CN219156514U - Production system of lithium bis (fluorosulfonyl) imide - Google Patents
Production system of lithium bis (fluorosulfonyl) imide Download PDFInfo
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Abstract
The utility model belongs to the technical field of chemical industry, and particularly relates to a production system of lithium difluorosulfimide, which comprises a sulfuryl fluoride synthesis reaction kettle, a loop reactor, an evaporator and a lithiation reaction kettle which are sequentially communicated, wherein the sulfuryl fluoride synthesis reaction kettle is provided with a liquid outlet, the loop reactor comprises a plurality of differential baffling reactors which are connected in series and are communicated, the lithiation reaction kettle is provided with a liquid outlet end, the upper part of the evaporator is provided with a first gas outlet, and the top of the evaporator is provided with a second gas outlet.
Description
Technical Field
The utility model belongs to the technical field of chemical industry, and particularly relates to a production system of lithium bis (fluorosulfonyl) imide.
Background
The lithium ion battery is widely applied to industries such as mobile phones, electric automobiles, electric tools, digital products and the like, and is particularly important as energy storage equipment of new energy automobiles under the environment-friendly theme of green low carbon and advanced energy conservation. The key materials of the lithium battery comprise a positive electrode, a negative electrode, electrolyte, a diaphragm and the like. Currently, lithium hexafluorophosphate (LiPF 6 ) The lithium salt is the lithium battery solute lithium salt which is most widely used commercially, however, in the use process, the lithium hexafluorophosphate has the problems of poor thermal stability, easiness in hydrolysis and the like, and the lithium hexafluorophosphate is easy to cause rapid attenuation of battery capacity and brings great potential safety hazard. The fluoride ion in the lithium bis (fluorosulfonyl) imide (LiFSI) has strong electron withdrawing property, so that the coordination effect between the yin and yang ions of the lithium salt is weakened, and the activity of the lithium ion is enhanced, therefore, compared with the lithium hexafluorophosphate, the lithium bis (fluorosulfonyl) imide (LiSSI) has better low temperature resistance, high temperature performance, conductivity, safety, compatibility and other performances, and the lithium bis (fluorosulfonyl) imide has physical and chemical properties far higher than those of the lithium hexafluorophosphate, and is the next-generation lithium ion battery electrolyte lithium salt capable of replacing the lithium hexafluorophosphate.
At present, the bisfluorosulfonyl imide is mainly used as a raw material at home and abroad, the bisfluorosulfonyl imide is obtained by fluorination with a fluorinating agent, and then the alkali metal salt is used for carrying out a lithiation technology to generate the lithium bisfluorosulfonyl imide. According to the difference of synthetic raw materials of the bis (chlorosulfonyl) imide, the synthesis of the bis (fluorosulfonyl) imide lithium is mainly divided into the following three types:
the method is characterized in that sulfonamide, thionyl chloride and chlorosulfonic acid are used as raw materials to react to generate dichlorosulfimide, hydrofluoric acid is used as a fluorinating agent, the dichlorosulfimide and alkali metal fluoride are reacted to generate difluoro sulfimide alkali metal salt, and lithium difluoro sulfimide is obtained through lithiation, such as CN103935970A, but a large amount of water is generated in the preparation process of the difluoro sulfimide alkali metal by adopting the method, and the problems of complex process, low yield and the like exist.
The method is characterized in that sulfonyl chloride or sulfuryl fluoride and ammonia gas are used as raw materials, HF fluorinating agent is utilized to react with the sulfuryl chloride and the ammonia gas to obtain dichloro sulfonyl imide, then fluorination reaction is carried out to obtain alkali salt of difluoro sulfonyl imide lithium, then the alkali salt is mixed with alkaline substances to obtain difluoro sulfonyl imide alkali metal salt, the alkali salt is subjected to displacement reaction with lithiation reagent to obtain difluoro sulfonyl imide lithium, such as CN104495767A, but the preparation of difluoro sulfonyl imide lithium by adopting the method is carried out under high pressure condition, the equipment investment cost is high, and the reaction process can be severely exothermic, so that great potential safety hazard exists.
The method is characterized in that fluorosulfonic acid and urea are used as raw materials, the fluorosulfonic acid and urea react to generate difluoro-sulfonyl imide, and then the difluoro-sulfonyl-imide lithium is generated by lithiation reaction with lithium fluoride, such as US5916475A, but the method is used for preparing the difluoro-sulfonyl-imide lithium, the adopted raw material fluorosulfonic acid has high cost and certain corrosiveness, hydrogen fluoride generated in the reaction process also has strong corrosiveness, equipment is easy to damage, and the performance of a lithium ion secondary battery is possibly reduced in the application process.
