening/closing door is equipped with the pressure equalization means, the inside of the sealed container cannot be evacuated or Even in an inert gas atmosphere, the inside of the glove covered by the opening/closing door is maintained at the same pressure as the inside of the container, and the rubber glove is damaged. Never.

[Example] A preferred embodiment of the present invention will be described in detail below with reference to the accompanying drawings.9 As shown in Figs. airtight containers 2a, 2b,
2c are connected in series. These airtight containers 2a, 2b, 2. Rubber gloves 3 for operation are placed on the front of c.
or installed.

The rubber gloves 3 are attached to the inside of the containers 2a, 2b, 2c by a kite ring 4 so as to face the inside of the containers 2a, 2b, 2c, as shown in FIG. 7, in order to perform internal work while maintaining an inert gas atmosphere. The attachment opening of this rubber glove 3 has a seventh
As shown in Figures 8 to 8, the opening/closing door 5 is attached via an O-ring 6 so as to be freely openable and closable so as to cover the above-mentioned opening from the outside.The opening/closing door 5 is equipped with a pressure equalizing means 7. 9 This pressure equalizing means 7 includes a pressure hose 8 that connects the inside of the glove covered by the opening/closing door 5 and the inside of the container to maintain them at the same atmospheric pressure, and an attachment part of the pressure hose 8 on the container side. It consists of an interposed electric on-off valve 9.

A viewing window IO for observing the inside of the container is provided above the attachment portion of the rubber grip @3 on the front side of the closed containers 2a, 2b2c.

Further, an exhaust nozzle 11 is provided at the top of the airtight container 2b located in the center, and an exhaust system 14 is connected to a vacuum pump 7.13 for evacuating the inside of the container, as shown in FIG. or connected. This exhaust system 1
4 includes a vacuum gauge 15 main switching valve 16 and exhaust switching valve 1.
7 are interposed in order. The exhaust system 14 between the vacuum gauge 15 and the main switching valve 16 is branched to form a pressure regulating system 18, which is connected to an accumulator 20 through an electric on-off valve 19 via L5 to make the internal pressure of the container equal to atmospheric pressure. has been done.

One of the electric on-off valves is provided with a foot pedal 21, and by stepping on the foot pedal 21, the electric on-off valve 19 is opened. The pressure regulating system 18 is connected by a flange joint 22 with an O-ring, and the accumulator 20 at the tip thereof is also connected by a flange joint 23 with an O-ring as shown in FIG. The accumulator 20 has a pressure-resistant mesh vinyl hose 25 attached to the tip of the backflow buffer 24.

It is crushed in oil (gelosin) 27 housed in a glass bottle 26. Furthermore, an inert gas pipe connection port 28 for introducing an inert gas into the inside of each of the closed containers 2a, 2c is provided at the lower front of each of the closed containers 2a, 2c. One side wall of b2c is equipped with two cryogenic cooling means for condensing moisture remaining in these containers. The two cryogenic cooling means include a cryogenic dew plate 30 formed as a part of the back wall of the container body, and a cryogenic dew plate 30 formed integrally with this to cool the cryogenic dew plate 30. A cooling box body 31 for accommodating a refrigerant, a funnel-shaped inlet 32 for supplying cryogenic refrigerant into the box body 31, and an automatic temperature regulator 33 for adjusting the cooling temperature by heat pipe heating. It has become. The cryogenic dew condensation plate 30 is attached to the container body via a double seal 34, and the cryogenic dew condensation plate 30 and the box body 31 integrally formed therewith are made of copper. 1. They are covered with a heat insulating material 35 9 and the airtight container 2
Illumination lights 36 are attached to the ceilings of a, 2b, and 2c, respectively.

In the figure, -37 is the operation panel, 38 is the power connector inside the container,
39 is container cleaning [].

The active metal (Il
a, IIIa, IVa, IVl) group metals) to produce high-purity fine powders.
a, ■a, IVa, IVb group metals) include, for example, strondium (Sr), barium (Ba), yllium (Y), lanthanum (La), which are raw materials for superconducting materials.
Zirconium (Zr) and hafnium (Hf), which is a raw material for superhard and super heat-resistant materials, are used9. Active metals (Ua, II[
In order to produce high-purity fine powder of group metals a, lVa, and IVb, the insides of the sealed containers 2a, 2b, and 2c are evacuated by the vacuum pump 13 connected to the evacuation system 14 to create a vacuum atmosphere 9 After that, the container 2: L 2+) 2C
9 These vacuum evacuations and inert gas replacements are performed by supplying an inert gas from the inert gas pipe connection port 28 to replace the
This is repeated four times. The degree of vacuum is measured by a vacuum gauge 15 provided in the exhaust system 14. Then, A-8 of the pressure regulating system 18, which is formed by branching into the exhaust system 14)
The pressure of the inert gas atmosphere is made the same as that by the +-mulator 20, and work inside the container can be carried out.9 Evacuation is performed by manually opening and closing the main switching valve 16 and the exhaust switching valve 17. Pressure adjustment by the accumulator 20 is carried out by opening and closing one of the electric on-off valves using the foot pedal 21.

