JP7674155B2 - Hydrogen sulfide production apparatus and method for producing hydrogen sulfide - Google Patents

Description

The present invention relates to a hydrogen sulfide production device and a method for producing hydrogen sulfide.

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

JP 2016-150860 A

However, with the hydrogen sulfide production technology described in Patent Document 1 and the like, it was difficult to achieve a sufficiently high production efficiency. There was also room for improvement in the stability of the production efficiency.

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

According to the present invention,
A hydrogen sulfide production apparatus for producing hydrogen sulfide by reacting sulfur vapor with hydrogen gas, comprising:
a reactor having a liquid sulfur filling therein;
a first heating means for heating the liquid sulfur to generate sulfur vapor;
A hydrogen supply member connected to the reactor;
Equipped with
The reactor is provided with a catalyst support member provided above the liquid sulfur-filled portion and a heat insulating member provided above the catalyst support member inside the reactor,
Further, a second heating means is provided for heating a space formed by the catalyst support member, the heat insulating member, and the inner wall of the reactor,
The hydrogen sulfide production apparatus includes an upper space and a lower space of the heat insulating member that are connected to 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 hydrogen sulfide, characterized in that sulfur vapor and hydrogen gas are reacted in the hydrogen sulfide production apparatus described above.

The present invention provides a hydrogen sulfide production device with excellent production efficiency.

FIG. 1 is a vertical cross-sectional view of an example of a hydrogen sulfide production apparatus according to an embodiment of the present invention. FIG. 2 is a top view of an example of a heat insulating member of the hydrogen sulfide production apparatus of the present embodiment. FIG. 2 is a top view of an example of a catalyst support member of the hydrogen sulfide production apparatus of the present embodiment. FIG. 2 is a vertical cross-sectional view of another example of the hydrogen sulfide production apparatus of the present embodiment. FIG. 2 is a vertical cross-sectional view of a hydrogen sulfide production apparatus according to Comparative Example 1. 1 is a graph showing temperatures in reactors of hydrogen sulfide production apparatuses in Example 1 and Comparative Example 1.

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 the hydrogen sulfide production apparatus of this embodiment is shown in FIG.

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

The hydrogen sulfide production apparatus 1 in this embodiment is an apparatus that produces hydrogen sulfide by reacting sulfur vapor with hydrogen gas.
The hydrogen sulfide production apparatus 1 includes a reactor 3 having a liquid sulfur-filled section 2 therein, a mantle heater 4 which is a first heating means for heating the liquid sulfur to generate sulfur vapor, and a hydrogen supply pipe 5 which is a hydrogen supply member connected to the reactor 3.

The hydrogen sulfide production device 1 includes a catalyst support member 6 disposed above the liquid sulfur-filled section 2 inside the reactor 3, and a heat insulating member 7 disposed above the catalyst support member 6.

The hydrogen sulfide production device 1 includes a catalyst-filled section 8 formed by a catalyst support member 6, a heat insulating member 7, and the inner wall of the reactor 3, and further includes a jacket heater 9 as a second heating means for heating the catalyst-filled section 8.

Inside the reactor 3, the upper space and the lower space of the insulating member 7 are connected to each other around a part of the insulating member 7 or around the insulating member 7.

The sulfur vapor generated in the liquid sulfur filled section 2 by the heating of the mantle heater 4 is supplied to the catalyst filled section 8 through the communication hole 161 provided in the catalyst support member 6.

The catalyst support member 6 is provided with a hydrogen supply pipe through hole 162, and the hydrogen supply pipe 5 passes through the hydrogen supply pipe through hole 162 and connects to the liquid sulfur filled section 2. The catalyst support member 6 is also provided with a temperature sensor through hole 163, and the temperature sensor 15 passes through the temperature sensor through hole 163 and connects to the liquid sulfur filled section 2.

The hydrogen gas supplied to the liquid sulfur-filled section 2 by the hydrogen supply pipe 5 is also supplied to the catalyst-filled section 8 through a communication hole 161 provided in the catalyst support member 6. The amount of hydrogen gas supplied can be adjusted by a hydrogen supply control valve 13 provided in the hydrogen supply pipe 5.

