JP7706940B2 - Lithium sulfide manufacturing apparatus and method for manufacturing lithium sulfide - Google Patents

Description

The present invention relates to an apparatus for producing lithium sulfide and a method for producing lithium sulfide.

A known method for producing lithium sulfide is to react hydrogen sulfide gas with lithium hydroxide. An example of a technique for producing lithium sulfide is described in Patent Document 1 (JP 2016-150860 A).

JP 2016-150860 A

However, with the lithium sulfide manufacturing technology described in Patent Document 1 and the like, it was difficult to achieve a sufficiently high manufacturing efficiency. In addition, there was room for improvement in the stability of the manufacturing efficiency.

The present invention has been made in consideration of the above circumstances, and aims to provide a lithium sulfide manufacturing apparatus that can produce lithium sulfide stably with high efficiency.

The inventors conducted extensive research into the reasons why the lithium sulfide production efficiency of conventional lithium sulfide production equipment was insufficient. As a result, they discovered that lithium sulfide can be produced stably and with high efficiency by precisely controlling the temperature distribution in the lithium hydroxide-filled section, where the lithium sulfide production reaction takes place. The present invention was made based on this discovery.

According to the present invention,
An apparatus for producing lithium sulfide by reacting hydrogen sulfide with lithium hydroxide, comprising:
A reactor having a lithium hydroxide filled portion therein;
A heating means for heating the lithium hydroxide;
A hydrogen sulfide supply member connected to the reactor;
Equipped with
a heat insulating member is provided inside the reactor above the lithium hydroxide filled portion,
an upper space and a lower space of the heat insulating member are in communication with each other at a part of the heat insulating member or around the heat insulating member,

The present invention also provides a method for producing lithium sulfide, which comprises reacting hydrogen sulfide gas with lithium hydroxide using the lithium sulfide production apparatus described above.

The present invention provides a lithium sulfide manufacturing device with excellent manufacturing efficiency.

FIG. 1 is a vertical sectional view of an example of an apparatus for manufacturing lithium sulfide according to an embodiment of the present invention. FIG. 2 is a top view of a heat insulating member of the apparatus for manufacturing lithium sulfide according to the present embodiment. FIG. 2 is a top view of a lithium hydroxide support member of the lithium sulfide manufacturing apparatus of the present embodiment. FIG. 2 is a vertical sectional view of another example of the apparatus for manufacturing lithium sulfide according to the present embodiment. FIG. 1 is a vertical sectional view of an apparatus for producing lithium sulfide according to a first embodiment. FIG. 1 is a vertical sectional view of an apparatus for producing lithium sulfide according to a second embodiment. FIG. 2 is a vertical sectional view of an apparatus for producing lithium sulfide according to Comparative Example 1. FIG. 1 is a vertical sectional view of an apparatus for producing lithium sulfide in Comparative Example 2. 1 is a graph showing the temperatures of reactors of lithium sulfide manufacturing apparatuses in Examples 1 and 2 and Comparative Examples 1 and 2.

Below, an embodiment of the present invention will be described with reference to the drawings. Note that in all drawings, similar components are given the same reference numerals and descriptions will be omitted as appropriate.

[First embodiment]
An example of an apparatus for producing lithium sulfide according to the present embodiment will be described with reference to FIGS. 1 to 3.

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

The lithium sulfide manufacturing apparatus 1 includes a reactor 3 having a lithium hydroxide-filled section 2 therein, a jacket heater 4 which is a heating means for heating the lithium hydroxide, and a hydrogen sulfide supply pipe 5 which is a hydrogen sulfide supply member connected to the reactor 3.
Inside the reactor 3, a heat insulating member 6 is provided above the lithium hydroxide filled section 2, and the upper space and the lower space of the heat insulating member 6 are communicated with each other at a part of the heat insulating member 6 or around the heat insulating member 6.

In the lithium sulfide manufacturing apparatus 1 of this embodiment, a heat insulating member 6 is provided above the reactor 3, which prevents heat from being released to the outside of the reactor 3 and maintains a high and uniform temperature throughout the lithium hydroxide filling section 2. This allows the reaction field between hydrogen sulfide gas and lithium hydroxide to be controlled at a high temperature with high precision, enabling stable production of lithium sulfide with high production efficiency.

The configuration of each part of the lithium sulfide manufacturing device of this embodiment will be described below.

