Lithium sulfide manufacturing equipment

Abstract

The lithium sulfide manufacturing apparatus according to the present invention includes a reaction chamber having a reaction space for producing lithium sulfide and configured to move a supplied lithium raw material along a predetermined direction, a lithium raw material supply unit configured to continuously supply a lithium raw material to an upstream side of the reaction chamber in the predetermined direction, a hydrogen sulfide supply unit configured to supply hydrogen sulfide to the reaction chamber, a heating unit configured to heat the reaction space, a lithium sulfide recovery unit provided on the downstream side of the reaction chamber in the predetermined direction and configured to recover lithium sulfide produced by a reaction between hydrogen sulfide and a lithium raw material in the reaction chamber, an inert gas supply unit provided on the upstream side of the reaction chamber in the predetermined direction and configured to supply an inert gas to the upstream side of the reaction chamber in the predetermined direction, and a moisture removal unit provided on the downstream side of the reaction chamber in the predetermined direction, recovered gas discharged from the reaction chamber, removed water vapor from the gas, and then re-supplied the gas to the upstream side of the reaction chamber in the predetermined direction, and the hydrogen sulfide supply unit is a hydrogen sulfide reactor that synthesizes hydrogen sulfide using liquid sulfur sprayed from a liquid sulfur spray tube and hydrogen gas.

Description

[Technical Field]

[0001] The present invention relates to an apparatus for producing lithium sulfide. [Background technology]

[0002] Lithium secondary batteries have high energy density and long lifespan, and are therefore widely used in electronic devices such as home appliances, laptops, and smartphones. Recently, their use has been greatly increasing, with them also being installed in electric vehicles (EVs) and hybrid electric vehicles (HEVs).

[0003] Lithium-ion secondary batteries, which are currently the most widely used type, have been widely used as the main power source for mobile phones, laptops, PCs, etc. since mass production began in 1991 due to their high energy density and output voltage. However, the organic electrolyte, which is used to ensure the smooth movement of lithium ions, has an inherent risk of explosion if overheated or overcharged. It is also prone to ignition if an ignition source is present. Furthermore, when side reactions occur within the battery, gas is generated, which can lead to a decrease in battery performance and stability.

[0004] Therefore, to overcome the shortcomings of lithium-ion secondary batteries, active research and development is being conducted on all-solid-state lithium secondary batteries. All-solid-state lithium secondary batteries not only reduce the risk of explosion by using a solid electrolyte instead of a volatile electrolyte solution, but also have the advantage of being able to use lithium metal or lithium alloy as the anode material, thereby dramatically improving the energy density of the battery.

[0005] Among the solid electrolyte candidates that can be used in solid-state batteries, sulfide-based solid electrolytes, known for their high ductility and ionic conductivity, are currently considered suitable for the production of large-scale, high-capacity secondary batteries, and lithium sulfide (Li2S) is considered a key material in the production process of such sulfide-based solid electrolytes. There are various methods known for synthesizing lithium sulfide, but the most common method is known to be the reaction of metallic lithium, such as lithium hydroxide (LiOH) or lithium carbonate (Li2CO3), with hydrogen sulfide (H2S).

[0006] Meanwhile, hydrogen sulfide gas is a highly corrosive gas, and when reacted with metallic lithium in a reactor made of a general metal material according to a conventional method, it corrodes equipment including the reactor and various piping, requiring frequent repairs and replacements, which reduces the economic viability when mass-producing lithium sulfide.

[0007] Furthermore, when metallic lithium such as lithium hydroxide is reacted with hydrogen sulfide, water vapor is inevitably generated. The generated water vapor not only prevents contact between metallic lithium and hydrogen sulfide, thereby reducing the yield of lithium sulfide, but also re-reacts with lithium sulfide, accelerating the reverse reaction to form lithium hydroxide, thereby reducing the purity of the produced lithium sulfide. Furthermore, moisture can cause aggregation between produced lithium sulfide particles, resulting in a deterioration in quality.

[0008] Therefore, the present inventors have studied a method for producing lithium sulfide with high purity and high yield by using a reaction of reacting metallic lithium with hydrogen sulfide, while effectively suppressing corrosion of a reactor and effectively removing water vapor generated as a reaction product, and have completed the present invention. Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been proposed to solve the above-mentioned problems, and provides an apparatus for manufacturing lithium sulfide, which is capable of mass-producing lithium sulfide with high purity and high yield by designing a reactor under specific materials and temperature conditions suitable for mass-producing lithium sulfide with high purity and high yield through the reaction of metallic lithium and hydrogen sulfide, and by selectively removing only moisture from gas generated during the reaction to minimize side reactions / reverse reactions. [Means for solving the problem]

[0010] In one example, the lithium sulfide manufacturing apparatus includes a reaction chamber having a reaction space for producing lithium sulfide and configured to move a supplied lithium source material along a predetermined direction, a lithium source supply unit configured to continuously supply the lithium source material to an upstream side of the reaction chamber in the predetermined direction, a hydrogen sulfide supply unit configured to supply hydrogen sulfide to the reaction chamber, a heating unit configured to heat the reaction space, a lithium sulfide recovery unit provided on the downstream side of the reaction chamber in the predetermined direction and configured to recover lithium sulfide produced by a reaction between the hydrogen sulfide and the lithium source material in the reaction chamber, an inert gas supply unit provided on the upstream side of the reaction chamber in the predetermined direction and configured to supply an inert gas to the upstream side of the reaction chamber in the predetermined direction, and a moisture removal unit provided on the downstream side of the reaction chamber in the predetermined direction and configured to recover gas discharged from the reaction chamber, remove water vapor from the gas, and then re-supply the gas to the upstream side of the reaction chamber in the predetermined direction, and the hydrogen sulfide supply unit is a hydrogen sulfide reactor that synthesizes hydrogen sulfide using liquid sulfur sprayed from a liquid sulfur spray pipe and hydrogen gas.

[0011] In another example, the moisture removal unit may include a liquefaction cooling unit that primarily cools the gas recovered from the reaction chamber and selectively removes only moisture from the gas.

[0012] In yet another example, the moisture removal unit may include a sublimation cooling unit that performs secondary cooling of the gas recovered from the reaction chamber and selectively removes only moisture from the gas.

[0013] In yet another example, the sublimation cooling unit may include a plurality of cooling chambers and a control unit that controls the sublimation cooling unit, and the control unit may control the cooling chamber to which the recovered gas is transferred so that secondary cooling is performed when the recovered gas is transferred to at least one predetermined cooling chamber among the plurality of cooling chambers.

[0014] In yet another example, the control unit may control the cooling chamber to which the recovered gas is transferred to be cooled for a predetermined period of time, and then the cooling chamber that has been cooled for the predetermined period of time may be heated, and the ice that has sublimated due to cooling may be liquefied and removed.

[0015] In yet another example, the sublimation cooling unit may include a plurality of branch lines for transferring the recovered gas to a plurality of cooling chambers, respectively, and valves provided on the branch lines for opening and closing each branch line, and the control unit may be configured to determine the cooling chamber to which the recovered gas is transferred by controlling the valves.

[0016] In yet another example, the sublimation cooling unit includes a main body rotatable about an axis parallel to the direction in which the recovered gas is transported, and a plurality of cooling chambers are formed through the main body along a direction parallel to the axis, at least one of which is provided to communicate with a recovery line through which the recovered gas is transported and a re-supply line through which the recovered gas is re-supplied to the reaction chamber, and the control unit may control the main body to rotate about the axis so that the cooling chamber performing cooling communicates with the recovery line and the re-supply line.

[0017] In yet another example, after the cooling chamber into which the recovered gas is transferred has been in cooling operation for a predetermined period of time, the control unit controls the main body to rotate around its axis so that the recovery line is connected to other cooling chambers that are scheduled to be in cooling operation, and heats the cooling chamber that has been in cooling operation for the predetermined period of time, thereby liquefying and removing the ice that has sublimated due to cooling.