Then, the sulfur vapor reacts with the hydrogen gas in the catalyst filled section 8 to produce hydrogen sulfide gas.

The hydrogen sulfide gas generated is supplied to the upper space of the insulating member 7 through the portion where the upper and lower spaces of the insulating member 7 are connected, and is recovered by the hydrogen sulfide recovery pipe 10, which is a hydrogen sulfide recovery member connected to the upper space of the insulating member 7. The amount of hydrogen sulfide gas recovered can be adjusted by the hydrogen sulfide recovery control valve 14 provided in the hydrogen sulfide recovery pipe 10.

The hydrogen sulfide recovery pipe 10 is provided with a pressure regulating valve 11, and the pressure inside the reactor 3 can be adjusted by opening and closing the pressure regulating valve 11. In addition, the hydrogen sulfide recovery pipe 10 is provided with a hydrogen sulfide detector 12, which can detect the flow rate of hydrogen sulfide.

The inventors conducted extensive research into the reasons why hydrogen sulfide production efficiency and hydrogen sulfide output stability were insufficient in conventional hydrogen sulfide production devices. As a result, they discovered that hydrogen sulfide can be produced stably and with high efficiency by precisely controlling the temperature distribution inside the catalyst-filled section 8, where the hydrogen sulfide production reaction takes place. The present invention was made based on this knowledge.

The hydrogen sulfide production apparatus 1 of this embodiment is provided with a heat insulating member 7 at the top of the apparatus, which prevents heat from being released from the top of the hydrogen sulfide production apparatus 1 and maintains a high temperature throughout the catalyst-filled section 8, where the hydrogen sulfide production reaction takes place. As a result, the temperature distribution within the catalyst-filled section 8 can be precisely controlled. Therefore, the hydrogen sulfide production apparatus 1 of this embodiment can produce hydrogen sulfide stably and with high efficiency.

The configuration of each part of the hydrogen sulfide production device 1 of this embodiment will be described below.

(Reactor 3)
In the reactor 3, hydrogen sulfide is produced by the reaction of hydrogen gas with sulfur vapor.

The reactor 3 includes a catalyst support member 6 provided above the liquid sulfur-filled section 2 , and a heat insulating member 7 provided above the catalyst support member 6 .
The sulfur vapor generated in the liquid sulfur-filled section 2 is supplied to a space (catalyst-filled section 8) surrounded by the catalyst support member 6, the heat insulating member 7 and the inner wall of the reactor 3, where the sulfur vapor reacts with hydrogen gas to produce hydrogen sulfide.
A hydrogen supply pipe 5 is connected to the reactor 3, and hydrogen gas is supplied from the hydrogen supply pipe 5.

The hydrogen supply pipe 5 is preferably arranged so that the hydrogen supply port 500, which is the outlet for hydrogen gas, is located below the catalyst support member 6. Hydrogen gas has a smaller specific gravity than air, and so when hydrogen gas is supplied from below to the catalyst support member 6, it vents toward the top of the reactor 3 and can efficiently come into contact with the catalyst packed in the catalyst packed section 8. In addition, by continuously venting hydrogen gas toward the top of the reactor 3, fresh hydrogen gas is constantly supplied.

As shown in FIG. 2, it is preferable that the heat insulating member 7 is provided with a plurality of communication holes 171. This allows the sulfur vapor generated in the liquid sulfur filled section 2 and the hydrogen gas supplied from the hydrogen supply pipe 5 to be efficiently supplied to the catalyst filled section 8 through the communication holes 171.

As shown in FIG. 3, it is preferable that the catalyst support member 6 is provided with a plurality of communication holes 161. This allows the sulfur vapor generated in the liquid sulfur-filled section 2 and the hydrogen gas supplied from the hydrogen supply pipe 5 to be efficiently supplied to the catalyst-filled section 8 through the communication holes 161.

In the catalyst packing section 8, it is preferable that the catalyst is packed in layers so as to contact the inner wall surface of the reactor 3. This allows the catalyst to be heated by heat transfer from the inner wall surface of the reactor 3, thereby increasing the heating efficiency.