(Reactor 3)
Inside the reactor 3, lithium hydroxide (solid) reacts with hydrogen sulfide gas to produce lithium sulfide (solid).

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

The reactor 3 is also equipped with a lithium hydroxide support member 7, and the space surrounded by the lithium hydroxide support member 7, the insulating member 6, and the inner wall of the reactor 3 is called the lithium hydroxide filling section 2.

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

The hydrogen sulfide supply pipe 5 is preferably located below the lithium hydroxide support member 7. By supplying hydrogen sulfide gas to the lithium hydroxide support member 7 from below, it is vented toward the top of the reactor 3, and when it comes into contact with the lithium hydroxide filled in the lithium hydroxide filling section 2, water (water vapor), a by-product with a smaller specific gravity than hydrogen sulfide gas, is efficiently discharged. In addition, by continuing to vent the hydrogen sulfide gas toward the top of the reactor 3, fresh hydrogen sulfide gas is constantly supplied.

As shown in FIG. 3, it is preferable that the lithium hydroxide support member 7 is provided with a plurality of communication holes 171. This allows the hydrogen sulfide gas supplied from the hydrogen sulfide supply pipe 5 to be efficiently supplied to the lithium hydroxide filling section 2 through the communication holes 171.

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

It is believed that a reaction as shown in formula (1) below occurs on the surface of lithium hydroxide (solid).
2LiOH+ _H2S → _Li2S + _2H2O (1)

In the lithium hydroxide-filled section 2 inside the reactor 3, the lithium hydroxide is preferably filled in layers so that the lithium hydroxide filled in layers is in contact with the inner wall surface of the reactor 3. This is because heating can be achieved by heat transfer from the inner wall surface of the lithium hydroxide-filled section 2, thereby increasing the heating efficiency.

The temperature of the lithium hydroxide-filled section 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 section 2 is usually measured at the horizontal center of the lithium hydroxide-filled section 2.

As shown in FIG. 2, it is preferable that the insulating member 6 is provided with a plurality of communication holes 161. By providing a plurality of communication holes 161 in the insulating member, unreacted hydrogen sulfide gas and exhaust gas containing water generated by the reaction of hydrogen sulfide gas with lithium hydroxide are discharged to the outside of the reactor 3 through the communication holes 171.

The reactor 3 may be made of metal or ceramic, but is preferably made of a sulfur-resistant material. Examples of sulfur-resistant materials include metal-based sulfur-resistant materials such as stainless steel and aluminum, and ceramic-based sulfur-resistant materials such as quartz, boron nitride, aluminum nitride, and silicon nitride.

It is preferable that the inner surface of the reactor 3 is treated to be sulfur-resistant.

Examples of sulfur-resistant treatment include plating with metals or alloys that have high sulfur resistance, such as tin plating, chrome plating, gold plating, hot-dip aluminum plating, or alloy plating containing these metals.

Alternatively, a metal diffusion infiltration treatment may be used as a means for sulfur resistance treatment. It is known that when a metal diffusion infiltration layer is formed on the surface of a treated object by subjecting the treated object to a metal diffusion infiltration treatment, the sulfur resistance performance is improved.
For example, a calorizing treatment for diffusing and infiltrating aluminum can be used. In the calorizing treatment, the workpiece is embedded in a steel case together with a mixture consisting of Fe-Al alloy powder and NH ₄ Cl powder, the case is sealed, and it is heated in a furnace to form an aluminum diffusion infiltration layer on the surface of the workpiece, thereby making it possible to improve the sulfurization resistance of the workpiece.

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

That is, the jacket heater 4 heats the lithium hydroxide support member 7 and the space above the lithium hydroxide support member 7. This heats the lithium hydroxide filled in the lithium hydroxide filling section 2, accelerating the lithium sulfide production reaction.

The temperature of the jacket heater 4 is configured so that the temperature of the lithium hydroxide-filled section 2 can be adjusted to the above-mentioned temperature range. The required heating temperature varies depending on the diameter of the lithium hydroxide-filled section 2 and the amount of catalyst filled, so the temperature range of the jacket heater 4 is not particularly limited, but is preferably 100 to 445°C, and more preferably 130 to 410°C.