In summary, the traditional synthesis process of the lithium bis (fluorosulfonyl) imide has the defects of more side reactions, more three wastes, high energy consumption, high cost, low safety performance and the like, and the prepared lithium bis (fluorosulfonyl) imide has low purity, high content of impurities such as moisture and the like, is difficult to reach the standard of battery level, and is not beneficial to large-scale commercial production of the lithium bis (fluorosulfonyl) imide. In addition, a large amount of water is generated in the reaction process, the material circulation rate is low, the lithium bis (fluorosulfonyl) imide is easy to decompose under the condition of being heated or at high temperature in the environment with water, and if other metal ions are introduced in the production process, the performance of the lithium bis (fluorosulfonyl) imide is adversely affected, so that in order to meet the use requirement of electrolyte, the indexes of the lithium bis (fluorosulfonyl) imide such as moisture (less than or equal to 0.005wt%, see YS/T1302-2019 power battery electrolyte bis (fluorosulfonyl) imide lithium salt) in detail), metal ions (such as K, fe, ca, cu, mg, ni, etc., less than or equal to 0.0005wt%, cr, zn, as, cd, pb, etc., less than or equal to 0.0002wt%, na (less than or equal to 0.001wt%, see YS/T1302-2019 power battery electrolyte bis (fluorosulfonyl) imide lithium salt) in detail) are strictly regulated.
In view of the above, there is a need for a lithium bis (fluorosulfonyl) imide production system that is free of wastewater generation, low in cost, and high in material circulation rate.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present utility model aims to provide a system for producing lithium bis (fluorosulfonyl) imide, which is used for solving the technical problems of more side reactions, more three wastes, high energy consumption, high cost, low safety performance, high moisture content and low purity of the produced product and the like in the existing equipment for producing lithium bis (fluorosulfonyl) imide.
The utility model provides a production system of difluoro sulfonyl imide lithium, production system is including sulfuryl fluoride synthetic reaction kettle, circulation reactor, evaporimeter and the lithiation reation kettle that communicate in proper order, sulfuryl fluoride synthetic reaction kettle is provided with the leakage fluid dram, circulation reactor includes a plurality of differential baffling reactors of establishing ties and intercommunication, the lithiation reation kettle is provided with out the liquid end, evaporimeter upper portion is provided with first gas outlet, the evaporimeter top is provided with the second gas outlet.
The principle of the production system of the utility model is as follows: by setting a new synthesis route, moisture is prevented from being generated in the preparation process of the lithium bis (fluorosulfonyl) imide, no additional moisture is generated in the whole reaction process, and the content of impurities such as moisture in the prepared lithium bis (fluorosulfonyl) imide is reduced; by connecting and communicating several differential baffled reactors (i.e., DSR reactors) in series, it is possible to continue the fluorination reaction of the unreacted complete sulfuryl fluoride gas, triethylamine and ammonium fluoride in the presence of a solvent selected from ethyl acetate or dimethyl carbonate or diethyl ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof, which has excellent mass and heat transfer effects and enables the fluorination reaction to be more complete. The differential baffled reactor (i.e., DSR reactor) is prior art and will not be described in detail herein.
Optionally, the production system of difluoro sulfimide lithium still includes first filter mechanism, first distillation tower, falling film crystallizer and the crystallization kettle that communicate in proper order, first filter mechanism is provided with the feed inlet and goes out the liquid end, the feed inlet intercommunication lithiation reation kettle of first filter mechanism goes out the liquid end, the liquid end intercommunication of first filter mechanism the first end of first distillation tower, the crystallization kettle is provided with the gas outlet, first distillation tower is provided with the gas outlet, the gas outlet intercommunication of first distillation tower lithiation reation kettle.
According to the utility model, the first filtering mechanism, the first distillation tower, the falling film crystallizer and the crystallization kettle which are sequentially communicated are arranged, so that the prepared lithium bis (fluorosulfonyl) imide can be separated and purified, the purity of the lithium bis (fluorosulfonyl) imide is improved, and the energy consumption is reduced. Through setting up first distillation tower, and will the gas outlet intercommunication of first distillation tower lithiation reation kettle can separate out unreacted raw materials from reaction system, and send into the lithiation reation kettle again and continue to participate in the reaction, improve the resource utilization of raw materials.
Optionally, the production system of lithium bis (fluorosulfonyl) imide further comprises a second distillation tower, wherein the second distillation tower is arranged on a communication pipeline between the first distillation tower and the falling film crystallizer, the second distillation tower is provided with an air outlet, and the air outlet of the second distillation tower is communicated with the sulfuryl fluoride synthesis reaction kettle and/or the differential baffling reactor and/or the lithiation reaction kettle.