The temperature of the catalyst-packed section 8 in all regions is preferably 300° C. or higher, more preferably 330° C. or higher, and even more preferably 360° C. or higher. When the temperature of the catalyst-packed section in all regions is equal to or higher than the above-mentioned lower limit, hydrogen sulfide can be produced stably with high efficiency.
The temperature of the catalyst filling section 8 is preferably 500° C. or less in all regions, more preferably 480° C. or less, and even more preferably 450° C. or less. By keeping the temperature of the catalyst filling section 8 at or below the upper limit value in all regions, it becomes possible to prevent deactivation of the catalyst due to excessive heating and to maintain the sulfur resistance of the device.
The temperature of catalyst-packed section 8 is usually measured at the center of catalyst-packed section 8 in the horizontal direction.

The catalyst packed in the catalyst packed section 8 is a catalyst for promoting the hydrogen sulfide generating reaction, and is preferably made of a material that is both resistant to sulfidation and resistant to hydrogenation, for example, made of one or more materials selected from activated carbon, zeolite, and activated alumina. From the viewpoint of reducing impurities, the catalyst is preferably made of one or more materials selected from zeolite and activated alumina, and is particularly preferably made of activated alumina, which is low-cost and highly stable at high temperatures.
In order to more effectively promote the reaction between hydrogen gas and sulfur vapor, the pores of the catalyst may support a metal such as silver, platinum, molybdenum, cobalt, nickel, iron, or vanadium.

The reactor 3 is preferably made of one or more sulfur-resistant materials selected from quartz, boron nitride, silicon nitride, aluminum, stainless steel, etc., from the viewpoint of preventing corrosion due to sulfur.

In addition, it is preferable that the inner surface of the reactor 3 is subjected to sulfur-proofing treatment.
Examples of the anti-sulfuration treatment include plating with a metal or alloy having high anti-sulfuration performance, such as tin plating, chromium plating, gold plating, hot-dip aluminum plating, or alloy plating containing these metals.

Metal diffusion and infiltration treatment (calorizing treatment) may also be used as a means of sulfur resistance treatment. Calorizing treatment is a treatment in which a metal such as aluminum is diffused and infiltrated into a workpiece. It is known that the sulfur resistance performance is improved when a metal diffusion and infiltration layer is formed on the surface of the workpiece by performing the calorizing treatment on the workpiece.
For example, by embedding the workpiece in a steel case together with a mixture consisting of Fe-Al alloy powder and _NH4Cl powder, sealing the case, and heating it in a furnace, it is possible to form an aluminum diffused and permeated layer on the surface of the workpiece in which aluminum has diffused and permeated.

(Mantle heater 4)
In the hydrogen sulfide production apparatus 1 of this embodiment, a mantle heater 4 is used as a first heating means for heating the liquid sulfur-filled section 2 to generate sulfur vapor.

The temperature of the liquid sulfur-filled section 2 is, for example, 180°C or higher and 445°C or lower, preferably 250°C or higher and 400°C or lower, and more preferably 300°C or higher and 350°C or lower. By keeping the temperature of the liquid sulfur-filled section 2 within the above range, it becomes possible to stably generate sulfur vapor.

The temperature of the mantle heater 4 is set so as to be able to adjust the temperature of the liquid sulfur-filled portion 2 within the above-mentioned temperature range.
Since the required heating temperature varies depending on the diameter of the liquid sulfur-filled section 2 and the amount of catalyst filled, the temperature range of the mantle heater 4 is not particularly limited, but is preferably 250°C or higher and 400°C or lower, and more preferably 300°C or higher and 350°C or lower.

In this embodiment, a mantle heater 4 is used as the first heating means, but this is not limited to this and any means capable of heating the liquid sulfur-filled section 2 may be used.

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

The hydrogen supply pipe 5 is preferably arranged so that the hydrogen supply port 500, which is the outlet for hydrogen gas, is located below the catalyst support member 6. Hydrogen gas has a smaller specific gravity than air, and so when hydrogen gas is supplied from below to the catalyst support member 6, it vents toward the top of the reactor 3 and can efficiently come into contact with the catalyst packed in the catalyst packed section 8. In addition, by continuously venting hydrogen gas toward the top of the reactor 3, fresh hydrogen gas is constantly supplied.