In addition, in this embodiment, a jacket heater 4 is used as the heating means, but this is not limited to this, and any heating means capable of heating lithium hydroxide may be used. For example, a method of introducing heated hydrogen sulfide gas, a high-frequency induction heating device, etc. may also 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 located below the lithium hydroxide support member 7. By supplying hydrogen sulfide gas to the lithium hydroxide support member 7 from below, it is vented toward the top of the reactor 3, and when it comes into contact with the lithium hydroxide filled in the lithium hydroxide filling section 2, water (water vapor), a by-product with a smaller specific gravity than hydrogen sulfide gas, is efficiently discharged. In addition, by continuing to vent the hydrogen sulfide gas toward the top of the reactor 3, fresh hydrogen sulfide gas is constantly supplied.

As shown in FIG. 1, the hydrogen sulfide supply pipe 5 may have a hydrogen sulfide supply control valve 8 that adjusts the amount of hydrogen sulfide gas supplied. 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 advantageous from the viewpoint of controlling the lithium sulfide production reaction carried out in the reactor 3.

The materials mentioned above for the reactor 3 can be used as the material for the hydrogen sulfide supply pipe 5.

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

In addition, in this embodiment, a hydrogen sulfide supply pipe 5 is used as the hydrogen sulfide supply member, but this is not limited to this, and any hydrogen sulfide supply member that can supply hydrogen sulfide gas to the reactor 3 may be used.

(Thermal insulation member 6)
The heat insulating member 6 is a member for insulating the inside of the reactor 3, and is provided above the lithium hydroxide filled section 2.

As shown in FIG. 1, the heat insulating member 6 is preferably configured to be located above the lithium hydroxide filled section 2 and to cover the entire lithium hydroxide filled section 2. This further prevents heat from being released to the outside of the reactor 3.

In addition, as shown in FIG. 1, it is preferable that the side of the insulating member 6 is provided so as to be in contact with the inner wall of the reactor 3. In this way, the insulating member 6 is also heated, and the insulating member 6 itself has a certain heat capacity, so the heat retention effect of the insulating member 6 is further enhanced.

As shown in FIG. 2, it is preferable that the insulating member 6 is provided with a plurality of communication holes 161. By providing a plurality of communication holes 161 in the insulating member, unreacted hydrogen sulfide gas and exhaust gas containing water generated by the reaction of hydrogen sulfide gas with lithium hydroxide are discharged to the outside of the reactor 3 through the communication holes 161.

The insulating member 6 may also be provided with a temperature sensor through hole 162 as shown in FIG. 2. In this case, the temperature sensor 9 inserted from above the reactor 3 passes through the temperature sensor through hole 162 and connects to the reactor 3.

The materials mentioned above as the materials for the reactor 3 can be used as the materials for the insulating member 6.

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

If necessary, two or more layers of the above-mentioned porous material may be stacked together to form the insulating member 6.

The area ratio of the communication holes 161 provided in the insulating member 6 is usually 0.2% or more and 50% or less, preferably 0.5% or more and 40% or less, from the viewpoint of the balance between improving the insulating efficiency and improving the recovery of exhaust gases, etc.

From the viewpoint of balancing between improving insulation efficiency and improving recovery of exhaust gas, etc., the diameter of the communication hole 161 provided in the insulation member 6 is usually 26 μm or more and 10,000 μm or less, and preferably 45 μm or more and 5,000 μm or less.

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

The shape of the heat insulating member may be an inverted funnel-shaped heat insulating member 46 as shown in FIG.
When an inverted funnel-shaped insulating member 46 is used as the insulating member, the temperature sensor 9 can be inserted into the legs of the inverted funnel-shaped insulating member 46 and connected to the lithium hydroxide filled section 2. In this case, by forming a gap between the temperature sensor 9 and the inner wall of the legs of the inverted funnel-shaped insulating member 46, the upper space and the lower space of the inverted funnel-shaped insulating member 46 can communicate with each other through the gap.

(Lithium hydroxide support member 7)
The lithium hydroxide support member 7 is a member for placing lithium hydroxide thereon.

As described above, in order to enable heating by heat transfer from the inner wall surface of the reactor 3, it is preferable that the lithium hydroxide is packed in layers in contact with the inner wall of the lithium hydroxide-filled section 2, and therefore it is preferable that the lithium hydroxide support member 7 is arranged in contact with the inner wall of the lithium hydroxide-filled section 2 so that the lithium hydroxide can be placed in this manner.

