Lithium sulfide production device, lithium sulfide production apparatus, and lithium sulfide production method

Abstract

A lithium sulfide manufacturing apparatus includes a reactor (1) for reacting hydrogen sulfide with a lithium source. The reactor (1) has: a hydrogen sulfide inlet line (4) for introducing hydrogen sulfide obtained from a desulfurization unit (2) into the reactor (1); and a hydrogen sulfide outlet line (5) for discharging unreacted hydrogen sulfide to the outside of the reactor.

Description

Technical Field

[0001] This invention relates to an apparatus for manufacturing lithium sulfide, equipment for manufacturing lithium sulfide, and a method for manufacturing lithium sulfide. Background Technology

[0002] Solid electrolytes are gaining significant attention as electrolytes for lithium-ion secondary batteries. Their application in all-solid-state batteries is expected to improve the safety and performance of secondary batteries. One example of a solid electrolyte is a sulfide solid electrolyte (see, for example, Patent Document 1). Lithium sulfide is used as a raw material for sulfide solid electrolytes.

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2010-163356 Summary of the Invention The technical problem that the invention aims to solve Patent document 1 discloses a method for manufacturing lithium sulfide, but further expansion of production is needed as a source of lithium sulfide supply. Previously, from an industrial perspective, research on efficient methods for manufacturing lithium sulfide has been insufficient.

[0004] Therefore, the object of the present invention is to provide an apparatus, equipment and method for manufacturing lithium sulfide using hydrogen sulfide obtained from an existing desulfurization unit.

[0005] Solution to the above technical problems One embodiment of the present invention relates to an apparatus for manufacturing lithium sulfide, comprising: A reactor that allows hydrogen sulfide to react with a lithium source; Hydrogen sulfide obtained from the desulfurization unit is introduced into the hydrogen sulfide inlet pipeline within the reactor; and Unreacted hydrogen sulfide is discharged to a hydrogen sulfide outlet pipeline outside the reactor.

[0006] One embodiment of the present invention relates to a lithium sulfide manufacturing apparatus, which is an apparatus for manufacturing lithium sulfide and includes: A reactor that allows hydrogen sulfide to react with lithium hydroxide; Desulfurization equipment; Sulfur recovery unit; Hydrogen sulfide obtained from the desulfurization unit is introduced into the hydrogen sulfide inlet pipeline within the reactor; and Unreacted hydrogen sulfide is discharged outside the reactor and introduced into the hydrogen sulfide outlet pipeline of the sulfur recovery unit.

[0007] One embodiment of the present invention relates to a method for manufacturing lithium sulfide, which includes: Hydrogen sulfide obtained from the desulfurization unit is introduced into the reactor; To cause hydrogen sulfide to react with lithium hydroxide; and Unreacted hydrogen sulfide is discharged outside the reactor and introduced into a sulfur recovery unit.

[0008] Invention Effects According to the present invention, an apparatus for manufacturing lithium sulfide, a device for manufacturing lithium sulfide, and a method for manufacturing lithium sulfide are provided, which utilize hydrogen sulfide obtained from an existing desulfurization device to manufacture lithium sulfide. Attached Figure Description

[0009] [ Figure 1 ] Figure 1 This is a block diagram illustrating the schematic structure of a lithium sulfide manufacturing apparatus.

[0010] [ Figure 2 ] Figure 2 This is a schematic diagram of equipment used for manufacturing lithium sulfide.

[0011] [ Figure 3 ] Figure 3 This is a schematic diagram of a desulfurization unit. Detailed Implementation

[0012] Hereinafter, embodiments of the present invention (hereinafter also referred to as this embodiment) will be described. Furthermore, in this specification, the expression of a numerical range, for example, "1 to 100," is intended to include both the lower limit "1" and the upper limit "100." Similarly, the expression of other numerical ranges is also used in this manner.

[0013] This embodiment relates to an apparatus for manufacturing lithium sulfide, which is an apparatus for manufacturing lithium sulfide and includes: A reactor that allows hydrogen sulfide to react with a lithium source; Hydrogen sulfide obtained from the desulfurization unit is introduced into the hydrogen sulfide inlet pipeline within the reactor; and Unreacted hydrogen sulfide is discharged to a hydrogen sulfide outlet pipeline outside the reactor.

[0014] According to this embodiment, an apparatus for manufacturing lithium sulfide can be provided, utilizing hydrogen sulfide obtained from a conventional desulfurization unit to produce lithium sulfide. Conventional desulfurization units, such as those installed in petroleum refineries, are used to remove sulfur from products. Hydrogen sulfide is generated during this desulfurization process, and this hydrogen sulfide is converted into sulfur through a sulfur recovery unit. By effectively utilizing the hydrogen sulfide obtained from the desulfurization unit as a raw material for lithium sulfide, lithium sulfide, which has a higher added value than sulfur, can be efficiently produced without consuming energy in the production of hydrogen sulfide.

[0015] In addition, this embodiment can also be a lithium sulfide manufacturing apparatus, which is an apparatus for manufacturing lithium sulfide, having a reactor for reacting hydrogen sulfide with a lithium source, and the reactor being connected to a hydrogen sulfide inlet pipeline for introducing hydrogen sulfide obtained from a desulfurization unit into the reactor and a hydrogen sulfide outlet pipeline for discharging unreacted hydrogen sulfide to the outside of the reactor.

[0016] "Lithium source" refers to a lithium raw material that reacts with hydrogen sulfide to produce lithium sulfide. Examples of lithium sources include: lithium metal, lithium sulfate, lithium hydroxide, lithium carbonate, and lithium oxide. Among these, lithium hydroxide and lithium carbonate are preferred, and lithium hydroxide is more preferred.