The hydrogen supply pipe 5 may have a hydrogen supply adjustment valve 13 that adjusts the amount of hydrogen gas supplied. The amount of hydrogen gas supplied can be controlled by adjusting the opening and closing of the hydrogen supply adjustment valve 13, which is advantageous from the viewpoint of controlling the hydrogen sulfide production reaction carried out in the reactor 3.

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

In this embodiment, a hydrogen supply pipe 5 is used as the hydrogen supply member, but this is not limited to this, and any hydrogen supply member capable of supplying hydrogen gas to the reactor 3 may be used.

(Catalyst support member 6)
The catalyst support member 6 is a member for mounting a catalyst for promoting the hydrogen sulfide production reaction, and is provided above the liquid sulfur-filled section 2 .

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 catalyst is packed in a layer so as to be in contact with the inner wall surface of the reactor 3. Therefore, in order to enable the catalyst to be placed in this manner, it is preferable that the catalyst support member 6 is arranged so as to be in contact with the inner wall surface of the reactor 3.

As shown in FIG. 3, it is preferable that the catalyst support member 6 is provided with a plurality of communication holes 161. By providing the catalyst support member 6 with a plurality of communication holes 161, the sulfur vapor generated in the liquid sulfur filling section 2 and the hydrogen supplied from the hydrogen supply pipe 5 are efficiently supplied to the catalyst filling section 8 through the plurality of communication holes 161.

The catalyst support member 6 may be of any material and shape as long as the catalyst can be placed on it. For example, the catalyst support member may be made of metal or ceramics.

The catalyst support member 6 is preferably shaped like a punched metal with communicating holes. For example, one or more types of porous plates 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 of the above-mentioned porous plates may be stacked together to form the catalyst support member 6.

The area ratio of the communication holes 161 provided in the catalyst support member 6 is usually 10% or more and 50% or less, and preferably 20% or more and 40% or less, from the viewpoint of improving the contact efficiency between the sulfur vapor and the catalyst.

The diameter of the communication holes provided in the catalyst support member 6 depends on the diameter of the catalyst to be placed, but is usually 26 μm or more and 1000 μm or less, and preferably 45 μm or more and 800 μm or less.

The catalyst support member 6 may be provided with a through hole 162 for a hydrogen supply pipe. In this case, the hydrogen supply pipe 5 passes through the through hole 162 for the hydrogen supply pipe and connects to the liquid sulfur-filled section 2 .
Furthermore, the catalyst support member 6 may be provided with a temperature sensor through hole 163 , in which case the temperature sensor 15 passes through the temperature sensor through hole 163 and connects to the liquid sulfur-filled section 2 .

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

(Thermal insulation member 7)
The heat insulating member 7 is a member for insulating the inside of the reactor 3 , and is provided above the catalyst support member 6 .

The provision of the heat insulating member 7 prevents heat from being released from the upper part of the hydrogen sulfide production apparatus 1 and maintains a high temperature throughout the inside of the catalyst packed section 8, where the hydrogen sulfide production reaction takes place, thereby enabling precise control of the temperature distribution within the catalyst packed section 8. Therefore, the hydrogen sulfide production apparatus 1 of this embodiment can produce hydrogen sulfide stably with high efficiency.
In the hydrogen sulfide production apparatus 1 of this embodiment, the temperature tends to drop more easily in the upper part of the apparatus than in the lower part where the liquid sulfur-filled section 2, which is the site of sulfur vapor generation, is located. Therefore, using the heat insulating member 7 to prevent heat release from the upper part of the hydrogen sulfide production apparatus 1 is an effective means for highly controlling the temperature distribution in the catalyst-filled section 8.

1, the heat insulating member 7 is preferably configured to be located above the catalyst packed section 8 and to cover the entire catalyst packed section 8. This further prevents heat from being released to the outside of the reactor 3.
1, the side surface of the heat insulating member 7 is preferably provided so as to be in contact with the inner wall of the reactor 3. In this way, the heat insulating member 7 is also heated, and the heat insulating member 7 itself has a certain heat capacity, so that the heat retaining effect of the heat insulating member 7 is further improved.

