CN114471430A - 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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CN114471430A
CN114471430A CN202210116136.3A CN202210116136A CN114471430A CN 114471430 A CN114471430 A CN 114471430A CN 202210116136 A CN202210116136 A CN 202210116136A CN 114471430 A CN114471430 A CN 114471430A
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storage tank
alkali metal
reaction kettle
pipeline
metal sulfide
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CN114471430B (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 sulfide 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, wherein the first pipeline is sequentially provided with a first storage tank, a condensing tower, a second storage tank, a third storage tank, a reaction kettle and a fourth storage tank, the first storage tank and the fourth storage tank are communicated with each other, 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 gas cylinder and the reaction kettle are communicated with each other. 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 as follows: 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 cathode material is widely applied to safe and high-capacity metal (M ═ Li, Na, K) sulfur batteries.
Disclosure of Invention
The invention aims to: aiming at the defects in the prior art, the device for continuously producing the alkali metal sulfide is provided, the process for preparing the alkali metal sulfide does not relate to high-temperature and high-pressure reaction, the energy consumption is low, greenhouse gas emission is avoided, the requirement of the national double-carbon target is 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 purpose, the invention adopts the following technical scheme: a device for continuously producing alkali metal sulfides 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 communicated with each other, an atmosphere furnace is sleeved outside the first storage tank and used for storing the alkali metal sulfides, and the atmosphere furnace is used for heating the alkali metal sulfides and evaporating alcohol solution in the alkali metal sulfides to obtain the alkali metal sulfides; a temperature control system for controlling the internal temperature of the reaction kettle is arranged outside the reaction kettle; the vacuumizing mechanism is communicated with the first pipeline; the refrigeration mechanism is connected with the condensation tower, and the refrigeration mechanism is used for reducing the temperature in the condensation 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 gas cylinder is communicated with the reaction kettle.
The gate valves are respectively arranged on the first pipeline and the second pipeline and are used for controlling the connection and disconnection 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.
The atmosphere furnace further 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; a second port of the second reversing valve is connected with the buffer bottle, and a 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 comprises the following steps:
step 1: vacuumizing the whole reaction system by using a vacuum pump, and filling the reaction system with inert gas to normal pressure;
step 2: putting alkali metal into a reaction kettle;
and step 3: pressing alcohol in a third storage tank into the reaction kettle by using inert gas to prepare an alcohol solution with the alkali metal alcohol compound, and simultaneously discharging hydrogen;
and 4, step 4: introducing hydrogen sulfide gas into the reaction kettle to prepare an alcohol solution containing alkali metal sulfide;
and 5: pressing the alkali metal sulfide alcohol solution in the reaction kettle into a fourth storage tank by using inert gas;
step 6: vacuumizing the condensing tower and the atmosphere furnace by using a vacuum pump, and sucking the alkali metal sulfide alcohol solution in the fourth storage tank into the first storage tank;
and 7: heating the atmosphere furnace to enable alcohol to enter the condensing tower for cooling after evaporation, and then entering a second storage tank, wherein the atmosphere furnace is heated in a stepped mode;
and 8: and opening the atmosphere furnace, sealing the first storage tank, and then putting the first storage tank into an inert atmosphere to store the alkali metal sulfide product.
The invention has the beneficial effects that:
compared with the conventional method for preparing the 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 only needs to be added into the closed system once, and can be infinitely circulated in the system without consumption, thereby greatly saving energy consumption and cost.
Compared with the industrialized carbothermic method for preparing the alkali metal sulfide, the method has the advantages that:
(1) the preparation process does not involve high-temperature and high-pressure reaction, has low energy consumption and no emission of greenhouse gases, and meets the requirement of the national double-carbon target.
(2) The production process is continuous, the operation is simple, and the method can be used for producing the sulfide powder in a large scale.
(3) The product sulfide has high purity and small grain size, and can be directly used as a composite anode material for preparing sulfide solid electrolyte and alkali metal-sulfur batteries.
Drawings
FIG. 1 is a schematic diagram of an apparatus suitable for large-scale continuous production of alkali metal sulfide according to an embodiment;
FIG. 2 is a schematic diagram of a first circuit in an embodiment;
FIG. 3 is a schematic diagram of a second circuit 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 meter; 10. an eighth gate valve; 11. a ninth gate valve; 12. a second vacuum pressure dual-purpose meter; 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 meter; 19. a fifteenth gate valve; 20. a sixteenth gate valve; 21. a fourth vacuum pressure dual-purpose meter; 22. a first pressure reducing valve; 23. a second pressure reducing valve; 24. a first direction changing valve; 25. a second directional control valve; 26. a third directional control valve; 27. a second storage tank; 28. a third reservoir 28; 29. a fourth reservoir 29; 30. a reaction kettle; 31. a vacuum pump; 32. a buffer bottle; 33. a refrigerator; 34. a condensing tower; 35. an atmosphere furnace; 36. a first storage tank; 37. an inert gas cylinder; 38. a hydrogen sulfide gas cylinder; 39. a temperature control system; 40. a thermometer; 41. a gas mass flow meter; 42. a 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 the third reversing valve; d. a fourth port of the third directional 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. a third port of the second reversing valve.
