JP2022184229A - Device and method for producing lithium sulfide - Google Patents

Abstract

To provide a device for producing lithium sulfide with high efficiency and stability.SOLUTION: A device 1 for producing lithium sulfide according to the present invention comprises: a reactor 3 having a lithium sulfide filling part 2 inside; a jacket heater 4 that is heating means of heating lithium sulfide; and a hydrogen sulfide supply pipe 5 that is a hydrogen sulfide supply member connected to the reactor 3. The inside of the reactor 3 is provided with a heat insulating member 6 above the lithium sulfide filling part 2. At a part of the heat insulating member 6 or around the heat insulating member 6, the upper and lower spaces of the heat insulating member 6 are in communication.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a lithium sulfide production apparatus and a lithium sulfide production method.

As a method for producing lithium sulfide, a method of reacting hydrogen sulfide gas and lithium hydroxide is known. Techniques related to such a method for producing lithium sulfide include, for example, those described in Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2016-150860).

JP 2016-150860 A

However, it has been difficult to achieve sufficiently high production efficiency with the technology for producing lithium sulfide disclosed in Patent Document 1 and the like. There is also room for improvement in the stability of production efficiency.

The present invention has been made in view of the above circumstances, and provides a lithium sulfide production apparatus capable of stably producing lithium sulfide with high efficiency.

The present inventor conducted various studies as to why the lithium sulfide production efficiency of the conventional lithium sulfide production apparatus was not sufficient. As a result, it was found that lithium sulfide can be stably produced with high efficiency by highly controlling the temperature distribution of the lithium hydroxide filling section, which is the site of the lithium sulfide production reaction. The present invention has been made based on such findings.

According to the invention,
A lithium sulfide production apparatus for producing lithium sulfide by reacting hydrogen sulfide and lithium hydroxide,
a reactor having a lithium hydroxide charge therein;
heating means for heating lithium hydroxide;
a hydrogen sulfide supply member connected to the reactor;
with
Inside the reactor, a heat insulating member is provided above the lithium hydroxide filling section,
A lithium sulfide production apparatus is provided, in which an upper space and a lower space of the heat insulating member communicate with each other at a part of the heat insulating member or around the heat insulating member.

Further, according to the present invention, there is provided a method for producing lithium sulfide, which comprises reacting hydrogen sulfide gas and lithium hydroxide using the lithium sulfide production apparatus described above.

ADVANTAGE OF THE INVENTION According to this invention, the lithium-sulfide manufacturing apparatus excellent in manufacturing efficiency can be provided.

1 is a vertical cross-sectional view of an example of a lithium sulfide production apparatus according to an embodiment; FIG. FIG. 3 is a top view of a heat insulating member of the lithium sulfide production apparatus of the present embodiment; FIG. 3 is a top view of a lithium hydroxide support member of the lithium sulfide production apparatus of the present embodiment; FIG. 3 is a vertical cross-sectional view of another example of the lithium sulfide production apparatus of the present embodiment; 1 is a longitudinal sectional view of a lithium sulfide production apparatus of Example 1. FIG. FIG. 2 is a longitudinal sectional view of a lithium sulfide production apparatus of Example 2; 1 is a vertical cross-sectional view of a lithium sulfide production apparatus of Comparative Example 1. FIG. 2 is a vertical cross-sectional view of a lithium sulfide production apparatus of Comparative Example 2. FIG. 4 is a graph showing reactor temperatures of lithium sulfide production apparatuses of Examples 1 and 2 and Comparative Examples 1 and 2. FIG.

An embodiment of the present invention will be described below with reference to the drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the explanation thereof is omitted as appropriate.

[First embodiment]
An example of the lithium sulfide production apparatus of the present embodiment will be described with reference to FIGS. 1 to 3. FIG.

FIG. 1 is a longitudinal sectional view of a lithium sulfide manufacturing apparatus 1. FIG. FIG. 2 is a top view of the heat insulating member 6 provided in the lithium sulfide manufacturing apparatus 1. FIG. FIG. 3 is a top view of the lithium hydroxide support member 7 provided in the lithium sulfide manufacturing apparatus 1. FIG.