In the hydrogen sulfide production device 1 of this embodiment, the upper space and the lower space of the insulating member 7 are connected to each other in a part of the insulating member 7 or around the insulating member 7. To realize such an embodiment, the insulating member is preferably a metal substrate or a ceramic substrate provided with a communication hole.

As shown in FIG. 2, the insulating member 7 is preferably provided with communication holes 171. By providing the communication holes 171, the generated hydrogen sulfide can move to the upper part of the insulating member 7 through the multiple communication holes 171 and be collected by the hydrogen sulfide collection pipe 10 connected to the upper space of the insulating member 7.

The heat insulating member 7 can be, for example, one or more types of porous plates 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.

If necessary, two or more of the above-mentioned porous plates can be stacked together to be used as the insulating member 7.

From the viewpoint of balancing between improved insulation efficiency and improved hydrogen sulfide recovery, the area ratio of the communication holes provided in the insulating member 7 is usually 0.2% or more and 50% or less, and preferably 0.5% or more and 40% or less.

The diameter of the communication holes provided in the insulating member 7 is usually 26 μm or more and 10,000 μm or less, and preferably 45 μm or more and 5,000 μm or less.

The insulating member 7 may be provided with a through hole 172 for the hydrogen supply pipe, in which case the hydrogen supply pipe 5 passes through the through hole 172 for the hydrogen supply pipe and connects to the liquid sulfur-filled section 2. The insulating member 7 may also be provided with a through hole 173 for the temperature sensor, in which case the temperature sensor 15 passes through the through hole 173 for the temperature sensor and connects to the liquid sulfur-filled section 2.

(Jacket heater 9)
In the hydrogen sulfide production apparatus 1 of this embodiment, a jacket heater 9 is used as the second heating means. The jacket heater 9 heats the space (catalyst packed section 8) formed by the catalyst support member, the heat insulating member, and the inner wall of the reactor. In other words, it heats the catalyst support member and the space above the catalyst support member. This heats the catalyst to promote the hydrogen sulfide production reaction.

The temperature of the jacket heater 9 is configured so that the temperature of the catalyst filled section 8 can be adjusted to the above-mentioned temperature range.

Since the required heating temperature varies depending on the diameter of the catalyst filling section 8 and the amount of catalyst filled, the temperature range of the jacket heater 9 is not particularly limited, but such a temperature range is preferably 300° C. or higher, more preferably 330° C. or higher, and even more preferably 360° C. or higher.
By adjusting the temperature of the jacket heater 9 to be equal to or higher than the above lower limit, hydrogen sulfide can be produced stably with high efficiency.

Moreover, the temperature range is preferably 500° C. or less, more preferably 480° C. or less, and even more preferably 450° C. or less.
By adjusting the temperature of the jacket heater 9 to be equal to or lower than the upper limit, it becomes possible to prevent the catalyst from being deactivated due to excessive heating and to maintain the sulfur resistance of the device.

In this embodiment, a jacket heater 9 is used as the second heating means, but this is not limited to this, and any heating means can be used as long as it can heat the space formed by the catalyst support member, the insulating member, and the inner wall of the reactor.

(Hydrogen sulfide recovery pipe 10)
In the hydrogen sulfide production apparatus 1 of this embodiment, a hydrogen sulfide recovery pipe 10 is used as a hydrogen sulfide recovery member for recovering hydrogen sulfide gas from the reactor 3.

The hydrogen sulfide recovery pipe 10 may have a hydrogen sulfide recovery control valve 14 that adjusts the amount of hydrogen sulfide gas recovered. By adjusting the opening and closing of the hydrogen sulfide recovery control valve 14, it is possible to adjust the amount of hydrogen sulfide gas recovered. This is advantageous, for example, from the viewpoint of being able to control the chemical reaction downstream when another reaction device is connected downstream of the hydrogen sulfide production device.

The hydrogen sulfide recovery pipe 10 may be provided with a pressure regulating valve 11. The pressure inside the reactor 3 can be adjusted by opening and closing the pressure regulating valve 11.

