CN114471430B - Device for continuously producing alkali metal sulfide and synthesis method thereof - Google Patents

Device for continuously producing alkali metal sulfide and synthesis method thereof Download PDF

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CN114471430B
CN114471430B CN202210116136.3A CN202210116136A CN114471430B CN 114471430 B CN114471430 B CN 114471430B CN 202210116136 A CN202210116136 A CN 202210116136A CN 114471430 B CN114471430 B CN 114471430B
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storage tank
alkali metal
pipeline
reaction kettle
metal sulfide
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CN114471430A (en
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杨永安
杨顺锦
万丰铭
张欣
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Tianjin University
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/008—Feed or outlet control devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • H01M10/3918—Sodium-sulfur cells characterised by the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

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Abstract

The invention belongs to the technical field of secondary batteries, and particularly discloses a device for continuously producing alkali metal sulfides and a synthesis method thereof, wherein the device comprises a first pipeline, a vacuumizing mechanism, a refrigerating mechanism, an inert gas cylinder and a hydrogen sulfide cylinder, a first storage tank, a condensing tower, a second storage tank, a third storage tank, a reaction kettle and a fourth storage tank are sequentially arranged on the first pipeline, the first storage tank and the fourth storage tank are mutually communicated, an atmosphere furnace is sleeved outside the first storage tank, and a temperature control system is arranged outside the reaction kettle; the inert gas cylinder is respectively communicated with the atmosphere furnace, the condensing tower, the second storage tank, the third storage tank, the reaction kettle and the fourth storage tank to form a second pipeline; the hydrogen sulfide cylinder is communicated with the reaction kettle. The process for preparing the alkali metal sulfide does not involve high-temperature high-pressure reaction, the energy consumption is low, and the prepared product is: the alkali metal sulfide has high purity and small particle size, and can be directly used as a composite positive electrode material for preparing sulfide solid electrolyte and alkali metal-sulfur batteries.

Description

Device for continuously producing alkali metal sulfide and synthesis method thereof
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a device for continuously producing alkali metal sulfide and a synthesis method thereof.
Background
The alkali metal sulfide is used as a key raw material in the production of all-solid batteries and metal-sulfur battery systems, so that the alkali metal sulfide anode material is widely applied to safe and large-capacity metal (M=Li, na, K) sulfur batteries, and at present, the production technology of industrial alkali metal sulfide is mainly based on a solid-phase method for carbothermic reduction of corresponding sulfate.
Disclosure of Invention
The invention aims at: aiming at the defects existing in the prior art, the device for continuously producing the alkali metal sulfide is provided, the process of preparing the alkali metal sulfide does not involve high-temperature and high-pressure reaction, the energy consumption is low, the emission of greenhouse gases is avoided, the requirements of national double-carbon targets are met, and the prepared product is: the alkali metal sulfide has high purity and small particle size, and can be directly used as a composite positive electrode material for preparing sulfide solid electrolyte and alkali metal-sulfur batteries.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the device for continuously producing the alkali metal sulfide comprises a first pipeline, a vacuumizing mechanism, a refrigerating mechanism, an inert gas cylinder and a hydrogen sulfide cylinder, wherein a first storage tank, a condensing tower, a second storage tank, a third storage tank, a reaction kettle and a fourth storage tank are sequentially arranged on the first pipeline, the first storage tank and the fourth storage tank are mutually communicated, an atmosphere furnace is sleeved outside the first storage tank, the first storage tank is used for storing the alkali metal sulfide, and the atmosphere furnace is used for heating the alkali metal sulfide and evaporating an alcohol solution in the alkali metal sulfide; the reaction kettle is externally provided with a temperature control system for controlling the internal temperature of the reaction kettle; the vacuumizing mechanism is communicated with the first pipeline; the refrigerating mechanism is connected with the condensing tower and is used for reducing the temperature in the condensing tower; the inert gas cylinder is respectively communicated with the atmosphere furnace, the condensing tower, the second storage tank, the third storage tank, the reaction kettle and the fourth storage tank to form a second pipeline; the hydrogen sulfide cylinder is communicated with the reaction kettle.