[0018] In yet another example, the reaction chamber may further include an inert gas discharge line connected to the reaction chamber for discharging the inert gas from the reaction chamber, and the inert gas discharge line may be located upstream in a predetermined direction from the hydrogen sulfide supply position where the hydrogen sulfide supply unit supplies hydrogen sulfide into the reaction chamber.

[0019] In yet another example, the reaction chamber may further include a partition plate disposed within the reaction chamber and extending along a direction transverse to the predetermined direction, and the partition plate may be disposed between the hydrogen sulfide supply position and the inert gas discharge line.

[0020] In yet another example, the partition plate may be provided at the upper end of the reaction chamber adjacent to the inert gas exhaust line and may be provided on the inner surface of the reaction chamber to provide a space for fluid flow.

[0021] In yet another example, the hydrogen sulfide reactor may include a hydrogen sulfide reaction chamber having a hollow hydrogen sulfide reaction space and a hydrogen sulfide outlet for discharging hydrogen sulfide synthesized in the hydrogen sulfide reaction space, a liquid sulfur spray pipe configured to recover liquid sulfur contained in the hydrogen sulfide reaction chamber and spray it into the hydrogen sulfide reaction space, a liquid sulfur heating device configured to heat the liquid sulfur, a hydrogen gas supply pipe configured to supply hydrogen gas to the hydrogen sulfide reaction space below the position where the liquid sulfur is sprayed from the liquid sulfur spray pipe, and a flow path changing member that changes the flow path to be longer than a straight path so that hydrogen gas, sulfur gas generated by vaporization of liquid sulfur, and hydrogen sulfide synthesized by reaction of hydrogen gas and sulfur gas do not flow in a straight path toward the hydrogen sulfide outlet.

[0022] In yet another example, the flow path change member may include a first partition member having a plate extending in a direction transverse to the linear path and a first outer wall extending from the plate so as to form a space into which liquid sulfur and hydrogen gas are supplied, and the first partition member may be positioned away from the hydrogen sulfide reaction chamber so as to form a first flow path between the outer surface of the first outer wall and the inner surface of the hydrogen sulfide reaction chamber.

[0023] In yet another example, the flow path change member may further include a second partition member having a second outer wall formed in a columnar shape with both sides open, the liquid sulfur and hydrogen gas being supplied to the internal space of the second outer wall, and the second partition member may be positioned apart from the first partition member so that a second flow path is formed between the second partition member and the first partition member.

[0024] In yet another example, the flow path change member may include at least one flow path forming plate extending in a direction transverse to the linear path, wherein one end of the flow path forming plate is coupled to the inner surface of the hydrogen sulfide reaction chamber and the other end extends away from the inner surface of the hydrogen sulfide reaction chamber, forming a space for fluid flow between the other end and the inner surface of the hydrogen sulfide reaction chamber.

[0025] In yet another example, the flow path changing member may include a plurality of flow path forming plates, and the plurality of flow path forming plates may be arranged such that the other ends of adjacent flow path forming plates are positioned in opposite directions to each other. [Effects of the Invention]

[0026] According to the present invention, when lithium sulfide is produced by the reaction between metallic lithium and hydrogen sulfide, corrosion of the reactor is minimized, and frequent repairs and replacements of equipment including the reactor and various piping can be prevented, thereby improving the economic efficiency of the process.

[0027] Furthermore, water vapor (moisture), a by-product of the reaction, is effectively removed, preventing the reverse reaction to form lithium hydroxide and promoting the forward reaction. In addition, agglomeration between lithium sulfide particles is prevented, making it possible to mass-produce high-quality lithium sulfide with high purity and high yield.

[0028] In addition, the hydrogen sulfide reactor generates hydrogen sulfide by atomizing heated liquid sulfur and contacting it with hydrogen gas, and the reaction heat generated during the reaction can be absorbed by the vaporization heat of the atomized liquid sulfur particles or by the atomized liquid sulfur particles. This prevents the temperature in the hydrogen sulfide reaction chamber from rising excessively, and reduces the amount of hydrogen polysulfide (H2S) generated. x ) and other by-products can be minimized.

[0029] In addition, the flow path change member installed in the hydrogen sulfide reaction chamber increases the length of the path through which sulfur gas and hydrogen gas flow, thereby increasing the contact area and contact time between liquid sulfur (sulfur gas) and hydrogen gas, thereby maximizing the hydrogen sulfide conversion rate and enabling the production of hydrogen sulfide with high yield and purity. [Brief explanation of the drawings]

[0030] [Figure 1] FIG. 1 is a schematic diagram showing an apparatus for producing lithium sulfide according to one embodiment of the present invention. [Figure 2] FIG. 2 is a schematic diagram illustrating a hydrogen sulfide reactor according to one embodiment of the present invention. [Figure 3] FIG. 3 is a horizontal cross-sectional view of the hydrogen sulfide reaction chamber showing the arrangement of the hydrogen gas supply pipes. [Figure 4] FIG. 4 is a cross-sectional view showing the internal configuration of the hydrogen sulfide reaction chamber. [Figure 5] FIG. 5 is a plan view of the cover plate. [Figure 6] FIG. 6 is a schematic diagram illustrating a hydrogen sulfide reactor according to another embodiment of the present invention. [Figure 7]FIG. 7 is a schematic diagram showing a moisture removal unit according to an embodiment of the present invention. [Figure 8] FIG. 8 is a perspective view showing a sublimation cooling unit according to an embodiment of the present invention. [Figure 9] FIG. 9 is a perspective view showing a sublimation cooling unit according to another embodiment of the present invention. [Figure 10] FIG. 10 is a front view showing a sublimation cooling unit according to still another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0031] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. When assigning reference numerals to components in each drawing, it should be noted that identical components are assigned the same numerals as much as possible, even if they appear in different drawings. Furthermore, when describing embodiments of the present invention, if a detailed description of related well-known structures or functions is deemed to hinder understanding of the embodiments of the present invention, the detailed description will be omitted.

[0032] 1 is a schematic diagram showing an apparatus for manufacturing lithium sulfide according to one embodiment of the present invention. Hereinafter, the apparatus for manufacturing lithium sulfide according to one embodiment of the present invention will be described with reference to FIG.

[0033] An apparatus for manufacturing lithium sulfide according to an embodiment of the present invention includes a reaction chamber 100, a heating unit 150, a lithium raw material supply unit 200, a hydrogen sulfide supply unit 300, a lithium sulfide recovery unit 400, a moisture removal unit 500, and an inert gas supply unit 600. Although not shown, a separate supply unit such as a circulation pump may be used to promote material transfer between components in the apparatus.

[0034] The reaction chamber 100 is a chamber having a reaction space for producing lithium sulfide. A lithium raw material and hydrogen sulfide react in the reaction space to synthesize lithium sulfide. The reaction chamber 100 is configured to move the supplied lithium raw material in a predetermined direction. For example, as shown in FIG. 1, the reaction chamber 100 may be configured so that the lithium raw material supplied to the right side of the reaction chamber 100 moves to the left side. The method and direction of moving the lithium raw material are not particularly limited. For example, a conveyor belt may be installed inside the reaction chamber 100, or the bottom of the reaction chamber 100 may be inclined so that the lithium raw material moves by gravity.

[0035] Meanwhile, a stirring member (not shown) for promoting the reaction may be further provided in the reaction chamber, and examples thereof include a rotating disk, a rotary, a propeller, etc., but are not particularly limited thereto.

[0036] The lithium source supply unit 200 is provided to continuously supply the lithium source to the reaction chamber 100. The lithium source supply unit 200 supplies the lithium source via the lithium source supply line 10 to the upstream side in a predetermined direction in which the lithium source moves from the reaction chamber 100. Here, the upstream side in the predetermined direction means the upstream side of the region of the reaction space heated by the heating unit 150, which will be described later. The size and shape of the lithium source supply unit 200 are not particularly limited. For example, the lithium source supply unit 200 may be a hopper.

