Lithium sulfide synthesis device and synthesis method

Abstract

The invention discloses a synthesis device and a synthesis method of lithium sulfide. The synthesis device comprises a reactor, a heating mechanism, a gas supply mechanism, a feeding mechanism and a separation mechanism, the heating mechanism is used for heating the reactor; the gas supply mechanism is communicated with the lower part of the reactor and is used for supplying a gas material into the reactor; the feeding mechanism is arranged at the upper part of the reactor and is used for adding solid materials into the reactor; and the separation mechanism is communicated with the upper part of the reactor and is used for separating substances entering the separation mechanism along with gas flow after the solid and gas reactants in the reactor react so as to extract lithium sulfide. Gaseous reactants enter from the lower part of the reactor, solid reactants enter from the upper part of the reactor, and gas drives materials to form a fluidized state in the reactor, so that the gas reactants and the solid reactants are in full contact, full and uniform reaction is promoted, and continuous synthesis production can be realized.

Description

Technical Field

[0001] The invention relates to a synthesis device and a synthesis method of lithium sulfide. Background Art

[0002] Sulfide solid electrolytes are the most valuable solid electrolytes and are the core materials for achieving high safety and high energy density all-solid-state batteries. Lithium sulfide is the key upstream raw material for sulfide solid electrolytes and is essential for all kinds of mainstream sulfide solid electrolytes. However, lithium sulfide has never been used in other fields, so there is no mature large-scale synthesis path and synthesis process for lithium sulfide. This has also led to the high price of lithium sulfide and the high raw material cost of solid electrolytes, which has largely hindered the development and commercial application of all-solid-state batteries.

[0003] At present, the synthesis process of lithium sulfide mainly includes two categories: one is solid-phase reaction, including direct solid-phase synthesis of lithium metal and sulfur powder, carbon thermal reduction of lithium sulfate, etc. However, the main disadvantage of solid-phase reaction is that the mixing and contact of solid-phase substances may not be sufficient, which will lead to an imbalance in the local stoichiometric ratio, or insufficient contact will lead to insufficient reaction, triggering side reactions. These problems will lead to more impurities in the product and affect the purity of the product. The other is liquid-phase (wet chemical) reaction, which mainly uses organic solvents as a medium to achieve various reaction methods, including liquid-phase reactions of lithium and sulfur, reactions of lithium hydroxide, lithium carbonate and hydrogen sulfide in liquid phase, etc. Liquid-phase reaction is conducive to large-scale continuous production, but due to its complex chemical environment, impurities may be produced in the product, resulting in reduced product purity.

[0004] Gas-solid phase reaction is an effective way to synthesize high-purity lithium sulfide. In the gas-solid phase reaction, since both the gas reactants and gas products are easy to remove, there is no residue of gas reactants and gas products (by-products) in the product. The product of the gas-solid phase reaction can have a very high purity, which is conducive to the further preparation of high-performance sulfide solid electrolyte products.

[0005] Although high-purity lithium sulfide can be synthesized through gas-solid phase reactions, the main challenges are that the contact between the gas and the solid may not be sufficient, the reaction mass transfer is insufficient, and large-scale synthesis is difficult.

[0006] Patent document CN117396427A protects a device for producing lithium sulfide by reacting lithium hydroxide (solid) with hydrogen sulfide (gas). In the device, lithium hydroxide is filled at the bottom of the reactor, and hydrogen sulfide gas is introduced upward from the bottom, contacts the solid lithium hydroxide powder and undergoes a gas-solid phase reaction. In this invention, the lithium hydroxide is fixed, so the invention also mentions that controlling the uniformity of temperature is the key to ensuring a high conversion rate. However, such a design has high requirements for the temperature uniformity of the entire reaction.

[0007] Patent document CN113401878B protects a process for producing lithium sulfide by reacting anhydrous lithium sulfate (solid) with carbon monoxide (gas). The invention uses a titanium barrel as a reaction container, and lithium sulfate is spread flat on the bottom of the titanium barrel. Such a design will result in limited contact between carbon monoxide and lithium sulfate, which may lead to relatively low reaction efficiency. Summary of the invention

[0008] The purpose of the present invention is to provide a synthesis device and a synthesis method of lithium sulfide to solve the problems encountered in the existing gas-solid phase reaction synthesis device and method of lithium sulfide, such as insufficient contact between gas and solid reactants, insufficient reaction mass transfer, and difficulty in large-scale synthesis. Through the synthesis device and method of the present invention, uniform contact between gas and solid reactants can be achieved, the reaction can be promoted to be sufficient and uniform, and continuous synthesis production can be achieved.