A lithium sulfide production apparatus 1 includes a reactor 3 having a lithium hydroxide filling section 2 therein, a jacket heater 4 as a heating means for heating lithium hydroxide, and a hydrogen sulfide supply member connected to the reactor 3. A hydrogen sulfide supply pipe 5 is provided.
Inside the reactor 3, a heat insulating member 6 is provided above the lithium hydroxide filling section 2, and the upper space and the lower space of the heat insulating member 6 are communicated at a part of the heat insulating member 6 or around the heat insulating member 6. is doing.

In the lithium sulfide production apparatus 1 of the present embodiment, since the heat insulating member 6 is provided above the reactor 3, heat release to the outside of the reactor 3 is prevented, and the temperature of the lithium hydroxide filling section 2 as a whole is is maintained high and uniform. Therefore, the reaction field between hydrogen sulfide gas and lithium hydroxide is controlled at a high temperature with high accuracy, and lithium sulfide can be stably produced with high production efficiency.

The configuration of each part of the lithium sulfide production apparatus of this embodiment will be described below.

(Reactor 3)
Inside the reactor 3, lithium sulfide (solid) is produced by the reaction between lithium hydroxide (solid) and hydrogen sulfide gas.

A hydrogen sulfide supply pipe 5 is connected to the reactor 3 and hydrogen sulfide is supplied from the hydrogen sulfide supply pipe 5 .

In addition, the reactor 3 is provided with a lithium hydroxide support member 7, and a space surrounded by the lithium hydroxide support member 7, the heat insulating member 6, and the inner wall of the reactor 3 is called a lithium hydroxide filling portion 2. .

Lithium hydroxide (not shown) is placed on the lithium hydroxide support member 7 .

The hydrogen sulfide supply pipe 5 is preferably positioned below the lithium hydroxide support member 7 . By supplying hydrogen sulfide gas to the lithium hydroxide support member 7 from below, the hydrogen sulfide gas is ventilated upwardly of the reactor 3 and comes into contact with the lithium hydroxide filled in the lithium hydroxide filling section 2. This is because water (steam), which is a by-product having a lower specific gravity than hydrogen sulfide gas, is efficiently discharged. In addition, fresh hydrogen sulfide gas is continuously supplied by continuously ventilating the hydrogen sulfide gas upwardly of the reactor 3 .

Preferably, the lithium hydroxide support member 7 is provided with a plurality of communication holes 171 as shown in FIG. By doing so, the hydrogen sulfide gas supplied from the hydrogen sulfide supply pipe 5 is efficiently supplied to the lithium hydroxide filling portion 2 through the communication hole 171 .

The hydrogen sulfide gas supplied from the hydrogen sulfide supply pipe 5 contacts the surface of lithium hydroxide (solid) filled in the lithium hydroxide filling section 2 .

On the surface of lithium hydroxide (solid), a reaction such as the following formula (1) is thought to occur.
2LiOH+ _H2S → _Li2S + _2H2O (1)

In the lithium hydroxide filling section 2 inside the reactor 3 , it is preferable that the lithium hydroxide is packed in layers so that the lithium hydroxide packed in layers is in contact with the inner wall surface of the reactor 3 . This is because, in this way, heating can be performed by heat transfer from the inner wall surface of the lithium hydroxide filled portion 2, so that the heating efficiency can be increased.

The temperature of the lithium hydroxide filled portion 2 is usually adjusted to 100 to 445° C., preferably 130 to 410° C., from the viewpoint of promoting the above reaction and preventing the lithium hydroxide from melting. The temperature of the lithium hydroxide filled portion 2 is usually measured at the horizontal central portion of the lithium hydroxide filled portion 2 .

Preferably, the heat insulating member 6 is provided with a plurality of communication holes 161 as shown in FIG. Since a plurality of communication holes 161 are provided in the heat insulating member, exhaust gas containing unreacted hydrogen sulfide gas and water generated by the reaction of hydrogen sulfide gas and lithium hydroxide flows through the communication holes 171 into the reactor. 3 is discharged to the outside.