[0017] Hydrogen sulfide is a compound represented by the chemical formula H₂S. Gaseous hydrogen sulfide refers to a compound represented by the chemical formula H₂S in a gaseous state. Furthermore, hydrogen sulfide introduced into the reactor may also contain other components.

[0018] The moisture content of the hydrogen sulfide introduced into the reactor is preferably 20 vol% or less relative to the hydrogen sulfide. More preferably, the moisture content of the hydrogen sulfide is 10 vol% or less relative to the hydrogen sulfide, and even more preferably, 5 vol% or less.

[0019] The temperature at which hydrogen sulfide is introduced into the reactor can be 100–300°C, 150–250°C, or 180–220°C. In the reactor of this embodiment, even at this temperature, the hydrogen sulfide can be directly introduced into the reactor without cooling. Furthermore, the hydrogen sulfide introduced into the reactor can contain water at the saturated water vapor content of that temperature. In the reaction within the reactor according to this embodiment, it is not necessary to remove the water from the hydrogen sulfide before introducing it into the reactor, thus reducing the energy consumption of the entire equipment operation.

[0020] The amount of hydrogen sulfide introduced from the hydrogen sulfide inlet pipe is preferably 0.05 mol% / h or more relative to 1 mol of lithium source, more preferably 0.08 mol% / h or more and 0.30 mol% / h or less, and even more preferably 0.10 mol% / h or more and 0.20 mol% / h or less. By introducing hydrogen sulfide into the reactor within this range, unreacted hydrogen sulfide is discharged outside the reactor, and water is also discharged, thereby enabling the reaction to proceed efficiently within the reactor.

[0021] Inside the reactor, hydrogen sulfide reacts with a lithium source. When lithium hydroxide (LiOH) and lithium carbonate (Li2CO3) are used as lithium sources, the following reactions occur respectively.

[0022] 2LiOH + H₂S → Li₂S + 2H₂O Li₂CO₃ + H₂S → Li₂S + H₂O + CO₂ The reactor can be any device capable of contacting hydrogen sulfide with a lithium source. The reactor can be any type of reaction device, such as a fixed bed, moving bed, rotating bed, or fluidized bed. Preferably, the reactor is a device capable of contacting gaseous hydrogen sulfide with a powdered lithium source. In this case, since the reactor only needs to allow the gas and solid to react by contacting them, a powder dryer can also be used. As a powder dryer, a heat transfer type dryer such as a disc dryer is preferred. Examples of disc dryers include, for example, the product names "Micron Thermo Processor," "Torus Disc" (manufactured by Hosokawa Micron Co., Ltd.), "Paddle Dryer" (manufactured by Nara Machinery Manufacturing Co., Ltd.), "Inclined Disc Dryer" (manufactured by Tsukishima Holdings Co., Ltd.), and CD dryers. The reaction of hydrogen sulfide with a lithium source produces lithium sulfide, and this reaction also produces water. Furthermore, the reaction of lithium sulfide with water may produce lithium hydroxide. By using a drying device for the gas-solid reaction of hydrogen sulfide and lithium hydroxide, more water generated during the reaction can be discharged outside the reactor, allowing the equilibrium reaction to proceed in a direction favorable to the formation of lithium sulfide, thus enabling the production of lithium sulfide in a higher yield. When using a drying device as the reactor, the lithium source introduced into the reactor only needs to be converted into powder within the drying device; it does not need to be in a powder state when introduced into the reactor.

[0023] The reactor preferably has a mechanism for flowing the powder. By flowing the powder within the reactor, the contact efficiency between the powdered lithium source and the gaseous hydrogen sulfide can be improved, thereby facilitating powder drying, discharging more water outside the reactor, and ultimately increasing the reaction yield. A disc is an example of such a powder-flowing mechanism.

[0024] A "desulfurization unit" refers to a device that removes sulfur-containing compounds from a substance and generates hydrogen sulfide. Hydrodesulfurization units are preferred. Because desulfurization units can provide a large amount of hydrogen sulfide, they can be used in oil refining equipment or natural gas purification equipment. Examples of desulfurization units include: lubricating oil desulfurization units, vacuum desulfurization units, lamp oil desulfurization units, gas recovery desulfurization units, and heavy oil desulfurization units.

[0025] The desulfurization unit may include a hydrogen sulfide treatment device that uses a liquid composition containing water, and the hydrogen sulfide treated by this device can be introduced into a hydrogen sulfide inlet pipeline. With this configuration, hydrogen sulfide can be treated and its purity improved. Furthermore, in the reaction within the reactor according to this embodiment, since the water content in the hydrogen sulfide has a relatively small impact on the reaction, it can be introduced into the reactor without the need for water removal or other treatments, thereby reducing the overall energy consumption of the equipment.

[0026] Examples of hydrogen sulfide treatment devices include: separation and recovery devices that separate and recover hydrogen from hydrogen sulfide, and water washing devices that wash hydrogen sulfide with water.

[0027] When the desulfurization unit is a hydrodesulfurization unit, it can include a separation and recovery unit that separates and recovers hydrogen and hydrogen sulfide as the aforementioned hydrogen sulfide treatment unit. Both dry and wet separation and recovery units are acceptable, but a wet separation and recovery unit is preferred. Furthermore, the separation and recovery unit is preferably an amine treatment unit. The wet separation and recovery unit preferably uses an aqueous solution of an amine such as ethanolamine or diethanolamine as an absorbent. The wet separation and recovery unit separates the hydrogen sulfide from the hydrogen by contacting the aqueous amine solution with a gas containing hydrogen and hydrogen sulfide through chemical adsorption. The chemically adsorbed hydrogen sulfide is desorbed under high temperature conditions to obtain gaseous hydrogen sulfide. In the lithium sulfide manufacturing apparatus of this embodiment, even with hydrogen sulfide containing a large amount of water, the reaction can proceed without significantly impairing the reaction yield. Therefore, even using hydrogen sulfide obtained from a desulfurization unit employing a separation and recovery unit using an aqueous amine solution as an absorbent, lithium sulfide can be synthesized in high yield.