[0009] To achieve the above object, the present invention provides the following technical solutions: A lithium sulfide synthesis device comprises a reactor, a heating mechanism, a gas supply mechanism, a feeding mechanism and a separation mechanism. The heating mechanism is used to heat the reactor. The gas supply mechanism is connected to the lower part of the reactor and is used to supply gaseous materials from the bottom to the reactor. The feeding mechanism is arranged at the upper part of the reactor and is used to add solid materials from the top to the reactor. The separation mechanism is connected to the upper part of the reactor and is used to separate the substances entering the separation mechanism with the gas flow after the solid and gaseous reactants in the reactor react, so as to extract lithium sulfide.

[0010] During production, gaseous reactants enter the reactor from the bottom through the gas supply mechanism, and solid reactants enter the reactor from the top through the feeding mechanism. The gas drives the materials into a fluidized state in the reactor, so that the gaseous and solid reactants are fully in contact, thereby promoting the full and uniform reaction.

[0011] Optionally, the heating mechanism may use electric heating, heating by electric heating wires, the heating wires being integrated into a heat-insulating material, and the heat-insulating material surrounding the outer wall of the reactor to heat the reactor.

[0012] Optionally, the reactor comprises a reaction chamber at the bottom and a buffer chamber at the top, and the reaction chamber is connected to the buffer chamber. Solid materials enter the buffer chamber and the reaction chamber downward in sequence through the upper feeding mechanism, and gas materials enter from the bottom of the reaction chamber through the gas supply mechanism, and the reaction of solid and gaseous reactants is mainly carried out in the reaction chamber. The buffer chamber plays a buffering role. During the reaction of solid and gaseous reactants, the reaction materials will be carried away from the reaction chamber by the airflow and enter the buffer chamber. After entering the buffer chamber, the flow rate of the gas and materials slows down, and the solid particles will settle with gravity. At a certain gas velocity, they can fall back to the reaction chamber to continue the reaction.

[0013] Optionally, the gaseous material may include a protective gas in addition to the gaseous reactants. The gaseous reactants include but are not limited to hydrogen, hydrogen sulfide, carbon monoxide, etc.; the protective gas includes but is not limited to argon, nitrogen, etc. The protective gas is introduced into the reactor to further support the fluidization of the solid material.

[0014] Optionally, the gas supply mechanism includes a first gas supply component for supplying gaseous reactants to the reactor, and a second gas supply component for supplying protective gas to the reactor.

[0015] Wherein, the first gas supply assembly is not limited to one group, and each group of the first gas supply assembly may include a first gas supply bottle, a first gas supply pipeline, and a first gas flow valve arranged on the first gas supply pipeline. The second gas supply assembly is not limited to one group, and each group of the second gas supply assembly may include a second gas supply bottle, a second gas supply pipeline, and a second gas flow valve arranged on the second gas supply pipeline. The first gas supply bottle stores a gaseous reactant, one end of the first gas supply pipeline is connected to the first gas supply bottle, and the other end is connected to the lower part of the reactor. The second gas supply bottle stores a protective gas, one end of the second gas supply pipeline is connected to the second gas supply bottle, and the other end is connected to the bottom of the reactor. The first gas flow valve can adjust the flow of the gaseous reactant supplied from the first gas supply pipeline to the reactor; the second gas flow valve can adjust the flow of the protective gas supplied from the second gas supply pipeline to the reactor.

[0016] Optionally, the separation mechanism includes at least one cyclone separator, and the cyclone separator is connected to the upper part of the reactor through a first pipeline. The cyclone separator mainly plays a role of separation. If necessary (such as when other solid materials such as catalysts or inert media are added), multiple cyclone separators can be connected in series to complete a multi-stage separation process. The cyclone separators in series can separate the gas entering the cyclone separator after the reaction and the solid particles of different particle sizes, and the separated lithium sulfide is discharged from the bottom of the cyclone separator. The cyclone separator needs to be heated, and the operating temperature is maintained above 100 degrees to prevent water from condensing in the cyclone separator, thereby causing hydrolysis or agglomeration of lithium sulfide.

