Lithium sulfide production device and method for producing lithium sulfide
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- FURUKAWA COMPANY
- Filing Date
- 2022-05-25
- Publication Date
- 2026-06-02
Smart Images
Figure CN117396427B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to an apparatus for manufacturing lithium sulfide and a method for manufacturing lithium sulfide. Background Technology
[0002] As a method for manufacturing lithium sulfide, it is known to generate sulfur vapor by heating sulfur disposed in the lower part of the reaction tank, reacting the generated sulfur vapor with hydrogen to generate hydrogen sulfide gas, and reacting the generated hydrogen sulfide gas with lithium hydroxide disposed in the upper part of the reaction tank to obtain lithium sulfide (Patent Document 1).
[0003] Patent Document 1 discloses a method for manufacturing lithium sulfide, which is a method for synthesizing lithium sulfide by reacting lithium hydroxide with hydrogen sulfide. The method includes: step (A), supplying hydrogen gas and sulfur vapor to a heated porous material disposed inside a reaction tank to react the hydrogen gas with the sulfur vapor, generating a reaction gas containing hydrogen sulfide gas and the hydrogen gas; and step (B), contacting the generated reaction gas with particulate lithium hydroxide to react the hydrogen sulfide gas with the lithium hydroxide, thereby generating particulate lithium sulfide. Furthermore, Patent Document 1 discloses that this manufacturing method can suppress the manufacturing cost of lithium sulfide, has excellent workability, and can thus obtain lithium sulfide with high purity.
[0004] Existing technical documents
[0005] Patent documents
[0006] Patent Document 1: Japanese Patent Application Publication No. 2016-150860. Summary of the Invention
[0007] The problem the invention aims to solve
[0008] However, the lithium sulfide manufacturing technology described in Patent Document 1 and the like has difficulty achieving sufficiently high manufacturing efficiency. Furthermore, there is room for improvement in the stability of manufacturing efficiency.
[0009] The present invention was made in view of the above circumstances, and provides a lithium sulfide manufacturing apparatus capable of producing lithium sulfide with high efficiency and stability.
[0010] means for solving problems
[0011] According to the present invention, an apparatus for manufacturing lithium sulfide and a method for manufacturing lithium sulfide are provided as shown below.
[0012] [1] A lithium sulfide manufacturing apparatus, which is a lithium sulfide manufacturing apparatus for producing lithium sulfide by reacting hydrogen sulfide with lithium hydroxide, comprising:
[0013] The reactor has a lithium hydroxide filling section inside;
[0014] A heating mechanism is used to heat lithium hydroxide; and
[0015] The hydrogen sulfide supply unit is connected to the reactor described above.
[0016] [2] The lithium sulfide manufacturing apparatus as described in [1] above,
[0017] Inside the reactor described above, a heat-insulating component is provided above the lithium hydroxide filling section.
[0018] In or around a portion of the aforementioned heat insulation component, the upper space of the aforementioned heat insulation component is in communication with the lower space.
[0019] [3] The lithium sulfide manufacturing apparatus as described in [2] above,
[0020] It also has a heat transfer component that is configured to contact or be close to the bottom surface of the lithium hydroxide filling portion.
[0021] [4] The lithium sulfide manufacturing apparatus as described in [2] or [3] above,
[0022] The inner surface of the device is treated with sulfur resistance.
[0023] [5] The lithium sulfide manufacturing apparatus as described in [1] above,
[0024] Inside the reactor, above the lithium hydroxide filling section, there is an inverted funnel-shaped lithium sulfide recovery component.
[0025] [6] The lithium sulfide manufacturing apparatus as described in [5] above,
[0026] The aforementioned funnel-shaped lithium sulfide recovery component also serves as a lithium hydroxide supply component.
[0027] [7] The lithium sulfide manufacturing apparatus as described in [5] or [6] above,
[0028] The aforementioned inverted funnel-shaped lithium sulfide recovery component is configured to move forward and backward in the vertical direction.
[0029] [8] The lithium sulfide manufacturing apparatus as described in any one of [5] to [7] above,
[0030] It also has a heat transfer component that is configured to contact or be close to the bottom surface of the lithium hydroxide filling portion.
[0031] [9] The lithium sulfide manufacturing apparatus as described in any one of [5] to [8] above,
[0032] The inner surface is treated with sulfur resistance.
[0033]
[10] A method for manufacturing lithium sulfide, characterized in that the lithium sulfide manufacturing apparatus described in any one of [1] to [9] above is used to react hydrogen sulfide gas with lithium hydroxide.
[0034] The effects of the invention
[0035] According to the present invention, a lithium sulfide manufacturing apparatus with excellent manufacturing efficiency can be provided. Attached Figure Description
[0036] Figure 1-1 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus of Embodiment 1-1.
[0037] Figure 1-2 This is a top view of the heat insulation component of the lithium sulfide manufacturing apparatus according to Embodiment 1-1.
[0038] Figure 1-3 This is a top view of the lithium hydroxide support component of the lithium sulfide manufacturing apparatus according to Embodiment 1-1.
[0039] Figure 1-4 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus according to Embodiments 1-2.
[0040] Figure 1-5 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus of Example 1.
[0041] Figure 1-6 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus of Example 2.
[0042] Figure 1-7 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus of Comparative Example 1.
[0043] Figure 1-8 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus of Comparative Example 2.
[0044] Figure 1-9 This is a graph showing the reactor temperatures of the lithium sulfide manufacturing apparatuses in Examples 1 and 2, and Comparative Examples 1 and 2.
[0045] Figure 2-1 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus of Embodiment 2-1.
[0046] Figure 2-2 These are cross-sectional and perspective views of the inverted funnel-shaped lithium sulfide recovery component of the lithium sulfide manufacturing apparatus of Embodiment 2-1.
[0047] Figure 2-3 This is a top view of the lithium hydroxide support component of the lithium sulfide manufacturing apparatus according to Embodiment 2-1.
[0048] Figure 2-4 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus of Embodiment 2-2.
[0049] Figure 2-5 This is a perspective view showing a specific example of the inverted funnel-shaped lithium sulfide recovery component of the lithium sulfide manufacturing apparatus of Embodiment 2-1. Detailed Implementation
[0050] Hereinafter, embodiments of the present invention will be described using the accompanying drawings. It should be noted that in all the drawings, the same constituent elements are marked with common symbols, and descriptions are omitted where appropriate.
[0051] The lithium sulfide manufacturing apparatus of the present invention is a lithium sulfide manufacturing apparatus that produces lithium sulfide by reacting hydrogen sulfide with lithium hydroxide, comprising: a reactor having a lithium hydroxide filling section inside; a heating mechanism for heating the lithium hydroxide; and a hydrogen sulfide supply component connected to the reactor.
[0052] The lithium sulfide manufacturing apparatus of the present invention includes a hydrogen sulfide supply unit connected to a reactor, through which hydrogen sulfide gas is supplied. This allows for precise control of the hydrogen sulfide gas supply, resulting in higher manufacturing efficiency. Furthermore, the precise control of the hydrogen sulfide gas supply ensures high manufacturing efficiency with high stability.
[0053] [Implementation Method 1-1]
[0054] An example of the lithium sulfide manufacturing apparatus of this embodiment (Embodiment 1-1) is shown below. Figure 1-1 .
[0055] Figure 1-1 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus 1-1 according to Embodiment 1-1. Figure 1-2 This is a top view of the heat insulation component 1-6 of the lithium sulfide manufacturing apparatus 1-1. Figure 1-3 This is a top view of the lithium hydroxide support component 1-7 of the lithium sulfide manufacturing apparatus 1-1.
[0056] The inventors conducted various studies on the reasons for the insufficient lithium sulfide production efficiency of conventional lithium sulfide manufacturing apparatuses. As a result, it was discovered that by highly controlling the temperature distribution of the lithium hydroxide filling section, which serves as the site of the lithium sulfide formation reaction, lithium sulfide can be produced efficiently and stably. The lithium sulfide manufacturing apparatus 1-1 was completed based on this discovery.
[0057] The lithium sulfide manufacturing apparatus 1-1 includes: a reactor 1-3 having a lithium hydroxide filling section 1-2 inside; a sheath heater 1-4 as a heating mechanism for heating lithium hydroxide; and a hydrogen sulfide supply pipe 1-5 as a hydrogen sulfide supply component connected to the reactor 1-3.
[0058] Inside the reactor 1-3, an insulating component 1-6 is provided above the lithium hydroxide filling section 1-2. The upper space of the insulating component 1-6 is connected to the lower space in part of or around the insulating component 1-6.
[0059] In the lithium sulfide manufacturing apparatus 1-1 of this embodiment, since a heat insulation component 1-6 is provided above the reactor 1-3, heat is prevented from being released to the outside of the reactor 1-3, and the temperature of the entire lithium hydroxide filling section 1-2 is maintained at a high level and uniformly. Therefore, by controlling the reaction site of hydrogen sulfide gas and lithium hydroxide with high temperature and high precision, lithium sulfide can be produced stably with high production efficiency.