[0028] A "desulfurization recovery unit" refers to a device that treats hydrogen sulfide to recover sulfur. For example, a desulfurization recovery unit can utilize the Claus reaction to recover hydrogen sulfide as elemental sulfur. In this unit, a portion of the hydrogen sulfide (H2S) decomposes and is oxidized to sulfur dioxide (SO2). In the presence of a catalyst, the Claus reaction between hydrogen sulfide and sulfur dioxide produces elemental sulfur (S) and water. Examples of catalysts include natural bauxite, activated alumina, and titanium dioxide.

[0029] In this specification, "pipeline" refers to a system that supplies gas or solids. A typical example of a system that supplies gas or solids is a pipe.

[0030] A "hydrogen sulfide inlet line" refers to a conduit that introduces hydrogen sulfide into the reactor. For example, it could be a pipe connecting the hydrogen sulfide outlet of the desulfurization unit to the hydrogen sulfide inlet of the reactor.

[0031] A “hydrogen sulfide outlet pipeline” refers to a conduit that discharges hydrogen sulfide to the outside of the reactor. For example, it could be a pipe connecting the hydrogen sulfide outlet of the reactor to the hydrogen sulfide inlet of a sulfur recovery unit.

[0032] In the reactor, hydrogen sulfide sometimes reacts with the lithium source at relatively high temperatures. Therefore, the hydrogen sulfide exiting the reactor may be at a high temperature due to heating within the reactor. Furthermore, since the reaction of hydrogen sulfide with the lithium source (e.g., lithium hydroxide) produces water, the exited hydrogen sulfide contains a significant amount of moisture. Directly introducing hydrogen sulfide in this state into the sulfur recovery unit can adversely affect the reactions in the sulfur production process, potentially leading to reduced sulfur yield and quality. Additionally, if the high-temperature hydrogen sulfide containing moisture condenses and stagnates in the gas delivery pipeline due to heat dissipation, it can create a corrosive environment, which is therefore undesirable.

[0033] The temperature of the hydrogen sulfide discharged from the reactor to the hydrogen sulfide outlet pipeline is preferably 150°C or higher, more preferably 150°C or higher and 300°C or lower, and even more preferably 150°C or higher and 250°C or lower. By setting the temperature to such a level, the water generated by the reaction becomes easier to be discharged from the reactor along with the unreacted hydrogen sulfide, thereby allowing the reaction to proceed well.

[0034] Therefore, it is preferable to install a cooling device on the hydrogen sulfide outlet pipeline for cooling the hydrogen sulfide discharged from the reactor. By installing a cooling device, the temperature is lowered, thereby reducing corrosion of the equipment. Furthermore, by utilizing the cooling device to lower the temperature, the gaseous water contained in the hydrogen sulfide condenses, producing liquid. Therefore, by installing a gas-liquid separator downstream of the cooling device as a moisture removal device (described later), moisture can be removed efficiently. Alternatively, from another perspective, since the condensation of gaseous water contained in the hydrogen sulfide due to the cooling device may sometimes produce a large amount of liquid, the moisture removal device (described later) can also be installed closer to the reactor than the cooling device.

[0035] Examples of cooling devices include air-cooled heat exchangers, water-cooled heat exchangers, and cooling water circulation devices.

[0036] Preferably, a cooling device is used to reduce the temperature of hydrogen sulfide by more than 10°C, more preferably by more than 50°C, even more preferably by more than 100°C, and even more preferably by more than 150°C.

[0037] As described above, since the hydrogen sulfide discharged from the reactor contains a large amount of moisture, it is preferable to install a moisture removal device on the hydrogen sulfide outlet pipeline to remove moisture from the hydrogen sulfide. The moisture removal device can be any device capable of removing at least a portion of the moisture from the gas; for example, it could be a gas-liquid separator.

[0038] A cooling device can also be installed on the hydrogen sulfide outlet pipeline to cool the hydrogen sulfide discharged from the reactor. The hydrogen sulfide discharged from the reactor is sometimes at a high temperature due to heating within the reactor. By using a cooling device to lower the temperature, the gaseous water contained in the hydrogen sulfide condenses, sometimes producing a large amount of liquid. Therefore, it is preferable to install the aforementioned moisture removal device on the side closer to the reactor than the cooling device itself.

[0039] The lithium sulfide manufacturing apparatus of this embodiment is preferably configured such that unreacted hydrogen sulfide is introduced from the hydrogen sulfide outlet line into a sulfur recovery unit. In the reactor, gaseous hydrogen sulfide reacts with a powdered lithium source, and by introducing unreacted hydrogen sulfide from the hydrogen sulfide outlet line into the sulfur recovery unit, hydrogen sulfide can be safely processed.

[0040] The lithium sulfide manufacturing apparatus of this embodiment preferably further includes a dryer for drying the lithium source, and is configured such that the lithium source dried by the dryer is introduced into the reactor. The lithium sulfide manufacturing apparatus includes a dryer, which removes moisture from the lithium source by drying it before it is introduced into the reactor, allowing it to be processed in powder form within the reactor, thus enabling a good reaction with gaseous hydrogen sulfide. Furthermore, when lithium hydroxide is used as the lithium source, the lithium sulfide manufacturing apparatus preferably includes this dryer.