[0017] Optionally, the separation mechanism may further include a water condenser and a water receiver, wherein the upper end of the cyclone separator is connected to the inlet end of the water condenser through a second pipe, and the outlet end of the water condenser is connected to the inlet end of the water receiver. The gas separated by the cyclone separator enters the water condenser, and the water and residual gas (hydrogen sulfide, hydrogen, argon, nitrogen, etc.) in the gas are further separated. A condensation water pipe is provided on the wall of the water condenser, and condensation is achieved by controlling the water temperature in the condensation water pipe. Under normal circumstances, water at room temperature can achieve sufficient condensation; however, in the case of large gas flow and high gas temperature, water at a lower temperature can also be used to achieve water condensation. The water condensed by the water condenser will enter the water receiver, and a drain valve may be provided at the bottom of the water receiver to drain the collected water. The main function of the water receiver is to store water in the reaction tail gas, and the degree of reaction can be monitored by measuring the amount of water produced.

[0018] Optionally, a plurality of baffles are arranged in the reaction chamber, and the plurality of baffles can be arranged side by side in the longitudinal direction, or can be arranged staggered in the longitudinal direction, etc. The baffles regulate the airflow entering the reaction chamber, so that the flow of solid materials and gas materials is more stable.

[0019] Based on the same inventive concept, the present invention also provides a synthesis method for producing lithium sulfide using the above synthesis device, comprising the following steps: (1) introducing a protective gas into the reactor; (2) heating the reactor to a temperature required for the reaction by the heating mechanism; (3) adding solid materials from the upper part of the reactor through the feeding mechanism; (4) introducing gaseous reactants into the lower part of the reactor through a gas supply mechanism; (5) The gaseous reactants in the gas material and the solid reactants in the solid material gradually react after contacting in the reactor to produce the target product lithium sulfide; (6) After the reaction is complete, the passage between the reactor and the separation mechanism is opened to allow the reacted material to be discharged into the separation mechanism along with the air flow; (7) Separating the synthesized lithium sulfide from other materials through a separation mechanism.

[0020] Based on the same inventive concept, the present invention also provides a synthesis method for continuously producing lithium sulfide using the above synthesis device, comprising the following steps: (1) introducing a protective gas into the reactor; (2) heating the reactor to a temperature required for the reaction by the heating mechanism; (3) introducing gaseous reactants into the lower part of the reactor through a gas supply mechanism; (4) After the gaseous reactants in the gas material reach a specified concentration, adding solid material to the upper part of the reactor through the feeding mechanism; (5) The gaseous reactants and the solid reactants gradually react after contacting in the reactor to produce the target product lithium sulfide; (6) After the reaction is complete, the passage between the reactor and the separation mechanism is opened to allow the reacted material to be discharged into the separation mechanism along with the air flow; (7) separating the synthesized lithium sulfide from other materials by a separation mechanism; (8) Repeat steps (1) to (7) to achieve continuous production.

[0021] The above steps are not limited to being performed in sequence, but may be performed alternately according to actual conditions.

[0022] Optionally, the solid material includes solid reactants and inert reaction media.

[0023] Optionally, the inert reaction medium includes one of quartz sand, zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide or any combination thereof, and the solid reactant includes one of lithium carbonate, lithium hydroxide, lithium sulfate or any combination thereof.

[0024] Optionally, the solid material is in granular form with a diameter of 500nm-1mm to ensure that the gas can drive the solid material into a fluidized state in the reactor.

[0025] Optionally, the protective gas is high-purity argon or nitrogen with a purity of >99.9% and a water content below 100 ppm to reduce the impact on the reaction of gas-solid reactants.

[0026] Optionally, in the step (2), the temperature ranges from 300 to 1000° C. depending on the reaction being performed.

[0027] Optionally, a plurality of temperature detectors are provided in the reactor. The temperature detector is mainly used to monitor the temperature of the gas in each temperature zone in the reactor. The ideal temperature depends on the specific reaction process. In order to maintain a better fluidized state, it is usually necessary to be higher than the lowest temperature at which the reaction occurs and slightly lower than the melting point of the reactants and products. For example, if lithium sulfate and hydrogen are used as raw materials for the reaction, the ideal temperature is between 700°C and 900°C, and more preferably between 750°C and 850°C.

[0028] Optionally, the water content of the gaseous reactants introduced into the reactor is below 100 ppm to reduce the effect of water on the reaction of the gas-solid reactants.

[0029] Optionally, to ensure the safety and smooth progress of the reaction, the gas pressure in the reaction chamber is controlled between 0-0.5 MPa.