According to the utility model, the second distillation tower is arranged, and the air outlet of the second distillation tower is communicated with the sulfuryl fluoride synthesis reaction kettle and/or the differential baffling reactor and/or the lithiation reaction kettle, so that the solvent in the reaction system can be separated from the reaction system, and the solvent is sent into the sulfuryl fluoride synthesis reaction kettle and/or the differential baffling reactor and/or the lithiation reaction kettle again for continuous use, and the resource utilization rate of the solvent is improved.
Optionally, the production system of difluoro sulfonimide lithium still includes the neutralization cauldron and the first phase separation mechanism of intercommunication, the neutralization cauldron intercommunication the gas outlet of crystallization kettle, first phase separation mechanism is provided with aqueous phase export and oil phase export, the oil phase export intercommunication of first phase separation mechanism has the rectifying column, has set gradually drying mechanism and second phase separation mechanism on the pipeline that communicates between oil phase export and the rectifying column, the second phase separation mechanism is provided with the oil phase export, the oil phase export intercommunication of second phase separation mechanism the rectifying column, the rectifying column is provided with the gas outlet.
Optionally, the air outlet is communicated with the differential baffled reactor.
Optionally, the production system of lithium bis (fluorosulfonyl) imide further comprises a gas collecting mechanism, wherein the gas collecting mechanism is arranged on a communication pipeline between the sulfonyl fluoride synthesis reaction kettle and the loop reactor.
Optionally, the production system of lithium bis (fluorosulfonyl) imide further comprises a second filtering mechanism, the second filtering mechanism is communicated with a liquid outlet of the sulfuryl fluoride synthesis reaction kettle, the second filtering mechanism is provided with a filtrate outlet, and the filtrate outlet of the second filtering mechanism is communicated with the sulfuryl fluoride synthesis reaction kettle through a circulating pipeline.
Optionally, the first gas outlet communicates with the differential baffled reactor.
According to the utility model, the first gas outlet is communicated with the differential baffling reactor, so that triethylamine and solvent separated from the system can be sent into the differential baffling reactor for continuous recycling, and the utilization rate of raw materials is improved.
Optionally, the second gas outlet is communicated with a sulfuryl fluoride synthesis reaction kettle, and a condenser is arranged on a communication pipeline between the second gas outlet and the sulfuryl fluoride synthesis reaction kettle.
According to the utility model, the second gas outlet is communicated with the sulfuryl fluoride synthesis reaction kettle, so that triethylamine hydrofluoric acid salt in the reaction system can be separated from the reaction system, and the triethylamine hydrofluoric acid salt is sent into the sulfuryl fluoride synthesis reaction kettle again to continuously participate in the reaction, thereby improving the resource utilization rate of the solvent.
Optionally, the production system further comprises a first filtering mechanism, a first distillation tower, a falling film crystallizer and a crystallization kettle which are sequentially communicated, wherein the first filtering mechanism is provided with a feed inlet and a liquid outlet, the feed inlet of the first filtering mechanism is communicated with the liquid outlet end of the lithiation reaction kettle, the liquid outlet end of the first filtering mechanism is communicated with the first end of the first distillation tower, and the crystallization kettle is provided with a discharge opening.
Optionally, the production system further comprises a gas collecting mechanism, wherein the gas collecting mechanism is arranged on a communication pipeline between the sulfuryl fluoride synthesis reaction kettle and the loop reactor.
Optionally, the production system further comprises a second filtering mechanism, the second filtering mechanism is communicated with a liquid outlet of the sulfuryl fluoride synthesis reaction kettle, the second filtering mechanism is provided with a filtrate outlet, and the filtrate outlet is communicated with the sulfuryl fluoride synthesis reaction kettle through a circulating pipeline.
Drawings
Fig. 1 is a schematic structural diagram of a production system of lithium bis-fluorosulfonyl imide of example 1.
Reference numerals
1-sulfuryl fluoride synthesis reaction kettle, 11-stirring component;
2-a gas collecting mechanism;
31-a dry differential baffled reactor;
4-an evaporator;
5-a first liquid collecting tank;
6-lithiation reaction kettle, 61-stirring component;
7-a first filtering mechanism;
8-a first distillation column;
9-a second liquid collecting tank;
10-a second distillation column;
11-falling film crystallizer;
12-crystallizing kettle;
13-a neutralization kettle;
14-a first phase separation mechanism;
15-a drying mechanism;
16-a second phase separation mechanism;
17-a rectifying tower;
18-a second filtration mechanism;
19-a centrifugal pump;
20-condenser.
Detailed Description
Other advantages and effects of the present utility model will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present utility model with reference to specific examples. The utility model may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present utility model.