[0041] This embodiment relates to a lithium sulfide manufacturing apparatus, which is an apparatus for manufacturing lithium sulfide and includes: A reactor that allows hydrogen sulfide to react with lithium hydroxide; Desulfurization equipment; Sulfur recovery unit; Hydrogen sulfide obtained from the desulfurization unit is introduced into the hydrogen sulfide inlet pipeline within the reactor; and Unreacted hydrogen sulfide is discharged outside the reactor and introduced into the hydrogen sulfide outlet pipeline of the sulfur recovery unit.

[0042] According to this embodiment, it is possible to provide a lithium sulfide manufacturing apparatus that uses hydrogen sulfide obtained from an existing desulfurization unit to manufacture lithium sulfide.

[0043] The desulfurization device in the lithium sulfide manufacturing equipment of this embodiment may include a hydrogen sulfide treatment device that uses a liquid composition containing water, and may be configured such that the hydrogen sulfide treated by the hydrogen sulfide treatment device is introduced into a hydrogen sulfide inlet pipeline. The hydrogen sulfide treatment device is as described above.

[0044] The lithium sulfide manufacturing equipment of this embodiment preferably includes a bypass line that directly supplies hydrogen sulfide from the desulfurization unit to the sulfur recovery unit. The "bypass line" is a conduit that supplies hydrogen sulfide directly from the desulfurization unit to the sulfur recovery unit without passing through the reactor. By having a bypass line, even if the reactor is an intermittent reactor, when it is necessary to stop supplying hydrogen sulfide to the reactor, such as during the introduction of a new batch of lithium source into the reactor or during reactor maintenance or inspection, the continuously generated hydrogen sulfide in the desulfurization unit can be safely introduced into the sulfur recovery unit.

[0045] This embodiment relates to a method for manufacturing lithium sulfide, which includes: Hydrogen sulfide obtained from the desulfurization unit is introduced into the reactor; Hydrogen sulfide and lithium hydroxide react in the reactor; and Unreacted hydrogen sulfide is discharged outside the reactor and introduced into a sulfur recovery unit.

[0046] According to this embodiment, a method for manufacturing lithium sulfide can be provided, which uses hydrogen sulfide obtained from an existing desulfurization device to manufacture lithium sulfide.

[0047] The lithium sulfide manufacturing method of this embodiment can be implemented using the lithium sulfide manufacturing equipment described in this embodiment. The lithium source, the amount of water in the introduced hydrogen sulfide, the temperature, the reactor, the desulfurization device, and the sulfur recovery device used in the lithium sulfide manufacturing method of this embodiment are all as described above.

[0048] The temperature inside the reactor can be 100℃~300℃, 150℃~250℃, or 180~220℃.

[0049] Preferably, when unreacted hydrogen sulfide is discharged outside the reactor, the water generated during the reaction is also discharged outside the reactor.

[0050] Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings, but the present invention is not limited thereto. Furthermore, in the drawings, the same elements are given the same reference numerals, and repeated descriptions are omitted.

[0051] The following is a more detailed description of the lithium sulfide manufacturing equipment using the lithium sulfide manufacturing apparatus according to this embodiment. Figure 1 This is a block diagram illustrating the schematic structure of an apparatus for manufacturing lithium sulfide. (Example) Figure 1As shown, the lithium sulfide manufacturing equipment according to this embodiment includes a reactor 1, a desulfurization unit 2, and a sulfur recovery unit 3. The reactor 1 is connected to a lithium source supply line 11, and the lithium source is introduced into the reactor 1. The lithium sulfide manufacturing equipment according to this embodiment includes: a hydrogen sulfide inlet line 4 for introducing hydrogen sulfide obtained from the desulfurization unit 2 into the reactor 1; and a hydrogen sulfide outlet line 5 for discharging unreacted hydrogen sulfide outside the reactor 1 and introducing it into the sulfur recovery unit 3. Hydrogen sulfide is introduced into the reactor 1 from the hydrogen sulfide inlet line 4 and reacts with the lithium source; unreacted hydrogen sulfide and the generated water are discharged from the hydrogen sulfide outlet line 5. The lithium sulfide obtained in the reactor 1 is discharged outside the reactor 1 from the lithium sulfide outlet line 7 and shipped as a product. According to the lithium sulfide manufacturing equipment according to this embodiment, by incorporating the lithium sulfide manufacturing equipment according to this embodiment into existing desulfurization equipment, lithium sulfide can be manufactured while effectively utilizing resources.

[0052] The following, combined with Figure 2 A more detailed description is provided of the equipment and apparatus for manufacturing lithium sulfide. Figure 2 This is a schematic diagram of lithium sulfide manufacturing equipment. Figure 2 In this embodiment, the apparatus located between the desulfurization unit 2 and the sulfur recovery unit 3 is the lithium sulfide manufacturing apparatus. For example... Figure 2 As shown, the lithium sulfide manufacturing apparatus according to this embodiment includes a reactor 1, a hydrogen sulfide inlet line 4, and a hydrogen sulfide outlet line 5. In the reactor 1, a powdered lithium source is introduced into the reactor 1 through a lithium source supply line 11, and gaseous hydrogen sulfide is introduced into the reactor 1 through the hydrogen sulfide inlet line 4, causing the gaseous hydrogen sulfide to react with the powdered lithium source. The hydrogen sulfide inlet line 4 may be equipped with a valve A7, and the hydrogen sulfide outlet line 5 may be equipped with a valve A8. When supplying hydrogen sulfide to the reactor 1, valves A7 and A8 are opened.