Further, the device also comprises a plurality of gate valves, wherein the gate valves are respectively arranged on the first pipeline and the second pipeline, and the gate valves are used for controlling the on-off of the first pipeline and the second pipeline.
Further, the vacuumizing mechanism comprises a buffer bottle and a vacuum pump communicated with the buffer bottle, and the buffer bottle is communicated with the first pipeline through a pipeline.
Further, the device also comprises a first reversing valve, a second reversing valve and a third reversing valve, wherein a first port of the first reversing valve is connected with the fourth storage tank, a second port of the first reversing valve is respectively connected with a first port of the second reversing valve and a fourth port of the third reversing valve, and a third port of the first reversing valve is respectively connected with the inert gas cylinder and the atmosphere furnace; the second port of the second reversing valve is connected with the buffer bottle, and the third port of the second reversing valve is connected with the condensing tower; and the other three ports of the third reversing valve are respectively connected with the second storage tank, the third storage tank and the reaction kettle.
Further, the refrigerating mechanism comprises a refrigerator and a refrigerating pipe arranged in the condensing tower, and the refrigerator and the refrigerating pipe are connected with each other.
A method for synthesizing alkali metal sulfide crystals, comprising the steps of:
step 1: pumping the whole reaction system to vacuum by using a vacuum pump, and filling the reaction system to normal pressure by using inert gas;
step 2: placing alkali metal into a reaction kettle;
step 3: pressing the alcohol in the third storage tank into the reaction kettle by using inert gas to prepare an alcohol solution with alkali metal alcohol compound, and discharging hydrogen;
step 4: introducing hydrogen sulfide gas into the reaction kettle to prepare an alcohol solution with alkali metal sulfide;
step 5: pressing an alkali metal sulfide alcohol solution in the reaction kettle into a fourth storage tank by using inert gas;
step 6: drawing the condensing tower and the atmosphere furnace to vacuum by using a vacuum pump, wherein the alkali metal sulfide alcohol solution in the fourth storage tank is sucked into the first storage tank;
step 7: heating the atmosphere furnace to evaporate the alcohol, then enabling the alcohol to enter the condensing tower for cooling, and then entering a second storage tank, wherein the atmosphere furnace is subjected to stepwise heating;
step 8: opening the atmosphere furnace, sealing the first storage tank, and then placing the first storage tank into an inert atmosphere to store alkali metal sulfide products.
The invention has the beneficial effects that:
compared with the conventional method for preparing alkali metal sulfide by a gas-liquid method, the device has the advantages that:
(1) The production process does not need a glove box, and the operation is simple.
(2) The production process is continuous, the automation degree is high, and the yield of the alkali metal sulfide is high.
(3) The only auxiliary solvent alcohol can be infinitely circulated in the system only by adding the auxiliary solvent alcohol into the closed system once without consumption, thereby greatly saving energy consumption and cost.
Compared with the industrialized carbothermic reduction method for preparing the alkali metal sulfide, the method has the advantages that:
(1) The preparation process does not involve high-temperature high-pressure reaction, has low energy consumption and no emission of greenhouse gases, and meets the requirements of national double-carbon targets.
(2) The production process is continuous, the operation is simple, and the method can be used for large-scale production of sulfide powder.
(3) The product sulfide has high purity and small particle size, and can be directly used for preparing sulfide solid electrolyte and composite positive electrode materials of alkali metal-sulfur batteries.
Drawings
FIG. 1 is a schematic structural view of an apparatus suitable for large-scale continuous production of alkali metal sulfides in an embodiment;
FIG. 2 is a schematic diagram of a first pipeline in an embodiment;
fig. 3 is a schematic diagram of a second pipeline in an embodiment.