It should be noted that, the illustrations provided in the present embodiment merely illustrate the basic concept of the present utility model by way of illustration, and only the components related to the present utility model are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complex. The structures, proportions, sizes, etc. shown in the drawings attached hereto are for illustration purposes only and are not intended to limit the scope of the utility model, which is defined by the claims, but rather by the claims. Also, the terms "upper", "lower", "top", "bottom" and the like are used herein for descriptive purposes only and not for limiting the scope of the utility model, and are intended to be construed as embodying the utility model without materially altering the technical scope thereof. It should be understood that the orientation word "inner and outer" refers to inner and outer relative to the contour of the components themselves.
In the description of the present utility model, it should be understood that the terms "first," "second," and the like are used for defining the components, and are merely for convenience in distinguishing the corresponding components, and the terms are not meant to have any special meaning unless otherwise indicated, so that the scope of the present utility model is not to be construed as being limited.
The application provides a lithium bis (fluorosulfonyl) imide production system, which comprises a sulfuryl fluoride synthesis reaction kettle, a circulation reactor, an evaporator, a lithiation reaction kettle, a first filtering mechanism, a first distillation tower, a second distillation tower, a falling film crystallizer, a crystallization kettle, a neutralization kettle and a first phase separation mechanism which are sequentially communicated;
the sulfuryl fluoride synthesis reaction kettle is provided with a liquid outlet;
the loop reactor comprises a plurality of differential baffling reactors which are connected in series and communicated;
the lithiation reaction kettle is provided with a liquid outlet end;
the upper part of the evaporator is provided with a first gas outlet, the top of the evaporator is provided with a second gas outlet, the first gas outlet is communicated with the differential baffling reactor, the second gas outlet is communicated with the sulfuryl fluoride synthesis reaction kettle, and a condenser is arranged on a communication pipeline between the second gas outlet and the sulfuryl fluoride synthesis reaction kettle;
the first filtering mechanism is provided with a feed inlet and a liquid outlet end, the feed inlet of the first filtering mechanism is communicated with the liquid outlet end of the lithiation reaction kettle, and the liquid outlet end of the first filtering mechanism is communicated with the first end of the first distillation tower;
the crystallization kettle is provided with a discharge hole;
the first distillation tower is provided with an air outlet, and the air outlet of the first distillation tower is communicated with the lithiation reaction kettle;
the second distillation tower is provided with an air outlet, and the air outlet of the second distillation tower is communicated with a sulfuryl fluoride synthesis reaction kettle and/or a differential baffling reactor and/or a lithiation reaction kettle;
the neutralization kettle is communicated with a discharge port of the crystallization kettle;
the first phase separation mechanism is provided with a water phase outlet and an oil phase outlet, the oil phase outlet of the first phase separation mechanism is communicated with a rectifying tower, a communication pipeline between the oil phase outlet and the rectifying tower is provided with a drying mechanism and a second phase separation mechanism in sequence, the second phase separation mechanism is provided with an oil phase outlet, the oil phase outlet of the second phase separation mechanism is communicated with the rectifying tower, the rectifying tower is provided with an air outlet, and the air outlet of the rectifying tower is communicated with a differential baffling reactor;
a gas collecting mechanism is arranged on a communication pipeline between the sulfuryl fluoride synthesis reaction kettle and the loop reactor;
the liquid outlet communicated with the sulfuryl fluoride synthesis reaction kettle is communicated with a second filtering mechanism, the second filtering mechanism is provided with a filtrate outlet, and the filtrate outlet of the second filtering mechanism is communicated with the sulfuryl fluoride synthesis reaction kettle through a circulating pipeline.
The present utility model will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the utility model, as many insubstantial modifications and variations are within the scope of the utility model as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
Referring to fig. 1, fig. 1 is a schematic structural diagram of a system for producing lithium bis (fluorosulfonyl) imide according to the present embodiment, which is used for preparing high-purity lithium bis (fluorosulfonyl) imide.
As shown in fig. 1, the production system of lithium bis (fluorosulfonyl) imide of the present embodiment includes a sulfuryl fluoride synthesis reaction kettle 1, a gas collecting mechanism 2, a loop reactor, an evaporator 4, a first liquid collecting tank 5, a lithiation reaction kettle 6, and a first filtering mechanism 7, which are sequentially connected.