[0037] The lithium raw material supply unit 200 may supply lithium hydroxide (LiOH) or lithium carbonate (Li2CO3), specifically lithium hydroxide, as a lithium raw material. The lithium hydroxide supplied to the reaction chamber 100 may react with hydrogen sulfide supplied by the hydrogen sulfide supply unit 300 (described later) to produce lithium sulfide as shown in the following formula. That is, it can be seen that when lithium hydroxide reacts with hydrogen sulfide, water is produced as a by-product.

[0038] 2LiOH+H2S → Li2S+2H2O

[0039] The lithium raw material to be supplied may have a particle size of 1 mm or less. This increases the reaction area with hydrogen sulfide, thereby enabling the production of high-purity lithium sulfide.

[0040] The heating unit 150 is configured to heat the reaction space. The manner in which the heating unit 150 heats the reaction space is not particularly limited. For example, the heating unit 150 may be a heater attached to the outer surface of the reaction chamber 100, an electric heating wire, or an infrared heater.

[0041] Furthermore, the heating unit 150 may heat the reaction space to a temperature of 160°C or higher but lower than 300°C. In order for the lithium raw material and hydrogen sulfide to react smoothly, the lithium raw material (lithium hydroxide) needs to be sufficiently heated. Furthermore, as described above, water (H2O) is produced as a by-product from the reaction between lithium hydroxide and hydrogen sulfide. If the water exists in a liquid phase, it may flow between the lithium hydroxide particles, reducing the area of ​​the lithium hydroxide that reacts with hydrogen sulfide. Therefore, by heating the reaction space to a temperature of 160°C or higher and evaporating the water, high-purity lithium sulfide can be obtained.

[0042] On the other hand, the higher the temperature of the reaction space, the more accelerated the reaction between lithium hydroxide and hydrogen sulfide may be. However, since the melting point of lithium hydroxide is 445°C, it is preferable that the temperature of the reaction space does not exceed 445°C.

[0043] Furthermore, the higher the temperature of the reaction space, the greater the risk of corrosion of the inner surface of the reaction chamber 100 due to hydrogen sulfide. Therefore, the reaction chamber 100 may be manufactured using a material that is highly heat-resistant and corrosion-resistant. For example, the reaction chamber 100 may be made of Hastelloy X or stainless steel 310 (SUS 310). Furthermore, the heating unit 150 may heat the reaction space to a temperature below 300°C. This prevents frequent repairs and replacements of equipment such as the reaction chamber 100 and piping, and also sufficiently promotes the reaction between hydrogen sulfide and the lithium raw material to obtain high-purity lithium sulfide.

[0044] The hydrogen sulfide supply unit 300 is configured to supply hydrogen sulfide to the reaction chamber 100. Specifically, the hydrogen sulfide supply unit 300 may be configured downstream of the lithium source supply position to supply hydrogen sulfide into the reaction chamber. This prevents hydrogen sulfide from flowing toward the lithium source supply line 10. Furthermore, when the hydrogen sulfide supply unit is configured at this position, high-concentration hydrogen sulfide supplied directly from the downstream side of the reaction chamber can react with hydrogen sulfide without leaving any unreacted lithium source downstream of the reaction chamber. Meanwhile, hydrogen sulfide resupplied to the reaction chamber via a resupply line (described below) travels from the upstream side to the downstream side of the reaction chamber and comes into contact with the lithium source supplied from the lithium source supply unit, ensuring sufficient reaction time to produce high-purity lithium sulfide. Furthermore, since the supplied hydrogen sulfide is nearly 100% consumed near the partition plate (described below), this effectively minimizes the presence of hydrogen sulfide in the gas discharged to the inert gas discharge line.

[0045] Meanwhile, the method by which the hydrogen sulfide supply unit 300 generates or supplies hydrogen sulfide is not particularly limited. Hydrogen sulfide is an industrially important intermediate used to synthesize various sulfur-containing compounds, and is widely used as a raw material for producing fine chemical products such as dyes, pesticides, plastics, pharmaceuticals, cosmetics, and sulfide-based all-solid-state batteries, as well as a starting material for producing metal sulfides. Furthermore, catalytic and non-catalytic reactions are known as methods for producing hydrogen sulfide from sulfur and hydrogen.

[0046] The catalytic reaction is a method of producing hydrogen sulfide by reacting sulfur gas with hydrogen gas in a reaction tube filled with a catalyst, and is carried out by circulating a heat transfer medium outside the reaction tube to remove the reaction heat. Such a catalytic reaction is disclosed in Japanese Patent Application Laid-Open No. 2010-515658.

[0047] However, if the concentration of sulfur is high in the catalytic reaction of hydrogen sulfide, the reaction heat will cause a large temperature rise, which can cause the catalyst to overheat and deteriorate. In addition, to increase the conversion rate to hydrogen sulfide, the reaction temperature must be increased, but this increases the by-product hydrogen polysulfide (H2S x ) and other impurities also increase.

[0048] On the other hand, the non-catalytic reaction is a method in which hydrogen gas is supplied into the liquid sulfur, and the sulfur gas generated by evaporation of the liquid sulfur reacts with the hydrogen gas to produce hydrogen sulfide.

[0049] The reaction heat generated when hydrogen gas and sulfur gas react is recovered during the contact with liquid sulfur, which has the advantage of preventing the reaction temperature from becoming excessively high. However, the contact area between liquid sulfur and hydrogen gas is small and the contact time is relatively short, which has the disadvantage of a low conversion rate to hydrogen sulfide.

[0050] The hydrogen sulfide supply unit 300 according to an embodiment of the present invention may be a hydrogen sulfide reactor that synthesizes hydrogen sulfide using liquid sulfur sprayed from a liquid sulfur spray pipe 304 (to be described later) and hydrogen gas.

[0051] Fig. 2 is a schematic diagram showing a hydrogen sulfide reactor according to one embodiment of the present invention. Fig. 3 is a horizontal cross-sectional view of a hydrogen sulfide reaction chamber showing the arrangement of hydrogen gas supply pipes. Fig. 4 is a cross-sectional view showing the internal configuration of a hydrogen sulfide reaction chamber. Fig. 5 is a plan view of a cover plate. Hereinafter, a hydrogen sulfide reactor according to one embodiment of the present invention will be described with reference to Figs. 2 to 5.

[0052] The hydrogen sulfide reactor 300 for synthesizing hydrogen sulfide according to the present invention includes a hydrogen sulfide reaction chamber 301, flow path change members 320, 330, a liquid sulfur heating device 303, a liquid sulfur spray pipe 304, and a hydrogen gas supply pipe 305.

[0053] First, the hydrogen sulfide reaction chamber 301 is a chamber having a hollow reaction space where synthesis of hydrogen sulfide takes place. Sulfur gas generated by vaporization from liquid sulfur reacts with hydrogen gas supplied to the reaction space to synthesize hydrogen sulfide. The hydrogen sulfide reaction chamber 301 has a hydrogen sulfide outlet 301a for discharging the hydrogen sulfide synthesized in the reaction space. The hydrogen sulfide reaction chamber 301 is also connected to other components, such as a liquid sulfur supply pipe 302, a liquid sulfur heater 303, a liquid sulfur spray pipe 304, a hydrogen gas supply pipe 305, and an outlet pipe 306. The shape of the hydrogen sulfide reaction chamber 301 is not particularly limited.

[0054] Liquid sulfur may be stored in the hydrogen sulfide reaction chamber 301. For example, the liquid sulfur may be supplied to the hydrogen sulfide reaction chamber 301 via a liquid sulfur supply pipe 302. The liquid sulfur spray pipe 304 is configured to recover the liquid sulfur contained in the hydrogen sulfide reaction chamber 301 and spray it back into the reaction space as ultrafine particles.