Wherein: 1. a first gate valve; 2. a second gate valve; 3. a vacuum gauge; 4. a third gate valve; 5. a fourth gate valve; 6. a fifth gate valve; 7. a sixth gate valve; 8. a seventh gate valve; 9. a first vacuum pressure dual-purpose gauge; 10. an eighth gate valve; 11. a ninth gate valve; 12. a second vacuum pressure dual-purpose gauge; 13. a tenth gate valve; 14. an eleventh gate valve; 15. a twelfth gate valve; 16. a thirteenth gate valve; 17. a fourteenth gate valve; 18. a third vacuum pressure dual-purpose gauge; 19. a fifteenth gate valve; 20. a sixteenth gate valve; 21. a fourth vacuum pressure dual-purpose gauge; 22. a first pressure reducing valve; 23. a second pressure reducing valve; 24. a first reversing valve; 25. a second reversing valve; 26. a third reversing valve; 27. a second storage tank; 28. a third reservoir 28; 29. a fourth tank 29; 30. a reaction kettle; 31. a vacuum pump; 32. a buffer bottle; 33. a refrigerating machine; 34. a condensing tower; 35. an atmosphere furnace; 36. a first storage tank; 37. an inert gas cylinder; 38. a hydrogen sulfide cylinder; 39. a temperature control system; 40. a thermometer; 41. a gas mass flow meter; 42. seventeenth gate valve; a. a first port of a third reversing valve; b. a second port of the third reversing valve; c. a third port of a third reversing valve; d. a fourth port of the third reversing valve; e. a first port of a first reversing valve; f. a second port of the first reversing valve; g. a third port of the first reversing valve; h. a first port of a second reversing valve; i. a second port of the second reversing valve; j. and a third port of the second reversing valve.
Detailed Description
In the description of the present application, it should be understood that the terms "upper," "lower," "front," "rear," "left," "right," "horizontal," and the like indicate an orientation or a positional relationship based on that shown in the drawings, and are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or element to be referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the description of the present application, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance unless explicitly specified or limited otherwise; the term "plurality" refers to two or more than two; unless specified or indicated otherwise, the terms "coupled," "fixed," and the like are to be construed broadly and are, for example, capable of being coupled either permanently or detachably, or integrally or electrically; "coupled" may be directly coupled or indirectly coupled through intermediaries. The specific meaning of the terms in this application will be understood by those of ordinary skill in the art as the case may be.
In the description of the present invention, unless explicitly stated and limited otherwise, the terms "mounted," "connected," and "secured" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
In order to make the technical scheme and advantages of the present invention more apparent, the present invention and its advantageous effects will be described in further detail below with reference to the detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
As shown in fig. 1 to 3, the specific embodiment designs a device suitable for large-scale continuous production of alkali metal sulfide by a gas-liquid method, solves a series of problems of low productivity, discontinuous production, glove box requirement and the like in the existing alkali metal sulfide production process, and reduces the production cost of the alkali metal sulfide by about 90 percent.
The total chemical reaction equation corresponding to the alkali metal sulfide prepared by the gas-liquid method is as follows:
metal M (solid) +Hydrogen sulfide H 2 S (gas) →sulfide M 2 S (solid) +Hydrogen H 2 (gas).
The solvent alcohol passes through the first pipeline to form a circulation loop, so that the solvent alcohol can be circulated in the system infinitely only by adding the solvent alcohol into the closed system once without consumption, and the energy consumption and the cost are greatly saved.
The inert gas is transported to each device through the second pipeline, so that the pressure in the reaction system reaches a normal pressure state.