With continued reference to fig. 1, the sulfuryl fluoride synthesis reactor 1 is used as a reaction vessel for synthesizing sulfuryl fluoride. In the sulfuryl fluoride synthesis reaction kettle 1, triethylamine hydrofluoric acid salt (specifically, triethylamine tri-hydrofluoric acid salt) and sulfuryl chloride are subjected to sulfuryl fluoride synthesis reaction in the presence of a solvent (the solvent is selected from ethyl acetate or dimethyl carbonate or diethyl ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof) to generate sulfuryl fluoride gas and triethylamine hydrochloride, so that a mixture of the sulfuryl fluoride gas, the triethylamine hydrochloride, the triethylamine hydrofluoric acid which is not fully reacted and the solvent is obtained. The sulfuryl fluoride synthesis reaction kettle 1 is provided with a temperature adjusting component (not shown), a feed inlet (not shown) and a first stirring component 11, wherein the first stirring component 11 is used for uniformly mixing reaction raw materials, and the first stirring component 11 can adopt stirring rods and the like. The sulfuryl fluoride synthesis reaction kettle 1 can adopt a comprehensive stirring reaction kettle and the like. The comprehensive stirring reaction kettle and the like are the prior art and are not described in detail here.
With continued reference to fig. 1, the gas collecting mechanism 2 is configured to collect sulfuryl fluoride gas obtained by the sulfuryl fluoride synthesis reaction, and prepare for a subsequent fluorination reaction, where the gas collecting mechanism 2 may employ a gas collecting tank or the like. The gas collection tank is the prior art and will not be described in detail here.
With continued reference to fig. 1, the loop reactor comprises a plurality of differential baffled reactors (i.e., DSR reactors) 31 connected in series and in communication with each other, and a centrifugal pump 19 is provided in the communication pipe between the differential baffled reactors (i.e., DSR reactors) 31. The differential deflection reactor 31 is used as a container for fluorination reaction, and in the differential deflection reactor 31, sulfuryl fluoride gas, triethylamine and ammonium fluoride are subjected to fluorination reaction in the presence of a solvent (the solvent is selected from ethyl acetate, dimethyl carbonate, diethyl ether, isopropyl ether, acetonitrile, ethanol, acetone or a combination thereof) to generate difluoro sulfonimide triethylamine salt and triethylamine hydrofluoric acid salt, so as to obtain a mixed solution containing difluoro sulfonimide, triethylamine hydrofluoric acid salt, triethylamine and acetonitrile.
Specifically, by connecting and communicating several differential baffled reactors (i.e., DSR reactors) 31 in series, it is possible to continue the fluorination reaction of the unreacted complete sulfuryl fluoride gas, triethylamine and ammonium fluoride in the presence of a solvent selected from ethyl acetate or dimethyl carbonate or diethyl ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof, and it is possible to make the fluorination reaction more complete. The differential baffled reactor (i.e., DSR reactor) is prior art and will not be described in detail herein.
With continued reference to fig. 1, a first end of the evaporator 4 is in communication with a communication conduit between a differential baffled reactor (i.e., DSR reactor) 31, and a second end of the evaporator 4 is in communication with a first end of the first liquid collection tank 5. The evaporator 4 is used for separating triethylamine, solvent and triethylamine hydrofluoric acid salt in the mixed solution from the mixed solution. The upper part of the evaporator 4 is provided with a first gas outlet, and the top of the evaporator 4 is provided with a second gas outlet. The first gas outlet is communicated with a differential baffled reactor (namely a DSR reactor) 31, the second gas outlet is communicated with the sulfuryl fluoride synthesis reaction kettle 1, and a condenser 20 is arranged on a communicating pipeline between the second gas outlet and the sulfuryl fluoride synthesis reaction kettle 1. The evaporator 4 may be a multi-effect plate type evaporator, which is a prior art and will not be described herein.
Specifically, by connecting the first gas outlet of the evaporator 4 to the differential baffled reactor (i.e., DSR reactor) 31 and connecting the second gas outlet of the evaporator 4 to the sulfuryl fluoride synthesis reaction vessel 1, triethylamine and solvent discharged from the first gas outlet can be made to enter the differential baffled reactor (i.e., DSR reactor) 31 again, thereby realizing recycling of triethylamine and solvent, and triethylamine hydrofluoric acid discharged from the second gas outlet can be sent to the sulfuryl fluoride synthesis reaction vessel 1 again, so that unreacted complete triethylamine hydrofluoric acid participates in the sulfuryl fluoride synthesis reaction again, and the utilization ratio of triethylamine hydrofluoric acid can be improved.
With continued reference to fig. 1, the second end of the first liquid collecting tank 5 is connected to the first end of the lithiation reaction kettle 6, and a centrifugal pump 19 is disposed on a communication pipeline between the first liquid collecting tank 5 and the lithiation reaction kettle 6.