[0053] The hydrogen sulfide inlet line 4 may include a heat exchanger 41. In the heat exchanger 41, the temperature of the gaseous hydrogen sulfide is regulated before it is introduced into the reactor 1. The preferred temperature for the hydrogen sulfide introduced into the reactor 1 is as described above.

[0054] Powdered lithium source is supplied to reactor 1 from lithium source supply line 11. Lithium source supply line 11 may include a dryer 111 for drying the lithium source and a hopper 112 for introducing the dried lithium source into the reactor. With this configuration, even when using a lithium source containing a high amount of moisture (e.g., lithium hydroxide monohydrate (LiOH·H2O)), anhydrous lithium hydroxide can be obtained through the dryer 111, allowing the powdered lithium hydroxide to be introduced into the reactor with a low moisture content, thereby further improving the reaction yield. Lithium source supply line 11 may be equipped with valve B1. Valve B1 is opened when supplying lithium source to reactor 1.

[0055] The hydrogen sulfide outlet line 5 may be equipped with a dust filter 53. In the reactor 1, since the reaction occurs simultaneously with the release of moisture, it becomes a gas-solid reaction. Therefore, powder flowing within the reactor may be discharged into the hydrogen sulfide outlet line 5 along with unreacted hydrogen sulfide. In such cases, since this may cause problems such as pipe blockage, it is preferable to install a dust filter 53.

[0056] The hydrogen sulfide outlet line 5 may be equipped with a moisture condenser 51 as a cooling device. The gas discharged from the reactor 1 contains unreacted hydrogen sulfide and moisture. The moisture condenser 51 cools the gas discharged from the reactor 1 and condenses the moisture.

[0057] The hydrogen sulfide outlet line 5 may be equipped with a gas-liquid separator 52. The gas-liquid separator 52 separates the gas, after the water has been condensed, into a liquid phase and a gas phase using a moisture condenser 51. The separated gas phase contains hydrogen sulfide and is sent to the sulfur recovery unit 3. The gas-liquid separator 52 may have a valve C1 at the bottom. The water-containing liquid phase accumulated in the gas-liquid separator 52 is discharged by opening valve C1.

[0058] The hydrogen sulfide outlet line 5 may be equipped with a blower 54. Lowering the pressure facilitates the evaporation of moisture in the hydrogen sulfide and its discharge outside the reactor system; however, it is preferable to increase the pressure when supplying it to the sulfur recovery unit 3. Furthermore, since the moisture contained in the hydrogen sulfide gas discharged from the reactor 1 condenses after passing through the gas-liquid separator 52, the pressure tends to decrease. Therefore, it is preferable to pressurize the hydrogen sulfide gas using the blower 54 before supplying it to the sulfur recovery unit 3.

[0059] The hydrogen sulfide outlet line 5 may have a circulation path 55 that recirculates the hydrogen sulfide separated by the gas-liquid separator 52 back into the moisture condenser 51. By providing the circulation path 55, it is easier to ensure the minimum flow rate required by the acid gas blower 54, and it is possible to prevent malfunction of the acid gas blower 54; therefore, it is preferred from a mechanical protection point of view. A variable valve A9 may be provided on the circulation path 55 to regulate the flow rate of the circulating hydrogen sulfide.

[0060] The lithium sulfide obtained in reactor 1 is sent to product filling equipment 8 via lithium sulfide outlet line 7. In product filling equipment 8, the obtained lithium sulfide is filled into a conveying container to obtain lithium sulfide product. Reactor 1 may have a valve B2 at the bottom. The lithium sulfide generated in reactor 1 is extracted by opening valve B1.

[0061] The lithium sulfide manufacturing equipment may include a bypass line 6 that directly supplies hydrogen sulfide from the desulfurization unit 2 to the sulfur recovery unit 3. With the bypass line 6, even if the reaction in the reactor 1 is intermittent, hydrogen sulfide can be directly sent from the desulfurization unit 2 to the sulfur recovery unit 3 via the bypass line 6, thereby enabling safe handling of hydrogen sulfide. Furthermore, the lithium sulfide manufacturing equipment may be equipped with valves A2, A3, A4, and A5 to switch between the hydrogen sulfide inlet line 4, which supplies hydrogen sulfide generated from the desulfurization unit 2 to the reactor 1, and the bypass line 6. When hydrogen sulfide generated from the desulfurization unit 2 is supplied to the hydrogen sulfide inlet line 4, valves A2 and A5 are opened, and valves A3 and A4 are closed. Conversely, when hydrogen sulfide is directly supplied from the desulfurization unit 2 to the sulfur recovery unit 3, valves A3 and A4 are opened, and valves A2 and A5 are closed.

[0062] like Figure 2 As shown, reactor 1 has a lithium source inlet 17, which introduces lithium source from lithium source supply line 11 into shell 12.

[0063] The lithium sulfide obtained in reactor 1 is extracted from lithium sulfide outlet 18 and sent to lithium sulfide outlet pipeline 7.

[0064] Next, the desulfurization unit will be explained using a hydrodesulfurization unit that uses light kerosene as an example. Figure 3 This is a schematic diagram of a desulfurization unit. (For example...) Figure 3 As shown, the desulfurization unit 2 includes a hydrodesulfurization tower 21 and a hydrogen sulfide separation and recovery unit 22. The hydrodesulfurization tower 21 has a catalyst packing layer 211 filled with hydrodesulfurization catalyst. The hydrodesulfurization tower 21 is connected to a hydrogen supply line 212 and a light oil supply line 213. Light oil supplied from the light oil supply line 213 and hydrogen supplied from the hydrogen supply line 212 come into contact with the catalyst in the catalyst packing layer 211 within the hydrodesulfurization tower 21. The sulfur compounds contained in the light oil react with the hydrogen to generate hydrogen sulfide. After the hydrodesulfurization reaction, the light oil, unreacted hydrogen, and generated hydrogen sulfide are discharged from the outlet 214 through the treated light oil pipeline 215 to the outside of the hydrodesulfurization tower 21.