[0030] Optionally, during the reaction, the flow rate of the gaseous reactant and the flow rate of the shielding gas are maintained at a specific ratio, which is between 5:1 and 1:100. The flow rate of the gaseous reactant and the flow rate of the shielding gas are determined based on factors such as the amount of the solid reactant, the reaction temperature, and the particle size.

[0031] Optionally, the reaction time of step (5) is between 1 and 10 hours.

[0032] In the present invention, the solid reactant may be lithium carbonate, lithium hydroxide, lithium sulfate, etc., and the corresponding gaseous reactant may be hydrogen sulfide, hydrogen, etc. The main chemical reaction formulas that can be implemented include: Path (a): 4H2+Li2SO4→Li2S+4H2O Path (b): H2S+2LiOH→Li2S+2H2O Path (c): H2S+Li2CO3→Li2S+H2O+CO2 The present invention adopts a fluidized bed synthesis device to realize the gas-solid phase reaction production of lithium sulfide. For the gas-solid phase reaction, the full contact between the gas and the solid, the temperature uniformity in the reactants, etc. are the key factors that determine the reaction efficiency.

[0033] In the prior art, for the gas-solid synthesis of high-purity lithium sulfide, a fixed bed method is mostly used. Compared with the fixed bed method, the fluidized bed method used in the present invention has the following advantages: (1) In existing fixed bed reactors, the gas may flow over the bed or pass through the bed. In the former case, the gas needs to rely on its own migration and penetration to enter between the reactant solid particles; in the latter case, the gas has a certain flow rate and pressure, so it penetrates through the bed with reactant solid particles. However, in these two forms, the contact between the gas and the solid reactant particles is limited, and the uniformity of the entire reaction degree and reaction temperature is insufficient. In the device of the present invention, the gaseous reactant and the protective gas can drive the solid material into a flowing state in the reactor, and the solid reactant particles can fully contact with the gaseous reactant and be wrapped by the gaseous reactant, so that the reaction is more complete.

[0034] (2) In the existing fixed bed reactor, since the solid material is not in a flowing state, it is difficult to control the temperature, reaction degree and side reaction degree of each area of ​​the reaction bed to be consistent. However, in the device of the present invention, the material can move and collide with the air flow in the reactor, thereby improving the uniformity of the reaction temperature and reactant concentration, and improving the consistency of the reaction product.

[0035] (3) In the gas-solid phase synthesis of lithium sulfide, no matter which of the above reaction pathways is used, the product is water. Water needs to be removed in time during the reaction. On the one hand, the residual water may cause hydrolysis of lithium sulfide after cooling, resulting in reduced purity of lithium sulfide; on the other hand, water may cause lithium sulfide product agglomeration, hindering the reaction. In the device of the present invention, the byproduct water can be taken away and condensed and separated in time with the flowing airflow, thereby reducing the negative impact of the product water on the reaction; (4) For reactions with significant exothermic effects, the device of the present invention can better dissipate heat and prevent the local temperature of the reactor from overheating, thereby inducing side reactions and reducing product quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is a schematic diagram of the overall structure of the present invention; The components in the accompanying drawings are marked as follows: 1. Reactor; 2. Heating mechanism; 3. Temperature detector; 4. Baffle; 5. Feeding mechanism; 6. Reaction chamber; 7. Buffer chamber; 8. First gas supply bottle; 9. First gas supply pipeline; 10. First gas flow valve; 11. Second gas supply bottle; 12. Second gas supply pipeline; 13. Second gas flow valve; 14. Cyclone separator; 15. First pipeline; 16. Water condenser; 17. Water receiver; 18. Second pipeline. DETAILED DESCRIPTION

[0037] The preferred embodiments of the present invention are described in detail below in conjunction with the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art. Example

[0038] See also Figure 1 , a lithium sulfide synthesis device, comprising a reactor 1, a heating mechanism 2, a gas supply mechanism, a feeding mechanism 5 and a separation mechanism. The heating mechanism 2 is used to heat the reactor 1. The gas supply mechanism is connected to the lower part of the reactor 1, and is used to supply gaseous materials from the bottom to the reactor 1. The feeding mechanism 5 is arranged at the upper part of the reactor 1, and is used to add solid materials from the top to the reactor 1. The separation mechanism is connected to the upper part of the reactor 1, and is used to separate the substances entering the separation mechanism with the air flow after the solid and gaseous reactants in the reactor 1 react, so as to extract lithium sulfide. During production, the gaseous material enters from the bottom of the reactor 1 through the gas supply mechanism, and the solid material enters from the top of the reactor 1 through the feeding mechanism 5. The gas drives the material to be fluidized in the reactor 1, so that the gas and solid reactants are fully contacted, which can promote the full and uniform progress of the reaction.