As the material of the reactor 3, metals, ceramics, and the like can be mentioned, but it is preferable to use a sulfur-resistant material. Examples of sulfur-resistant materials include sulfur-resistant metallic materials such as stainless steel and aluminum, and sulfur-resistant ceramic materials such as quartz, boron nitride, aluminum nitride, and silicon nitride. .

The inner surface of the reactor 3 is preferably anti-sulfurized.

Examples of sulfur-resistant treatment include plating with metals or alloys having high resistance to sulfurization, such as tin plating, chromium plating, gold plating, hot-dip aluminum plating, or alloy plating containing these metals.

Moreover, a metal diffusion permeation treatment may be used as a means of anti-sulfur treatment. It is known that when a metal diffusion and permeation layer is formed on the surface of the article to be treated by subjecting the article to metal diffusion and permeation treatment, the anti-sulfurization performance is improved.
For example, a calorizing treatment that diffuses and permeates aluminum can be used. In the calorizing treatment, an object to be treated is embedded in a steel case together with a compounding agent consisting of Fe—Al alloy powder and NH ₄ Cl powder, the case is sealed, and the case is heated in a furnace to remove the surface of the object to be treated. It is possible to improve the anti-sulfuration performance of the object to be treated by forming an aluminum diffused and permeated layer in which aluminum is diffused and permeated.

(Jacket heater 4)
In this embodiment, a jacket heater 4 is used as heating means for heating lithium hydroxide.

That is, the jacket heater 4 heats the lithium hydroxide supporting member 7 and the space above the lithium hydroxide supporting member 7 . As a result, the lithium hydroxide filled in the lithium hydroxide filling portion 2 can be heated to promote the lithium sulfide production reaction.

The temperature of the jacket heater 4 is configured so that the temperature of the lithium hydroxide filled portion 2 can be adjusted within the above temperature range. Since the required heating temperature changes with the diameter of the lithium hydroxide filled portion 2 and the amount of catalyst filled, the temperature range of the jacket heater 4 is not particularly limited, but is preferably 100 to 445° C., more preferably 130 to 410°C.

Moreover, in the present embodiment, the jacket heater 4 is used as the heating means, but the heating means is not limited to this, and any heating means may be used as long as it can heat the lithium hydroxide. For example, a method of introducing heated hydrogen sulfide gas, a high-frequency induction heating device, or the like can be used.

(Hydrogen sulfide supply pipe 5)
The hydrogen sulfide supply pipe 5 is a member for supplying hydrogen sulfide gas to the reactor 3 .

The hydrogen sulfide supply pipe 5 is preferably positioned below the lithium hydroxide support member 7 . By supplying hydrogen sulfide gas to the lithium hydroxide support member 7 from below, the hydrogen sulfide gas is ventilated upwardly of the reactor 3 and comes into contact with the lithium hydroxide filled in the lithium hydroxide filling section 2. This is because water (steam), which is a by-product having a lower specific gravity than hydrogen sulfide gas, is efficiently discharged. In addition, fresh hydrogen sulfide gas is continuously supplied by continuously ventilating the hydrogen sulfide gas upwardly of the reactor 3 .

As shown in FIG. 1, the hydrogen sulfide supply pipe 5 may have a hydrogen sulfide supply control valve 8 for adjusting the supply amount of hydrogen sulfide gas. The amount of hydrogen sulfide supplied can be controlled by adjusting the opening and closing of the hydrogen sulfide supply control valve 8, which is preferable from the viewpoint of controlling the lithium sulfide production reaction that takes place in the reactor 3. .

As the material of the hydrogen sulfide supply pipe 5, the material described above as the material of the reactor 3 can be used.

It is preferable that the inner surface of the hydrogen sulfide supply pipe 5 is anti-sulfurized. As means for anti-sulfur treatment, the method described above as the method used for the anti-sulfur treatment of the inner surface of the reactor 3 can be used.

Further, in the present embodiment, the hydrogen sulfide supply pipe 5 was used as the hydrogen sulfide supply member, but the present invention is not limited to this, and any hydrogen sulfide supply can be used as long as it is possible to supply hydrogen sulfide gas to the reactor 3. It may be a member.