Detailed Description
In the description of the application, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", horizontal ", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
In the description of the present application, unless explicitly stated or limited otherwise, the terms "first", "second", "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more; the terms "connected," "secured," and the like are to be construed broadly and unless otherwise stated or indicated, and for example, "connected" may be a fixed connection, a removable connection, an integral connection, or an electrical connection; "connected" may be directly connected or indirectly connected through an intermediate. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
In the description of the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "fixed" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral part; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled 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 attributes 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 solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to specific embodiments and drawings of the specification, but the embodiments of the present invention are not limited thereto.
As shown in fig. 1 to 3, in the present embodiment, a device suitable for large-scale continuous production of alkali metal sulfides is designed by a gas-liquid method, so that a series of problems of low productivity, discontinuous production, need of a glove box and the like in the existing production process of alkali metal sulfides are solved, and the production cost of alkali metal sulfides is reduced by about 90%.
The total chemical reaction equation corresponding to the preparation of the alkali metal sulfide by the gas-liquid method is as follows:
metal M (solid) + Hydrogen sulfide H2S (gas) → sulfide M2S (solid) + Hydrogen H2(gas).
The solvent alcohol forms a circulation loop through the first pipeline, so that the solvent alcohol can be infinitely circulated in the system 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 apparatus through the second pipeline, so that the pressure in the reaction system reaches a normal pressure state.
Specifically, the method for continuously synthesizing the alkali metal sulfide crystal without the glove box 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 portions, described by steps 2) -8) and 9) -18), respectively. Note: in the initial state, a certain amount of alcohol is present in both the second 27 and third 28 reservoirs;
2) the whole reaction system (except for the third storage tank 28) is evacuated by using the vacuum pump 31, then the reaction system is filled with the inert gas in the inert gas cylinder 37 to make the pressure thereof reach the normal pressure, and then all valves in the reaction system are closed;
3) quickly putting the alkali metal calculated and weighed in advance into a reaction kettle 30;
4) starting a temperature control system 39 (namely 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 indicated by a thermometer 40 for feedback;
5) the first pressure reducing valve 22 of the inert gas cylinder 37 is opened, the first direction changing valve 24 is turned in the left direction in the figure (so that g to f are conducted), the third direction changing valve 26 is then turned to the third storage tank 28 in which alcohol is stored (so 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 prepare an alcohol solution of an alkali metal alkoxide by pressurizing an alcohol into the reaction vessel 30 with an inert gas and reacting the alcohol with an alkali metal previously added, while discharging by-product hydrogen through the ninth gate valve 11;
6) after the reaction is completed, that is, no more hydrogen is discharged from the ninth gate valve 11, closing the fifth gate valve 6, the seventh gate valve 8, the eighth gate valve 10 and the ninth gate valve 11, opening the second pressure reducing valve 23 and the eleventh gate valve 14, introducing the hydrogen sulfide gas in the hydrogen sulfide gas cylinder 38 into the reaction kettle 30 by bubbling through the gas mass flow meter 41, and reacting with the alkali metal alcohol compound to prepare an alcohol solution of the alkali metal sulfide;
7) and calculating and controlling the molar quantity of the hydrogen sulfide according to the gas mass flow meter 41, closing the second reducing valve 23 and the eleventh gate valve 14 after the required flow is introduced, turning the third reversing valve 26 to the reaction kettle 30 (conducting d to a), and opening the tenth gate valve 13 and the twelfth gate valve 15. The purpose of the above operation is to press the alkali metal sulfide alcohol solution in the reaction kettle 30 into the fourth storage tank 29 through the third directional valve 26 by using inert gas, and after the alkali metal sulfide alcohol solution is completely transferred, the tenth gate valve 13 and the twelfth gate valve 15 are closed;
8) then, the third change valve 26 is changed to the second storage tank 27 containing alcohol (so that d to c are conducted), the fourth gate valve 5, the fifth gate valve 6 and the sixth gate valve 7 are opened, and the alcohol in the second storage tank 27 is pressed into the third storage tank 28;
9) steps (2) - (8) may be repeated;
10) it is necessary to ensure that the tenth gate valve 13 and the twelfth gate valve 15 are in a closed state, the first direction changing valve 24 is directed to the right in the figure (so that g to e are conducted), the fourteenth gate valve 17, the first gate valve 1 and the second gate valve 2 are opened, the second direction changing valve 25 is directed to the lower direction in the figure (so that j to i are conducted), the condensing tower 34 and the atmosphere furnace 35 are evacuated by using the vacuum pump 31 connected to the condensing tower 34, and the alkali metal sulfide alcohol solution in the fourth storage tank 29 is sucked into the first storage tank 36 due to the change in pressure. Note that: in this step, the pressure in the fourth storage tank 29 is closely monitored to avoid potential safety hazards due to too low pressure, and the pressure in the fourth storage tank 29 is balanced through the thirteenth gate valve 16 when necessary;