With continued reference to fig. 1, a first end of the lithiation reaction kettle 6 is connected to a second end of the first liquid collecting tank 5, and a second end of the lithiation reaction kettle 6 is connected to a liquid inlet of the first filtering mechanism 7. The lithiation reactor 6 is used as a reaction vessel for the lithiation reaction. In the lithiation reaction kettle 6, the lithium difluorosulfimide triethylamine salt and lithium fluoride are subjected to lithiation reaction in the presence of protective gas (such as nitrogen, helium, argon, neon and the like) and solvent (solvent is selected from ethyl acetate or dimethyl carbonate or diethyl ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof) to obtain a crude lithium difluorosulfimide product. The lithiation reactor 6 is provided with a temperature adjusting assembly (not shown) and a second stirring assembly 61, the second stirring assembly 61 is used for uniformly mixing the reaction raw materials, and a stirring rod or the like can be adopted for the second stirring assembly 61. The lithiation reaction kettle 6 may be a comprehensive stirring reaction kettle or the like. The comprehensive stirring reaction kettle is in the prior art, and is not described in detail here.
With continued reference to fig. 1, a first filter mechanism 7 is provided for removing unreacted lithium fluoride. The first filtering mechanism 7 is located below the lithiation reaction kettle 6, the first filtering mechanism 7 is provided with a liquid outlet end and a solid outlet, and the first filtering mechanism 7 can adopt a filter and the like. The filter is prior art and will not be described in detail here.
With continued reference to fig. 1, the production system of the present embodiment further includes a first distillation column 8, a second liquid collection tank 9, a second distillation column 10, a falling film crystallizer 11, and a crystallization kettle 12.
With continued reference to fig. 1, a first end of the first distillation tower 8 is connected to the liquid outlet end of the first filtering mechanism 7, an air outlet is disposed at the top of the first distillation tower 8, a liquid outlet is disposed at the bottom of the first distillation tower 8, the air outlet of the first distillation tower 8 is connected to the lithiation reaction kettle 6, and the liquid outlet of the first distillation tower 8 is connected to the first end of the second liquid collecting tank 9.
Specifically, the gas outlet of the first distillation tower 8 is communicated with the lithiation reaction kettle 6, so that unreacted bis (fluorosulfonyl) imide triethylamine salt separated from the bis (fluorosulfonyl) imide lithium crude product can be sent back to the lithiation reaction kettle 6 to continuously participate in the reaction, and the recycling of raw materials is realized.
With continued reference to fig. 1, a second distillation column 10 is used to separate the solvent from the crude lithium bis-fluorosulfonamide. The feed inlet of the second distillation column 10 is communicated with the second end of the second liquid collection tank 9, the top of the second distillation column 10 is provided with an air outlet, the bottom of the second distillation column 10 is provided with a liquid outlet, the air outlet of the second distillation column 10 is communicated with the sulfuryl fluoride synthesis reaction kettle 1 and/or the differential baffling reactor (i.e. DSR reactor) 31 and/or the lithiation reaction kettle 6, and the liquid outlet of the distillation column 10 is communicated with the falling film crystallizer 11. The condenser 20 and the centrifugal pump 19 are arranged on the communication pipeline between the air outlet of the second distillation column 10 and the sulfuryl fluoride synthesis reaction kettle 1 and/or the differential baffled reactor (i.e. DSR reactor) 31 and/or the lithiation reaction kettle 6.
Specifically, the air outlet of the second distillation tower 10 is communicated with the sulfuryl fluoride synthesis reaction kettle 1 and/or the differential baffled reactor (i.e. DSR reactor) 31 and/or the lithiation reaction kettle 6, and a condenser 20 and a centrifugal pump 19 are arranged on a communication pipeline between the air outlet of the second distillation tower 10 and the sulfuryl fluoride synthesis reaction kettle 1 and/or the differential baffled reactor (i.e. DSR reactor) 31 and/or the lithiation reaction kettle 6, so that the solvent in the reaction system can be sent back to the sulfuryl fluoride synthesis reaction kettle 1 and/or the differential baffled reactor (i.e. DSR reactor) 31 and/or the lithiation reaction kettle 6 for continuous use, and the recycling of the solvent is realized.
With continued reference to fig. 1, the falling film crystallizer 11 is configured to melt and crystallize the crude lithium bis (fluorosulfonyl) imide after the solvent is removed, so as to obtain a refined lithium bis (fluorosulfonyl) imide (in liquid state). The feed end of the falling film crystallizer 11 is communicated with the liquid outlet of the distillation tower 10, and the discharge end of the falling film crystallizer 11 is communicated with the first end of the crystallization kettle 12. The falling film crystallizer is the prior art and is not described in detail here.
With continued reference to fig. 1, a first end of the crystallization kettle 12 is connected to a discharge end of the falling film crystallizer 11. The crystallization kettle 12 is used for crystallizing the lithium bis (fluorosulfonyl) imide refined product obtained through the melting falling film crystallization treatment. The crystallization kettle 12 is provided with an air outlet, and is of the prior art and will not be described in detail here.