[0060] The following describes the configuration of each part of the lithium sulfide manufacturing apparatus according to this embodiment.
[0061] (Reactors 1-3)
[0062] Inside reactors 1-3, lithium sulfide (solid) is generated by the reaction of lithium hydroxide (solid) with hydrogen sulfide gas.
[0063] Hydrogen sulfide supply pipe 1-5 is connected to reactor 1-3, and hydrogen sulfide is supplied by hydrogen sulfide supply pipe 1-5.
[0064] In addition, the reactor 1-3 has a lithium hydroxide support component 1-7, and the space surrounded by the lithium hydroxide support component 1-7, the heat insulation component 1-6 and the inner wall of the reactor 1-3 is called the lithium hydroxide filling part 1-2.
[0065] Lithium hydroxide (not shown) is placed on lithium hydroxide support components 1-7.
[0066] Preferably, the hydrogen sulfide supply pipe 1-5 is located below the lithium hydroxide support component 1-7. This is because by supplying hydrogen sulfide gas from below the lithium hydroxide support component 1-7 and venting it upwards towards the reactor 1-3, it comes into contact with the lithium hydroxide filled in the lithium hydroxide filling section 1-2, thereby efficiently discharging water (water vapor), a byproduct with a smaller specific gravity than hydrogen sulfide gas. Furthermore, by continuously venting hydrogen sulfide gas upwards towards the reactor 1-3, fresh hydrogen sulfide gas is continuously supplied.
[0067] like Figure 1-3 As shown, it is preferable to provide a plurality of connecting holes 1-171 on the lithium hydroxide support member 1-7. This is because, with such a arrangement, hydrogen sulfide gas supplied from the hydrogen sulfide supply pipe 1-5 is efficiently supplied to the lithium hydroxide filling part 1-2 via the connecting holes 1-171.
[0068] Hydrogen sulfide gas supplied from hydrogen sulfide supply pipe 1-5 comes into contact with the surface of lithium hydroxide (solid) filled in lithium hydroxide filling section 1-2.
[0069] It is believed that a reaction as shown in equation (1-1) occurs on the surface of lithium hydroxide (solid).
[0070] 2LiOH+H2S→Li2S+2H2O (1-1)
[0071] Preferably, in the lithium hydroxide filling section 1-2 inside the reactor 1-3, the lithium hydroxide is filled in layers, and the layered lithium hydroxide is in contact with the inner wall surface of the reactor 1-3. This is because heating can be achieved through heat transfer from the inner wall surface of the lithium hydroxide filling section 1-2, thus improving heating efficiency.
[0072] From the viewpoint of promoting the above reaction and preventing the melting of lithium hydroxide, the temperature of the lithium hydroxide filling section 1-2 is usually adjusted to 100-445°C, preferably 130-410°C. It should be noted that the temperature of the lithium hydroxide filling section 1-2 is usually measured at the center of the lithium hydroxide filling section 1-2 in the horizontal direction.
[0073] like Figure 1-2 As shown, it is preferable to provide a plurality of connecting holes 1-161 in the heat insulation component 1-6. This is because, by providing a plurality of connecting holes 1-161 in the heat insulation component 1-6, exhaust gas containing unreacted hydrogen sulfide gas and water generated in the reaction of hydrogen sulfide gas with lithium hydroxide is discharged to the outside of the reactor 1-3 through connecting holes 1-171.
[0074] Materials for reactors 1-3 include metals and ceramics, with sulfur-resistant materials being preferred. Examples of sulfur-resistant materials include metal-based sulfur-resistant materials such as stainless steel and aluminum, and ceramic-based sulfur-resistant materials such as quartz, boron nitride, aluminum nitride, and silicon nitride.
[0075] It is preferable to treat the inner surfaces of reactors 1-3 with sulfur resistance.
[0076] Examples of sulfur-resistant treatments include plating with metals or alloys that have high sulfur resistance, such as tin plating, chromium plating, gold plating, plating with molten aluminum or alloys containing these metals.
[0077] Alternatively, metal diffusion infiltration treatment can be used as a method for sulfur resistance treatment. It is known that when a metal diffusion infiltration layer is formed on the surface of the treated object by performing metal diffusion infiltration treatment, the sulfur resistance is improved.
[0078] For example, aluminizing treatment, which involves diffusion penetration of aluminum, can be used. In aluminizing treatment, the workpiece to be treated is buried in a steel shell along with a compound consisting of Fe-Al alloy powder and NH4Cl powder. The shell is then sealed, and the workpiece is heated in a furnace. This process forms an aluminum diffusion-penetrated layer on the surface of the workpiece, thereby improving its resistance to sulfidation.
[0079] (Sheath heaters 1-4)
[0080] In this embodiment, sheath heaters 1-4 are used as heating mechanisms for heating lithium hydroxide.
[0081] That is, the sheath heater 1-4 heats the lithium hydroxide support member 1-7 and the space above the lithium hydroxide support member 1-7. This heats the lithium hydroxide filled in the lithium hydroxide filling part 1-2 to promote the lithium sulfide formation reaction.
[0082] The temperature configuration of the sheath heater 1-4 is such that the temperature of the lithium hydroxide filling part 1-2 can be adjusted to the temperature range described above. Since the required heating temperature varies with the diameter of the lithium hydroxide filling part 1-2 and the amount of lithium hydroxide filled, the temperature range of the sheath heater 1-4 is not particularly limited, but is preferably 100 to 445°C, and more preferably 130 to 410°C.
[0083] Furthermore, in this embodiment, sheath heaters 1-4 are used as the heating mechanism, but it is not limited to this. Any heating mechanism can be used as long as it can heat lithium hydroxide. For example, a method of introducing heated hydrogen sulfide gas or a high-frequency induction heating device can also be used.
[0084] (Hydrogen sulfide supply pipes 1-5)
[0085] Hydrogen sulfide supply pipe 1-5 is a component used to supply hydrogen sulfide gas to reactor 1-3.
[0086] Preferably, the hydrogen sulfide supply pipe 1-5 is located below the lithium hydroxide support component 1-7. This is because by supplying hydrogen sulfide gas from below the lithium hydroxide support component 1-7 and venting it upwards towards the reactor 1-3, it comes into contact with the lithium hydroxide filled in the lithium hydroxide filling section 1-2, thereby efficiently discharging water (water vapor), a byproduct with a smaller specific gravity than hydrogen sulfide gas. Furthermore, by continuously venting hydrogen sulfide gas upwards towards the reactor 1-3, fresh hydrogen sulfide gas is continuously supplied.
[0087] like Figure 1-1As shown, the hydrogen sulfide supply pipe 1-5 may also have a hydrogen sulfide supply regulating valve 1-8 for adjusting the supply amount of hydrogen sulfide gas. From the viewpoint of controlling the lithium sulfide formation reaction in reactor 1-3, it is preferable that the supply amount of hydrogen sulfide can be controlled by adjusting the opening and closing of the hydrogen sulfide supply regulating valve 1-8.
[0088] The aforementioned material, which is also the material used for reactors 1-3, can be used as the material for hydrogen sulfide supply pipes 1-5.
[0089] It is preferable to perform sulfur-resistant treatment on the inner surface of the hydrogen sulfide supply pipes 1-5. As a method for sulfur-resistant treatment, the above-described method used in the sulfur-resistant treatment of the inner surface of reactors 1-3 can be used.
[0090] In addition, in this embodiment, hydrogen sulfide supply pipe 1-5 is used as a hydrogen sulfide supply component, but it is not limited to this. As long as it can supply hydrogen sulfide gas to reactor 1-3, it can be any hydrogen sulfide supply component.
[0091] (Insulation components 1-6)
[0092] Insulation component 1-6 is a component used to insulate the interior of reactor 1-3, and is located above lithium hydroxide filling section 1-2.
[0093] like Figure 1-1 As shown, the preferred heat insulation component 1-6 is configured to be located above and cover the entire lithium hydroxide filling section 1-2. This further prevents heat from being released to the outside of the reactor 1-3.
[0094] In addition, such as Figure 1-1 As shown, the side of the insulation component 1-6 is preferably positioned to contact the inner wall of the reactor 1-3. In this way, the insulation component 1-6 is also heated, and since the insulation component 1-6 itself has a fixed heat capacity, the heat preservation effect provided by the insulation component 1-6 is further improved.
[0095] like Figure 1-2 As shown, it is preferable to provide a plurality of connecting holes 1-161 in the heat insulation component 1-6. This is because, by providing a plurality of connecting holes 1-161 in the heat insulation component 1-6, exhaust gas containing unreacted hydrogen sulfide gas and water generated in the reaction of hydrogen sulfide gas with lithium hydroxide is discharged to the outside of the reactor 1-3 through the connecting holes 1-161.