[0055] More specifically, one end of the liquid sulfur spray pipe 304 is connected to a portion of the hydrogen sulfide reaction chamber 301 where liquid sulfur is stored, and the other end extends through the hydrogen sulfide reaction chamber 301 into the reaction space. For example, one end of the liquid sulfur spray pipe 304 is connected to the bottom surface of the hydrogen sulfide reaction chamber 301, which facilitates the recovery of liquid sulfur. In addition, the other end of the liquid sulfur spray pipe 304 is provided with a liquid sulfur spray nozzle 304a configured to spray liquid sulfur, and the recovered liquid sulfur is sprayed into the reaction space through the liquid sulfur spray nozzle 304a.

[0056] A plurality of liquid sulfur injection nozzles 304a may be provided. For example, a plurality of liquid sulfur injection nozzles 304a may be formed at the other end of the liquid sulfur injection pipe 304. Alternatively, a plurality of branch lines may be provided from the liquid sulfur injection pipe 304, and a liquid sulfur injection nozzle 304a may be provided at the end of each branch line so that liquid sulfur is sprayed at different heights in the reaction space.

[0057] Meanwhile, to synthesize hydrogen sulfide using liquid sulfur, it is necessary to vaporize the liquid sulfur with sulfur gas and then react it with hydrogen gas. The vaporization of liquid sulfur with sulfur gas can be promoted by appropriately adjusting the size, pressure, and temperature of the liquid sulfur particles sprayed from the liquid sulfur spray pipe 304.

[0058] For this purpose, the liquid sulfur injection nozzle 304a may be provided so that the particle size of the sprayed liquid sulfur is 10 μm to 1000 μm or 10 μm to 500 μm, which makes it easier for the sprayed liquid sulfur to vaporize with sulfur gas and increases the contact area with hydrogen gas, thereby improving the conversion rate to hydrogen sulfide.

[0059] Furthermore, the liquid sulfur spray pipe 304 is provided with a pump 304b, which may be controlled by a control unit (not shown) so that the liquid sulfur sprayed from the liquid sulfur spray pipe 304 is compressed to 1 bar to 10 bar, or 2 bar to 5 bar. Furthermore, the pump 304b may be controlled so that the flow rate of the liquid sulfur sprayed into the liquid sulfur spray pipe 304 is 100 L / h to 10,000 L / h, or 500 L / h to 3,000 L / h.

[0060] Furthermore, the liquid sulfur heating device 303 is configured to heat the liquid sulfur. For example, the liquid sulfur heating device 303 may be disposed in the hydrogen sulfide reaction chamber 301 and heat the liquid sulfur stored in the hydrogen sulfide reaction chamber 301. Alternatively, the liquid sulfur heating device 303 may be provided midway along the liquid sulfur spray pipe 304 and configured to heat the liquid sulfur flowing along the liquid sulfur spray pipe 304.

[0061] At this time, the liquid sulfur heating device 303 is controlled to heat the liquid sulfur sprayed from the liquid sulfur spray pipe 304 to 300°C or more and 600°C or less. Alternatively, the liquid sulfur may be heated to 350°C or more and 500°C or less. Therefore, the liquid sulfur sprayed through the liquid sulfur spray pipe 304 may be easily vaporized by sulfur gas or may be easily converted into hydrogen sulfide by reacting with hydrogen gas, which will be described later.

[0062] The hydrogen gas supply pipe 305 is configured to supply hydrogen gas to the reaction space below the position where liquid sulfur is sprayed from the liquid sulfur spray pipe 304. In other words, the hydrogen gas is supplied below the liquid sulfur. As the supplied hydrogen gas flows upward, it reacts with sulfur gas generated by vaporization of the liquid sulfur, synthesizing hydrogen sulfide.

[0063] The hydrogen gas supply pipe 305 includes a hydrogen gas supply nozzle 305a configured to spray hydrogen gas. Referring to Fig. 3, a plurality of hydrogen gas supply nozzles 305a may be provided. For example, the plurality of hydrogen gas supply nozzles 305a may be arranged at equal intervals along the circumferential direction of a circle to allow the hydrogen gas to be uniformly dispersed within the reaction space.

[0064] The hydrogen gas supply nozzle 305a may be formed to face downward. Specifically, the hydrogen gas may be supplied downward relative to a horizontal direction, which is a direction perpendicular to the vertical direction. Therefore, compared to when the hydrogen gas is supplied directly toward the liquid sulfur injection nozzle 304a, the hydrogen gas can be retained in the reaction space for a longer period of time, thereby improving the reaction time with the sulfur gas.

[0065] On the other hand, if hydrogen gas is supplied toward the liquid sulfur stored in the hydrogen sulfide reaction chamber 301 and comes into direct contact with the liquid sulfur, the hydrogen gas cannot diffuse upward, which may result in a low conversion rate to hydrogen sulfide. Furthermore, the pressure of the supplied hydrogen gas may cause the liquid sulfur to scatter, potentially contaminating the hydrogen gas supply nozzle 305a. Therefore, a cover plate 310 may be provided in the hydrogen sulfide reaction chamber 301 to cover the space containing the liquid sulfur from above.

[0066] The cover plate 310 prevents the supplied hydrogen gas from coming into direct contact with the liquid sulfur, and also has the effect of heating the hydrogen gas by heat transferred from the heated liquid sulfur.

[0067] 3 and 5, radial channels 312 may be formed on the upper surface of the cover plate 310, and the radial channels 312 may have a groove shape extending radially from a position corresponding to the position where the hydrogen gas supply nozzle 305a is disposed when viewed from above the hydrogen sulfide reaction chamber 301. Therefore, the supplied hydrogen gas is dispersed along the radial channels 312, and more heat is transferred through the cover plate 310, further improving the conversion rate to hydrogen sulfide.

[0068] 4, the cover plate 310 may be formed so that its upper surface decreases in height as it approaches the inner surface of the hydrogen sulfide reaction chamber 301. That is, the upper surface of the cover plate 310 may be inclined. The cover plate 310 may also be disposed spaced apart from the inner surface of the hydrogen sulfide reaction chamber 301. Therefore, liquid sulfur that has not yet been vaporized may flow along the cover plate 310 and then be stored again in the hydrogen sulfide reaction chamber 301.

[0069] As described above, the liquid sulfur (sulfur gas) and hydrogen gas supplied into the hydrogen sulfide reaction chamber 301 synthesize hydrogen sulfide while diffusing within the reaction space, and the synthesized hydrogen sulfide is discharged to the outside through the hydrogen sulfide outlet 301a provided in the hydrogen sulfide reaction chamber 301. The hydrogen sulfide outlet 301a is connected to an outlet pipe 306 for drawing the hydrogen sulfide out of the hydrogen sulfide reaction chamber 301, and the drawn hydrogen sulfide is transferred to a condenser 308 where it is condensed, and then discharged through an outlet pipe 309 and supplied to the reaction chamber 100 via the hydrogen sulfide supply line 20 (see FIG. 1). The liquid sulfur generated during the condensation process may be recovered again in the hydrogen sulfide reaction chamber 301.

[0070] However, if hydrogen gas and sulfur gas are supplied to the reaction space and then flow in a straight path toward the hydrogen sulfide outlet 301a, there may not be enough time for the hydrogen gas and sulfur gas to react, resulting in a low conversion rate to hydrogen sulfide. Therefore, the present invention includes flow path changing members 320 and 330 that change the flow path of hydrogen gas, sulfur gas, and hydrogen sulfide to a longer path than a straight path so that they do not flow in a straight path toward the hydrogen sulfide outlet 301a.

[0071] 2 , the flow path changing member may include a first partition member 320. The first partition member 320 has a plate 321 extending in a direction transverse to the linear path and a first outer wall 322 extending from the plate 321. The first outer wall 322 extends from the plate 321 to form a space therein into which liquid sulfur and hydrogen gas are supplied. In this case, the first partition member 320 may be disposed spaced apart from the inner surface of the hydrogen sulfide reaction chamber 301 so that a first flow path P1 is formed between the outer surface of the first outer wall 322 and the inner surface of the hydrogen sulfide reaction chamber 301.