As shown in FIG. 3, it is preferable that the lithium hydroxide support member 7 is provided with a plurality of communication holes 171. By providing the lithium hydroxide support member 7 with a plurality of communication holes 171, the hydrogen sulfide supplied from the hydrogen sulfide supply pipe 5 can be efficiently supplied to the lithium hydroxide filling section 2 through the plurality of communication holes 171.

The materials mentioned above as the materials for the reactor 3 can be used as the material for the lithium hydroxide support member 7.

The shape of the lithium hydroxide support member 7 is not particularly limited as long as lithium hydroxide can be placed on it, but it is preferable that it has a plurality of communication holes 171 as described above. For example, one or more types of porous materials selected from metal meshes such as stainless steel mesh and aluminum mesh; punched metals such as stainless steel punching and aluminum punching; and expanded metals such as stainless steel expand can be used.

If necessary, two or more of the above-mentioned porous materials may be stacked together to form the lithium hydroxide support member 7.

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

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

The gas exhaust pipe 10 is preferably located above the lithium hydroxide support member 7. By-product water (water vapor) and unreacted hydrogen sulfide gas are vented toward the top of the reactor, so it is more efficient to exhaust gas when the gas exhaust pipe 10 is located at the top. By improving the efficiency of gas exhaust, fresh hydrogen sulfide gas is constantly supplied.

It is preferable that the gas exhaust pipe 10 is provided with a cooling section that captures the water generated 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 during the production of lithium sulfide will no longer condense in the cooling section. In other words, the progress of the lithium sulfide production reaction can be monitored by the amount of condensed water.

(Temperature sensor 9)
The 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 to a higher degree.

[Second embodiment]
The apparatus for manufacturing lithium sulfide of the present embodiment may further include a heat transfer member 22 arranged in contact with or in the vicinity of the bottom surface of the lithium hydroxide loading section 2. Fig. 4 is a vertical sectional view of an apparatus 21 for manufacturing lithium sulfide in this manner.
By providing the heat transfer member 22 at the bottom of the lithium hydroxide-filled section 2, heat from the jacket heater 4 covering the outside of the reactor 3 is easily transferred in the horizontal direction of the cross section of the lithium hydroxide-filled section 2, thereby improving the thermal uniformity in the horizontal direction of the lithium hydroxide-filled section 2.

The heat transfer member 22 is preferably arranged so as to contact the inner wall of the lithium hydroxide filled section. This is to more efficiently transfer heat from the jacket heater 4 that covers the outside of the reactor 3.

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

The material of the heat transfer member 22 is not particularly limited, and the materials mentioned above as the materials of the reactor 3 can be used, but it is preferable to use a material with excellent sulfur resistance and thermal conductivity, such as aluminum, aluminum alloy, aluminum nitride, silicon nitride, etc.

The shape of the heat transfer member 22 is not particularly limited, but it is preferable that the heat transfer member 22 has a plurality of communicating holes, such as a punched metal. For example, one or more types of porous materials selected from metal meshes such as stainless steel mesh and aluminum mesh; punched metals such as stainless steel punched and aluminum punched; and expanded metals such as stainless steel expanded and aluminum expanded can be used.

If necessary, two or more layers of the above-mentioned porous material may be stacked together to form the heat transfer member 22.

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

The diameter of the communication holes provided in the heat transfer member 22 is usually 26 μm or more and 10,000 μm or less, and preferably 45 μm or more and 5,000 μm or less.

[Modification]
The apparatus for manufacturing lithium sulfide of the present embodiment may include components other than the components described above.

In addition, the lithium sulfide manufacturing apparatus of this embodiment may have each part formed integrally.

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

First, lithium hydroxide is filled into the lithium hydroxide-filled section 2, and the lithium hydroxide-filled section 2 filled with lithium hydroxide is heated by the jacket heater 4, which is a heating means. Next, hydrogen sulfide gas is supplied to the lithium hydroxide-filled section 2, and the lithium hydroxide is brought into contact with the hydrogen sulfide gas, causing the lithium hydroxide to react with the hydrogen sulfide gas to produce lithium sulfide.

The upper part of the reactor 3 of the lithium sulfide manufacturing apparatus 1 is provided with a heat insulating member 6, which prevents heat from being released to the outside of the reactor 3 and maintains a high and uniform temperature throughout the lithium hydroxide filling section 2. Therefore, the lithium sulfide manufacturing apparatus 1 can stably produce lithium sulfide with high efficiency.