[0096] In addition, such as Figure 1-2 As shown, the temperature sensor can also be installed in the insulation component 1-6 via the through hole 1-162. In this case, the temperature sensor 1-9, inserted from above the reactor 1-3, passes through the temperature sensor through hole 1-162 and is connected to the reactor 1-3.
[0097] The same materials used as the materials for reactors 1-3 can be used as the materials for the insulation components 1-6.
[0098] The shape of the heat insulation components 1-6 is not particularly limited, but the shape with a plurality of connecting holes 1-161 as described above is preferred. For example, one or more porous materials selected from metal screens such as stainless steel screens and aluminum screens; perforated metals such as perforated stainless steel and perforated aluminum; and expanded metals such as expanded stainless steel and expanded aluminum can be used.
[0099] As needed, two or more of the above-mentioned porous materials can be used overlappingly as insulation components 1-6.
[0100] From the viewpoint of balancing the improvement of insulation efficiency and the improvement of exhaust gas recovery, the area ratio of the connecting holes 1-161 provided in the insulation components 1-6 is generally 0.2% or more and 50% or less, preferably 0.5% or more and 40% or less.
[0101] From the viewpoint of balancing the improvement of insulation efficiency and the improvement of exhaust gas recovery, the diameter of the connecting holes 1-161 provided in the insulation components 1-6 is generally 26 μm or more and 10,000 μm or less, preferably 45 μm or more and 5,000 μm or less.
[0102] From the viewpoint of improving thermal insulation efficiency, the thickness of the thermal insulation components 1-6 is preferably 0.5 mm or more, more preferably 1.5 mm or more. Furthermore, there is no particular upper limit to the thickness of the thermal insulation components 1-6, and it is typically 20 mm or less.
[0103] As a shape for thermal insulation components, it can also be used as follows: Figure 1-6 Insulating components 1-46 in the shape of an inverted funnel, as shown.
[0104] When the inverted funnel-shaped insulation component 1-46 is used as the insulation component, the temperature sensor 1-9 is inserted into the foot of the inverted funnel-shaped insulation component 1-46, allowing it to connect with the lithium hydroxide filling part 1-2. In this case, by forming a gap between the temperature sensor 1-9 and the inner wall of the foot of the inverted funnel-shaped insulation component 1-46, the upper space and the lower space of the inverted funnel-shaped insulation component 1-46 can be connected through this gap.
[0105] (Lithium hydroxide support components 1-7)
[0106] The lithium hydroxide support components 1-7 are components used to hold lithium hydroxide.
[0107] As described above, in order to be able to use heat transfer from the inner wall of reactor 1-3 for heating, lithium hydroxide is preferably filled in layers in a manner that contacts the inner wall of lithium hydroxide filling part 1-2. Therefore, in order to enable lithium hydroxide support member 1-7 to carry lithium hydroxide as described above, it is preferably configured to contact the inner wall of lithium hydroxide filling part 1-2.
[0108] like Figure 1-3 As shown, it is preferable to provide a plurality of connecting holes 1-171 on the lithium hydroxide support member 1-7. This is because, by providing a plurality of connecting holes 1-171 on the lithium hydroxide support member 1-7, hydrogen sulfide supplied from the hydrogen sulfide supply pipe 1-5 can be efficiently supplied to the lithium hydroxide filling part 1-2 through the plurality of connecting holes 1-171.
[0109] The same material used as the material for reactors 1-3 can be used as the material for the lithium hydroxide support components 1-7.
[0110] There are no particular limitations as long as the shape of the lithium hydroxide support components 1-7 is suitable for holding lithium hydroxide, but the shape with a plurality of connecting holes 1-171 as described above is preferred. For example, one or more porous materials selected from metal screens such as stainless steel screens and aluminum screens; perforated metals such as perforated stainless steel and perforated aluminum; and expanded metals such as expanded stainless steel can be used.
[0111] As needed, two or more of the above-mentioned porous materials can be used overlappingly as lithium hydroxide support components 1-7.
[0112] The diameter of the connecting hole 1-171 provided in the lithium hydroxide support member 1-7 also depends on the diameter of the lithium hydroxide placed thereon, and is usually 26 μm or more and 300 μm or less, preferably 45 μm or more and 154 μm or less.
[0113] (Gas exhaust pipes 1-10)
[0114] Gas exhaust pipe 1-10 is a component used to discharge exhaust gas containing unreacted hydrogen sulfide and water generated in the reaction of hydrogen sulfide gas with lithium hydroxide to the outside of reactor 1-3.
[0115] Preferably, the gas discharge pipe 1-10 is located above the lithium hydroxide support component 1-7. This is because, since byproducts such as water (water vapor) and unreacted hydrogen sulfide gas are introduced towards the top of the reactor 1-3, the gas discharge efficiency is better when the gas discharge pipe 1-10 is positioned above. By ensuring good gas discharge efficiency, fresh hydrogen sulfide gas is continuously supplied.
[0116] Preferably, a cooling section is provided in the gas discharge pipe 1-10 to capture the water generated during the reaction of hydrogen sulfide gas and lithium hydroxide. If the reaction between hydrogen sulfide gas and lithium hydroxide ends, the water generated during the formation of lithium sulfide will not condense in the cooling section. That is, the progress of the lithium sulfide formation reaction can be monitored based on the amount of condensed water.
[0117] (Temperature sensors 1-9)
[0118] Temperature sensor 1-9 is a component used to measure the temperature inside reactor 1-3. For example, by measuring the temperature inside reactor 1-3 using temperature sensor 1-9 and adjusting the heating based on the measurement results, the production of lithium sulfide can be more precisely controlled.
[0119] [Implementation Methods 1-2]
[0120] An example of the lithium sulfide manufacturing apparatus of this embodiment (Embodiments 1-2) is shown below. Figure 1-4 .
[0121] Figure 1-4 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus 1-21 according to Embodiments 1-2.
[0122] The lithium sulfide manufacturing apparatus 1-21 also has a heat transfer component 1-22 configured to contact or be close to the bottom surface of the lithium hydroxide filling section 1-2. By providing the heat transfer component 1-22 at the bottom of the lithium hydroxide filling section 1-2, heat from the sheath heater 1-4 covering the outside of the reactor 1-3 is easily conducted in the horizontal direction of the cross-section of the lithium hydroxide filling section 1-2, thereby improving the horizontal heat uniformity of the lithium hydroxide filling section 1-2.
[0123] Preferably, the heat transfer component 1-22 is configured to contact the inner wall of the lithium hydroxide filling section 1-2. This is because heat from the sheath heater 1-4 covering the outside of the reactor 1-3 is transferred more efficiently.
[0124] Preferably, a plurality of connecting holes are provided in the heat transfer components 1-22. This is because, by providing a plurality of connecting holes in the heat transfer components 1-22, hydrogen sulfide supplied from the hydrogen sulfide supply pipe 1-5 can be efficiently supplied to the lithium hydroxide filling part 1-2 through the plurality of connecting holes.
[0125] There are no particular limitations on the material of the heat transfer components 1-22. The aforementioned materials used as the materials for reactors 1-3 can be used. It is preferable to use materials with excellent resistance to sulfidation and thermal conductivity, such as aluminum, aluminum alloy, aluminum nitride, silicon nitride, etc.
[0126] Furthermore, the shape of the heat transfer components 1-22 is not particularly limited, but it is preferable to have a plurality of connecting holes, such as perforated metal. For example, one or more porous materials selected from metal screens such as stainless steel screens and aluminum screens; perforated metals such as perforated stainless steel and perforated aluminum; and expanded metals such as expanded stainless steel and expanded aluminum can be used.
[0127] As needed, two or more of the above-mentioned porous materials can be used overlappingly as heat transfer components 1-22.
[0128] From the viewpoint of balancing the improvement of heat transfer efficiency and the improvement of the contact efficiency between sulfur vapor and lithium hydroxide, the area ratio of the connecting holes provided in the heat transfer components 1-22 is generally 0.2% or more and 50% or less, preferably 0.5% or more and 40% or less.
[0129] The diameter of the connecting holes provided in the heat transfer components 1-22 is generally 26 μm or more and 10,000 μm or less, preferably 45 μm or more and 5,000 μm or less.
[0130] [Method for manufacturing lithium sulfide using the lithium sulfide manufacturing apparatus of Embodiment 1-1 or 1-2]
[0131] A method for manufacturing lithium sulfide using the lithium sulfide manufacturing apparatus of Embodiment 1-1 or 1-2 will be described.