Specifically, the glove-free box type continuous synthesis method for alkali metal sulfide crystals comprises the following steps:
1) The full cycle of the closed-loop continuous production of alkali metal sulfides can be divided into two separate recycle sections, described by steps 2) -8) and 9) -18), respectively. And (3) injection: in the initial state, a certain amount of alcohol is contained in both the second tank 27 and the third tank 28;
2) The whole reaction system (except the third storage tank 28) is evacuated by using the vacuum pump 31, then the inert gas in the inert gas cylinder 37 is filled with the inert gas to make the pressure reach the normal pressure, and then all valves in the reaction system are closed;
3) Rapidly placing the alkali metal which is calculated and weighed in advance into a reaction kettle 30;
4) Starting a temperature control system 39 (i.e. an interlayer temperature control device) of the reaction kettle 30 to maintain the temperature in the reaction kettle 30 at a target temperature, wherein the temperature is fed back by a thermometer 40;
5) The first pressure reducing valve 22 on the inert gas cylinder 37 is opened, the first direction changing valve 24 is turned to the left direction in the drawing (such that g to f are conducted), and then the third direction changing valve 26 is turned to the third tank 28 storing alcohol (such that d to b are conducted), and the fifth gate valve 6, the seventh gate valve 8, the eighth gate valve 10, and the ninth gate valve 11 are opened. The purpose of the above operation is to press an alcohol into the reaction vessel 30 with an inert gas, react the alcohol with an alkali metal added in advance, prepare an alcohol solution of an alkali metal alcohol compound, and simultaneously discharge a byproduct hydrogen through the ninth gate valve 11;
6) After the reaction is completed, namely, no more hydrogen is discharged from the ninth gate valve 11, the fifth gate valve 6, the seventh gate valve 8, the eighth gate valve 10 and the ninth gate valve 11 are closed, the second pressure reducing valve 23 and the eleventh gate valve 14 are opened, and the hydrogen sulfide gas in the hydrogen sulfide gas cylinder 38 is introduced into the reaction kettle 30 in a bubbling mode through the gas mass flowmeter 41 to react with the alkali metal alcohol compound to prepare an alcohol solution of alkali metal sulfide;
7) The molar amount of hydrogen sulfide is calculated and controlled based on the gas mass flow meter 41, and after the required flow rate is introduced, the second pressure reducing valve 23 and the eleventh gate valve 14 are closed, the third reversing valve 26 is turned to the reaction vessel 30 (such that d to a are turned on), and the tenth gate valve 13 and the twelfth gate valve 15 are opened. The purpose of the above operation is to press the alkali metal sulfide alcoholic solution in the reaction vessel 30 into the fourth tank 29 by means of the inert gas through the third reversing valve 26, and after the transfer of the alkali metal sulfide alcoholic solution is completed, the tenth gate valve 13 and the twelfth gate valve 15 are closed;
8) Then the third reversing valve 26 is turned to the second tank 27 storing alcohol (so that d to c are conducted), the fourth gate valve 5, the fifth gate valve 6, the sixth gate valve 7 are opened, and the alcohol in the second tank 27 is pressed into the third tank 28;
9) Steps (2) - (8) may be repeated;
10 It is necessary to secure the tenth gate valve 13 and the twelfth gate valve 15 in a closed state, direct the first switching valve 24 to the right direction in the drawing (so that g to e are conducted), open the fourteenth gate valve 17, the first gate valve 1 and the second gate valve 2, direct the second switching valve 25 to the lower direction in the drawing (so that j to i are conducted), and vacuum the condensing tower 34 and the atmosphere furnace 35 using the vacuum pump 31 connected to the condensing tower 34, and the alkali metal sulfide alcohol solution in the fourth tank 29 is sucked into the first tank 36 due to the change of pressure. Note that: the pressure in the fourth storage tank 29 is closely monitored, so that potential safety hazards caused by too low pressure are avoided, and the pressure in the fourth storage tank 29 is balanced through the thirteenth gate valve 16 when necessary;
11 An alcohol solution of alkali metal sulfide is heated in an atmosphere furnace 35, the alcohol is evaporated and then enters a condensing tower 34 to be condensed, and then enters a second storage tank 27 to be stored, and alkali metal sulfide crystals are left in a first storage tank 36 in the atmosphere furnace 35;
12 After the liquid level in the fourth tank 29 has fallen to a certain extent, the tenth gate valve 13 and the twelfth gate valve 15 are opened, and the fourth tank 29 can be replenished with the alkali metal sulfide alcohol solution newly prepared in the reaction vessel 30.
13 When the liquid level of the second tank 27 rises by a certain height, the fourteenth gate valve 17 is closed; the heating evaporation process in the atmosphere furnace 35 is stopped, the first gate valve 1 and the second gate valve 2 are closed, the first reversing valve 24 is turned to the left in the figure (g to f are made conductive), the third reversing valve 26 is turned to the direction of the second tank 27 (d to c are made conductive), the fourth gate valve 5, the fifth gate valve 6 and the sixth gate valve 7 are opened, the pressure is regulated by using inert gas, and the alcohol in the second tank 27 is rapidly pressed into the third tank 28;
14 After the above alcohol transfer process is completed, the fourth gate valve 5, the fifth gate valve 6 and the sixth gate valve 7 are closed, so that the alcohol returns to the starting point after running for a complete circle in the reaction system;
15 Then the first gate valve 1, the second gate valve 2 and the fourteenth gate valve 17 are opened, and the atmosphere furnace 35 starts to reheat, so that the alcohol in the new alkali metal sulfide alcohol solution transferred from the fourth tank 29 is evaporated, while the pressure is regulated by the thirteenth gate valve 16.
