JPH01317105A - Production of metal sulfide - Google Patents

Abstract

PURPOSE:To enable the repeated use of a reaction vessel without breaking the vessel after each reaction process and to safely produce various kinds of metal sulfides in large quantities by using a specific bell-shaped reaction vessel and heating and reacting elemental metal and elemental sulfur in the vessel. CONSTITUTION:One or more kinds of elemental metals and elemental sulfur (raw material 15) are sealed in a bell-shaped reaction vessel (composed of a main body 1, a flange 2, a bottom plate 3, a clamping plate 4 and a table 5 for the reaction vessel) furnished with a detachable bottom plate 3. After evacuating the gas in the reaction vessel with evacuation means (8, 9, 10, 11), the contents of the vessel are heated in closed state with heaters 16, 17.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing metal sulfides. More specifically, the present invention relates to a method for producing metal sulfide from an elemental metal and an elemental sulfur.

Titanium sulfide (TiS2, Ti53), vanadium sulfide (
VS2), molybdenum sulfide (MO52, MO6Se)
, niobium sulfide (NbS3), tungsten sulfide (wsz
), zinc sulfide (ZnS), zirconium sulfide (ZrS)
2), cadmium sulfide (CdS), nickel sulfide (N
iS), lead sulfide (PbS), antimony sulfide (Sb2
Metal sulfides such as S3), bismuth sulfide (Btzh), and copper molybdenum sulfide (CLI2MO6Sll, CuaMo6Se) have recently been used in many fields such as battery electrode materials, luminescent materials, catalysts, highly refractory materials, lubricants, and thermoelectric materials. has been in the spotlight.

[Prior art and problems to be solved by the invention] Although the physical and chemical properties of these metal sulfides, such as their crystal structure and electronic structure, have been extensively studied, there is no industrial manufacturing method. Most of the methods for this are based on the direct reaction between an elemental metal and an elemental sulfur.

Methods for producing these metal sulfides include a precipitation reaction using hydrogen sulfide or ammonium sulfide from an acidic solution, and a method of reacting metal salts or simple metals with hydrogen sulfide, but most of these methods are No research and development has been conducted on this, and therefore, the direct reaction method in which an elemental metal and an elemental sulfur are sealed in a sealed tube and then heated to react has been exclusively employed.

Most metal sulfides can be produced using this method, and metal sulfides of various compositions can be produced by changing the molar ratio of elemental metal and elemental sulfur sealed in the sealed tube. can. Furthermore, since this reaction is carried out in a sealed tube as described above, there is no contamination of foreign substances from outside the system, and it is possible to obtain a product of high purity and a high degree of crystallinity.

However, in this method, elemental sulfur is partially vaporized in the sealed tube by heating and exists as a gas, so the material of the sealed tube must be one that does not react with this gaseous elemental sulfur.

For this reason, a sealed tube made of metal cannot be used, and a sealed tube made of glass or quartz glass is used. However, when such a sealed tube made of glass or quartz glass is used as a reaction vessel, 1) After the reaction is completed, the sealed tube is destroyed and the generated metal sulfide is taken out, so a new sealed tube must be manufactured each time. have to,
This method is complicated and increases manufacturing costs, which is a problem when producing it on an industrial scale. 2) Furthermore, since elemental sulfur exists in a gaseous state as described above, the sealed tube has an internal pressure, which often causes it to break during the heating up to the reaction temperature or during the reaction, which is extremely dangerous.

3) Therefore, in order to prevent this destruction as much as possible, sealed tubes must be made small, with an internal volume of at most 1000 mff or less, and therefore mass production is not possible and metal sulfides are expensive. .

[Means to solve the problem]

In view of the above problems, the present inventors have developed a method suitable for producing various metal sulfides from elemental metals and elemental sulfur, that is, a reaction vessel that can be used repeatedly without being destroyed each time, and is safe. The present invention has been completed as a result of extensive research into methods that can produce various metal sulfides in large quantities.

That is, in the present invention, one or more elemental metals and elemental sulfur are sealed in a bell-shaped reaction vessel equipped with a removable bottom plate, and after the gas in the reaction vessel is evacuated, the reaction vessel is heated in a sealed state. The present invention provides a method for producing a metal sulfide characterized by the following.

[Detailed disclosure of the invention] The present invention will be explained in detail below.

The type of metal sulfide that can be produced by the present invention is not particularly limited, and the present invention can be applied to metal sulfides that have been conventionally produced from elemental metals and elemental sulfur using sealed tubes made of glass or quartz glass. Specific examples of such metal sulfides include sulfides of titanium, vanadium, chromium, molybdenum, manganese, iron, nickel, copper, lead, antimony, zinc, blue lead, zirconium, tantalum, niobium, etc., and sulfides of these metals. Examples include complex sulfides. Also included are sulfides containing phosphorus and halogen, such as CuxPSyl.