[0132] First, lithium hydroxide is filled into the lithium hydroxide filling section 1-2, and the lithium hydroxide filling section 1-2 is heated by the sheath heater 1-4, which serves as a heating mechanism. Next, hydrogen sulfide gas is supplied to the lithium hydroxide filling section 1-2, so that the hydrogen sulfide gas comes into contact with the lithium hydroxide, and lithium sulfide is generated through the reaction between the lithium hydroxide and the hydrogen sulfide gas.
[0133] Because an insulating component 1-6 is provided above the reactor 1-3 in the lithium sulfide manufacturing apparatus 1-1, heat is prevented from being released to the outside of the reactor 1-3, and the temperature of the entire lithium hydroxide filling section 1-2 is maintained at a high level and uniformly. Therefore, lithium sulfide can be produced efficiently and stably in the lithium sulfide manufacturing apparatus 1-1.
[0134] In the lithium sulfide manufacturing process using the lithium sulfide manufacturing apparatus 1-1, the temperature inside the lithium hydroxide filling section 1-2 is generally above 100°C throughout the entire region, preferably above 130°C, more preferably above 150°C, even more preferably above 170°C, and even more preferably above 200°C.
[0135] When the temperature inside the lithium hydroxide filling section 1-2 is above the aforementioned lower limit value throughout the entire region, the reaction rate between hydrogen sulfide gas and lithium hydroxide can be further increased.
[0136] In the lithium sulfide manufacturing process using the lithium sulfide manufacturing apparatus 1-1, the temperature of the lithium hydroxide filling section 1-2 is preferably below 445°C throughout the entire region, more preferably below 430°C, and even more preferably below 410°C. When the temperature of the lithium hydroxide filling section 1-2 is below the above-mentioned upper limit value throughout the entire region, the melting of lithium hydroxide can be suppressed, and therefore, the fusion of lithium hydroxide with each other to form lumps can be suppressed. As a result, the reaction between the reactant gas and lithium hydroxide can be carried out more efficiently.
[0137] In the lithium sulfide manufacturing process using lithium sulfide manufacturing apparatus 1-1, the highest temperature T measured at various locations in the lithium hydroxide filling section 1-2 is... max With the lowest temperature T min The difference (T) max -T min Preferably, the temperature is below 50°C, more preferably below 30°C, and even more preferably below 20°C; ideally, it should be as low as possible. For example, T... max -T min When the temperature deviation of each part of the lithium hydroxide filling section 1-2 is small, the reaction between hydrogen sulfide gas and lithium hydroxide can be carried out more efficiently and stably.
[0138] d in the weight-based particle size distribution of lithium hydroxide based on laser diffraction scattering particle size distribution determination method 50 Preferably, it is 1.5 mm or less, more preferably 1.0 mm or less. 50 When the concentration is below the aforementioned upper limit, the contact area between lithium hydroxide and the reactant gas increases, promoting the reaction. Therefore, it is possible to further reduce the amount of unreacted raw materials in the obtained lithium sulfide. As a result, lithium sulfide with higher purity can be obtained.
[0139] In addition, the d in the weight-based particle size distribution of lithium hydroxide based on laser diffraction scattering particle size distribution determination method 50 Preferably, it is 0.1 mm or more, more preferably 0.2 mm or more. 50 When the value is above the aforementioned lower limit, it is possible to prevent water generated in the reaction system from adhering to the lithium sulfide particles and thus fixing the particles. Furthermore, since it is possible to suppress the emission of lithium hydroxide and the resulting lithium sulfide along with the reaction gas, exhaust treatment is simplified. Additionally, since it is possible to suppress the dispersion of lithium hydroxide and the resulting lithium sulfide due to the reaction gas, the yield of lithium sulfide can be improved.
[0140] Preferably, lithium hydroxide is pre-treated by dehydrating its water of crystallization and drying any adhering water. This prevents the lithium hydroxide from clumping or forming hydrogen sulfides, thus allowing for a more efficient reaction between hydrogen sulfide gas and lithium hydroxide. Examples of methods for dehydrating and drying lithium hydroxide include heating in the atmosphere, heating while a gas such as hydrogen, nitrogen, or argon flows through it, and heating under reduced pressure.
[0141] Hydrogen sulfide gas can be a commercially available product filled in gas cylinders, etc., or it can be a gas produced in a hydrogen sulfide manufacturing device connected upstream of the lithium sulfide manufacturing device 1-1.
[0142] When the hydrogen sulfide manufacturing unit is connected upstream of the lithium sulfide manufacturing unit 1-1, the amount of hydrogen sulfide gas required for lithium sulfide production can be generated without the need for separate storage of the hydrogen sulfide gas. Furthermore, since hydrogen sulfide gas can be generated as needed, hydrogen sulfide gas with high purity that does not deteriorate over time can be used in the reaction.
[0143] [Implementation Method 2-1]
[0144] An example of the lithium sulfide manufacturing apparatus of this embodiment (Embodiment 2-1) is shown below. Figure 2-1 .
[0145] Figure 2-1 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus 2-1 according to Embodiment 2-1. Figure 2-2 a is a longitudinal cross-sectional view of the inverted funnel-shaped lithium sulfide recovery component 2-6 of the lithium sulfide manufacturing apparatus 2-1 of this embodiment. Figure 2-2 b is a perspective view of the inverted funnel-shaped lithium sulfide recovery component 2-6 of the lithium sulfide manufacturing apparatus 2-1 of this embodiment. Figure 2-3 This is a top view of the lithium hydroxide support component 2-7 of the lithium sulfide manufacturing apparatus 2-1.
[0146] The lithium sulfide manufacturing apparatus 2-1 includes: a reactor 2-3, which has a lithium hydroxide filling section 2-2 inside; a sheath heater 2-4, which serves as a heating mechanism for heating the lithium hydroxide; and a hydrogen sulfide supply pipe 2-5, which serves as a hydrogen sulfide supply component connected to the reactor 2-3. Inside the reactor 2-3, above the lithium hydroxide filling section 2-2, is an inverted funnel-shaped lithium sulfide recovery component 2-6.
[0147] In the lithium sulfide manufacturing apparatus 2-1 of this embodiment, since an inverted funnel-shaped lithium sulfide recovery component 2-6 is provided above the reactor 2-3, lithium sulfide generated in the reactor 2-3 can be recovered by drawing it from the foot of the inverted funnel-shaped lithium sulfide recovery component 2-6. Therefore, lithium sulfide can be recovered without dismantling the lithium sulfide manufacturing apparatus 2-1, improving the lithium sulfide recovery efficiency and enabling the production of lithium sulfide with high production efficiency.
[0148] The following describes the configuration of each part of the lithium sulfide manufacturing apparatus according to this embodiment.
[0149] (Reactor 2-3)
[0150] Inside reactors 2-3, lithium sulfide (solid) is generated by the reaction of lithium hydroxide (solid) with hydrogen sulfide gas.
[0151] Hydrogen sulfide supply pipe 2-5 is connected to reactor 2-3, and hydrogen sulfide is supplied from hydrogen sulfide supply pipe 2-5.
[0152] In addition, the reactor 2-3 has a lithium hydroxide support component 2-7, and the space surrounded by the lithium hydroxide support component 2-7 and the inner wall of the reactor 2-3 is called the lithium hydroxide filling part 2-2.
[0153] Lithium hydroxide (not shown) is placed on lithium hydroxide support components 2-7.
[0154] Preferably, the hydrogen sulfide supply pipe 2-5 is located below the lithium hydroxide support component 2-7. This is because by supplying hydrogen sulfide gas from below the lithium hydroxide support component 2-7, gas is introduced into the upper part of the reactor 2-3, allowing it to contact the lithium hydroxide filled in the lithium hydroxide filling section 2-2, thereby efficiently discharging water (water vapor), a byproduct with a smaller specific gravity than hydrogen sulfide gas. Furthermore, by continuously introducing hydrogen sulfide gas into the upper part of the reactor 2-3, fresh hydrogen sulfide gas is continuously supplied.
[0155] like Figure 2-3 As shown, it is preferable to provide a plurality of connecting holes 2-171 on the lithium hydroxide support member 2-7. This is because, by such arrangement, hydrogen sulfide gas supplied from the hydrogen sulfide supply pipe 2-5 is efficiently supplied to the lithium hydroxide filling part 2-2 via the connecting holes 2-171.
[0156] Hydrogen sulfide gas supplied from hydrogen sulfide supply pipe 2-5 comes into contact with the surface of lithium hydroxide (solid) filled in lithium hydroxide filling section 2-2.
[0157] It is believed that a reaction as shown in equation (2-1) occurs on the surface of lithium hydroxide (solid).
[0158] 2LiOH+H2S→Li2S+2H2O (2-1)
[0159] Preferably, in the lithium hydroxide filling section 2-2 inside the reactor 2-3, the lithium hydroxide is filled in layers, and the layered lithium hydroxide is in contact with the inner wall surface of the reactor 2-3. This is because, in this way, heating efficiency can be improved since heating can be carried out through heat transfer from the inner wall surface of the lithium hydroxide filling section 2-2.