The hydrogen sulfide recovery pipe 10 may also be provided with a hydrogen sulfide detector 12 that detects the flow rate of hydrogen sulfide.

(Temperature sensor 15)
The temperature sensor 15 is a member for measuring the temperature in each region of the reactor 3 .

The temperature of the reactor 3 is usually measured at the horizontal center of the reactor 3, so it is preferable that the temperature sensor 15 is positioned at the horizontal center of the reactor 3.

[Second embodiment]
The hydrogen sulfide production apparatus of the present embodiment may further include a heat transfer member disposed in contact with or in close proximity to the lower surface of the catalyst support member.
FIG. 4 is a schematic diagram showing a vertical cross section of the hydrogen sulfide production apparatus 21 thus constructed.

By providing a heat transfer member 22 at the bottom of the catalyst support member 6, heat from the jacket heater 9 covering the outside of the reactor 3 is easily transferred toward the center of the catalyst-filled section, improving the horizontal thermal uniformity of the catalyst-filled section.

The heat transfer member 22 is preferably arranged so as to contact the inner wall of the catalyst filling section 8. This is to transfer heat from the jacket heater 9 more efficiently.

It is preferable that the heat transfer member 22 is provided with a plurality of communication holes. By providing a plurality of communication holes in the heat transfer member, the sulfur vapor generated in the liquid sulfur-filled section 2 and the hydrogen gas supplied from the hydrogen supply pipe 5 can be efficiently supplied to the catalyst-filled section 8 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, an aluminum alloy, aluminum nitride, etc.

The heat transfer member 22 is preferably in the form of a plate having a suitable thickness and through holes. For example, one or more types of porous plates selected from stainless steel or aluminum plates having through holes and a thickness of 20 mm or more can be used.

If necessary, two or more of the above-mentioned porous plates can be stacked together and used as a heat transfer member.

By providing a communication hole in the heat transfer member 22, it is possible to improve the contact efficiency between the sulfur vapor supplied from the liquid sulfur filling section 2 and the catalyst.

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 improving heat transfer 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.

The heat transfer member 22 may be provided with a through hole for a hydrogen supply pipe, in which case the hydrogen supply pipe 5 passes through the through hole for the hydrogen supply pipe and connects to the liquid sulfur filled section 2. The heat transfer member 22 may also be provided with a through hole for a temperature sensor, in which case the temperature sensor 15 passes through the through hole for the temperature sensor and connects to the liquid sulfur filled section 2.

[Modification]
The hydrogen sulfide production apparatus of the present embodiment may include components other than those described above.

In addition, the hydrogen sulfide production device of this embodiment may have each part formed integrally.

Another reaction device may be further connected downstream of the hydrogen sulfide production device of this embodiment.
For example, a reaction device for producing a sulfide of a metal such as lithium may be connected downstream of the hydrogen sulfide production apparatus of this embodiment, and hydrogen sulfide produced by the hydrogen sulfide production apparatus of this embodiment may be supplied to the reaction device.

[Hydrogen sulfide production process]
A process for producing hydrogen sulfide using the hydrogen sulfide production apparatus of this embodiment will be described.

First, the liquid sulfur filled in the liquid sulfur filling section 2 is heated by the mantle heater 4 to generate sulfur vapor.

The temperature of the liquid sulfur-filled section 2 is not particularly limited as long as it is a temperature at which sulfur vapor is generated, and is, for example, 180°C or higher and 445°C or lower, preferably 250°C or higher and 400°C or lower, and more preferably 300°C or higher and 350°C or lower.
By keeping the temperature of the liquid sulfur-filled section 2 at or above the lower limit, the sulfur vapor pressure becomes more appropriate, and the concentration of the resulting hydrogen sulfide gas becomes higher, so that hydrogen sulfide can be generated more efficiently. Also, by keeping the temperature of the liquid sulfur at or below the upper limit, the sulfur vapor pressure can be made 1 atmosphere or less, so that the amount of sulfur passing through the reactor without reacting with hydrogen gas can be suppressed.