[0039] Among them, a plurality of temperature detectors 3 are arranged in the reactor 1. The temperature detector 3 is mainly used to monitor the temperature of the gas in each temperature zone in the reactor 1. The ideal temperature depends on the specific reaction process implemented. In order to maintain a better fluidized state, it is usually necessary to be higher than the lowest temperature at which the reaction occurs and slightly lower than the melting point of the reactants and products. For example, if lithium sulfate and hydrogen are used as raw materials for the reaction, the ideal temperature is between 700°C and 900°C, and the better temperature is between 750°C and 850°C.

[0040] The reactor 1 includes a reaction chamber 6 at the bottom and a buffer chamber 7 at the top, and the reaction chamber 6 is connected to the buffer chamber 7. Solid materials enter the buffer chamber 7 and the reaction chamber 6 in turn downward through the upper feeding mechanism 5, and gas materials enter from the bottom of the reaction chamber 6 through the gas supply mechanism, wherein the reaction of solid and gaseous reactants is mainly carried out in the reaction chamber 6. The buffer chamber 7 plays a buffering role. During the reaction of solid and gaseous reactants, the materials will be carried away from the reaction chamber 6 by the airflow and enter the buffer chamber 7. After entering the buffer chamber 7, the flow rate of the gas and the material slows down, and the solid particles will settle with gravity. At a certain gas velocity, they can fall back to the reaction chamber 6 to continue the reaction, thereby promoting the full progress of the reaction. A discharge port is provided at the bottom of the reaction chamber 6, and when necessary, the solid materials can be discharged from the bottom of the reaction chamber 6.

[0041] The heating mechanism 2 may use electric heating to heat the reaction chamber 6 through an electric heating wire, wherein the heating wire is integrated into a heat-insulating material, and the heat-insulating material surrounds the outer wall of the reaction chamber 6 to heat the reaction chamber 6 .

[0042] The gas supply mechanism includes a first gas supply component for supplying gaseous reactants to the reactor 1, and a second gas supply component for supplying protective gas to the reactor 1. The gaseous reactants include but are not limited to hydrogen, hydrogen sulfide, carbon monoxide, etc.; the protective gas includes but is not limited to argon, nitrogen, etc. The protective gas is introduced into the reactor 1 to further support the fluidization of the solid material.

[0043] Among them, the first gas supply assembly may include a first gas supply bottle 8, a first gas supply pipeline 9, and a first gas flow valve 10 arranged on the first gas supply pipeline 9. The second gas supply assembly may include a second gas supply bottle 11, a second gas supply pipeline 12, and a second gas flow valve 13 arranged on the second gas supply pipeline 12. The first gas supply bottle 8 stores gaseous reactants, one end of the first gas supply pipeline 9 is connected to the first gas supply bottle 8, and the other end is connected to the lower part of the reactor 1. The second gas supply bottle 11 stores protective gas, one end of the second gas supply pipeline 12 is connected to the second gas supply bottle 11, and the other end is connected to the bottom of the reactor 1. The first gas flow valve 10 can adjust the flow rate of the gaseous reactants supplied from the first gas supply pipeline 9 to the reactor 1; the second gas flow valve 13 can adjust the flow rate of the protective gas supplied from the second gas supply pipeline 12 to the reactor 1.

[0044] The separation mechanism includes at least one cyclone separator 14, which is connected to the upper part of the reactor 1 through a first pipe 15. The cyclone separator 14 mainly plays a role of separation. If necessary (such as when other solid materials such as catalysts or inert media are added), multiple cyclone separators 14 can be connected in series to complete a multi-stage separation process. The cyclone separators 14 connected in series can separate the gas entering the cyclone separator 14 after the reaction and the solid particles of different particle sizes, and the separated lithium sulfide is discharged from the bottom of the cyclone separator 14. The cyclone separator 14 needs to be heated, and the working temperature needs to be kept above 100 degrees to prevent water from condensing in the cyclone separator 14.