11) heating the alcohol solution of the alkali metal sulfide in an atmosphere furnace 35, condensing the alcohol in a condensing tower 34 after the alcohol is evaporated, and then storing the alcohol in a second storage tank 27, wherein the 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 storage tank 29 has decreased to a certain level, the tenth gate valve 13 and the twelfth gate valve 15 are opened, and the fourth storage 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 storage tank 27 rises to 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 direction changing valve 24 is turned to the left side in the figure (so that g to f are conducted), the third direction changing valve 26 is turned to the second storage tank 27 (so that d to c are conducted), the fourth gate valve 5, the fifth gate valve 6 and the sixth gate valve 7 are opened, the pressure is adjusted by using inert gas, and the alcohol in the second storage tank 27 is quickly pressed into the third storage tank 28;
14) after the alcohol transfer process is finished, closing the fourth gate valve 5, the fifth gate valve 6 and the sixth gate valve 7, and returning to the starting point after the alcohol runs for a whole 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 is heated again, so that the alcohol in the new alkali sulfide alcohol solution transferred from the fourth stock tank 29 is evaporated while the pressure is adjusted by the thirteenth gate valve 16.
16) Repeating the steps 2-15, and repeating the prefabrication of the alkali metal alcohol compound and the preparation of the alkali metal sulfide to realize 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 heated to 700 ℃ in a stepped manner in an inert gas purging atmosphere, the calcination is carried out for a certain time, the residual alcohol is fully removed, and finally, the high-purity battery-grade alkali metal sulfide powder product can be obtained.
18) The atmosphere furnace 35 is opened, the first storage tank 36 is quickly covered and sealed, the alkali metal sulfide product is quickly transferred into the inert atmosphere to be stored, and then the next round of large-scale production process can be started.
Description of the invention: in this embodiment, the alcohol may be an aliphatic alcohol, an aromatic alcohol or a thiol, such as methanol, ethanol, benzyl alcohol, propyl thiol. The inert gas may be various gases which do not react with the raw materials and products, such as helium, nitrogen, argon, etc.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should understand that the embodiments as a whole may be combined as appropriate to form other embodiments understood by those skilled in the art.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (7)

1. An apparatus for continuously producing an alkali metal sulfide, characterized in that: comprises that
The device comprises a first pipeline, wherein a first storage tank (36), a condensation 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 communicated with each other, 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 interconnected with the condensation column (34), the refrigeration mechanism for reducing the temperature within the condensation column (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) and forms a second pipeline;
a hydrogen sulfide gas cylinder (38), wherein the hydrogen sulfide gas cylinder (38) and the reaction kettle (30) are communicated with each other.
2. The apparatus for continuously producing an alkali metal sulfide as claimed in claim 1, wherein: the gate valve is arranged on the first pipeline and the second pipeline respectively, 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 an 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 an alkali metal sulfide as claimed in claim 3, wherein: the gas stove 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 stove (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 an 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 comprising the steps of:
step 1: pumping all devices except the third storage tank (28) to vacuum by using a vacuum pump (31), and filling the reaction system to normal pressure by using inert gas;
step 2: putting alkali metal into a reaction kettle (30);
and step 3: using inert gas to press the alcohol in the third storage tank (28) into the reaction kettle (30) to prepare an alcohol solution with the alkali metal alcohol compound, and simultaneously discharging hydrogen;
and 4, step 4: introducing hydrogen sulfide gas into the reaction kettle (30) to prepare an alcohol solution containing alkali metal sulfide;
and 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: vacuumizing the condensing tower (34) and the atmosphere furnace (35), and sucking the alkali metal sulfide alcohol solution in the fourth storage tank (29) into a first storage tank (36);
and 7: heating the atmosphere furnace (35) to evaporate alcohol, cooling the evaporated alcohol in the condensing tower (34), and then feeding the cooled alcohol into the second storage tank (27);
and 8: and opening the atmosphere furnace (35), closing the first storage tank (36) and putting the first storage tank into an inert atmosphere for storage.
7. The method for synthesizing an alkali metal sulfide crystal according to claim 6, wherein: the heating mode of the atmosphere furnace (35) is a step-type temperature rise.
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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
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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