[0160] From the viewpoint of promoting the above reaction and preventing the melting of lithium hydroxide, the temperature of the lithium hydroxide filling section 2-2 is usually adjusted to 100–445°C, preferably 130–410°C. It should be noted that the temperature of the lithium hydroxide filling section 2-2 is usually measured at the center of the lithium hydroxide filling section 2-2 in the horizontal direction.
[0161] Materials for reactors 2-3 include metals and ceramics, with sulfur-resistant materials being preferred. Examples of sulfur-resistant materials include metal-based sulfur-resistant materials such as stainless steel and aluminum, and ceramic-based sulfur-resistant materials such as quartz, boron nitride, aluminum nitride, and silicon nitride.
[0162] It is preferable to treat the inner surface of reactors 2-3 with sulfur resistance.
[0163] Examples of sulfur-resistant treatments include plating with metals or alloys that have high sulfur resistance, such as tin plating, chromium plating, gold plating, plating with molten aluminum or alloys containing these metals.
[0164] Alternatively, metal diffusion infiltration treatment can be used as a method for sulfur resistance treatment. It is known that when a metal diffusion infiltration layer is formed on the surface of the treated object by performing metal diffusion infiltration treatment, the sulfur resistance is improved.
[0165] For example, aluminizing treatment, which involves diffusion penetration of aluminum, can be used. In aluminizing treatment, the workpiece to be treated is buried in a steel shell along with a compound consisting of Fe-Al alloy powder and NH4Cl powder. The shell is then sealed, and the workpiece is heated in a furnace. This process forms an aluminum diffusion-penetrated layer on the surface of the workpiece, thereby improving its resistance to sulfidation.
[0166] (Sheath heater 2-4)
[0167] In this embodiment, a sheath heater 2-4 is used as the heating mechanism for heating lithium hydroxide.
[0168] That is, the sheath heater 2-4 heats the lithium hydroxide support component 2-7 and the space above the lithium hydroxide support component 2-7. This heats the lithium hydroxide filled in the lithium hydroxide filling section 2-2 to promote the lithium sulfide formation reaction.
[0169] The temperature configuration of the sheath heater 2-4 is such that the temperature of the lithium hydroxide filling part 2-2 can be adjusted to the temperature range described above. Since the required heating temperature varies with the diameter of the liquid lithium hydroxide filling part 2-2 and the amount of lithium hydroxide filled, the temperature range of the sheath heater 2-4 is not particularly limited, but is preferably 100 to 445°C, and more preferably 130 to 410°C.
[0170] Furthermore, in this embodiment, a sheath heater 2-4 is used as the heating mechanism, but it is not limited to this. Any heating mechanism can be used as long as it can heat lithium hydroxide. For example, a method of introducing heated hydrogen sulfide gas or a high-frequency induction heating device can also be used.
[0171] (Hydrogen sulfide supply pipe 2-5)
[0172] Hydrogen sulfide supply pipe 2-5 is a component used to supply hydrogen sulfide gas to reactor 2-3.
[0173] Preferably, the hydrogen sulfide supply pipe 2-5 is located below the lithium hydroxide support component 2-7. This is because by supplying hydrogen sulfide gas from below the lithium hydroxide support component 2-7, gas is introduced into the upper part of the reactor 2-3, allowing it to contact the lithium hydroxide filled in the lithium hydroxide filling section 2-2, thereby efficiently discharging water (water vapor), a byproduct with a smaller specific gravity than hydrogen sulfide gas. Furthermore, by continuously introducing hydrogen sulfide gas into the upper part of the reactor 2-3, fresh hydrogen sulfide gas is continuously supplied.
[0174] like Figure 2-1 As shown, the hydrogen sulfide supply pipe 2-5 may also have a hydrogen sulfide supply regulating valve 2-8 to adjust the supply amount of hydrogen sulfide gas. From the viewpoint of controlling the lithium sulfide formation reaction in reactor 2-3, it is preferable that the supply amount of hydrogen sulfide can be controlled by adjusting the opening and closing of the hydrogen sulfide supply regulating valve 2-8.
[0175] The material used for the hydrogen sulfide supply pipe 2-5 can be the same as the material used for the reactor 2-3.
[0176] It is preferable to treat the inner surface of the hydrogen sulfide supply pipe 2-5 with sulfur resistance. As a method for sulfur resistance treatment, the method described above, which is used in the sulfur resistance treatment of the inner surface of reactor 2-3, can be used.
[0177] In addition, in this embodiment, hydrogen sulfide supply pipe 2-5 is used as a hydrogen sulfide supply component, but it is not limited to this. As long as it can supply hydrogen sulfide gas to reactor 2-3, it can be any hydrogen sulfide supply component.
[0178] (Inverted funnel-shaped lithium sulfide recovery components 2-6)
[0179] The inverted funnel-shaped lithium sulfide recovery component 2-6 is an inverted funnel-shaped component disposed above the lithium hydroxide filling section 2-2, having a foot portion 2-61 and a main body portion 2-62. Additionally, an opening portion 2-63 is provided on the main body portion 2-62.
[0180] In the funnel-shaped lithium sulfide recovery unit 2-6, the foot 2-61 of the funnel-shaped unit 2-6 functions as a lithium sulfide recovery section. That is, lithium sulfide is recovered by connecting the recovery device to the foot 2-61, which serves as the lithium sulfide recovery section. By having the funnel-shaped lithium sulfide recovery unit 2-6, lithium sulfide can be recovered without dismantling the lithium sulfide manufacturing unit 2-1, thus improving the lithium sulfide recovery efficiency.
[0181] As a recycling device, any recycling device can be used. For example, when using a suction-type recycling device, a suction component such as a suction tube is connected to the foot 2-61, and lithium sulfide is drawn into the suction-type recycling device via the suction component for recycling. In this case, the suction component may also be equipped with a filter.
[0182] Because the inverted funnel-shaped lithium sulfide recovery component 2-6 is inverted funnel-shaped, the inner diameter of the opening 2-63 is larger than the inner diameter of the foot 2-61. Therefore, a larger area can be drawn in through the larger inner diameter opening 2-63, thus enabling more efficient recovery of lithium sulfide from the reactor 2-3.
[0183] In this embodiment, the lithium sulfide manufacturing apparatus 2-1 connects the upper and lower spaces of the inverted funnel-shaped lithium sulfide recovery component 2-6 via its foot 2-61. This allows water (water vapor), a byproduct of the lithium sulfide generation reaction, and unreacted hydrogen sulfide gas to move to the upper space of the inverted funnel-shaped lithium sulfide recovery component 2-6 and be recovered by the gas recovery pipe 2-10.
[0184] The preferred inverted funnel-shaped lithium sulfide recovery components 2-6 also function as lithium hydroxide inlets.
[0185] When the inverted funnel-shaped lithium sulfide recovery component 2-6 also functions as a lithium hydroxide inlet, lithium hydroxide is filled from the foot 2-61 of the inverted funnel-shaped lithium sulfide recovery component 2-6. In this case, the dust generated during the filling of lithium hydroxide is protected by the inner wall of the main body 2-62, thus enabling more efficient filling of lithium hydroxide.
[0186] Preferably, the inverted funnel-shaped lithium sulfide recovery component 2-6 is arranged in a manner that allows it to move forward and backward in the vertical direction. In this way, the inverted funnel-shaped lithium sulfide recovery component 2-6 can move to near the bottom of the reactor 2-3, enabling efficient recovery of lithium sulfide.
[0187] Preferably, the inverted funnel-shaped lithium sulfide recovery component 2-6 is configured with a gap between itself and the inner wall of the reactor 2-3. This is because, with a gap between itself and the inner wall of the reactor 2-3, if the volume of lithium sulfide filled in the reactor 2-3 is reduced by recovery, the inverted funnel-shaped lithium sulfide recovery component 2-6 can move downward accordingly.
[0188] There are no particular limitations as long as the shape of the inverted funnel-shaped lithium sulfide recovery component 2-6 is inverted funnel-shaped. From the viewpoint of improving lithium sulfide recovery efficiency, the ratio (L1 / R1) of the inner diameter R1 of the foot 2-61 to the length L1 of the foot 2-61 is preferably 1.0 to 10, more preferably 1.6 to 2.5.
[0189] As long as the shape of the inverted funnel-shaped lithium sulfide recovery component 2-6 is inverted funnel-shaped, there is no particular limitation. From the viewpoint of improving the lithium sulfide recovery efficiency, the ratio (R2 / R1) of the inner diameter R1 of the foot 2-61 to the inner diameter R2 of the opening 2-63 is preferably 2.0 to 20, more preferably 4.0 to 12.
[0190] The material used for the inverted funnel-shaped lithium sulfide recovery component 2-6 can be the same material used for the reactor 2-3.