In the hydrogen sulfide production process using the hydrogen sulfide production apparatus of this embodiment, sulfur vapor and hydrogen gas are supplied to a catalyst heated by a jacket heater 9, causing the hydrogen gas and sulfur vapor to react on the catalyst surface, generating hydrogen sulfide gas.

In this case, by supplying an excess amount of hydrogen gas, it is possible to recover the hydrogen sulfide gas in a state diluted with hydrogen gas. This makes it possible to reduce the concentration of hydrogen sulfide gas contained in the exhaust gas generated when adjusting the pressure or at the end of the reaction, making the exhaust gas treatment process simpler.

The concentration of hydrogen sulfide gas during recovery is preferably 1% by volume or more, and more preferably 3% by volume or more. The concentration of hydrogen sulfide gas during recovery is preferably 50% by volume or less, and more preferably 30% by volume or less.

In the hydrogen sulfide production process using the hydrogen sulfide production apparatus of this embodiment, a heat insulating member 7 is provided at the top of the hydrogen sulfide production apparatus 1, preventing a drop in temperature in areas far from the liquid sulfur filled section 2 (the source of hydrogen sulfide gas) provided at the bottom of the apparatus, and maintaining a high temperature throughout the catalyst filled section 8. As a result, the temperature of the catalyst, which is the site of the hydrogen sulfide production reaction, can be precisely controlled, and hydrogen sulfide can be produced stably and efficiently.

The temperature within the catalyst-packed section 8 is preferably 300° C. or higher, more preferably 330° C. or higher, and even more preferably 360° C. or higher, in all regions.
By keeping the temperature of the catalyst-packed section at or above the lower limit in all regions, hydrogen sulfide can be produced stably with high efficiency.

The temperature within the catalyst-packed section 8 is preferably 500° C. or less, more preferably 480° C. or less, and even more preferably 450° C. or less in all regions.
By keeping the temperature of the catalyst-filled section at or below the above upper limit in all regions, it becomes possible to prevent deactivation of the catalyst due to excessive heating and to maintain the sulfur resistance of the device.

The hydrogen sulfide obtained by the production process using the hydrogen sulfide production apparatus of this embodiment can be used, for example, in a reaction for sulfurizing a metal such as lithium.
The sulfide obtained by sulfurization using the hydrogen sulfide obtained by the production process using the hydrogen sulfide production apparatus of the present embodiment can be suitably used, for example, as a positive electrode active material, a negative electrode active material, a solid electrolyte material, or an intermediate raw material for chemicals for batteries.

Example 1
The hydrogen sulfide production apparatus shown in FIG. 4 described in the second embodiment was manufactured.

The components used in constructing the hydrogen sulfide production device are as follows:
Reactor 3: SUS316L reaction tube (inner diameter 133.8 mm, height 672 mm) with an aluminum inner wall calorized
Hydrogen supply pipe 5: SUS316L pipe with an aluminum inner wall calorized (diameter 15 mm, length 750 mm)
Catalyst support member 6: Aluminum punched metal (diameter 133 mm, thickness 0.5 mm, hole diameter 0.5 mm, hole diameter area ratio 27.9%)
- Heat insulating member 7: One sheet of aluminum punched metal (diameter 133 mm, thickness 1.5 mm, hole diameter 5 mm, hole diameter area ratio 32.1%) and one sheet of aluminum punched metal (diameter 133 mm, thickness 0.5 mm, hole diameter 0.5 mm, hole diameter area ratio 27.9%) stacked at 8 mm intervals. - Heat transfer member 22: Aluminum plate material (diameter 133 mm, thickness 20 mm, hole diameter 5 mm, hole diameter area ratio 8.3%)

The reactor 3 was filled with 520 g of sulfur, and a heat transfer member 22 was placed on top of the sulfur. A catalyst support member 6 was placed on top of the heat transfer member 22, and 1.1 kg of activated alumina (diameter 1 to 2 mm, specific surface area 270 ^m2 /g) was packed on the catalyst support member 6. A heat insulating member 7 was placed on top of the activated alumina.
The temperature sensor 15 penetrates from above the reactor 3, and the tip of the temperature sensor 15 reaches the bottom surface of the reactor 3. The temperature sensor 15 penetrates the horizontal center of the reactor 3. In addition, the hydrogen supply pipe 5 penetrates from above the reactor 3, and the hydrogen supply port 500 of the hydrogen supply pipe 5 reaches the liquid sulfur-filled portion 2.