[0072] Therefore, the supplied liquid sulfur (sulfur gas) and hydrogen gas are prevented by the plate 321 from being directly discharged into the hydrogen sulfide outlet 301a and diffuse along the first outer wall 322 in the opposite direction from the hydrogen sulfide outlet 301a. Because the side of the first outer wall 322 opposite the plate 321 is open, the supplied gas flows along the first flow path P1 toward the hydrogen sulfide outlet 301a. This increases the contact time between the hydrogen gas and the sulfur gas, improving the conversion rate to hydrogen sulfide. Conventionally, a separate hydrogenation catalytic reaction column was required to further react hydrogen gas and sulfur gas, which otherwise could not react. However, the present invention allows for the production of highly pure hydrogen sulfide at a sufficient conversion rate without a separate catalytic reaction column.

[0073] Meanwhile, the density of hydrogen is 0.08988 g / L at standard condition (STP: 0°C, 1 atm), and the density of hydrogen sulfide is 1.539 g / L at standard condition (STP). Therefore, hydrogen that has not yet been converted to hydrogen sulfide flows upward to the top of the reactor due to the difference in specific gravity, while hydrogen sulfide flows downward along the first flow path toward the outlet. At this time, the hydrogen whose upward movement is restricted by the extended plate 321 remains near the plate and reacts with sulfur gas to be converted to hydrogen sulfide, before flowing downward toward the outlet, thereby further improving the hydrogen sulfide conversion rate.

[0074] Meanwhile, the first partition member 320 includes a first flange 325 configured to fix the first outer wall 322 to the inner surface of the hydrogen sulfide reaction chamber 301. The first flange 325 extends from the outer surface of the first outer wall 322 and is coupled to the inner surface of the hydrogen sulfide reaction chamber 301. A first through-hole 325a is formed in the first flange 325. Therefore, the fluid flowing along the first flow path P1 can flow to the hydrogen sulfide outlet 301a through the first through-hole 325a.

[0075] The flow path changing member may further include a second partition member 330. The second partition member 330 has a second outer wall 331 formed in a columnar shape with both sides open. In this case, liquid sulfur and hydrogen gas are supplied to the internal space of the second outer wall 331. In addition, the second partition member 330 is disposed at a distance from the first partition member 320 so that a second flow path P2 is formed between the second partition member 330 and the first partition member 320.

[0076] Therefore, the supplied liquid sulfur and hydrogen gas flow along the second outer wall 331 toward the upper opening of the second outer wall 331, then flow along the second flow path P2 in the opposite direction to the hydrogen sulfide discharge outlet 301a, and then flow again along the first flow path P1 toward the hydrogen sulfide discharge outlet 301a.This increases the contact time between the unreacted hydrogen gas and the sulfur gas, and further reaction occurs between the hydrogen gas and the sulfur gas while passing through the flow paths, thereby further improving the hydrogen sulfide conversion rate.

[0077] The second partition member 330 also includes a second flange 335 configured to fix the second outer wall 331 to the inner surface of the hydrogen sulfide reaction chamber 301. The second flange 335 extends from the outer surface of the second outer wall 331 and is coupled to the inner surface of the hydrogen sulfide reaction chamber 301. Alternatively, the second flange 335 may be provided between the outer surface of the second outer wall 331 and the inner surface of the first outer wall 322. A second through-hole (not shown) may also be formed in the second flange 335.

[0078] As described above, according to the present invention, the liquid sulfur sprayed from the liquid sulfur spray pipe 304 is sprayed under conditions that make it easy for it to vaporize into sulfur gas, so that the reaction heat generated during the synthesis of hydrogen sulfide is absorbed by the heat of vaporization of the liquid sulfur or by the liquid sulfur particles. This promotes the conversion to hydrogen sulfide while preventing an excessive rise in the temperature inside the hydrogen sulfide reaction chamber 301, thereby minimizing the generation of by-products such as hydrogen polysulfide.

[0079] In addition, the present invention includes a flow path changer, which lengthens the flow path of the sulfur gas and hydrogen gas toward the outlet 301a rather than a straight path, thereby increasing the contact area and contact time between the finely atomized liquid sulfur and vaporized sulfur gas and the hydrogen gas. Therefore, while a hydrogenation catalytic reaction column for further reaction was previously provided outside the hydrogen sulfide reaction chamber 301 to re-react the previously unreacted hydrogen gas and sulfur gas, the present invention maximizes the hydrogen sulfide conversion rate without a separate catalytic reaction column, and can produce hydrogen sulfide with a high yield and purity, for example, of about 99.6% or more.

[0080] 6 is a schematic diagram showing a hydrogen sulfide reactor according to another embodiment of the present invention. Hereinafter, a hydrogen sulfide reactor according to another embodiment of the present invention will be described with reference to FIG. 6. The hydrogen sulfide reactor according to this embodiment differs from the hydrogen sulfide reactor according to the previous embodiment in the shape of the flow path forming member. Components that are the same as or correspond to those in the previous embodiment are designated by the same or corresponding reference numerals, and detailed descriptions thereof will be omitted.

[0081] The flow path-forming member according to this embodiment includes a flow path-forming plate 350 extending in a direction crossing the linear path. One end of the flow path-forming plate 350 is connected to the inner surface of the hydrogen sulfide reaction chamber 301, and the other end extends away from the inner surface of the hydrogen sulfide reaction chamber 301. As a result, a space for fluid flow is formed between the other end of the flow path-forming plate 350 and the inner surface of the hydrogen sulfide reaction chamber 301. Therefore, the linear path along which hydrogen gas and sulfur gas move toward the hydrogen sulfide outlet 301a is blocked by the flow path-forming plate 350, which may increase the reaction time between the gases.

[0082] The flow path forming plate 350 may be disposed above the liquid sulfur supply pipe 302. This allows the length of the path through which the supplied hydrogen gas travels until it is discharged to the hydrogen sulfide discharge port 301a to ensure sufficient reaction time without preventing the supplied hydrogen gas from coming into contact with the sulfur gas. This increases the contact time between the unreacted hydrogen gas and the sulfur gas, and further reaction between the hydrogen gas and the sulfur gas occurs while the hydrogen gas passes through the flow path, thereby further improving the hydrogen sulfide conversion rate.

[0083] A plurality of flow path forming plates 350 may be provided. In this case, a flow path P for fluid flow is provided between adjacent flow path forming plates 350. The plurality of flow path forming plates 350 are arranged such that the other ends of adjacent flow path forming plates 350 are positioned in opposite directions. This further increases the length of the path along which hydrogen gas and sulfur gas flow along the plurality of flow path forming plates 350.

[0084] Furthermore, a protruding piece may be formed on the other extended end of the flow path forming plate, protruding in the vertical direction parallel to the linear path. When the protruding piece configuration is provided, when hydrogen gas, sulfur gas, and hydrogen sulfide gas move along the flow path P, the movement of the relatively low-density hydrogen gas is delayed by the protruding piece between the flow paths, which has the effect of increasing the time available for hydrogen gas to react with sulfur gas in the reactor, and as a result, the hydrogen sulfide conversion rate can be improved.

[0085] 1 again, the lithium sulfide recovery unit 400 is provided to recover lithium sulfide produced by the reaction of hydrogen sulfide with a lithium raw material in the reaction chamber 100 via the lithium sulfide recovery line 30. The lithium sulfide recovery unit 400 is provided downstream in a predetermined direction in the reaction chamber 100. Here, the term "downstream in the predetermined direction" refers to the downstream side of the region of the reaction space heated by the heating unit 150. The structure of the lithium sulfide recovery unit 400 is not particularly limited. For example, it may be a chamber for collecting lithium sulfide.