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

In the lithium sulfide manufacturing process using the lithium sulfide manufacturing apparatus 1, the temperature of the lithium hydroxide filling section 2 is preferably 445°C or less in all regions, more preferably 430°C or less, and even more preferably 410°C or less. When the temperature of the catalyst filling section is equal to or less than the above upper limit in all regions, the lithium hydroxide can be prevented from melting, and therefore, the lithium hydroxide can be prevented from fusing together and forming clumps. This allows the reaction between the reaction gas and the 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 maximum temperature T _max and the minimum temperature T _min measured at each point in the lithium hydroxide loading section 2 is preferably 50° C. or less, more preferably 30° C. or less, and even more preferably 20° C. or less, and is preferably as small as possible. When _{T max} - T _min is small, in other words, when there is little variation in temperature at each point in the lithium hydroxide loading section 2, the reaction between 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 the d50 is equal to or less than the upper limit, the contact area between the lithium hydroxide and the reaction gas increases, and the reaction is promoted, so that the amount of unreacted raw material in the obtained lithium sulfide can be further reduced. As a result, lithium sulfide with higher purity can be obtained.
In addition, 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 0.1 mm or more, more preferably 0.2 mm or more. When the d50 is equal to or more than the 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, the lithium hydroxide and the obtained lithium sulfide can be prevented from being discharged together with the reaction gas, so that the exhaust gas treatment can be simplified. In addition, the lithium hydroxide and the obtained lithium sulfide can be prevented from being scattered by the reaction gas, so that the yield of lithium sulfide can be improved.

It is preferable to dehydrate the water of crystallization and dry the adhering water from lithium hydroxide beforehand. This prevents the lithium hydroxide from agglomerating and inhibits the production of hydrosulfides, allowing the reaction between hydrogen sulfide gas and lithium hydroxide to proceed more effectively. Examples of methods for dehydrating and drying lithium hydroxide include heating in the atmosphere, heating while passing gas such as hydrogen, nitrogen, or argon gas, and heating under reduced pressure.

The hydrogen sulfide gas may be a commercially available product filled in a gas cylinder or the like, or may be produced in a hydrogen sulfide production apparatus connected upstream of the lithium sulfide production apparatus 1.
When a hydrogen sulfide production apparatus is connected upstream of the lithium sulfide production apparatus 1, it is possible to generate hydrogen sulfide gas in an amount necessary for the production of lithium sulfide, and there is no need to store hydrogen sulfide gas separately. In addition, since hydrogen sulfide gas can be generated as needed, high-purity hydrogen sulfide gas that has not deteriorated over time can be used in the reaction.

The 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, a negative electrode active material, solid electrolyte material, and intermediate raw material for chemicals for batteries.

The above describes embodiments of the present invention, but these are merely examples of the present invention, and various configurations other than those described above can also be adopted.

Example 1
The lithium sulfide manufacturing apparatus 31 was fabricated using the following members. FIG.
Reactor 3: A reaction tube made of SUS316L, the inner wall of which is 450 mm from the bottom surface and has been subjected to aluminum calorizing treatment (inner diameter 124 mm, height 615 mm)
Heat insulating member 36: Two aluminum plates (diameter 116 mm, thickness 0.5 mm, hole diameter 0.5 mm, hole diameter area ratio 1.7%) are stacked on one aluminum punched metal (diameter 116 mm, thickness 0.5 mm, hole diameter 5 mm, hole diameter area ratio 1.7%) with a gap of 8 mm between each. Lithium hydroxide support member 37: #100 aluminum mesh stacked on #300 SUS mesh. Heat transfer member 22: Aluminum plate material (diameter 123 mm, thickness 20 mm, hole diameter 5 mm, hole diameter area ratio 9.7%)

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

The temperature sensor 9 is inserted through a temperature sensor through hole provided in the insulating member 36 and reaches the bottom surface of the lithium hydroxide loading section 2, i.e., the lithium hydroxide support member 37, so that the temperature sensor 9 can measure the temperature at each point in the vertical direction at the horizontal center of the lithium hydroxide loading section 2.

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 increased to 410°C, and the lithium hydroxide filling section 2 was heated. This caused the hydrogen sulfide gas to react with the lithium hydroxide, producing lithium sulfide.