[0045] The separation mechanism further includes a water condenser 16 and a water receiver 17. The upper end of the cyclone separator 14 is connected to the inlet end of the water condenser 16 through a second pipe 18, and the outlet end of the water condenser 16 is connected to the inlet end of the water receiver 17. The gas separated by the cyclone separator 14 enters the water condenser 16, and the water and residual gas substances (hydrogen sulfide, hydrogen, argon, nitrogen, etc.) in the gas are further separated. The wall of the water condenser 16 is equipped with a condensation water pipe, and condensation is achieved by controlling the water temperature. Under normal circumstances, water at room temperature can achieve sufficient condensation; but in the case of large gas flow and high gas temperature, water at a lower temperature can also be used to achieve water condensation. The water condensed by the water condenser 16 will enter the water receiver 17, and a drain valve can be set at the bottom of the water receiver 17 to drain the collected water. The main function of the water receiver 17 is to store water in the reaction tail gas, and the degree of reaction can be monitored by measuring the amount of water produced.

[0046] A plurality of baffles 4 are arranged in the reaction chamber 6. The baffles 4 regulate the airflow entering the reaction chamber 6, so that the flow of solid materials and gas materials is more stable.

[0047] When using the above synthesis device to produce lithium sulfide, the following steps are included: (1) A protective gas (such as argon and / or nitrogen) is introduced into the reactor 1, with a purity of >99.9% and a water content of less than 100 ppm, to reduce the impact on the reaction of gaseous and solid reactants; (2) The reaction chamber 6 is heated to a temperature required for the reaction by the heating mechanism 2. Depending on the reaction being performed, the temperature ranges from 300 to 1000°C. If lithium sulfate and hydrogen are used as raw materials for the reaction, the ideal temperature is between 700°C and 900°C, and more preferably between 750°C and 850°C. (3) Solid granular materials with a diameter of 500nm-1mm (including solid reactants such as lithium carbonate, lithium hydroxide, lithium sulfate, etc.; and may further include inert reaction media such as quartz sand, zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide, etc.) are added from the upper part of the buffer chamber 7 through the feeding mechanism 5 (such as a feeding hopper); the solid granular materials enter the reaction chamber 6 after passing through the buffer chamber 7. In the reactor 1, the flowing protective gas blows the solid granular materials, so that the solid granular materials are continuously stirred in the reactor 1.

[0048] (4) introducing gaseous reactants (such as hydrogen sulfide or hydrogen, etc., the water content of the gaseous reactants is below 100 ppm to reduce the effect of water on the reaction of gas-solid reactants; and during the reaction, the flow rate of the gaseous reactants and the flow rate of the protective gas need to be maintained at a specific ratio, the ratio is between 5:1 and 1:100, and the specific ratio depends on factors such as the amount of solid reactants, reaction temperature, and particle size. At the same time, to ensure the safety and smooth progress of the reaction, the gas pressure in the reaction chamber is controlled between 0-0.5 MPa), so that the gaseous reactants and the solid reactants are fully contacted and mixed in the reaction chamber 6, and gradually react to produce the target product lithium sulfide; at the same time, the flowing gas and reactants increase the temperature uniformity in the reactor 1, and also increase the uniformity of the material concentration in the reactor 1, so that the reaction is sufficient and the conditions are consistent; (6) After the reaction is sufficient (the reaction time is generally between 1 and 10 hours, which is determined according to the size of the reactor, the reaction temperature, the amount of gaseous and solid materials introduced, etc.), the first pipeline 15 is opened to connect the reactor 1 with the cyclone separator 14, and the reacted materials in the reactor 1 are carried out to the cyclone separator 14 with the air flow; the cyclone separator 14 separates the lithium sulfide solid particles from other gaseous substances and other solid particles (if any), and the lithium sulfide solid particles are collected from the lower part of the cyclone separator 14, and the other gaseous substances enter the water condenser 16 after the second pipeline 18 is opened.

[0049] (7) The water is condensed by the water condenser 16 and falls into the water receiver 17 for collection, and the remaining gaseous substances are discharged from the upper part of the water receiver 17 for treatment or recycling.

[0050] Among them, the chemical substances entering the buffer chamber 7 from the reaction chamber 6 are: (path a) lithium sulfate, lithium sulfide, hydrogen, argon, nitrogen, water and possible by-products; (path b) lithium hydroxide, lithium sulfide, water, hydrogen sulfide, argon, nitrogen and possible by-products; (path c) lithium carbonate, hydrogen sulfide, lithium sulfide, water, carbon dioxide, hydrogen, nitrogen and possible by-products.

[0051] The chemical substances entering the cyclone separator 14 from the buffer chamber 7 are: (path a) lithium sulfide, hydrogen, argon, nitrogen, water and possible by-products; (path b) lithium sulfide, water, hydrogen sulfide, argon, nitrogen and possible by-products; (path c) hydrogen sulfide, lithium sulfide, water, carbon dioxide, hydrogen, nitrogen and possible by-products.