In the present invention, the elemental metal used as the raw material is preferably in the form of a sponge or powder in order to complete the reaction in as short a time as possible. There are no particular restrictions on purity, but
It may be selected depending on the required purity of the product metal sulfide.

Since the raw material elemental sulfur is in a liquid state or partially vaporized and gaseous at the reaction temperature, it does not necessarily have to be in a powder form, and may be in a granular or lump form. Moreover, the purity may be selected according to the purity of the product, as in the case of single metals.

The ratio of the elemental metal and elemental sulfur charged into the reaction vessel may be adjusted to match the molar ratio of the metal sulfide to be obtained.

The reaction vessel charged with elemental metals and elemental sulfur is sealed after evacuating the air and other gases inside. Regarding evacuation, it is preferable that the inside of the reaction vessel be in a high vacuum after evacuation, and this In the invention, the vacuum is normally evacuated to less than 1 Torr.

A bell-shaped (Herjar-type) reaction vessel (hereinafter simply referred to as reaction vessel) equipped with a removable bottom plate used in the present invention
Since the charged elemental metal and elemental sulfur are heated to the reaction temperature, the elemental sulfur is vaporized and exists in a gaseous state in the reaction vessel during the heating up to the reaction temperature and during the reaction. Therefore, all parts of the reaction vessel that come into contact with the gasified elemental sulfur must be made of glass or quartz glass.

The metal sulfides produced by the method of the present invention have different reactivities depending on the type of metal, as will be described later, and therefore the reaction temperatures are also varied accordingly. For this reason, the reaction temperature is selected in the range of 200-1200'C, but the reaction temperature is 50'C because the above reaction vessel is heat resistant.
If the reaction temperature is below about 0°C, it may be made of glass, but if the reaction temperature exceeds this temperature, it is necessary to use quartz glass.

The above-mentioned reaction temperature is the same as in the case of a conventional manufacturing method using a sealed tube made of glass or quartz glass. Specifically speaking, when obtaining relatively highly reactive sulfides such as nickel, zinc, and bismuth, the
°C1 When obtaining sulfides such as zirconium, molybdenum, kuntal, and niobium with low reactivity, the temperature is 800 to 1200.
A temperature of °C is required. The elemental metal and the elemental sulfur are sealed in the reaction vessel used in the present invention, and are reacted at the above temperature for a predetermined time, then naturally cooled, and the reaction product is taken out from the reaction vessel. As an example is shown in the figure, since the bottom plate has a removable structure, it can be taken out separately from the bottom plate.

The method for producing a metal sulfide of the present invention described above will be explained with reference to FIG.

FIG. 1 is a front view of a reaction vessel and a heating device used in the present invention, and in FIG. 1, the right half of the reaction vessel is shown as a sectional view.

The bell-shaped reaction vessel main body 1 has a flange-like structure at the bottom, and a bottom plate 3 is provided below the flange portion 2. The flange portion 2 and bottom plate 3 of the reaction vessel 1 are tightened with bolts by a tightening plate 4 and a reaction vessel seat 5, thereby sealing the reaction vessel main body 1.

Note that the lower surface of the flange portion 2 and the upper surface of the upper bottom plate 3 are in a sliding shape, and the inside of the reaction vessel main body 1 is sealed by the above-mentioned tightening. A gasket 6 is inserted between the reaction vessel seat 50 and the reaction vessel seat 50.

Further, the reaction vessel seat 5 is provided with a seal box 8 and an air cylinder 9, and gas such as air in the reaction vessel main body 1 is passed through the seal box 8, air cylinder 9, and piping 10 to the vacuum pump 11. After evacuation, the air cylinder 9 is closed to prevent outside air from entering the reaction vessel body 1.

Furthermore, a thermocouple protection tube 12 is inserted into the reaction vessel body 1, and the temperature inside the reaction vessel body 1 can be measured by the thermocouple inside the thermocouple protection tube 12.

A pedestal 14 is provided in the reaction vessel main body 1, and a tray 13 is placed on the pedestal 14.
3 contains elemental metal and elemental sulfur as raw materials.

Note that a plurality of pedestals 14 and trays 13 can be installed in the reaction vessel main body 1. Further, the pedestal 14 may be omitted depending on the case.

A heating device 16 such as an electric furnace that can be lifted up and lowered is provided on the outside of the reaction container body 1, so that the reaction container body 1 can be heated.

In the above apparatus, the reaction vessel main body 1, the flange portion 2, the bottom Fi3, the thermal lightning protection tube 12, the pedestal 14, and the tray 13 must be made of glass or quartz glass.