The airtight containers 2a2b, 2c are configured so that the inside can be observed through a viewing window 10, and are equipped with a rubber hand dyer 3 that can be operated from the outside without impairing the sealing properties. ”−
1. When evacuating the inside of the containers 2a, 2b, and 2c and creating an inert gas atmosphere, the opening/closing door 5 attached to the opening of the rubber gloves 3 (=j) is closed, and the opening/closing door 5 is closed. The inside of the 1,000 bags covered by the opening/closing door 5 and the inside of the container are maintained at the same atmospheric pressure by means of pressure equalizing means 7 which is highly rated, thereby preventing the rubber gloves 3 from being damaged.

Even if the atmosphere to which active metals that generate hydroxide compounds are exposed is made into a vacuum or inert gas atmosphere as described in 2, moisture remains in the atmosphere. Remove residual moisture using the "removal method". A cryogenic dew condensation device 29 is provided on one side wall of the airtight container 2a2+), 2C, and a cryogenic dew condensation device 29 is provided to supply cryogenic refrigerant from an inlet 32 into the box body 31.
touch it. For example, liquid nitrogen is used as the cryogenic refrigerant and is cooled to below -150°C. Then, the remaining moisture in the atmospheric gas is condensed on the inner wall of the container 2a2b 2c.
Bring the lium lumps into contact.

Since the second rod-shaped metallic sodium lump is used in the above-mentioned inert gas atmosphere, it does not catch fire and acts as a so-called solid-phase getter. The dew-condensed moisture (1) is stored in the containers 2a, 2b, 2c while being immersed in oil such as petroleum to prevent ignition.
- When metal tin (Na) acts as a solid phase getter on [0], 2 Na + 2 H
20-" 2N a OH-1-82, a reaction occurs and sodium to lithium hydroxide (NaOII) is produced, and -11 the remaining moisture is decomposed and removed as hydroxyl groups.9 However, the atmospheric gas There is a trace amount of moisture remaining inside that does not dew7 even when cooled to a cryogenic temperature.The solid phase getter cannot remove the dew condensed moisture9. To prevent ignition, metal sodium is heated and melted at about 600° (゛) in 2C to generate sodium vapor.Similarly, this metal sodium is immersed in oil such as petroleum (G) to prevent ignition. The helium vapor is stored in the containers 2a, 2b, 2c and taken out in an inert gas.The helium vapor is dispersed in the sealed containers 2a1, 2b, 2c and used as a gas phase getter for removing moisture. 9Residual trace moisture in the acting atmospheric gas (
When 1~lium vapor (Na) acts as a gas phase getter on H2O), 2 Na + 2 H20 → 2 Na
Reacts like OH+H2 to form sulfur and lithium hydroxide (N
aOH), and the remaining water is decomposed and removed as hydroxyl groups to an extremely low concentration (10 to 100 W, /Vρpb). It becomes two.

The moisture removal method in which sodium vapor (Na) acts as a vapor phase getter is carried out using the apparatus disclosed in "S1 - Thulium Vapor Generator", which has been filed separately.

It is necessary to confirm whether the residual moisture in the inert gas atmosphere is removed to an extremely low concentration (10 to 100 W, /Vppb) by the residual moisture removal method as in 2. L7 Kashi 1,
Even if a "method for removing residual moisture in atmospheric gas" is established, the concentration in the gas is extremely low (10 to 100 W, /Vp p b ).
There is no conventional technology that can simply and qualitatively detect the moisture present in water. Therefore, the present applicant has devised a "Method and Detector for Detecting Trace Moisture in Atmospheric Gas" and has separately applied for a method for detecting trace moisture in atmospheric gas. The atmospheric gas is brought into contact with black barium powder, and the presence or absence of trace moisture in the atmospheric gas is detected by the change in color of the black barium powder. In addition, the trace moisture detector in atmospheric gas is
A cylinder whose contents can be seen through, a black barium powder housed in the second cylinder, and the black paris and rum powder are held in the cylinder to maintain them, and an atmospheric gas to be measured is introduced. a ventilating member for the cylinder, a lid removably provided at both open ends of the cylinder to prevent gas from entering the cylinder, and a lid for sealing the gap between the lid and the cylinder. It consists of a sealant. , As shown in step 2, use black barium powder as an indicator of extremely trace moisture, and confirm the remaining trace moisture by the color change from black to white.If the extremely low concentration is reached and there is no moisture, remove the moisture using sodium vapor. is repeated.