[0052] After separation by the cyclone separator 14, the chemical substances entering the water condenser 16 are: (path a) hydrogen, argon, nitrogen, water; (path b) water, hydrogen sulfide, argon, nitrogen; (path c) hydrogen sulfide, water, carbon dioxide, hydrogen, nitrogen and possible by-products.

[0053] After the water is condensed by the water condenser 16, the remaining gaseous substances (hydrogen, hydrogen sulfide, carbon dioxide) and protective gas (argon, nitrogen) can be recycled after passing through the corresponding purification and pressurization systems.

[0054] When the above synthesis device is used to continuously produce lithium sulfide, the following steps are included: (1) A protective gas (such as argon and / or nitrogen) with a purity of >99.9% and a water content of less than 100 ppm is introduced into the reactor 1 to reduce the impact on the reaction of gaseous and solid reactants.

[0055] (2) The reactor 1 is heated to the required reaction temperature by the heating mechanism 2. Depending on the reaction being carried out, the temperature ranges from 300 to 1000°C. If lithium sulfate and hydrogen are used as raw materials for the reaction, the ideal temperature is between 700°C and 900°C, and more preferably between 750°C and 850°C.

[0056] (3) A gaseous reactant (such as hydrogen sulfide or hydrogen) is introduced into the lower part of the reactor 1. The water content of the gaseous reactant is less than 100 ppm. The ratio of the flow rate of the gaseous reactant to the flow rate of the protective gas is between 5:1 and 1:100. The gas pressure in the reaction chamber is between 0-0.5 MPa. The specific flow rate of the reaction gas and the flow rate of the protective gas are determined according to factors such as the amount of the solid reactant, the reaction temperature, and the particle size.

[0057] (4) After the gaseous reactants reach the specified concentration, solid granular materials with a diameter of 500nm-1mm (including solid reactants such as lithium carbonate, lithium hydroxide, lithium sulfate, etc.; and may further include inert reaction media such as quartz sand, zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide, etc.) are added from the upper part of the buffer chamber 7 through the feeding mechanism 5 (such as a feeding hopper); the solid granular materials enter the reaction chamber 6 after passing through the buffer chamber 7. In the reaction chamber 6, the flowing protective gas blows the solid granular materials, so that the solid granular materials are constantly stirred in the reactor 1 and are fully contacted and mixed with the gaseous reactants.

[0058] (5) The gaseous reactants and the solid reactants are fully contacted and mixed in the reaction chamber 6, and gradually react to produce the target product lithium sulfide; at the same time, the flowing gas and reactants increase the temperature uniformity in the reactor 1, and also increase the uniformity of the material concentration in the reactor 1, so that the reaction is sufficient and the conditions are consistent. The entire reaction time is between 1 and 10 hours, which needs to be determined according to the size of the reactor, the reaction temperature, the amount of gaseous and solid materials introduced, etc.

[0059] (6) After the reaction is sufficient, the first pipeline 15 is opened to connect the reactor 1 with the cyclone separator 14, and the reacted materials in the reactor 1 are carried out to the cyclone separator 14 along with the air flow; the cyclone separator 14 separates the lithium sulfide solid particles from other gaseous substances and other solid substances (if any), and the lithium sulfide solid particles are collected from the lower part of the cyclone separator 14, and the other gaseous substances enter the water condenser 16 after the second pipeline 18 is opened.

[0060] (7) The water is condensed by the water condenser 16 and falls into the water receiver 17 for collection, and the remaining gaseous substances are discharged from the upper part of the water receiver 17 for treatment or recycling.

[0061] (8) Repeat steps (1) to (7) to achieve continuous production.

[0062] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A lithium sulfide synthesis device, characterized in that: include: Reactor; A heating mechanism, used for heating the reactor; A gas supply mechanism, the gas supply mechanism is communicated with the lower part of the reactor and is used to supply gaseous materials from the lower part of the reactor into the reactor; A feeding mechanism, which is arranged at the upper part of the reactor and is used to add solid materials from the upper part of the reactor into the reactor; The separation mechanism is connected to the upper part of the reactor and is used to separate the substances entering the separation mechanism along with the air flow after the solid and gaseous reactants in the reactor react, so as to extract lithium sulfide.