16 Repeating the steps 2-15, and repeatedly prefabricating the alkali metal alcohol compound and preparing the alkali metal sulfide to realize the closed-loop continuous production of the alkali metal sulfide;
17 After a certain amount of alkali metal sulfide is accumulated in the atmosphere furnace 35, the production process is stopped, the first reversing valve 24 is closed, the sixteenth gate valve 20 and the seventeenth gate valve 42 are opened, the atmosphere furnace 35 is stepped to be heated to 700 ℃ under the inert gas purging atmosphere, the mixture is calcined for a certain time, residual alcohol is fully removed, and finally, the high-purity battery-level alkali metal sulfide powder product can be obtained.
18 Opening the atmosphere furnace 35, rapidly closing and sealing the first storage tank 36, rapidly transferring the first storage tank into an inert atmosphere to store the alkali metal sulfide product, and then starting the next round of mass production process.
Description: in this embodiment, the alcohol may be a fatty alcohol, an aromatic alcohol, or a thiol, such as methanol, ethanol, benzyl alcohol, propyl mercaptan. The inert gas may be various gases that do not react with the raw materials and products, such as helium, nitrogen, argon, etc.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the embodiments of the disclosure may be suitably combined to form other embodiments as will be understood by those skilled in the art.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.

Claims (7)

1. An apparatus for continuously producing alkali metal sulfide, characterized in that: comprising
The device comprises a first pipeline, wherein a first storage tank (36), a condensing tower (34), a second storage tank (27), a third storage tank (28), a reaction kettle (30) and a fourth storage tank (29) are sequentially arranged on the first pipeline, the first storage tank (36) and the fourth storage tank (29) are mutually communicated, an atmosphere furnace (35) is sleeved outside the first storage tank (36), the first storage tank (36) is used for storing alkali metal sulfides, and the atmosphere furnace (35) is used for heating the alkali metal sulfides and evaporating alcohol solution in the alkali metal sulfides; a temperature control system (39) for controlling the internal temperature of the reaction kettle (30) is arranged outside the reaction kettle (30);
the vacuumizing mechanism is communicated with the first pipeline;
a refrigeration mechanism, the refrigeration mechanism and the condensing tower (34) being connected to each other, the refrigeration mechanism being for reducing the temperature within the condensing tower (34);
an inert gas cylinder (37), wherein the inert gas cylinder (37) is respectively communicated with the atmosphere furnace (35), the condensing tower (34), the second storage tank (27), the third storage tank (28), the reaction kettle (30) and the fourth storage tank (29) to form a second pipeline;
and the hydrogen sulfide gas cylinder (38), and the hydrogen sulfide gas cylinder (38) and the reaction kettle (30) are communicated with each other.
2. An apparatus for continuously producing alkali metal sulfide as claimed in claim 1, wherein: the device comprises a first pipeline, a second pipeline, a gate valve, a plurality of gate valves, a control valve and a control valve, wherein the gate valves are respectively arranged on the first pipeline and the second pipeline, and the gate valves are used for controlling the on-off of the first pipeline and the second pipeline.
3. An apparatus for continuously producing alkali metal sulfide as claimed in claim 1, wherein: the vacuumizing mechanism comprises a buffer bottle (32) and a vacuum pump (31) communicated with the buffer bottle (32), and the buffer bottle (32) is communicated with the first pipeline through a pipeline.