[0191] Alternatively, grooves or protrusions can be provided on the inner wall of the funnel-shaped lithium sulfide recovery component 2-6. By providing grooves or protrusions, lithium sulfide is less likely to adhere to the inner wall of the funnel-shaped lithium sulfide recovery component 2-6 during recovery, thus enabling more efficient recovery. Furthermore, applying an antistatic treatment to the inner wall of the funnel-shaped lithium sulfide recovery component 2-6 also makes it difficult for lithium sulfide to adhere.
[0192] Additionally, the main body of the funnel-shaped lithium sulfide recovery component 2-6 can be connected to the foot 2-61a. Figure 2-5 The component consisting of the conical main body 2-63a shown in Figure a can also be a component consisting of the foot 2-61b and... Figure 2-5 The component formed by combining the hemispherical main body 2-63b as shown in b can also be a component that combines the foot 2-61c with... Figure 2-5 The component is composed of cylindrical main body parts 2-63c as shown in Figure c.
[0193] When the lithium sulfide manufacturing apparatus 2-1 of this embodiment has a temperature sensor 2-9, the temperature sensor 2-9 can be inserted into the foot 2-61 of the inverted funnel-shaped lithium sulfide recovery component 2-6 and connected to the lithium hydroxide filling part 2-2. In this case, by forming a gap between the temperature sensor 2-9 and the inner wall of the foot 2-61 of the inverted funnel-shaped lithium sulfide recovery component 2-6, the upper space and the lower space of the inverted funnel-shaped lithium sulfide recovery component 2-6 can be connected through this gap.
[0194] (Lithium hydroxide support components 2-7)
[0195] The lithium hydroxide support components 2-7 are components used to hold lithium hydroxide.
[0196] As described above, in order to utilize heat transfer from the inner wall of reactor 2-3 for heating, lithium hydroxide is preferably filled in layers in a manner that contacts the inner wall of lithium hydroxide filling portion 2-2. Therefore, in order for lithium hydroxide support member 2-7 to be able to support lithium hydroxide as described above, it is preferably configured to contact the inner wall of lithium hydroxide filling portion 2-2.
[0197] like Figure 2-3 As shown, it is preferable to provide a plurality of connecting holes 2-171 on the lithium hydroxide support member 2-7. This is because, by providing a plurality of connecting holes 2-171 on the lithium hydroxide support member 2-7, hydrogen sulfide supplied from the hydrogen sulfide supply pipe 2-5 can be efficiently supplied to the lithium hydroxide filling part 2-2 through the plurality of connecting holes 2-171.
[0198] The same material used as the material for reactor 2-3 can be used as the material for the lithium hydroxide support component 2-7.
[0199] There are no particular limitations as long as the shape of the lithium hydroxide support components 2-7 is suitable for holding lithium hydroxide, but the shape with a plurality of connecting holes 2-171 as described above is preferred. For example, one or more porous materials selected from metal screens such as stainless steel screens and aluminum screens; perforated metals such as perforated stainless steel and perforated aluminum; and expanded metals such as expanded stainless steel and expanded aluminum can be used.
[0200] As needed, two or more of the above-mentioned porous materials can be used overlappingly as lithium hydroxide support components 2-7.
[0201] The diameter of the connecting hole 2-171 provided in the lithium hydroxide support member 2-7 also depends on the diameter of the lithium hydroxide being placed, and is usually 26 μm or more and 300 μm or less, preferably 45 μm or more and 154 μm or less.
[0202] (Gas exhaust pipe 2-10)
[0203] Gas exhaust pipe 2-10 is a component used to exhaust gas containing unreacted hydrogen sulfide and water generated in the reaction of hydrogen sulfide gas with lithium hydroxide to the outside of reactor 2-3.
[0204] Preferably, the gas discharge pipe 2-10 is located above the lithium hydroxide support component 2-7. This is because, since water (water vapor) and unreacted hydrogen sulfide gas, which are byproducts, are introduced into the reactor 2-3, the gas discharge efficiency is better when the gas discharge pipe 2-10 is positioned above. By ensuring good gas discharge efficiency, fresh hydrogen sulfide gas is continuously supplied.
[0205] Preferably, a cooling section is pre-installed in the gas discharge pipe 2-10 to capture the water generated during the reaction of hydrogen sulfide gas and lithium hydroxide. If the reaction between hydrogen sulfide gas and lithium hydroxide ends, the water generated during the formation of lithium sulfide will not condense in the cooling section. That is, the progress of the lithium sulfide formation reaction can be monitored based on the amount of condensed water.
[0206] (Temperature sensor 2-9)
[0207] Temperature sensor 2-9 is a component used to measure the temperature inside reactor 2-3. For example, by measuring the temperature inside reactor 2-3 with temperature sensor 2-9 and adjusting the heating based on the measurement results, the production of lithium sulfide can be more precisely controlled.
[0208] [Implementation Method 2-2]
[0209] An example of the lithium sulfide manufacturing apparatus of this embodiment (Embodiment 2-2) is shown below. Figure 2-4 .
[0210] Figure 2-4 This is a longitudinal cross-sectional view of the lithium sulfide manufacturing apparatus 2-21 of Embodiment 2-2.
[0211] The lithium sulfide manufacturing apparatus 2-21 also has a heat transfer component 2-22 configured to contact or be close to the bottom surface of the lithium hydroxide filling section 2-2.
[0212] By providing a heat transfer component 2-22 at the lower part of the lithium hydroxide filling section 2-2, heat from the outer side of the sheath heater 2-4 covering the reactor 2-3 can be easily conducted to the horizontal direction of the cross-section of the lithium hydroxide filling section 2-2, thereby improving the horizontal heat uniformity of the lithium hydroxide filling section 2-2.
[0213] Preferably, the heat transfer component 2-22 is configured to contact the inner wall of the lithium hydroxide filling section 2-2. This is because heat from the sheath heater 2-4 covering the outside of the reactor 2-3 is transferred more efficiently.
[0214] Preferably, a plurality of connecting holes are provided in the heat transfer component 2-22. This is because, by providing a plurality of connecting holes in the heat transfer component 2-22, hydrogen sulfide supplied from the hydrogen sulfide supply pipe 2-5 can be efficiently supplied to the lithium hydroxide filling part 2-2 through the plurality of connecting holes.
[0215] There are no particular limitations on the material of the heat transfer components 2-22. The aforementioned materials used as the material of the reactor 2-3 can be used. It is preferable to use materials with excellent resistance to sulfidation and thermal conductivity, such as aluminum, aluminum alloy, aluminum nitride, silicon nitride, etc.
[0216] In addition, there are no particular restrictions on the shape of the heat transfer components 2-22. For example, one or more porous plates selected from plates with a thickness of 20 mm or more that have connecting holes in stainless steel or aluminum plates can be used.
[0217] As needed, two or more of the above-mentioned porous materials can be used overlappingly as heat transfer components 2-22.
[0218] From the viewpoint of balancing the improvement of heat transfer efficiency and the improvement of the contact efficiency between sulfur vapor and lithium hydroxide, the area ratio of the connecting holes provided in the heat transfer components 2-22 is generally 0.2% or more and 50% or less, preferably 0.5% or more and 40% or less.
[0219] The diameter of the connecting holes provided in the heat transfer components 2-22 is generally 26 μm or more and 10,000 μm or less, preferably 45 μm or more and 5,000 μm or less.
[0220] [Method for manufacturing lithium sulfide using the lithium sulfide manufacturing apparatus of Embodiment 2-1 or 2-2]
[0221] A method for manufacturing lithium sulfide using the lithium sulfide manufacturing apparatus of Embodiment 2-1 or 2-2 will be described.
[0222] First, lithium hydroxide is filled into the lithium hydroxide filling section 2-2, and the lithium hydroxide filling section 2-2 filled with lithium hydroxide is heated by the sheath heater 2-4, which serves as a heating mechanism.
[0223] In the lithium sulfide manufacturing apparatus 2-1 of this embodiment, the inverted funnel-shaped lithium sulfide recovery component 2-6 preferably also functions as a lithium hydroxide inlet. In this case, lithium hydroxide is filled from the foot 2-61 of the inverted funnel-shaped lithium sulfide recovery component 2-6. In this case, the dust generated during lithium hydroxide filling is protected by the inner wall of the opening 2-63, thus enabling more efficient filling of lithium hydroxide.
[0224] Next, hydrogen sulfide gas is supplied to the lithium hydroxide filling section 2-2, so that the hydrogen sulfide gas comes into contact with the lithium hydroxide, and lithium sulfide is generated through the reaction of lithium hydroxide and hydrogen sulfide gas.