2. A lithium sulfide synthesis device according to claim 1, characterized in that: The reactor comprises a reaction chamber at the lower part and a buffer chamber at the upper part, and the reaction chamber is communicated with the buffer chamber.

3. A lithium sulfide synthesis device according to claim 1, characterized in that: The gas material includes the gaseous reactants and the protective gas, and the gas supply mechanism includes a first gas supply component for supplying the gaseous reactants to the reactor and a second gas supply component for supplying the protective gas to the reactor.

4. A lithium sulfide synthesis device according to claim 3, characterized in that: The gaseous reactant includes one of hydrogen, hydrogen sulfide, carbon monoxide or any combination thereof; the protective gas includes one of argon and nitrogen or any combination thereof.

5. A lithium sulfide synthesis device according to claim 1, characterized in that: The separation mechanism comprises at least one cyclone separator, and the cyclone separator is connected with the upper part of the reactor through a first pipeline.

6. A lithium sulfide synthesis device according to claim 5, characterized in that: The separation mechanism also includes a water condenser and a water receiver. The upper end of the cyclone separator is connected to the inlet end of the water condenser through a second pipe, and the outlet end of the water condenser is connected to the inlet end of the water receiver.

7. A lithium sulfide synthesis device according to claim 2, characterized in that: A plurality of baffles are also arranged in the reaction chamber.

8. A method for producing lithium sulfide using the synthesis device according to any one of claims 1 to 7, characterized in that: The steps include: (1) introducing a protective gas into the reactor; (2) heating the reactor to a temperature required for the reaction by the heating mechanism; (3) adding solid materials from the upper part of the reactor through the feeding mechanism; (4) introducing gaseous reactants into the lower part of the reactor through a gas supply mechanism; (5) The gaseous reactants and the solid reactants gradually react after contacting in the reactor to produce the target product lithium sulfide; (6) After the reaction is complete, the passage between the reactor and the separation mechanism is opened to allow the reacted material to be discharged into the separation mechanism along with the air flow; (7) Separating the synthesized lithium sulfide from other materials through a separation mechanism.

9. A method for producing lithium sulfide using the synthesis device according to any one of claims 1 to 7, characterized in that: The steps include: (1) introducing a protective gas into the reactor; (2) heating the reactor to a temperature required for the reaction by the heating mechanism; (3) introducing gaseous reactants into the lower part of the reactor through a gas supply mechanism; (4) After the gaseous reactants reach a specified concentration, adding solid materials to the upper part of the reactor through the feeding mechanism; (5) The gaseous reactants and the solid reactants gradually react after contacting in the reactor to produce the target product lithium sulfide; (6) After the reaction is complete, the passage between the reactor and the separation mechanism is opened to allow the reacted material to be discharged into the separation mechanism along with the air flow; (7) separating the synthesized lithium sulfide from other materials by a separation mechanism; (8) Repeat steps (1) to (7) to achieve continuous production.

10. A method for synthesizing lithium sulfide according to claim 8 or 9, characterized in that: The solid material comprises the solid reactant and an inert reaction medium.

11. A method for synthesizing lithium sulfide according to claim 10, characterized in that: The inert reaction medium includes one of quartz sand, zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide or any combination thereof, and the solid reactant includes one of lithium carbonate, lithium hydroxide, lithium sulfate or any combination thereof.

12. A method for synthesizing lithium sulfide according to claim 8 or 9, characterized in that: The solid material is in granular form with a diameter of 500nm-1mm.

13. A method for synthesizing lithium sulfide according to claim 8 or 9, characterized in that: The protective gas is high-purity argon or nitrogen with a purity of >99.9% and a water content of less than 100 ppm.

14. A method for synthesizing lithium sulfide according to claim 8 or 9, characterized in that: In the step (2), the temperature ranges from 300 to 1000° C. depending on the reaction being performed.

15. A method for synthesizing lithium sulfide according to claim 8 or 9, characterized in that: The water content of the gaseous reactant introduced into the reactor is below 100 ppm.

16. A method for synthesizing lithium sulfide according to claim 8 or 9, characterized in that: The gas pressure in the reaction chamber is controlled between 0-0.5 MPa.

17. A method for synthesizing lithium sulfide according to claim 8 or 9, characterized in that: During the reaction, the flow rate of the gaseous reactant and the flow rate of the protective gas are maintained at a specific ratio, which is between 5:1 and 1:

100.

18. A method for synthesizing lithium sulfide according to claim 8 or 9, characterized in that: The reaction time of step (5) is between 1 and 10 hours.

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