4. An apparatus for continuously producing alkali metal sulfide as claimed in claim 3, wherein: the device further comprises a first reversing valve (24), a second reversing valve (25) and a third reversing valve (26), wherein a first port of the first reversing valve (24) is connected with the fourth storage tank (29), a second port of the first reversing valve (24) is respectively connected with a first port of the second reversing valve (25) and a fourth port of the third reversing valve (26), and a third port of the first reversing valve (24) is respectively connected with the inert gas cylinder (37) and the atmosphere furnace (35); a second port of the second reversing valve (25) is connected with the buffer bottle (32), and a third port of the second reversing valve (25) is connected with the condensing tower (34); the other three ports of the third reversing valve (26) are respectively connected with the second storage tank (27), the third storage tank (28) and the reaction kettle (30).
5. An apparatus for continuously producing alkali metal sulfide as claimed in claim 1, wherein: the refrigerating mechanism comprises a refrigerator (33) and a refrigerating pipe arranged in the condensing tower (34), and the refrigerator (33) and the refrigerating pipe are connected with each other.
6. A method for synthesizing an alkali metal sulfide crystal, characterized by using the apparatus for continuously producing an alkali metal sulfide according to any one of claims 1 to 5, comprising the steps of:
step 1: all devices except the third storage tank (28) are vacuumized by using a vacuum pump (31), and the reaction system is filled with inert gas to normal pressure;
step 2: placing alkali metal into a reaction kettle (30);
step 3: pressing the alcohol in the third storage tank (28) into the reaction kettle (30) by using inert gas to prepare an alcohol solution with alkali metal alcohol compound, and discharging hydrogen;
step 4: introducing hydrogen sulfide gas into the reaction kettle (30) to prepare an alcohol solution with alkali metal sulfide;
step 5: pressing the alkali metal sulfide alcohol solution in the reaction kettle (30) into a fourth storage tank (29) by using inert gas;
step 6: drawing a vacuum from the condensing tower (34) and the atmosphere furnace (35), wherein the alkali metal sulfide alcohol solution in the fourth storage tank (29) is sucked into the first storage tank (36);
step 7: heating the atmosphere furnace (35) so that the alcohol is evaporated and then enters the condensing tower (34) for cooling and then enters the second storage tank (27);
step 8: the atmosphere furnace (35) is opened, and the first storage tank (36) is capped and placed in an inert atmosphere for preservation.
7. The method for synthesizing an alkali metal sulfide crystal according to claim 6, wherein: the heating mode of the atmosphere furnace (35) is stepwise heating.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB354607A (en) * 1930-09-27 1931-08-13 Courtaulds Ltd Improvements in the regeneration of sulphides of the alkali or alkaline earth metals
JP2014234318A (en) * 2013-05-31 2014-12-15 出光興産株式会社 Method of producing alkali metal sulfide
CN104471058A (en) * 2012-06-13 2015-03-25 弗雷德哈钦森癌症研究中心 Compositions comprising chalcogenides and related methods
CN109671571A (en) * 2018-06-08 2019-04-23 天津大学 A kind of preparation method of fabricated in situ multicomponent metal sulfide composite material
CN112551491A (en) * 2020-12-10 2021-03-26 天津大学 Preparation method of lithium sulfide, lithium sulfide and application of lithium sulfide
CN112607712A (en) * 2020-12-31 2021-04-06 江西赣锋锂业股份有限公司 Method for preparing lithium sulfide by using metal lithium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB354607A (en) * 1930-09-27 1931-08-13 Courtaulds Ltd Improvements in the regeneration of sulphides of the alkali or alkaline earth metals
CN104471058A (en) * 2012-06-13 2015-03-25 弗雷德哈钦森癌症研究中心 Compositions comprising chalcogenides and related methods
JP2014234318A (en) * 2013-05-31 2014-12-15 出光興産株式会社 Method of producing alkali metal sulfide
CN109671571A (en) * 2018-06-08 2019-04-23 天津大学 A kind of preparation method of fabricated in situ multicomponent metal sulfide composite material
CN112551491A (en) * 2020-12-10 2021-03-26 天津大学 Preparation method of lithium sulfide, lithium sulfide and application of lithium sulfide
CN112607712A (en) * 2020-12-31 2021-04-06 江西赣锋锂业股份有限公司 Method for preparing lithium sulfide by using metal lithium

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