[0086] The inert gas supply unit 600 is configured to supply an inert gas to the upstream side of the reaction chamber 100 in a predetermined direction. The inert gas supplied through the inert gas supply line 60 can prevent gas in the reaction chamber 100 from flowing back into the lithium source supply line 10. The inert gas supply line 60 may be connected to the lithium source supply line 10 or to the reaction chamber 100.

[0087] Furthermore, when the inert gas supply line 60 is directly connected to the reaction chamber 100, the inert gas supply line 60 may be arranged to face the position in the reaction chamber 100 where the lithium source is supplied. Therefore, the inert gas may also serve to agitate the lithium source and promote the reaction with hydrogen sulfide. The type of inert gas supplied is not particularly limited. For example, helium, neon, argon, nitrogen, etc. may be used.

[0088] Furthermore, the apparatus for manufacturing lithium sulfide according to an embodiment of the present invention may include a second inert gas supply unit 700 configured to supply an inert gas to the lithium sulfide recovery unit 400. Gases in the reaction chamber 100, such as hydrogen sulfide supplied into the reaction chamber 100 and water vapor generated as a by-product of the reaction, need to be discharged to the outside of the reaction chamber 100 without flowing into the lithium sulfide recovery unit 400. The inert gas supplied into the lithium sulfide recovery unit 400 is discharged from the inside to the outside of the lithium sulfide recovery unit 400 via the lithium sulfide recovery line 30, thereby preventing the gases in the reaction chamber 100 from flowing into the lithium sulfide recovery unit 400.

[0089] In this case, the lithium sulfide recovery line 30 may be provided at a position opposite to the exhaust line 40 described below. This can promote the gas in the reaction chamber 100 to be exhausted to the exhaust line 40 by the inert gas. Meanwhile, the type of inert gas supplied from the second inert gas supply unit 700 is not particularly limited. For example, helium, neon, argon, nitrogen, etc. may be used.

[0090] 7 is a schematic diagram showing a moisture removing unit according to an embodiment of the present invention. Hereinafter, the moisture removing unit 500 according to an embodiment of the present invention will be described with reference to FIGS.

[0091] The moisture remover 500 is configured to collect gas discharged from the reaction chamber 100, remove water vapor from the gas, and then resupply the gas from which water vapor has been removed to the upstream side of the reaction chamber 100. As described above, unreacted hydrogen sulfide that does not react with lithium hydroxide from the supplied hydrogen sulfide and water vapor generated by the reaction of hydrogen sulfide and lithium hydroxide may exist within the reaction chamber 100. While this unreacted hydrogen sulfide is resupplied to the upstream side of the reaction chamber 100, water vapor generated during the reaction must be removed. To this end, the moisture remover 500 may collect gas from the reaction chamber 100 from the downstream side of the reaction chamber 100 via the exhaust line 40, remove water vapor, and supply the gas to the upstream side of the reaction chamber 100. Meanwhile, a supply means such as a circulation pump (not shown) may be used to supply the hydrogen sulfide gas from which water vapor has been removed into the reaction chamber.

[0092] 7, the moisture removal unit 500 may include a liquefaction cooling unit 510 and a sublimation cooling unit 520. The liquefaction cooling unit 510 may selectively remove only moisture from the recovered gas by primarily cooling the gas recovered from the reaction chamber 100. For example, the liquefaction cooling unit 510 may be configured to liquefy water vapor by cooling the gas recovered via the exhaust line 40 to approximately 40°C, and the liquefied water may be removed via the discharge unit 515. The cooling structure of the liquefaction cooling unit 510 is not particularly limited, and may be, for example, a chamber provided with a cooling means (not shown).

[0093] Meanwhile, the sublimation cooling unit 520 may be configured to perform secondary cooling of the gas recovered from the reaction chamber 100 to remove moisture. For example, water vapor may be removed by sublimating it by cooling it to approximately -30°C. The sublimation cooling unit 520 may recover the gas that has passed through the liquefaction cooling unit 510 via a recovery line 45, and further remove water vapor that has not been removed from the liquefaction cooling unit 510. Meanwhile, the terms "primary" and "secondary" used throughout this specification and claims should be understood as being arbitrarily given an order for distinction.

[0094] Meanwhile, the terms "primary cooling" and "secondary cooling" do not refer to the order of cooling, and the moisture removal unit 500 may include only the liquefaction cooling unit 510 or only the sublimation cooling unit 520. Alternatively, the moisture removal unit 500 may include both the liquefaction cooling unit 510 and the sublimation cooling unit 520.

[0095] 8 is a perspective view showing a sublimation cooling unit according to an embodiment of the present invention. Sublimation cooling unit 520 may include a cooling chamber 521, a cooling means 525 provided in cooling chamber 521, and a control unit (not shown) that controls sublimation cooling unit 520. The control unit may be a control unit that controls an apparatus for manufacturing lithium sulfide.

[0096] The water vapor supplied to the cooling chamber 521 is sublimated by the cooling means 525 and frozen on the inner surface of the cooling chamber 521, and hydrogen sulfide has a boiling point of −59.6° C., so it may pass through the cooling chamber 521 as is. Therefore, the cooling chamber 521 removes only the water vapor from the recovered gas, and the hydrogen sulfide may be re-supplied to the reaction chamber 100.

[0097] However, since the sublimation cooling unit 520 sublimates water vapor to cause a phase change into ice, which freezes on the inner surface of the cooling chamber, it is necessary to reheat the cooling chamber 521 to liquefy it in order to remove the water frozen on the inner surface of the cooling chamber 521. In other words, if only one cooling chamber 521 is provided, the operation of the lithium sulfide manufacturing apparatus must be stopped to heat the cooling chamber 521, which causes a problem that it becomes difficult to proceed with the process continuously.

[0098] Therefore, the sublimation cooling unit 520 according to an embodiment of the present invention may include a plurality of cooling chambers 521a, 521b, a plurality of branch lines 46 for transferring the recovered gas to each of the plurality of cooling chambers 521a, 521b, and a plurality of second branch lines 48 for supplying the gas in the plurality of cooling chambers 521 to the re-supply line 50. The re-supply line 50 refers to a line for re-supplying the recovered gas to the reaction chamber 100. The control unit may also control the cooling chamber to which the recovered gas is transferred, so that when the recovered gas is transferred to a predetermined one of the plurality of cooling chambers 521, cooling is performed in the cooling chamber to which the recovered gas is transferred.

[0099] The branch lines 46a, 46b and the second branch lines 48a, 48b may be provided with first through fourth branch valves 47a, 47b, 49a, 49b, respectively. The control unit may be configured to determine the cooling chambers 521a, 521b to which the recovered gas is transferred by controlling the branch valves 47a, 47b, 49a, 49b provided in the branch lines 46a, 46b and the second branch lines 48a, 48b. For example, to transfer the recovered gas to the cooling chamber 521a located at the top of FIG. 8, the first branch valve 47a and the third branch valve 49a may be opened, and the second branch valve 47b and the fourth branch valve 49b may be closed.

[0100] After the upper cooling chamber 521a, to which the recovered gas is transferred, has been in cooling operation for a predetermined period of time, it is necessary to heat and remove the ice that has sublimated and frozen to the inner wall of the cooling chamber 521a. In this case, the control unit may control the transfer of the recovered gas to the lower cooling chamber 521b after operating a cooling means (not shown) provided in the lower cooling chamber 521b so that the lower cooling chamber 521b performs cooling. That is, the first branch valve 47a and the third branch valve 49a may be closed and the second branch valve 47b and the fourth branch valve 49b may be opened, so that the recovered gas is transferred to the lower cooling chamber 521b. This not only enables lithium sulfide to be continuously produced without stopping the lithium sulfide production apparatus, but also improves the production efficiency of lithium sulfide by further removing moisture from the recovered gas, thereby obtaining high-purity lithium sulfide.