When the residual moisture in the containers 2a, 2b, 2C reaches the extremely low concentration, the active metal (IIa
, nIa, IVa, IVb group metals). First, the active pure metal lump is roughly pulverized, especially hafnium (H
Regarding f) coarse grinding of crystal bars, a separate application will be filed.
The method and apparatus disclosed in "Method and Apparatus for Coarse Grinding of Hafnium Crystal Bars" are employed. 7. Then, the second coarse mixed crystal powder is immersed in a cryogenic coolant such as liquid nitrogen, and maintained at -150°C or lower (1) to reduce its ductility by cryogenic cooling. Furthermore, in order to mechanically crush this, the crushing container and vibrator are similarly maintained at -150°C or less with a cryogenic refrigerant such as liquid nitrogen. . This pulverization step may be performed by a method other than the pulverization method, but the purity is not impaired and the apparatus is more compact than pulverization using curvature.

Thereafter, the process moves to a storage process to store the pulverized active pure metal. This storage process prevents gas adsorption, occlusion, and surface oxidation due to the increase in surface area due to pulverization, and also uses an inert gas that removes the residual moisture to an extremely low concentration to prevent the formation of hydroxide compounds. Store tightly in a storage container in an atmosphere. This storage container is sealed with a tuple seal to prevent contamination from oxygen and moisture in the atmosphere.

Incidentally, active metals (Il) that generate hydroxide compounds in this way
In order to manufacture high-purity fine powder of group a, lIa, IVa, IVb metals), three closed containers with the rubber gloves 3 attached were installed in communication. Since another work can be done at the same time, assembly work can be performed. Only one closed container may be provided, or all processes may be performed in the same container.

In addition, take one module of the above airtight container and place it on the conveyor (
Purposes such as installation module, kneading work module, powder metallurgy forming press module, sintering furnace module, weighing/packing module, raw material preparation module, demolition work module, etc. In short, according to claim 1 of the present invention, active metals (IIa, I[a ,IVa,IV
High purity fine powder of Group B metals can be obtained.

In addition, according to claim 2, since different operations can be performed individually in each container, it is possible to perform assembly line work. Even in a gas atmosphere, the inside of the glove covered by the opening/closing door is maintained at the same pressure as the inside of the container, thereby preventing damage to the rubber glove. I can do something like two.

[Brief explanation of the drawing]

FIG. 1 is a front view showing one embodiment of the container for producing high-purity fine powder of active metal of the present invention, FIG. 2 is a back view of FIG. 1, FIG. 3 is a right side view of FIG. 1, and FIG. The figure is a schematic side view showing a cryogenic cooling device for a container for producing high-purity fine powder of active metal of the present invention;
FIG. 5 is a system diagram showing the installation of the actuator of the container for producing high-purity fine powder of active metal of the present invention, FIG. 6 is a schematic diagram showing the actuator of the container for producing high-purity fine powder of active metal of the present invention, and FIG. The figure is a schematic view showing the rubber glove 2 opening/closing door and pressure equalization means of the container for producing high-purity fine powder of active metal of the present invention.
The figure is a schematic view showing the rubber gloves and opening/closing door of the container for producing high purity fine powder of active metal of the present invention, and FIG. 9 shows the opening/closing door and pressure equalization means of the container for producing high purity fine powder of active metal of the present invention. Schematic diagram 9 In the figure, 1 is a container for manufacturing high-purity fine powder of active metal, 2 is a closed container, 3 is a rubber glove, 5 is an opening/closing door, 7 is a pressure equalizing means, 20
is an accumulator, two 6. ll Cryogenic cooling means 9 Patent applicant Ishikawajima Harima Heavy Industries Co., Ltd. Ishikawajima Master Metal Representative Patent attorney Nobuo Kinutani ~ / Ha ・′;,・tsu

Claims (1)

[Scope of Claims] 1. Cryogenic cooling for condensing moisture remaining in a sealed container on one side wall of a sealed container to which rubber gloves are attached facing the inside in order to perform internal work in an inert gas atmosphere. 1. A container for producing high-purity fine powder of an active metal, characterized in that it is equipped with means and an accumulator for making the internal pressure equal to atmospheric pressure. 2. The container for producing high-purity fine powder of active metal according to claim 1, wherein a plurality of closed containers to which the rubber gloves are attached are provided in communication. 3. An opening/closing door is provided at the attachment opening of the rubber glove so as to cover it from the outside, and the opening/closing door is connected to the opening/closing door so as to maintain the interior of the glove covered by the opening at the same pressure as the inside of the container. 3. The container for producing high-purity fine powder of active metal according to claim 1, further comprising a pressure equalizing means for producing a fine powder of active metal.