[0225] In the lithium sulfide manufacturing process using the lithium sulfide manufacturing apparatus 2-1, the temperature of the lithium hydroxide filling section 2-2 is preferably 150°C or higher throughout the entire region, more preferably 170°C or higher, and even more preferably 200°C or higher. When the temperature of the lithium hydroxide filling section 2-2 is at or above the aforementioned lower limit value throughout the entire region, the reaction rate between hydrogen sulfide gas and lithium hydroxide can be further increased.
[0226] In the lithium sulfide manufacturing process using the lithium sulfide manufacturing apparatus 2-1, the temperature of the lithium hydroxide filling section 2-2 is preferably below 445°C throughout the entire region, more preferably below 430°C, and even more preferably below 410°C. When the temperature of the lithium hydroxide filling section 2-2 is below the above-mentioned upper limit value throughout the entire region, the melting of lithium hydroxide can be suppressed, and therefore, the fusion of lithium hydroxide with each other to form lumps can be suppressed. As a result, the reaction between the reactant gas and lithium hydroxide can be carried out more efficiently.
[0227] d in the weight-based particle size distribution of lithium hydroxide based on laser diffraction scattering particle size distribution determination method 50 Preferably, it is 1.5 mm or less, more preferably 1.0 mm or less. 50 When the concentration is below the aforementioned upper limit, the contact area between lithium hydroxide and the reactant gas increases, promoting the reaction. Therefore, it is possible to further reduce the amount of unreacted raw materials in the obtained lithium sulfide. As a result, lithium sulfide with higher purity can be obtained.
[0228] In addition, the d in the weight-based particle size distribution of lithium hydroxide based on laser diffraction scattering particle size distribution determination method 50 Preferably, the average particle size is 0.1 mm or more, more preferably 0.2 mm or more. When the average particle size is at or above the lower limit mentioned above, it is possible to prevent water generated in the reaction system from adhering to the lithium sulfide particles and fixing the particles. In addition, since it is possible to suppress the emission of lithium hydroxide and the obtained lithium sulfide along with the reaction gas, the exhaust gas treatment can be simplified. Furthermore, since it is possible to suppress the dispersion of lithium hydroxide and the obtained lithium sulfide due to the reaction gas, the yield of lithium sulfide can be improved.
[0229] Preferably, lithium hydroxide is pre-treated by dehydrating its water of crystallization and drying any adhering water. This suppresses the formation of lumps or hydrogen sulfides, allowing for a more efficient reaction between hydrogen sulfide gas and lithium hydroxide. Methods for dehydrating and drying lithium hydroxide include, for example, heating in the atmosphere, heating while a gas such as hydrogen, nitrogen, or argon flows through it, and heating under reduced pressure.
[0230] Hydrogen sulfide gas can be a commercially available product filled in gas cylinders, etc., or it can be a gas produced in a hydrogen sulfide manufacturing device connected upstream of the lithium sulfide manufacturing device 2-1.
[0231] When the hydrogen sulfide manufacturing unit is connected upstream of the lithium sulfide manufacturing unit 2-1, the amount of hydrogen sulfide gas required for lithium sulfide production can be generated without the need for separate storage of the hydrogen sulfide gas. Furthermore, since hydrogen sulfide gas can be generated as needed, hydrogen sulfide gas with high purity that does not deteriorate over time can be used in the reaction.
[0232] In the lithium sulfide manufacturing apparatus 2-1 of this embodiment, since an inverted funnel-shaped lithium sulfide recovery component 2-6 is provided above the reactor 2-3, lithium sulfide generated in the reactor 2-3 can be recovered by drawing it from the foot 2-61 of the inverted funnel-shaped lithium sulfide recovery component 2-6. Therefore, lithium sulfide can be recovered without dismantling the lithium sulfide manufacturing apparatus 2-1, improving the lithium sulfide recovery efficiency and enabling the production of lithium sulfide with high production efficiency.
[0233] In the lithium sulfide manufacturing apparatus 2-1 of this embodiment, it is preferable that the inverted funnel-shaped lithium sulfide recovery component 2-6 is arranged in a manner that allows it to move forward and backward in the vertical direction. In this way, the inverted funnel-shaped lithium sulfide recovery component 2-6 can move to the vicinity of the bottom of the reactor 2-3, and can efficiently recover lithium sulfide.
[0234] [Variation Example]
[0235] The lithium sulfide manufacturing apparatus of this embodiment may also have components other than those described above.
[0236] Furthermore, the various parts of the lithium sulfide manufacturing apparatus of this embodiment can also be integrally formed.
[0237] [Uses of Lithium Sulfide]
[0238] The lithium sulfide obtained by the manufacturing method of the lithium sulfide manufacturing apparatus of this embodiment is suitable for use as a positive electrode active material, a negative electrode active material, a solid electrolyte material, or an intermediate raw material for chemicals in batteries.
[0239] The embodiments of the present invention have been described above, but these embodiments are examples of the present invention, and various configurations other than those described above can also be adopted.
[0240] Example
[0241] Examples 1 and 2 are embodiments of the above-described embodiments 1-2.
[0242] (Example 1)
[0243] Lithium sulfide manufacturing apparatus 1-31 is constructed using the following components. Figure 1-5 This is a longitudinal cross-sectional view of manufacturing apparatus 1-31.
[0244] Reactors 1-3: These are SUS316L reaction tubes, with the inner wall 450mm from the bottom surface treated with aluminum aluminizing (inner diameter 124mm, height 615mm).
[0245] Insulation component 1-36: Two aluminum plates (116mm in diameter, 0.5mm in thickness, 0.5mm in hole diameter, and 27.9% of hole diameter area) are overlapped on one sheet of perforated aluminum metal (116mm in diameter, 0.5mm in thickness, 5mm in hole diameter, and 1.7% of hole diameter area) with an 8mm gap between them.
[0246] Lithium hydroxide support component 1-37: formed by overlapping a #100 aluminum screen with a #300 SUS screen.
[0247] Heat transfer components 1-22: Aluminum sheet (diameter 123mm, thickness 20mm, aperture 5mm, aperture area ratio 9.7%).
[0248] A heat transfer component 1-22 is disposed at the lower interior of reactor 1-3, and a lithium hydroxide support component 1-37 is disposed above the heat transfer component 1-22. 773g of lithium hydroxide (particle size 0.05–0.75mm, not shown) is filled onto the lithium hydroxide support component 1-37. The height of the filled lithium hydroxide is 100mm. Then, the heat transfer component 1-22 is disposed above the lithium hydroxide-filled component.
[0249] Temperature sensor 1-9, which is inserted through a through hole in the insulation component 1-36, reaches the bottom surface of the lithium hydroxide filling part 1-2, i.e., the lithium hydroxide support component 1-37. Temperature sensor 1-9 can measure the temperature of various parts in the vertical direction at the center of the horizontal direction of the lithium hydroxide filling part 1-2.
[0250] Next, a mixture of hydrogen and hydrogen sulfide (hydrogen sulfide concentration 13%) is supplied to reactor 1-3 from the lower part via hydrogen sulfide supply pipe 1-5 at a flow rate of 2.0 L / min. Then, the temperature of the sheath heater 1-4 is set to 410°C to heat the lithium hydroxide filling section 1-2. This causes the hydrogen sulfide gas to react with the lithium hydroxide to obtain lithium sulfide.
[0251] (Example 2)
[0252] As an insulating component, an inverted funnel-shaped insulating component 1-46 is used instead of an insulating component 1-36. A temperature sensor 1-9 is inserted into the foot of the inverted funnel-shaped insulating component 1-46 so that it reaches the lithium hydroxide support component 1-37. Otherwise, the lithium sulfide manufacturing apparatus 1-41 is made in the same manner as in Example 1 to manufacture lithium sulfide.
[0253] It should be noted that a gap is formed between the temperature sensor 1-9 and the inner wall of the foot of the inverted funnel-shaped heat insulation component 1-46, through which the upper space and lower space of the inverted funnel-shaped heat insulation component 1-46 are connected.
[0254] Figure 1-6 This is a longitudinal cross-sectional view of manufacturing apparatus 1-41.
[0255] (Comparative Example 1)
[0256] Excluding the heat insulation components 1-36 and the heat transfer components 1-22, a component consisting of a #300 SUS screen superimposed on a SUS perforated metal with a diameter of 123 mm, a thickness of 0.5 mm, and a hole diameter of 0.5 mm, and further superimposed on a #100 aluminum screen, is used as the lithium hydroxide support component 1-57. Otherwise, the lithium sulfide manufacturing apparatus 1-51 is manufactured in the same manner as in Example 1 to manufacture lithium sulfide.
[0257] Figure 1-7 This is a longitudinal cross-sectional view of manufacturing apparatus 1-51.
[0258] (Comparative Example 2)
[0259] Except for removing the heat insulation components 1-36, the lithium sulfide manufacturing apparatus 1-61 is manufactured in the same manner as in Example 1 to manufacture lithium sulfide.
[0260] Figure 1-8 This is a longitudinal cross-sectional view of manufacturing apparatus 1-61.