[0101] Meanwhile, the control unit may switch to heating the upper cooling chamber 521a that has been cooled for a predetermined time, thereby liquefying and removing the ice that has sublimated due to cooling. A separate heating means may be provided in the cooling chamber 521, or moisture may be removed simply by stopping the operation of the cooling means 525 and keeping the cooling chamber 521 at room temperature. The removed moisture may be transferred to the discharge unit 515 and removed.

[0102] Also, instead of providing branch valves 47a, 47b, 49a, and 49b in branch lines 46a, 46b, 48a, and 48b, respectively, three-way valves (not shown) may be provided at the branch point between recovery line 45 and branch line 46 and at the branch point between branch line 48 and re-supply line 50. The control unit may control the three-way valves to determine the chamber to which the recovered gas is transferred.

[0103] Furthermore, there is no particular limitation on the number of cooling chambers 521. When three or more cooling chambers 521 are provided, cooling may be performed simultaneously in the plurality of cooling chambers 521. The number of cooling chambers 521 may be appropriately set depending on the size of the reaction chamber 100, the amount of water vapor generated based on the temperature at which the heating unit 150 heats the reaction space, and the like.

[0104] 9 is a perspective view showing a sublimation cooling unit according to another embodiment of the present invention. Sublimation cooling unit 520' according to this embodiment differs from sublimation cooling unit 520 according to the above-described embodiment in that it includes a main body 523 that is rotatable about an axis C parallel to the direction in which the recovered gas is transferred. In addition, a plurality of cooling chambers 521 may be formed penetrating main body 523 along axis C parallel to the direction in which the recovered gas is transferred. In addition, sublimation cooling unit 520' according to this embodiment may not include branch line 46, and instead, at least one of the plurality of cooling chambers 521 may be configured to communicate with recovery line 45 and re-supply line 50.

[0105] That is, the control unit controls some of the multiple cooling chambers 521 to perform cooling, but may also control the main body 523 to rotate around the axis C so that the cooling chamber 521 performing cooling is connected to the recovery line 45 and the re-supply line 50.

[0106] More specifically, when the cooling chamber 521a located at the upper side in FIG. 9 is cooled by a cooling means (not shown) while in communication with the recovery line 45 and the resupply line 50, water vapor sublimes and freezes in the cooling chamber as the recovered gas passes through the upper cooling chamber 521a, and may be removed from the recovered gas. However, if the space inside the upper cooling chamber 521a, to which the recovered gas is transferred, becomes narrow after the cooling operation has been performed for a predetermined time, and the frozen ice must be removed, the control unit may control the lower cooling chamber 521b to perform cooling, and then rotate the main body 523 about the axis C to change the cooling chamber 521 to the lower cooling chamber 521b. Then, the cooling chamber 521a, which has been subjected to the cooling operation for a predetermined time, may be switched to heating, so that the ice sublimated by cooling may be liquefied and removed.

[0107] In the sublimation cooling unit 520′ according to this embodiment, too, the cooling chamber 521 to which the recovered gas is transferred can be changed simply by rotating the main body 523 about the axis C. Therefore, lithium sulfide can be continuously produced without stopping the lithium sulfide manufacturing apparatus, which is efficient and allows moisture to be removed more reliably to obtain high-purity lithium sulfide.

[0108] 10 is a front view showing a sublimation cooling unit according to yet another embodiment of the present invention. The sublimation cooling unit 520'' according to this embodiment differs from the above-described sublimation cooling unit 520' in that it includes three or more cooling chambers 521. The number of cooling chambers 521 is not particularly limited.

[0109] 10, when four cooling chambers 521a, 521b, 521c, and 521d are formed through main body 523, at least one of the cooling chambers may be provided to communicate with recovery line 45 and re-supply line 50. The control unit may control the cooling chambers 521a, 521b, 521c, and 521d to be sequentially operated for cooling, and may control main body 523 to rotate about axis C so that the recovered gas is transferred to the cooling chamber where cooling is being performed. Similarly, the cooling chamber that has been operated for a predetermined time for cooling may be heated to liquefy and remove ice that has sublimated due to cooling.

[0110] Alternatively, the sublimation cooling unit 520'' according to this embodiment may be controlled so that cooling is performed in a plurality of cooling chambers 521a, 521b. In this case, a plurality of lines branching from the recovery line 45 may be provided to communicate with the plurality of cooling chambers 521a, 521b that perform cooling, respectively. The number of cooling chambers 521 may be appropriately determined depending on the size of the reaction chamber 100, the amount of water vapor generated based on the temperature at which the heating unit 150 heats the reaction space, etc.

[0111] The gas recovered from the reaction chamber 100 and from which moisture has been removed may be resupplied to the upstream side of the reaction chamber 100 via a resupply line 50 (see FIG. 1). The resupply line 50 may be connected to the upstream end of the reaction chamber 100. Alternatively, the resupply line 50 may be connected to the bottom side of the reaction chamber 100. The lithium source material supplied into the reaction chamber 100 falls to the bottom side of the reaction chamber 100 by gravity and then moves, so that the hydrogen sulfide supplied via the resupply line 50 may have sufficient time to react with the lithium source material.

[0112] 1 again, the apparatus for manufacturing lithium sulfide according to an embodiment of the present invention may further include an inert gas discharge line 800. The inert gas discharge line 800 may be a discharge line for discharging an inert gas or the like from the reaction chamber 100. The inert gas discharge line 800 may be located upstream in a predetermined direction from a hydrogen sulfide supply position where the hydrogen sulfide supply unit 300 supplies hydrogen sulfide into the reaction chamber 100. That is, the inert gas discharge line 800 may be located upstream from the hydrogen sulfide supply line 20.

[0113] Therefore, only a portion of the hydrogen sulfide supplied to the reaction chamber 100 reacts with the lithium source, and is then supplied again to the upstream side of the reaction chamber 100 via the exhaust line 40 and the re-supply line 50. The gas supplied via the re-supply line 50 contains hydrogen sulfide from which moisture has been removed. The supplied hydrogen sulfide flows together with the inert gas to the inert gas exhaust line 800, where it reacts mostly with the lithium source, and the inert gas may be discharged via the inert gas exhaust line 800. That is, the inert gas exhaust line 800 may be configured to suppress the discharge of hydrogen sulfide and promote only the discharge of the inert gas. For this purpose, the hydrogen sulfide supply line 20 may be located downstream of the center of the reaction chamber 100.

[0114] A partition plate 120 may also be provided within the reaction chamber 100. The partition plate 120 may be a flat plate extending in a direction transverse to the predetermined direction. The partition plate 120 is provided between the hydrogen sulfide supply position and the inert gas discharge line 800, and can prevent the hydrogen sulfide supplied via the hydrogen sulfide supply line 20 from being directly discharged into the inert gas discharge line 800.

[0115] The partition plate 120 may be provided at the upper end of the reaction chamber adjacent to the inert gas exhaust line 800 and may be provided on the inner surface of the reaction chamber 100 to provide a space for fluid flow, thereby preventing the inert gas from passing through the inert gas exhaust line 800 and flowing directly into the exhaust line 40.