With continued reference to fig. 1, the production system of the present embodiment further includes a neutralization tank 13, a first phase separation mechanism 14, a drying mechanism 15, a second phase separation mechanism 16, and a rectifying tower 17.
With continued reference to fig. 1, a first end of the neutralization tank 13 is connected to an air outlet of the crystallization tank 12, and the neutralization tank 13 is used as a neutralization reaction vessel. In the neutralization tank 13, a neutralization reaction of triethylamine hydrochloride and an alkali solution (potassium hydroxide solution and/or sodium hydroxide solution) occurs to produce potassium chloride and triethylamine. The neutralization kettle is in the prior art, and is not described in detail herein.
Specifically, through setting up neutralization cauldron 13, can retrieve intermediate product triethylamine hydrochloride, obtain potassium chloride and triethylamine, when improving the recycle rate of triethylamine, the by-product potassium chloride can sell directly, has improved economic benefits.
With continued reference to fig. 1, a first end of the first phase separation mechanism 14 is connected to a second end of the neutralization kettle 13, the first phase separation mechanism 14 is configured to separate a mixed solution obtained after the neutralization reaction into an oil phase (a main component is triethylamine) and a water phase (a main component is potassium fluoride aqueous solution), the first phase separation mechanism 14 adopts an auto-phase separator or a liquid-liquid phase separation centrifuge, the first phase separation mechanism 14 is provided with an oil phase outlet and a water phase outlet, and the oil phase outlet of the first phase separation mechanism 14 is connected to the first end of the drying mechanism 15.
With continued reference to fig. 1, the drying mechanism 15 is used as a drying container for oil phase, and the drying mechanism 15 is provided with a feed inlet through which a material drying agent (such as potassium hydroxide and/or sodium hydroxide) can be fed into the drying mechanism 15.
With continued reference to fig. 1, a first end of the second phase separation mechanism 16 is connected to a second end of the drying mechanism 15, the second phase separation mechanism 16 is used for performing phase separation on the dried oil phase, the second phase separation mechanism 16 adopts an auto-phase separator or a liquid-liquid phase separation centrifuge, the second phase separation mechanism 16 is provided with an oil phase outlet and a water phase outlet, and the oil phase outlet of the second phase separation mechanism 16 is connected to the first end of the rectifying tower.
With continued reference to fig. 1, the rectifying tower 17 is used for separating and purifying a triethylamine oil phase to remove impurities in the triethylamine oil phase, a gas outlet is disposed at the top of the rectifying tower 17, the gas outlet of the rectifying tower 17 is connected to a differential baffled reactor (i.e., DSR reactor) 31, and a condenser 20 and a centrifugal pump 19 are disposed on a communication pipeline between the gas outlet of the rectifying tower 17 and the differential baffled reactor (i.e., DSR reactor) 31.
Specifically, the gas outlet of the rectifying tower 17 is communicated with the differential baffled reactor (i.e., DSR reactor) 31, and the condenser 20 and the centrifugal pump 19 are arranged on a communication pipeline between the gas outlet of the rectifying tower 17 and the differential baffled reactor (i.e., DSR reactor) 31, so that the triethylamine after separation and purification can be condensed and then pumped into the differential baffled reactor (i.e., DSR reactor) 31 by the centrifugal pump 19, thereby realizing the recycling of the triethylamine.
With continued reference to fig. 1, the bottom of the sulfuryl fluoride synthesis reaction kettle 1 is connected to a second filtering mechanism 18. The second filtering mechanism 18 is positioned below the sulfuryl fluoride synthesis reaction kettle 1, and the second filtering mechanism 18 is used for filtering a mixture formed by triethylamine hydrochloride obtained after the sulfuryl fluoride reaction, triethylamine hydrofluoric acid which is not fully reacted and a solvent. The second filtering mechanism 18 is provided with a filtrate outlet and a solid outlet, the filtrate outlet of the second filtering mechanism 18 is communicated with the sulfuryl fluoride synthesis reaction kettle 1 through a circulating pipeline, and a centrifugal pump 19 is arranged on the circulating pipeline. The second filter mechanism 18 may employ a filter. The filter is prior art and will not be described in detail here.