[0065] The desulfurization unit 2 may include a gas-liquid separator 23. Light oil containing hydrogen sulfide is discharged from the hydrodesulfurization tower 21 to the gas-liquid separator 23, where it is separated into a gaseous liquid containing hydrogen and hydrogen sulfide, and a liquid light oil. The separated light oil is purified as needed and becomes the desulfurized light oil product. The gas containing hydrogen and hydrogen sulfide separated by the gas-liquid separator 23 is sent to the hydrogen sulfide separation and recovery unit 22 via the gas supply line 231.

[0066] The hydrogen sulfide separation and recovery unit 22 separates hydrogen and hydrogen sulfide, and recovers them separately. In the hydrogen sulfide separation and recovery unit 22, the gas containing hydrogen and hydrogen sulfide is treated with an aqueous amine solution to chemically adsorb the hydrogen sulfide. The chemically adsorbed hydrogen sulfide is desorbed by heating the aqueous amine solution, and the desorbed hydrogen sulfide, containing moisture, is discharged into the reactor 1 via the hydrogen sulfide inlet line 4.

[0067] Although the detailed structure of the sulfur recovery unit 3 is not illustrated, hydrogen sulfide can be treated using the Claus process to generate elemental sulfur for recovery. The Claus process, for example, involves partially burning hydrogen sulfide in a reactor using air to generate a mixed gas containing 1 mole of sulfur dioxide for every 2 moles of hydrogen sulfide. This mixed gas is then brought into contact with a catalyst to generate elemental sulfur. The sulfur recovery unit 3 can be equipped with a cooler to recover the vaporized sulfur as molten sulfur.

[0068] [Method for manufacturing lithium sulfide] This embodiment relates to a method for manufacturing lithium sulfide, which includes: Hydrogen sulfide obtained from the desulfurization unit is introduced into the reactor; The gaseous hydrogen sulfide reacts with the powdered lithium hydroxide within the reactor; and Unreacted hydrogen sulfide is discharged outside the reactor and introduced into a sulfur recovery unit.

[0069] The manufacturing method described above will be explained below in conjunction with the operation mode of the lithium sulfide manufacturing apparatus involved in this embodiment.

[0070] First, hydrogen sulfide obtained from the desulfurization unit 2 is introduced into the reactor 1. At this time, hydrogen sulfide is introduced from the gas inlet 13 into the shell 12 of the reactor 1 via the hydrogen sulfide inlet pipeline 4. Hydrogen sulfide can be continuously supplied to the reactor 1. The temperature of the gaseous hydrogen sulfide can be regulated using a heat exchanger 41 installed on the hydrogen sulfide inlet pipeline 4.

[0071] The moisture content of the hydrogen sulfide gas introduced into the reactor is preferably 20 vol% or less, more preferably 10 vol% or less, and even more preferably 5 vol% or less. Even within this range, the reaction can proceed without compromising the yield. The moisture content of the hydrogen sulfide can be controlled by moisture condensation caused by the heat exchanger.

[0072] The temperature of the hydrogen sulfide gas introduced into the reactor is preferably 100–300°C, more preferably 150–250°C, and even more preferably 180–220°C.

[0073] By setting the temperature within this range, it is possible to achieve high reactivity while using common materials such as fluoropolymers as components within the device. The temperature of the hydrogen sulfide can be controlled via a heat exchanger.

[0074] Furthermore, the lithium source is pre-introduced into the housing 12 from the lithium source inlet 17 of the reactor 1. Inside the housing 12, where hydrogen sulfide has been introduced, the gaseous hydrogen sulfide reacts with the powdered lithium hydroxide within the reactor 1.

[0075] The moisture content of the lithium source is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less. The moisture content of the lithium source can be adjusted by drying using dryer 111. This moisture content is measured using a Karl Fischer moisture analyzer at 280°C by vaporization.

[0076] At this time, the temperature inside reactor 1 is controlled by the heat medium flowing in the hollow part of the rotating shaft 151 and the fan-shaped stirring blades 152 and the heat medium flowing in the jacket 16.

[0077] Furthermore, the preferred temperature range within the reactor is as described above.

[0078] In the lithium sulfide manufacturing method according to this embodiment, unreacted hydrogen sulfide is discharged outside the reactor 1 and introduced into the sulfur recovery unit 3. Furthermore, while hydrogen sulfide is continuously introduced into the reactor 1, unreacted hydrogen sulfide is continuously discharged outside the reactor. By continuously introducing unreacted hydrogen sulfide into the sulfur recovery unit 3, hydrogen sulfide can be safely processed.

[0079] Since the emitted hydrogen sulfide contains moisture generated within reactor 1, it is preferable to use a moisture condenser 51 to condense and remove the moisture. Furthermore, the condensed moisture is separated into gas and liquid by a gas-liquid separator 52, and the gas containing hydrogen sulfide is sent to the sulfur recovery unit 3.

[0080] The embodiments described above are for the purpose of understanding the present invention, and not for limiting the interpretation of the present invention. The elements, their configurations, materials, conditions, shapes, and dimensions included in the embodiments are not limited to those illustrated, but can be appropriately modified. Furthermore, the components shown in different embodiments may be partially substituted or combined with each other.