The reaction vessel used in the present invention has the structure and configuration as described above. Therefore, after the elemental metal and elemental sulfur are housed in the tray 13, the flange portion 2 and bottom plate 3 of the reaction vessel main body 1 are tightened and sealed by the clamping plate 4 and the reaction vessel seat 5.

After the reaction vessel main body 1 sealed in this way is evacuated from the internal gas such as air as described above, the air cylinder 9 is closed. Thereafter, the heating device 16 is hung down to heat the reaction vessel main body 1 to raise the temperature to the reaction temperature.

After the temperature is raised, the reaction is carried out at that temperature for a predetermined period of time, and then the heating device 16 is lifted up and allowed to cool naturally to room temperature, the bottom plate 3 and the reaction vessel main body 1 are separated, and the reaction product in the tray 13 is taken out. be.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. still,
In the following, percentages are by weight.

Example 1 Titanium disulfide was produced using the apparatus shown in FIG. That is, spongy metal titanium 4 with a purity of 99.0%.
788 g of powdered elemental sulfur 6413 with a purity of 99.9%
(Ti:S molar ratio -1.0:2.0)
After that, they were placed approximately equally in ten trays 13 made of quartz. After that, the flange part 2 and bottom plate 3 of the reaction vessel body 1 are tightened with bolts using the tightening plate 4 and the reaction vessel seat 5, and then the pressure inside the reaction vessel body 1 is reduced to 1O- by the vacuum pump 11. After evacuation to 2 Torr, the air cylinder 9 was closed.

After evacuation, lower the heating device 16 to 20°C/h.
The temperature was raised to 700°C at a heating rate of 700°C.
The reaction was carried out for 2 hours. After the reaction was completed, the heating device 16 was lifted to allow it to cool naturally to room temperature, and then the reaction vessel main body 1 and the bottom plate 3 were separated, and the reaction product in the tray 13 was taken out.

The result of analysis of the obtained reaction product using an X-ray diffraction apparatus confirmed that it was a single-phase compound and was titanium disulfide (TiSz). Moreover, this TiS2 has a specific surface area of 0.
It was 8%/g and was fine particles.

-11 Example 2 Nickel (Ni), zinc (Zn), zirconium (Zr), lead (Pb), vanadium (V), antimony (Sb), bismuth (Bi), molybdenum (M
o) Metal sulfides of the types shown in Table 1 were produced under the conditions shown in Table 1 using copper (Cu) and elemental sulfur of the same quality as used in Example 1. Conditions other than those shown in the table are the same as in Example 1).

The obtained metal sulfides were analyzed using an X-ray diffraction apparatus in the same manner as in Example 1, and the results showed that they were single-phase compounds.
It was confirmed that it was a metal sulfide shown in Table 1. Further, the results of measuring the specific surface area of each metal sulfide are as shown in Table 1, and all were found to be fine particles.

〔Effect of the invention〕

As explained in detail above, the present invention uses a bell-shaped reaction vessel equipped with a removable bottom plate in producing various metal sulfides from elemental metals and elemental sulfur.

In the conventional method using a sealed tube, the sealed tube had to be broken each time to take out the generated metal sulfide, but in the present invention, the reaction vessel as described above is used, so this reaction vessel can be repeatedly used. It is extremely economical. In addition, with conventional methods, there was a risk that the sealed tube would often break during heating or reaction, but the reaction vessel of the present invention, which corresponds to a conventional sealed tube, has increased strength by increasing the wall thickness. Because it can be designed, there is no such risk.

Further, as shown in the examples, the productivity is extremely high compared to the conventional method using sealed tubes, and the effects of the present invention are extremely large.

[Brief explanation of the drawing]

FIG. 1 is a front view of a reaction container and a heating bag holder used in the present invention, and in FIG. 1, the right half of the reaction container is shown as a sectional view. FIG. 2 shows a conventional sealed tube type reaction vessel. In the figure, 1--m-reaction vessel main body 2--m-flange portion 3 of the reaction vessel--one bottom plate 4--me one-tightening plate 5--
- Reaction vessel seats 6a, 6b - Gasket 7 - Bolt hole 8 - Seal box 9 - Air cylinder 10 - Piping 11 - Vacuum pump 12 - --- Thermocouple protection tube 13 --- Tray 1
4--m-pedestal 15--one raw material 16--
-- Heating device 17 --- Heating element 18 ---
A sealed tube reaction vessel is shown. Patent applicant Mitsui Toatsu Chemical Co., Ltd. Figure 1 Figure 2

Claims (1)

[Claims] A metal characterized in that one or more elemental metals and elemental sulfur are sealed in a bell-shaped reaction vessel equipped with a removable bottom plate, and after the gas in the reaction vessel is evacuated, the reaction vessel is heated in a sealed state. Method for producing sulfides.