(Heat insulation member 6)
The heat insulating member 6 is a member for insulating the interior of the reactor 3 and is provided above the lithium hydroxide filling section 2 .

As shown in FIG. 1 , it is preferable that the heat insulating member 6 is arranged above the lithium hydroxide filling section 2 so as to cover the entire lithium hydroxide filling section 2 . By doing so, the release of heat to the outside of the reactor 3 is further prevented.

Moreover, the side surface of the heat insulating member 6 is preferably provided so as to be in contact with the inner wall of the reactor 3, as shown in FIG. By doing so, the heat insulating member 6 is also heated, and the heat insulating member 6 itself has a certain heat capacity, so that the heat insulating effect of the heat insulating member 6 is further enhanced.

Preferably, the heat insulating member 6 is provided with a plurality of communication holes 161 as shown in FIG. Since a plurality of communication holes 161 are provided in the heat insulating member, the exhaust gas containing unreacted hydrogen sulfide gas and water generated by the reaction of the hydrogen sulfide gas and lithium hydroxide flows through the communication holes 161 into the reactor. 3 is discharged to the outside.

Further, the heat insulating member 6 may be provided with a temperature sensor through hole 162 as shown in FIG. In this case, the temperature sensor 9 inserted from above the reactor 3 passes through the temperature sensor through-hole 162 and is connected to the reactor 3 .

As the material of the heat insulating member 6, it is possible to use the material described above as the material of the reactor 3. FIG.

Although the shape of the heat insulating member 6 is not particularly limited, it preferably has a plurality of communication holes 161 as described above. For example, one or more porous materials selected from metal meshes such as stainless steel mesh and aluminum mesh; punching metals such as stainless steel punching and aluminum punching; expanded metals such as stainless steel expanded and aluminum expanded, etc. can be used. .

As the heat insulating member 6, two or more of the porous materials described above may be stacked and used as necessary.

The area ratio of the communication holes 161 provided in the heat insulating member 6 is usually 0.2% or more and 50% or less, preferably 0.5%, from the viewpoint of the balance between the improvement of the heat insulation efficiency and the improvement of the collection of exhaust gas and the like. 40% or less.

The diameter of the communication hole 161 provided in the heat insulating member 6 is usually 26 μm or more and 10000 μm or less, preferably 45 μm or more and 5000 μm or less, from the viewpoint of the balance between the improvement of heat insulation efficiency and the improvement of collection of exhaust gas and the like.

The thickness of the heat insulating member 6 is preferably 0.5 mm or more, more preferably 1.5 mm or more, from the viewpoint of improving heat insulation efficiency. There is no particular upper limit to the thickness of the heat insulating member 6, but it is usually 20 mm or less.

As for the shape of the heat insulating member, an inverted funnel-shaped heat insulating member 46 as shown in FIG. 6 may be used.
When the inverted funnel-shaped heat insulating member 46 is used as the heat insulating member, the temperature sensor 9 can be inserted into the legs of the inverted funnel-shaped heat insulating member 46 and connected to the lithium hydroxide filling portion 2 . In this case, a gap is formed between the temperature sensor 9 and the inner wall of the leg portion of the inverted funnel-shaped heat insulating member 46, so that the upper space and the lower space of the inverted funnel-shaped heat insulating member 46 are separated by the gap. It is possible for spaces to communicate.

(Lithium hydroxide supporting member 7)
The lithium hydroxide support member 7 is a member for mounting lithium hydroxide.

As described above, in order to enable heating by heat transfer from the inner wall surface of the reactor 3, lithium hydroxide is preferably filled in a layer so as to be in contact with the inner wall of the lithium hydroxide filling section 2. The lithium hydroxide supporting member 7 is preferably arranged so as to be in contact with the inner wall of the lithium hydroxide filling portion 2 so that the lithium hydroxide can be placed in this manner.

Preferably, the lithium hydroxide support member 7 is provided with a plurality of communication holes 171 as shown in FIG. Since the plurality of communication holes 171 are provided in the lithium hydroxide support member 7, the hydrogen sulfide supplied from the hydrogen sulfide supply pipe 5 is efficiently supplied to the lithium hydroxide filling portion 2 through the plurality of communication holes 171. This is so that

As the material of the lithium hydroxide support member 7, the material described above as the material of the reactor 3 can be used.