Example 2
An inverted funnel-shaped insulating member 46 was used instead of the insulating member 36 as the insulating member, and the temperature sensor 9 was inserted into the leg portion of the inverted funnel-shaped insulating member 46 and reached the lithium hydroxide support member 37 in the same manner as in Example 1, except that an apparatus for manufacturing lithium sulfide 41 was fabricated and lithium sulfide was manufactured.
Furthermore, a gap is formed between the temperature sensor 9 and the inner wall of the leg of the inverted funnel-shaped insulating member 46, and this gap allows the upper and lower spaces of the inverted funnel-shaped insulating member 46 to communicate with each other.
FIG. 6 is a vertical cross-sectional view of the manufacturing apparatus 41.

(Comparative Example 1)
An apparatus for manufacturing lithium sulfide 51 was fabricated and lithium sulfide was produced in the same manner as in Example 1, except that the heat insulating member 36 and the heat transfer member 22 were omitted, and a lithium hydroxide support member 57 was used in which a #300 SUS mesh was layered on a SUS punched metal having a diameter of 123 mm, a thickness of 0.5 mm, and a hole diameter of 0.5 mm, and an #100 aluminum mesh was further layered on the #300 SUS mesh.
FIG. 7 is a vertical cross-sectional view of the manufacturing apparatus 51.

(Comparative Example 2)
A lithium sulfide manufacturing apparatus 61 was produced in the same manner as in Example 1 except that the heat insulating member 36 was omitted, and lithium sulfide was manufactured.
FIG. 8 is a vertical cross-sectional view of the manufacturing apparatus 61.

Figure 9 shows a graph of the temperatures at each point in the lithium hydroxide loading section 2 measured by the temperature sensor 9 150 minutes after the start of heating in the lithium sulfide manufacturing apparatuses of Examples 1 and 2 and Comparative Examples 1 and 2.

According to Figure 9, in the lithium sulfide manufacturing apparatus of Examples 1 and 2, a high temperature is maintained even in the upper part of the lithium hydroxide filling section 2, and lithium sulfide can be produced stably with high efficiency. This is thought to be because the reaction field between hydrogen sulfide gas and lithium hydroxide is 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 ) measured at each point in the lithium hydroxide-filled section 2 .

According to Table 1, the value of T _max - T _min was small in the lithium sulfide manufacturing apparatuses of Examples 1 and 2. That is, in the lithium sulfide manufacturing apparatuses of Examples 1 and 2, the temperature variation at each point in the lithium hydroxide loading section 2 was small, so that lithium sulfide could be produced stably with high efficiency, and it is believed that this is because the reaction field between hydrogen sulfide gas and lithium hydroxide was controlled at a high temperature with high precision.

REFERENCE SIGNS LIST 1 Lithium sulfide manufacturing apparatus 2 Lithium hydroxide charging 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 exhaust pipe 21 Lithium sulfide manufacturing apparatus 22 Heat transfer member 31 Lithium sulfide manufacturing apparatus 36 Heat insulating member 37 Lithium hydroxide support member 41 Lithium sulfide manufacturing apparatus 46 Heat insulating member 51 Lithium sulfide manufacturing apparatus 57 Lithium hydroxide support member 61 Lithium sulfide manufacturing apparatus 161 Communication hole 162 Through hole for temperature sensor

Claims (4)

An apparatus for producing lithium sulfide by reacting hydrogen sulfide with lithium hydroxide, comprising:
A reactor having a lithium hydroxide filled portion therein;
A heating means for heating the lithium hydroxide;
A hydrogen sulfide supply member connected to the reactor;
Equipped with
a heat insulating member is provided inside the reactor above the lithium hydroxide filled portion,
an upper space and a lower space of the heat insulating member are in communication with each other at a part of the heat insulating member or around the heat insulating member. The lithium sulfide manufacturing apparatus according to claim 1,
The apparatus for manufacturing lithium sulfide, further comprising a heat transfer member arranged in contact with or in close proximity to a bottom surface of the lithium hydroxide filled section. The lithium sulfide manufacturing apparatus according to claim 1 or 2,
An apparatus for manufacturing lithium sulfide , the inner surface of which is subjected to sulfur-resistant treatment. A method for producing lithium sulfide, comprising reacting hydrogen sulfide gas with lithium hydroxide using the lithium sulfide production apparatus according to any one of claims 1 to 3.

Images