[0081] The implementation methods described above include the following implementation methods.

[0082] <1> An apparatus for manufacturing lithium sulfide, comprising: A reactor that allows hydrogen sulfide to react with a lithium source; Hydrogen sulfide obtained from the desulfurization unit is introduced into the hydrogen sulfide inlet pipeline within the reactor; and Unreacted hydrogen sulfide is discharged to a hydrogen sulfide outlet pipeline outside the reactor.

[0083] <2> like <1> The lithium sulfide manufacturing apparatus wherein the hydrogen sulfide outlet pipeline introduces unreacted hydrogen sulfide into a sulfur recovery unit.

[0084] <3> like <1> or <2> The lithium sulfide manufacturing apparatus wherein the hydrogen sulfide outlet line is equipped with a heat exchanger for lowering the temperature of the hydrogen sulfide.

[0085] <4> like <1> ~ <3> The lithium sulfide manufacturing apparatus according to any one of the following, wherein the hydrogen sulfide outlet line is equipped with a moisture remover to reduce the moisture content of the hydrogen sulfide.

[0086] <5> like <1> ~ <4> The lithium sulfide manufacturing apparatus according to any one of the following is configured such that the amount of hydrogen sulfide introduced from the hydrogen sulfide inlet line is 0.05 mol% / h or more relative to 1 mol of lithium source.

[0087] <6> like <1> ~ <5> The lithium sulfide manufacturing apparatus described in any one of the following is configured such that the temperature of the hydrogen sulfide discharged from the reactor to the hydrogen sulfide outlet pipeline is 150°C or higher.

[0088] <7> like <1> ~ <6> The lithium sulfide manufacturing apparatus described in any one of the following further comprises: Dryer for drying lithium sources; and The lithium source dried by the dryer is introduced into the lithium source inlet pipeline inside the reactor.

[0089] <8> like <1> ~ <7> The lithium sulfide manufacturing apparatus according to any one of the following methods, wherein the water content of the hydrogen sulfide introduced into the reactor is less than 20 vol%.

[0090] <9> like <1> ~ <8> The lithium sulfide manufacturing apparatus according to any one of the following methods, wherein the temperature of the hydrogen sulfide introduced into the reactor is 100 to 300°C.

[0091] <10> like <1> ~ <9> The lithium sulfide manufacturing apparatus according to any one of the following methods, wherein the reactor has a mechanism for causing powder to flow.

[0092] <11> like <1> ~ <10> The lithium sulfide manufacturing apparatus according to any one of the following methods, wherein the lithium source is lithium hydroxide.

[0093] <12> like <1> ~ <11> The lithium sulfide manufacturing apparatus according to any one of the following methods, wherein the lithium source is lithium carbonate.

[0094] <13> A lithium sulfide manufacturing apparatus, comprising: A reactor that allows hydrogen sulfide to react with a lithium source; Desulfurization equipment; Sulfur recovery unit; Hydrogen sulfide obtained from the desulfurization unit is introduced into the hydrogen sulfide inlet pipeline within the reactor; and Unreacted hydrogen sulfide is discharged outside the reactor and introduced into the hydrogen sulfide outlet pipeline of the sulfur recovery unit.

[0095] <14> like <13> The lithium sulfide manufacturing equipment, wherein, The desulfurization unit includes a hydrogen sulfide treatment device that uses a liquid composition containing water. Hydrogen sulfide treated by the hydrogen sulfide treatment device is introduced into the hydrogen sulfide inlet pipeline.

[0096] <15> like <13> or <14> The lithium sulfide manufacturing equipment has a bypass line that supplies hydrogen sulfide directly from the desulfurization unit to the sulfur recovery unit.

[0097] <16> like <13> ~ <15> The lithium sulfide manufacturing apparatus according to any one of the following, wherein the hydrogen sulfide outlet pipeline is equipped with a heat exchanger for lowering the temperature of the hydrogen sulfide.

[0098] <17> like <13> ~ <16> The lithium sulfide manufacturing apparatus according to any one of the following, wherein the hydrogen sulfide outlet pipeline is equipped with a moisture remover that reduces the moisture content of the hydrogen sulfide.

[0099] <18> like <13> ~ <17> The lithium sulfide manufacturing apparatus according to any one of the following is configured such that the amount of hydrogen sulfide introduced from the hydrogen sulfide inlet line is 0.05 mol% / h or more relative to 1 mol of lithium source.

[0100] <19> like <13> ~ <18> The lithium sulfide manufacturing apparatus according to any one of the following is configured such that the temperature of the aforementioned hydrogen sulfide discharged from the reactor to the hydrogen sulfide outlet pipeline is 150°C or higher.

[0101] <20> A method for manufacturing lithium sulfide, comprising: Hydrogen sulfide obtained from the desulfurization unit is introduced into the reactor; The hydrogen sulfide reacts with the lithium source within the reactor; and Unreacted hydrogen sulfide is discharged outside the reactor and introduced into a sulfur recovery unit.

[0102] <21> like <20> The method for manufacturing lithium sulfide, wherein the lithium source is lithium hydroxide.

[0103] <22> like <20> or <21> In the method for manufacturing lithium sulfide, the amount of hydrogen sulfide introduced into the reactor is 0.05 mol% or more relative to 1 mol of lithium source.

[0104] <23> like <20> ~ <22> The method for manufacturing lithium sulfide according to any one of the following methods, wherein the temperature of the hydrogen sulfide discharged from the reactor is 150°C or higher.