The shape of the lithium hydroxide support member 7 is not particularly limited as long as the lithium hydroxide can be placed thereon, but it is preferably provided with a plurality of communication holes 171 as described above. For example, one or two or more porous materials selected from metal mesh such as stainless steel mesh and aluminum mesh; punching metal such as stainless steel punching and aluminum punching; expanded metal such as stainless steel expand, etc. can be used.

As the lithium hydroxide supporting member 7, two or more of the porous materials described above may be stacked and used as necessary.

The diameter of the communication hole 171 provided in the lithium hydroxide supporting member 7 depends on the diameter of lithium hydroxide to be placed, but is usually 26 μm or more and 300 μm or less, preferably 45 μm or more and 154 μm or less.

(Gas exhaust pipe 10)
The gas discharge pipe 10 is a member for discharging the exhaust gas containing unreacted hydrogen sulfide and water produced by the reaction of the hydrogen sulfide gas and lithium hydroxide to the outside of the reactor 3 .

The gas discharge pipe 10 is preferably positioned above the lithium hydroxide support member 7 . By-product water (steam) and unreacted hydrogen sulfide gas are ventilated upward in the reactor, so the gas discharge pipe 10 is provided at the top for better gas discharge efficiency. be. By improving the efficiency of gas discharge, fresh hydrogen sulfide gas will be continuously supplied.

It is preferable that the gas discharge pipe 10 is provided with a cooling portion for capturing water produced by the reaction between hydrogen sulfide gas and lithium hydroxide. When the reaction between hydrogen sulfide gas and lithium hydroxide is completed, the water generated when lithium sulfide is produced will no longer condense in the cooling section. That is, the progress of the lithium sulfide formation reaction can be monitored by the amount of condensed water.

(Temperature sensor 9)
A temperature sensor 9 is a member for measuring the temperature inside the reactor 3 . For example, by measuring the temperature inside the reactor 3 with the temperature sensor 9 and adjusting the heating based on the measurement result, it becomes possible to control the production of lithium sulfide at a higher level.

[Second embodiment]
The apparatus for producing lithium sulfide according to the present embodiment may further include a heat transfer member 22 arranged in contact with or in close proximity to the bottom surface of the lithium hydroxide filling section 2 . FIG. 4 is a vertical cross-sectional view of the lithium sulfide production apparatus 21 constructed as described above.
By providing the heat transfer member 22 in the lower part of the lithium hydroxide filling section 2, the heat from the jacket heater 4 covering the outside of the reactor 3 is easily transmitted in the horizontal direction of the cross section of the lithium hydroxide filling section 2. This is because the heat uniformity in the horizontal direction of the lithium hydroxide filled portion 2 is improved.

Heat transfer member 22 is preferably arranged so as to be in contact with the inner wall of the lithium hydroxide filled portion. This is for more efficient transmission of heat from the jacket heater 4 covering the outside of the reactor 3 .

It is preferable that the heat transfer member 22 is provided with a plurality of communication holes. Since the plurality of communication holes are provided in the heat transfer member, the hydrogen sulfide supplied from the hydrogen sulfide supply pipe 5 is efficiently supplied to the lithium hydroxide filling portion 2 through the plurality of communication holes. is.

The material of the heat transfer member 22 is not particularly limited, and the materials described above as the material of the reactor 3 can be used. It is preferable to use an aluminum alloy, aluminum nitride, silicon nitride, or the like.

Moreover, the shape of the heat transfer member 22 is not particularly limited, but it is preferable that the heat transfer member 22 is provided with a plurality of communication holes like punching metal. For example, one or more porous materials selected from metal meshes such as stainless steel mesh and aluminum mesh; punching metals such as stainless steel punching and aluminum punching; expanded metals such as stainless steel expanded aluminum expanded, etc. can be used.

As the heat transfer member 22, two or more of the porous materials described above may be stacked and used as necessary.