Next, hydrogen gas was introduced from the hydrogen supply pipe 5 to the liquid sulfur-filled section 2 at a flow rate of 1.0 L/min. Next, the temperature of the mantle heater 4 was increased to 200°C, and the temperature of the jacket heater 9 to 400°C, heating the liquid sulfur-filled section 2 and the catalyst-filled section 8, respectively. This caused the hydrogen gas to react with the sulfur vapor, generating hydrogen sulfide gas.

(Comparative Example 1)
A hydrogen sulfide production apparatus 31 was produced in the same manner as in Example 1, except that the heat insulating member 7 and the heat transfer member 22 were omitted, and hydrogen sulfide gas was generated. The configuration of the hydrogen sulfide production apparatus 31 is shown in FIG.

Figure 6 shows the temperatures in each region of the reactor 3 measured by the temperature sensor 15 150 minutes after the start of heating in the hydrogen sulfide production apparatus of Example 1 and Comparative Example 1.

According to FIG. 6, in the hydrogen sulfide production apparatus of Example 1, which is equipped with an insulating member and a heat transfer member, the temperature of the catalyst-filled section exceeded 400°C. On the other hand, in the hydrogen sulfide production apparatus of Comparative Example 1, which is not equipped with an insulating member and a heat transfer member, the temperature of the catalyst-filled section was lower than in Example 1, falling below 400°C. From this, it can be understood that the hydrogen sulfide production apparatus of this embodiment can stably produce hydrogen sulfide with high efficiency because the inside of the catalyst-filled section is maintained at a high temperature.

REFERENCE SIGNS LIST 1 Hydrogen sulfide production device 2 Liquid sulfur-filled section 3 Reactor 4 Mantle heater 5 Hydrogen supply pipe 6 Catalyst support member 7 Heat insulating member 8 Catalyst-filled section 9 Jacket heater 10 Hydrogen sulfide recovery pipe 11 Pressure regulating valve 12 Hydrogen sulfide detector 13 Hydrogen supply control valve 14 Hydrogen sulfide recovery control valve 15 Temperature sensor 21 Hydrogen sulfide production device 22 Heat transfer member 31 Hydrogen sulfide production device 51 Communication hole 161 Communication hole 162 Through hole for hydrogen supply pipe 163 Through hole for temperature sensor 171 Communication hole 172 Through hole for hydrogen supply pipe 173 Through hole for temperature sensor 500 Hydrogen supply port

Claims (5)

A hydrogen sulfide production apparatus for producing hydrogen sulfide by reacting sulfur vapor with hydrogen gas, comprising:
a reactor having a liquid sulfur filling therein;
a first heating means for heating the liquid sulfur to generate sulfur vapor;
A hydrogen supply member connected to the reactor;
Equipped with
The inside of the reactor is provided with a catalyst support member provided above the liquid sulfur-filled portion, and a heat insulating member provided above the catalyst support member,
Further, a second heating means is provided for heating a space formed by the catalyst support member, the heat insulating member, and the inner wall of the reactor,
An apparatus for producing hydrogen sulfide, wherein an upper space and a lower space of the insulating member are connected to each other at a portion of the insulating member or around the insulating member. The hydrogen sulfide production apparatus according to claim 1,
The hydrogen sulfide manufacturing apparatus, wherein the heat insulating member is a metal substrate or a ceramic substrate having communicating holes. The hydrogen sulfide production apparatus according to claim 1 or 2,
The hydrogen sulfide production apparatus further comprises a heat transfer member disposed in contact with or in close proximity to a lower surface of the catalyst support member. The hydrogen sulfide production apparatus according to any one of claims 1 to 3,
A hydrogen sulfide production apparatus, the inner surface of which is treated to be sulfur resistant. A method for producing hydrogen sulfide, comprising reacting sulfur vapor with hydrogen gas using the hydrogen sulfide production apparatus according to any one of claims 1 to 4.

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