[0261] The temperatures of various portions of the lithium hydroxide filling section 1-2, measured by temperature sensors 1-9, in the lithium sulfide manufacturing apparatus of Examples 1-2 and Comparative Examples 1-2 after 150 minutes from the start of heating are plotted and shown in the figure. Figure 1-9 .
[0262] according to Figure 1-9 It is believed that in the lithium sulfide manufacturing apparatus of Examples 1-2, a high temperature is maintained in the upper part of the lithium hydroxide filling section 1-2, which enables the efficient and stable production of lithium sulfide and the high-temperature and high-precision control of the reaction site between hydrogen sulfide gas and lithium hydroxide.
[0263] The highest temperature T measured at each part of the lithium hydroxide filling section 1-2 will be... max Minimum temperature Tmin And the difference between the two (T) max -T min (See Table 1.)
[0264] Table 1
[0265]
[0266] According to Table 1, in the lithium sulfide manufacturing apparatus of Examples 1-2, T max -T min The value is small. That is, it is believed that the temperature deviation of each part of the lithium hydroxide filling section 1-2 in the lithium sulfide manufacturing apparatus of Examples 1-2 is small. Therefore, it is possible to produce lithium sulfide with higher efficiency and stability, and to control the reaction site of hydrogen sulfide gas and lithium hydroxide with high temperature and high precision.
[0267] Explanation of reference numerals in the attached figures
[0268] 1-1 Lithium sulfide manufacturing apparatus.
[0269] 1-2 Lithium hydroxide filling section.
[0270] 1-3 Reactors.
[0271] 1-4 Sheathed heater.
[0272] 1-5 Hydrogen sulfide supply pipe.
[0273] 1-6 Thermal insulation components.
[0274] 1-7 Lithium hydroxide support components.
[0275] 1-8 Hydrogen sulfide supply regulating valve.
[0276] 1-9 Temperature sensor.
[0277] 1-10 Gas discharge pipe.
[0278] 1-21 Lithium sulfide manufacturing apparatus.
[0279] 1-22 Heat transfer components.
[0280] 1-31 Lithium sulfide manufacturing apparatus.
[0281] 1-36 Thermal insulation components.
[0282] 1-37 Lithium hydroxide support components.
[0283] 1-41 Lithium sulfide manufacturing apparatus.
[0284] 1-46 Thermal insulation components.
[0285] 1-51 Lithium sulfide manufacturing apparatus.
[0286] 1-57 Lithium hydroxide support component.
[0287] 1-61 Lithium sulfide manufacturing apparatus.
[0288] 1-161 Connecting hole.
[0289] 1-162 Through-hole for temperature sensor.
[0290] 2-1 Lithium sulfide manufacturing apparatus.
[0291] 2-2 Lithium hydroxide filling section.
[0292] 2-3 Reactor.
[0293] 2-4 Sheathed heater.
[0294] 2-5 Hydrogen sulfide supply pipe.
[0295] 2-6 Inverted funnel-shaped lithium sulfide recovery component.
[0296] 2-7 Lithium hydroxide support components.
[0297] 2-8 Hydrogen sulfide supply regulating valve.
[0298] 2-9 Temperature sensor.
[0299] 2-10 Gas discharge pipe.
[0300] 2-21 Lithium sulfide manufacturing equipment.
[0301] 2-22 Heat transfer components.
[0302] 2-61 Feet.
[0303] 2-62 Main body.
[0304] 2-63 Opening.
[0305] 2-61a Foot.
[0306] 2-62a Conical main body.
[0307] 2-61b Foot.
[0308] 2-62b Hemispherical main body.
[0309] 2-61c Foot.
[0310] 2-62c Cylindrical main body.
[0311] 2-171 Connecting hole.
[0312] This application claims priority based on Japanese Patent Application No. 2021-091946 and Japanese Patent Application No. 2021-091947, filed on May 31, 2021, the entire contents of which are included herein.
[0313] In addition to the embodiments described above, the present invention also discloses the following hydrogen sulfide manufacturing apparatus and method.
[0314] [A1] A lithium sulfide manufacturing apparatus, which is a lithium sulfide manufacturing apparatus for producing lithium sulfide by reacting hydrogen sulfide with lithium hydroxide, comprising:
[0315] The reactor has a lithium hydroxide filling section inside;
[0316] A heating mechanism is used to heat lithium hydroxide; and
[0317] The hydrogen sulfide supply unit is connected to the aforementioned reactor.
[0318] Inside the reactor described above, a heat-insulating component is provided above the lithium hydroxide filling section.
[0319] In or around a portion of the aforementioned heat insulation component, the upper space of the aforementioned heat insulation component is in communication with the lower space.
[0320] [A2] The lithium sulfide manufacturing apparatus as described in [A1] above,
[0321] It also has a heat transfer component that is configured to contact or be close to the bottom surface of the lithium hydroxide filling portion.
[0322] [A3] The lithium sulfide manufacturing apparatus as described in [A1] or [A2] above,
[0323] The inner surface of the device is treated with sulfur resistance.
[0324] [A4] A method for manufacturing lithium sulfide, characterized in that,
[0325] The lithium sulfide manufacturing apparatus described in any one of [A1] to [A3] above is used to react hydrogen sulfide gas with lithium hydroxide.
[0326] [B1] A lithium sulfide manufacturing apparatus, which is a lithium sulfide manufacturing apparatus for producing lithium sulfide by reacting hydrogen sulfide with lithium hydroxide, comprising:
[0327] The reactor has a lithium hydroxide filling section inside;
[0328] A heating mechanism is used to heat lithium hydroxide; and
[0329] The hydrogen sulfide supply unit is connected to the aforementioned reactor.
[0330] Inside the reactor, above the lithium hydroxide filling section, there is an inverted funnel-shaped lithium sulfide recovery component.
[0331] [B2] The lithium sulfide manufacturing apparatus as described in [B1] above,
[0332] The aforementioned funnel-shaped lithium sulfide recovery component also serves as a lithium hydroxide supply component.
[0333] [B3] A lithium sulfide manufacturing apparatus as described in [B1] or [B2] above.
[0334] The aforementioned inverted funnel-shaped lithium sulfide recovery component is configured to move forward and backward in the vertical direction.
[0335] [B4] A lithium sulfide manufacturing apparatus as described in any one of [B1] to [B3] above,
[0336] It also has a heat transfer component that is configured to contact or be close to the bottom surface of the lithium hydroxide filling portion.
[0337] [B5] A lithium sulfide manufacturing apparatus as described in any one of [B1] to [B4] above,
[0338] The inner surface is treated with sulfur resistance.
[0339] [B6] A method for manufacturing lithium sulfide, characterized in that,
[0340] The lithium sulfide manufacturing apparatus described in any one of [B1] to [B5] above is used to react hydrogen sulfide gas with lithium hydroxide.
Claims
1. A lithium sulfide manufacturing apparatus, comprising reacting hydrogen sulfide with lithium hydroxide to produce lithium sulfide, wherein, have: The reactor has a lithium hydroxide filling section inside; A heating mechanism is used to heat lithium hydroxide; and Hydrogen sulfide supply components are connected to the reactor. Inside the reactor, above the lithium hydroxide filling section, a heat insulation component is provided. The upper space of the insulation component is in communication with the lower space of the insulation component, either in part of the insulation component or around the insulation component.
2. The lithium sulfide manufacturing apparatus as described in claim 1, wherein, It also has a heat transfer component configured to contact or be close to the bottom surface of the lithium hydroxide filling portion.
3. The lithium sulfide manufacturing apparatus as described in claim 1 or 2, wherein, The inner surface of the device was treated with sulfur resistance.
4. The lithium sulfide manufacturing apparatus as described in claim 1, wherein, Inside the reactor, above the lithium hydroxide filling section, is an inverted funnel-shaped lithium sulfide recovery component. The inverted funnel-shaped lithium sulfide recovery component also serves as the heat insulation component.
5. The lithium sulfide manufacturing apparatus as described in claim 4, wherein, The inverted funnel-shaped lithium sulfide recovery component also serves as a lithium hydroxide supply component.
6. The lithium sulfide manufacturing apparatus as described in claim 4 or 5, wherein, The inverted funnel-shaped lithium sulfide recovery component is configured to move forward and backward in the vertical direction.
7. The lithium sulfide manufacturing apparatus as described in claim 4 or 5, wherein, It also has a heat transfer component configured to contact or be close to the bottom surface of the lithium hydroxide filling portion.
8. The lithium sulfide manufacturing apparatus as described in claim 4 or 5, wherein, The inner surface has been treated with sulfur resistance.
9. A method for manufacturing lithium sulfide, characterized in that, The lithium sulfide manufacturing apparatus according to any one of claims 1 to 8 is used to react hydrogen sulfide gas with lithium hydroxide.