The area ratio of the communication holes provided in the heat transfer member 22 is usually 0.2% or more and 50% or less, which is preferable, from the viewpoint of the balance between the improvement of the heat transfer efficiency and the improvement of the contact efficiency between the sulfur vapor and the catalyst. is 0.5% or more and 40% or less.

The diameter of the communication hole provided in the heat transfer member 22 is usually 26 μm or more and 10000 μm or less, preferably 45 μm or more and 5000 μm or less.

[Modification]
The lithium sulfide production apparatus of the present embodiment may include members other than the members described above.

Further, each part of the lithium sulfide production apparatus of the present embodiment may be integrally formed.

[Production process of lithium sulfide]
A lithium sulfide manufacturing process using the lithium sulfide manufacturing apparatus 1 of the present embodiment will be described.

First, the lithium hydroxide filling portion 2 is filled with lithium hydroxide, and the lithium hydroxide filling portion 2 filled with lithium hydroxide is heated by the jacket heater 4 as a heating means. Next, hydrogen sulfide gas is supplied to the lithium hydroxide filling section 2 to bring the hydrogen sulfide gas into contact with the lithium hydroxide, thereby producing lithium sulfide through a reaction between the lithium hydroxide and the hydrogen sulfide gas.

Since the upper part of the reactor 3 of the lithium sulfide production apparatus 1 is provided with a heat insulating member 6, the release of heat to the outside of the reactor 3 is prevented, and the temperature of the entire lithium hydroxide filling section 2 is high and uniform. is maintained at Therefore, the lithium sulfide production apparatus 1 can stably produce lithium sulfide with high efficiency.

In the lithium sulfide production process using the lithium sulfide production apparatus 1, the temperature inside the lithium hydroxide filled portion 2 is usually 100° C. or higher, preferably 130° C. or higher, more preferably 150° C. or higher in the entire region. More preferably 170°C or higher, more preferably 200°C or higher.
When the temperature inside the lithium hydroxide filled portion 2 is equal to or higher than the above lower limit over the entire region, the reaction rate between hydrogen sulfide gas and lithium hydroxide can be further improved.

In the lithium sulfide production process using the lithium sulfide production apparatus 1, the temperature of the lithium hydroxide filled portion 2 is preferably 445° C. or lower, more preferably 430° C. or lower in the entire region, and more preferably 430° C. or lower. is below 410°C. When the temperature of the catalyst-filled portion is equal to or lower than the above upper limit in all regions, it is possible to suppress the lithium hydroxide from melting, thereby suppressing the formation of lumps due to mutual fusion between the lithium hydroxides. This allows the reaction between the reaction gas and lithium hydroxide to proceed more effectively.

In the lithium sulfide production process using the lithium sulfide production apparatus 1, the difference (T _max −T _min ) between the highest temperature T _max and the lowest temperature T _min measured at each point in the lithium hydroxide filling section 2 is It is preferably 50° C. or lower, more preferably 30° C. or lower, and even more preferably 20° C. or lower, preferably as low as possible. When T _max −T _min is small, that is, when the variation in temperature at each point in the lithium hydroxide filling section 2 is small, the reaction between the hydrogen sulfide gas and lithium hydroxide can proceed more efficiently and stably.

The d50 in the weight-based particle size distribution of lithium hydroxide measured by a laser diffraction scattering particle size distribution measurement method is preferably 1.5 mm or less, more preferably 1.0 mm or less. When d50 is equal to or less than the above upper limit, the contact area between lithium hydroxide and the reaction gas is increased to promote the reaction, so that the amount of unreacted raw materials in the resulting lithium sulfide can be further reduced. As a result, higher purity lithium sulfide can be obtained.
In addition, d50 in the weight-based particle size distribution of lithium hydroxide measured by a laser diffraction scattering particle size distribution measurement method is preferably 0.1 mm or more, and more preferably 0.2 mm or more. When d50 is at least the above lower limit, water generated in the reaction system can be prevented from adhering to the lithium sulfide particles and causing the particles to stick. In addition, since it is possible to suppress the discharge of lithium hydroxide and obtained lithium sulfide together with the reaction gas, it is possible to simplify the exhaust gas treatment. Moreover, it is possible to suppress scattering of lithium hydroxide and obtained lithium sulfide by the reaction gas, so that the yield of lithium sulfide can be improved.