[0116] The above description merely exemplifies the technical concept of the present invention, and various modifications and variations may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are for illustrative purposes only, and are not intended to limit the technical concept of the present invention. The scope of the present invention should be interpreted in accordance with the following claims, and all technical concepts within the scope equivalent thereto should be interpreted as being included in the scope of the present invention. [Explanation of symbols]

[0117] 10 Lithium raw material supply line 20 Hydrogen sulfide supply line 30 Lithium sulfide recovery line 40 Exhaust line 45 Recovery Line 46(46a, 46b) Branch Line 47(47a, 47b) Branch valve 48(48a, 48b) Branch Line 49(49a, 49b) Branch valve 50 Resupply Line 60 Inert gas supply line 100 Reaction Chambers 120 compartment plate 150 Heating section 200 Lithium Raw Material Supply Department 300 Hydrogen sulfide supply section (hydrogen sulfide reactor) 301 Hydrogen sulfide reaction chamber 301a Hydrogen sulfide outlet 302 Liquid sulfur supply pipe 303 Liquid sulfur heating equipment 304 Liquid sulfur spray pipe 304a Liquid sulfur injection nozzle 304b Pump 305 Hydrogen gas supply pipe 306 Pull-out pipe 308 Condenser 309 Discharge pipe 310 Cover Plate 320 First partition member 321 Plate 322 First outer wall 325 First flange 330 Second partition member 331 Second outer wall 335 Second flange 350 Flow path forming plate 400 Lithium sulfide recovery section 500 Moisture removal section 510 Liquefaction cooling section 515 Discharge section 520, 520', 520'' sublimation cooling section 521 (521a, 521b, 521c, 521d) Cooling chamber 523 Main Unit 525 Cooling means 600 Inert gas supply unit 700 Second inert gas supply unit 800 Inert gas exhaust line P1 First flow path P2 Second flow path

Claims

1. a reaction chamber having a reaction space for producing lithium sulfide and configured to move a supplied lithium raw material along a predetermined direction; a lithium raw material supply unit provided upstream of the reaction chamber in the predetermined direction and configured to continuously supply the lithium raw material; a hydrogen sulfide supply configured to supply hydrogen sulfide to the reaction chamber; a heating unit configured to heat the reaction space; a lithium sulfide recovery unit that is provided downstream of the reaction chamber in the predetermined direction and is configured to recover lithium sulfide generated by a reaction between hydrogen sulfide and a lithium raw material in the reaction chamber; an inert gas supply unit provided upstream of the reaction chamber in the predetermined direction and configured to supply an inert gas; a moisture removal unit that is provided downstream of the reaction chamber in the predetermined direction, and is configured to recover gas discharged from the reaction chamber, remove water vapor from the gas, and then resupply the gas upstream of the reaction chamber in the predetermined direction; The apparatus for manufacturing lithium sulfide, wherein the hydrogen sulfide supply unit is a hydrogen sulfide reactor that synthesizes hydrogen sulfide using liquid sulfur sprayed from a liquid sulfur spray pipe and hydrogen gas.

2. 2. The apparatus for manufacturing lithium sulfide according to claim 1, wherein the moisture removing unit includes a liquefaction cooling unit that primarily cools the gas recovered from the reaction chamber and selectively removes only moisture from the gas.

3. 2. The apparatus for manufacturing lithium sulfide according to claim 1, wherein the moisture removing unit includes a sublimation cooling unit that performs secondary cooling of the gas recovered from the reaction chamber to selectively remove only moisture from the gas.

4. the sublimation cooling unit includes a plurality of cooling chambers and a control unit that controls the sublimation cooling unit; 4. The apparatus for manufacturing lithium sulfide according to claim 3, wherein the control unit controls so that, when the recovered gas is transferred to at least one predetermined cooling chamber among the plurality of cooling chambers, secondary cooling is performed in the cooling chamber to which the recovered gas is transferred.

5. 5. The apparatus for manufacturing lithium sulfide according to claim 4, wherein the control unit performs control so that the collected gas is further transferred to another cooling chamber after the cooling chamber to which the collected gas is transferred has been operated for a predetermined time, and controls the cooling chamber that has been operated for the predetermined time to be heated, and liquefies and removes ice sublimated by cooling.

6. the sublimation cooling unit includes a plurality of branch lines for transferring the recovered gas to the plurality of cooling chambers, respectively, and valves provided in the branch lines for opening and closing the respective branch lines; 6. The apparatus for manufacturing lithium sulfide according to claim 5, wherein the control unit is configured to determine a cooling chamber to which the recovered gas is transferred by controlling the valve.

7. the sublimation cooling unit includes a main body that is rotatable about an axis parallel to a direction in which the recovered gas is transferred, the plurality of cooling chambers are formed through the body in a direction parallel to the axis, and at least one of the cooling chambers is provided to communicate with a recovery line through which the recovered gas is transferred and a resupply line through which the recovered gas is resupplied to the reaction chamber; 6. The apparatus for manufacturing lithium sulfide according to claim 5, wherein the control unit controls the main body to rotate around the axis so that the cooling chamber performing cooling is communicated with the recovery line and the re-supply line.

8. 8. The apparatus for manufacturing lithium sulfide according to claim 7, wherein after the cooling chamber to which the recovered gas is transferred has undergone a cooling operation for a predetermined time, the control unit controls the main body to rotate about the axis so that the recovery line communicates with another cooling chamber scheduled to undergo a cooling operation, and controls the cooling chamber that has undergone the cooling operation for the predetermined time to be heated, and liquefies and removes ice sublimated by cooling.

9. further comprising an inert gas exhaust line connected to the reaction chamber for exhausting the inert gas from the reaction chamber; 2. The apparatus for manufacturing lithium sulfide according to claim 1, wherein the inert gas discharge line is arranged upstream in the predetermined direction of a hydrogen sulfide supply position at which the hydrogen sulfide supply unit supplies hydrogen sulfide into the reaction chamber.

10. a partition plate disposed within the reaction chamber and extending in a direction transverse to the predetermined direction; 10. The apparatus for manufacturing lithium sulfide according to claim 9, wherein the partition plate is provided between the hydrogen sulfide supply position and the inert gas discharge line.

11. 11. The apparatus for manufacturing lithium sulfide according to claim 10, wherein the partition plate is provided at an upper end position of the reaction chamber adjacent to the inert gas discharge line and is provided on an inner surface of the reaction chamber so as to provide a space for fluid flow.

12. The hydrogen sulfide reactor comprises: a hydrogen sulfide reaction chamber having a hollow hydrogen sulfide reaction space and a hydrogen sulfide outlet for discharging hydrogen sulfide synthesized in the hydrogen sulfide reaction space; a liquid sulfur spray pipe configured to collect liquid sulfur contained in the hydrogen sulfide reaction chamber and spray it into the hydrogen sulfide reaction space; a liquid sulfur heating device configured to heat the liquid sulfur; a hydrogen gas supply pipe configured to supply hydrogen gas to the hydrogen sulfide reaction space below a position where the liquid sulfur is sprayed from the liquid sulfur spray pipe; 2. The apparatus for manufacturing lithium sulfide according to claim 1, further comprising a flow path changing member that changes a flow path to be longer than the straight path so that the hydrogen gas, the sulfur gas generated by vaporizing the liquid sulfur, and the hydrogen sulfide synthesized by the reaction of the hydrogen gas and the sulfur gas do not flow in a straight path toward the hydrogen sulfide discharge port.

13. the flow path change member includes a plate extending in a direction intersecting the linear path, and a first partition member having a first outer wall extending from the plate so as to form a space into which the liquid sulfur and the hydrogen gas are supplied, 13. The apparatus for manufacturing lithium sulfide according to claim 12, wherein the first partition member is disposed spaced apart from the hydrogen sulfide reaction chamber such that a first flow path is formed between an outer surface of the first outer wall and an inner surface of the hydrogen sulfide reaction chamber.

14. the flow path changing member further includes a second partition member having a second outer wall formed in a columnar shape with both sides open, The liquid sulfur and the hydrogen gas are supplied to the interior space of the second outer wall, 14. The apparatus for manufacturing lithium sulfide according to claim 13, wherein the second partition member is disposed apart from the first partition member so that a second flow path is formed between the second partition member and the first partition member.

15. the flow path changing member includes at least one flow path forming plate extending along a direction transverse to the linear path; 13. The apparatus for producing lithium sulfide according to claim 12, wherein one end of the flow path forming plate is connected to the inner surface of the hydrogen sulfide reaction chamber and the other end extends to be spaced apart from the inner surface of the hydrogen sulfide reaction chamber, thereby forming a space for a fluid to flow between the other end and the inner surface of the hydrogen sulfide reaction chamber.

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