[0105] <24> like <20> ~ <23> In any one of the methods for manufacturing lithium sulfide, the amount of hydrogen sulfide introduced into the reactor is 0.05 mol% or more relative to 1 mol of lithium source.

[0106] Explanation of reference numerals in the attached figures 1 Reactor, 2 Desulfurization Unit, 3 Sulfur Recovery Unit, 4 Hydrogen Sulfide Inlet Pipeline, 5 Hydrogen Sulfide Outlet Pipeline, 6 Bypass Pipeline, 7 Lithium Sulfide Outlet Pipeline, 11 Lithium Source Supply Pipeline, 12 Shell, 13 Gas Inlet, 16 Jacket, 17 Lithium Source Inlet, 18 Lithium Sulfide Outlet, 21 Hydrodesulfurization Tower, 22 Hydrogen Sulfide Separation and Recovery Unit, 23 Gas-Liquid Separator, 41 Heat Exchanger, 51 Moisture Condenser, 52 Gas-Liquid Separator, 53 Dust Filter, 54 Blower, 55 Circulation Flow Path, 111 Dryer, 112 Hopper, 151 Rotating Shaft, 152 Fan-Shaped Stirring Blades, 211 Catalyst Packing Layer, 212 Hydrogen Supply Pipeline, 213 Light Oil Supply Pipeline, 214 Discharge Port, 215 After treatment, light oil pipeline, 231 gas supply pipeline, valves A2, A3, A4, A5, A7, A8, B1, B2, C1, and variable valve A9.

Claims

1. An apparatus for manufacturing lithium sulfide, characterized in that, have: A reactor that allows hydrogen sulfide to react with a lithium source; Hydrogen sulfide obtained from the desulfurization unit is introduced into the hydrogen sulfide inlet pipeline within the reactor; and Unreacted hydrogen sulfide is discharged to a hydrogen sulfide outlet pipeline outside the reactor.

2. The lithium sulfide manufacturing apparatus as described in claim 1, characterized in that, The hydrogen sulfide outlet pipeline introduces unreacted hydrogen sulfide into the sulfur recovery unit.

3. The lithium sulfide manufacturing apparatus as described in claim 1 or 2, characterized in that, The hydrogen sulfide outlet pipeline is equipped with a heat exchanger that lowers the temperature of the hydrogen sulfide.

4. The apparatus for manufacturing lithium sulfide as described in any one of claims 1 to 3, characterized in that, The hydrogen sulfide outlet pipeline is equipped with a moisture remover that reduces the water content of the hydrogen sulfide.

5. The apparatus for manufacturing lithium sulfide as described in any one of claims 1 to 4, characterized in that, It also has: Dryer for drying lithium sources; and The lithium source dried by the dryer is introduced into the lithium source inlet pipeline inside the reactor.

6. The apparatus for manufacturing lithium sulfide as described in any one of claims 1 to 5, characterized in that, The reactor has a mechanism for causing the powder to flow.

7. The apparatus for manufacturing lithium sulfide as described in any one of claims 1 to 6, characterized in that, The lithium source is lithium hydroxide.

8. The apparatus for manufacturing lithium sulfide as claimed in any one of claims 1 to 7, characterized in that, The lithium source is lithium carbonate.

9. A lithium sulfide manufacturing apparatus, characterized in that, have: A reactor that allows hydrogen sulfide to react with a lithium source; Desulfurization equipment; Sulfur recovery unit; Hydrogen sulfide obtained from the desulfurization unit is introduced into the hydrogen sulfide inlet pipeline inside the reactor; as well as Unreacted hydrogen sulfide is discharged outside the reactor and introduced into the hydrogen sulfide outlet pipeline of the sulfur recovery unit.

10. The lithium sulfide manufacturing apparatus as described in claim 9, characterized in that, The desulfurization unit includes a hydrogen sulfide treatment device that uses a liquid composition containing water. Hydrogen sulfide treated by the hydrogen sulfide treatment device is introduced into the hydrogen sulfide inlet pipeline.

11. The lithium sulfide manufacturing apparatus as described in claim 9 or 10, characterized in that, It has a bypass line that supplies hydrogen sulfide directly from the desulfurization unit to the sulfur recovery unit.

12. The lithium sulfide manufacturing apparatus according to any one of claims 9 to 11, characterized in that, The hydrogen sulfide outlet pipeline is equipped with a heat exchanger that lowers the temperature of the hydrogen sulfide.

13. The lithium sulfide manufacturing apparatus according to any one of claims 9 to 12, characterized in that, The hydrogen sulfide outlet pipeline is equipped with a moisture remover that reduces the water content of the hydrogen sulfide.

14. A method for manufacturing lithium sulfide, characterized in that, include: Hydrogen sulfide obtained from the desulfurization unit is introduced into the reactor; The hydrogen sulfide reacts with the lithium source within the reactor; as well as Unreacted hydrogen sulfide is discharged outside the reactor and introduced into a sulfur recovery unit.

15. The method for manufacturing lithium sulfide as described in claim 14, characterized in that, The lithium source is lithium hydroxide.

16. The method for manufacturing lithium sulfide as described in claim 14 or 15, characterized in that, The amount of hydrogen sulfide introduced into the reactor is greater than 0.05 mol% relative to 1 mol of lithium source.

17. The method for manufacturing lithium sulfide according to any one of claims 14 to 16, characterized in that, The temperature of the hydrogen sulfide emitted from the reactor is above 150°C.

18. The method for manufacturing lithium sulfide according to any one of claims 14 to 17, characterized in that, The amount of hydrogen sulfide introduced into the reactor is greater than 0.05 mol% relative to 1 mol of lithium source.

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