Lithium hydroxide is preferably subjected in advance to dehydration of water of crystallization and drying of adhering water. As a result, it is possible to suppress agglomeration of lithium hydroxide and suppress formation of hydrosulfide, so that the reaction between hydrogen sulfide gas and lithium hydroxide can be promoted more effectively. Methods for dehydrating or drying lithium hydroxide include, for example, a method of heating in the air, a method of heating while flowing a gas such as hydrogen, nitrogen, or argon gas, a method of heating under reduced pressure, and the like.

The hydrogen sulfide gas may be a commercial product filled in a gas cylinder or the like, or may be produced by a hydrogen sulfide production device connected upstream of the lithium sulfide production device 1 .
When the hydrogen sulfide production device is connected upstream of the lithium sulfide production device 1, it is possible to generate hydrogen sulfide gas in an amount necessary for producing lithium sulfide, eliminating the need to separately store the hydrogen sulfide gas. . Moreover, since hydrogen sulfide gas can be generated as needed, hydrogen sulfide gas of high purity, which is not degraded over time, can be used for the reaction.

Lithium sulfide obtained by the manufacturing process using the lithium sulfide manufacturing apparatus 1 can be suitably used, for example, as a positive electrode active material for batteries, a negative electrode active material, a solid electrolyte material, and an intermediate raw material for chemicals.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can also be adopted.

(Example 1)
A lithium sulfide production apparatus 31 was produced using the following members. FIG. 5 is a longitudinal sectional view of the manufacturing apparatus 31. As shown in FIG.
・Reactor 3 A reaction tube made of SUS316L, in which the inner wall of 450 mm from the bottom is calorized with aluminum (inner diameter 124 mm, height 615 mm)
・Insulation member 36 Aluminum plate (diameter 116 mm, thickness 0.5 mm, hole diameter 5 mm) on one sheet of aluminum punching metal (diameter 116 mm, thickness 0.5 mm, hole diameter 0.5 mm, hole diameter area ratio 27.9%) , area ratio of hole diameter 1.7%) two sheets are stacked and the distance between them is 8 mm ・ Lithium hydroxide support member 37 #100 aluminum mesh is stacked on #300 SUS mesh ・Heat transfer member 22 Aluminum plate (diameter 123 mm, thickness 20 mm, hole diameter 5 mm, hole diameter area ratio 9.7%)

A heat transfer member 22 was arranged in the reactor 3 , and a lithium hydroxide support member 37 was arranged above the heat transfer member 22 . The lithium hydroxide support member 37 was filled with 773 g of lithium hydroxide (particle size: 0.05 to 0.75 mm). The height of the filled lithium hydroxide was 100 mm. Next, the heat transfer member 22 was arranged on the top filled with lithium hydroxide.

The temperature sensor 9 inserted from the temperature sensor through hole provided in the heat insulating member 36 reaches the bottom surface of the lithium hydroxide filling portion 2, that is, the lithium hydroxide support member 37, and the temperature sensor 9 detects the lithium hydroxide filling portion. 2, the temperature at each point in the vertical direction can be measured.

Next, a mixed gas of hydrogen and hydrogen sulfide (hydrogen sulfide concentration: 13%) was supplied to the reactor 3 through the hydrogen sulfide supply pipe 5 at a flow rate of 2.0 L/min. Next, the temperature of the jacket heater 4 was set to 410° C. to heat the lithium hydroxide filled portion 2 . Thereby, hydrogen sulfide gas and lithium hydroxide were reacted to obtain lithium sulfide.

(Example 2)
As the heat insulating member, an inverted funnel-shaped heat insulating member 46 was used instead of the heat insulating member 36, and the temperature sensor 9 was inserted into the leg portion of the inverted funnel-shaped heat insulating member 46 to reach the lithium hydroxide support member 37. A lithium sulfide production apparatus 41 was produced in the same manner as in Example 1 to produce lithium sulfide.
A gap is formed between the temperature sensor 9 and the inner wall of the leg portion of the inverted funnel-shaped heat insulating member 46, and the gap communicates the upper space and the lower space of the inverted funnel-shaped heat insulating member 46. I made it
FIG. 6 is a longitudinal sectional view of the manufacturing apparatus 41. As shown in FIG.

(Comparative example 1)
The heat insulating member 36 and the heat transfer member 22 are removed, and as the lithium hydroxide support member 57, a #300 SUS mesh is placed on a SUS punching metal having a diameter of 123 mm, a thickness of 0.5 mm, and a hole diameter of 0.5 mm. Lithium sulfide was produced by fabricating a lithium sulfide production apparatus 51 in the same manner as in Example 1, except that a #100 aluminum mesh was used.
FIG. 7 is a longitudinal sectional view of the manufacturing apparatus 51. As shown in FIG.

(Comparative example 2)
A lithium sulfide manufacturing apparatus 61 was fabricated in the same manner as in Example 1 except that the heat insulating member 36 was removed, and lithium sulfide was manufactured.
FIG. 8 is a longitudinal sectional view of the manufacturing apparatus 61. As shown in FIG.

FIG. 10 is a graph showing the temperature at each point of the lithium hydroxide filling section 2 measured by the temperature sensor 9 after 150 minutes from the start of heating in the lithium sulfide production apparatuses of Examples 1 and 2 and Comparative Examples 1 and 2; 9.

According to FIG. 9, in the lithium sulfide production apparatus of Examples 1 and 2, a high temperature is maintained even in the upper portion of the lithium hydroxide filling section 2, lithium sulfide can be stably produced with high efficiency, and hydrogen sulfide can be produced. This is probably because the reaction field between the gas and lithium hydroxide was controlled at a high temperature with high precision.

Table 1 shows the maximum temperature T _max , the minimum temperature T _min , and the difference between the two (T _max −T _min ) of the temperatures measured at various points in the lithium hydroxide filled portion 2 .

According to Table 1, the value of T _max -T _min was small in the lithium sulfide production apparatuses of Examples 1 and 2. That is, in the lithium sulfide production apparatus of Examples 1 and 2, since the variation in temperature at each point of the lithium hydroxide filling section 2 is small, lithium sulfide can be produced stably with high efficiency. This is probably because the reaction field with lithium oxide was controlled at a high temperature with high precision.

Reference Signs List 1 lithium sulfide production device 2 lithium hydroxide filling section 3 reactor 4 jacket heater 5 hydrogen sulfide supply pipe 6 heat insulating member 7 lithium hydroxide support member 8 hydrogen sulfide supply control valve 9 temperature sensor 10 gas discharge pipe 21 lithium sulfide production device 22 Heat transfer member 31 lithium sulfide manufacturing device 36 heat insulating member 37 lithium hydroxide supporting member 41 lithium sulfide manufacturing device 46 heat insulating member 51 lithium sulfide manufacturing device 57 lithium hydroxide supporting member 61 lithium sulfide manufacturing device 161 communicating hole 162 through hole for temperature sensor

Claims (4)

A lithium sulfide production apparatus for producing lithium sulfide by reacting hydrogen sulfide and lithium hydroxide,
a reactor having a lithium hydroxide charge therein;
heating means for heating lithium hydroxide;
a hydrogen sulfide supply member connected to the reactor;
with
A heat insulating member is provided inside the reactor above the lithium hydroxide filling section,
A lithium sulfide production apparatus, wherein an upper space and a lower space of the heat insulating member communicate with each other at a part of the heat insulating member or around the heat insulating member. The lithium sulfide production apparatus according to claim 1,
The apparatus for producing lithium sulfide, further comprising a heat transfer member arranged in contact with or in close proximity to the bottom surface of the lithium hydroxide filling section. The lithium sulfide production apparatus according to claim 1 or 2,
A lithium sulfide production device, wherein the inner surface of the device is anti-sulfurized. A method for producing lithium sulfide, which comprises reacting hydrogen sulfide gas with lithium hydroxide using the apparatus for producing lithium sulfide according to any one of claims 1 to 3.

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