The working procedure of the production system of this embodiment is as follows:
s1, adding a solvent and triethylamine hydrofluoric acid salt into a sulfuryl fluoride synthesis reaction kettle 1, controlling the temperature to be 20-45 ℃, adding sulfuryl chloride, and fully stirring for reacting for 1-2 hours to obtain a mixture of sulfuryl fluoride gas, triethylamine hydrochloride and unreacted triethylamine hydrofluoric acid and acetonitrile, wherein the solvent is selected from ethyl acetate, dimethyl carbonate, diethyl ether, isopropyl ether, acetonitrile, ethanol, acetone or a composition, and the molar ratio of the triethylamine hydrofluoric acid salt to the sulfuryl chloride is 1-3:1, the mol ratio of triethylamine hydrofluoric acid salt to solvent is 1-3:1, a step of;
the sulfuryl fluoride gas is processed by the gas collecting mechanism 2 and flows to the differential baffling reactor (namely a DSR reactor) 31 through a pipeline;
the mixture of triethylamine hydrochloride, and the insufficiently reacted triethylamine hydrofluoric acid and acetonitrile is filtered by a second filtering mechanism 18 to obtain triethylamine hydrochloride solid and a filtrate containing the triethylamine hydrofluoric acid and the acetonitrile, the triethylamine hydrochloride solid is manually recovered, and the filtrate is pumped to a sulfuryl fluoride synthesis reaction kettle 1 by a centrifugal pump 19 to continuously participate in the reaction;
s2, pumping the pressure in the differential baffling reactor (namely the DSR reactor) 31 to 0-0.1Mpa, adding ammonium fluoride, triethylamine and solvent, slowly introducing sulfuryl fluoride gas to ensure that the pressure of the differential baffling reactor (namely the DSR reactor) 31 is about 0.1-0.4Mpa, controlling the temperature to be about 20-60 ℃, continuously supplementing sulfuryl fluoride to 0.1-0.4Mpa, and continuously circulating until the pressure drop is very slow or does not obviously indicate that the sulfuryl fluoride does not participate in the reaction any more, indicating that the reaction is finished, wherein the reaction time is 4-12h, and obtaining a mixed solution containing difluoro sulfonimide, triethylamine hydrofluoric acid salt, triethylamine and solvent, wherein the molar ratio of the triethylamine to the ammonium fluoride is 3-5:1, a step of;
the mixed solution containing the bisfluorosulfonyl imide, triethylamine hydrofluoric acid salt, triethylamine and acetonitrile is pumped into the sender 4 by a centrifugal pump 19;
the temperature of the evaporator 4 is controlled to be 90 ℃, triethylamine and acetonitrile separated from the evaporator 4 are circulated to a differential baffled reactor (namely a DSR reactor) 31, triethylamine hydrofluoric acid salt separated from the top of the evaporator 4 is circulated to a sulfuryl fluoride synthesis reaction kettle 1 to continuously participate in the reaction, and pure bis-fluoro-sulfonyl imide triethylamine salt is obtained at the bottom of the evaporator 4.
S3, treating the pure bis (fluorosulfonyl) imide triethylamine salt through a first liquid collection tank 5, pumping the treated bis (fluorosulfonyl) imide triethylamine salt into a lithiation reaction kettle 6, adding a solvent and lithium fluoride into the lithiation reaction kettle 6 under the protection of nitrogen, regulating the temperature in the lithiation reaction kettle 6 to be 20-40 ℃, reacting the bis (fluorosulfonyl) imide triethylamine salt with the lithium fluoride for 8-12 hours to obtain a bis (fluorosulfonyl) imide lithium crude product, wherein the molar ratio of the bis (fluorosulfonyl) imide triethylamine salt to the lithium fluoride is 1:1-3;
the crude lithium bis (fluorosulfonyl) imide is sent to a first filtering mechanism 7; the first filtering mechanism 7 filters and removes unreacted lithium fluoride solids in the crude product of the lithium bis (fluorosulfonyl) imide to obtain lithium fluoride solids and filtrate containing the lithium bis (fluorosulfonyl) imide, triethylamine hydrofluoric acid salt and acetonitrile;
manually recovering lithium fluoride, and adding the lithium fluoride into a lithiation reaction kettle 6 to continuously participate in the reaction;
the filtrate is sent to a first distillation tower 8, the temperature of an evaporator is controlled to be 90 ℃, triethylamine hydrofluoric acid salt in the filtrate is discharged from the first distillation tower 8 and then is sent to a sulfuryl fluoride synthesis reaction kettle 1 and/or a differential baffling reactor (i.e. a DSR reactor) 31 and/or a lithiation reaction kettle 6 to continuously participate in the reaction after being separated and purified by the first distillation tower 8, and a crude product of the lithium difluorosulfimide is obtained at the bottom of the first distillation tower 8;
the crude product of the lithium bis (fluorosulfonyl) imide is sent into a second distillation tower 10 after being treated by a second liquid collecting tank 9, the temperature of the distillation tower 10 is controlled to be 90 ℃, acetonitrile of the crude product of the lithium bis (fluorosulfonyl) imide is distilled out, and acetonitrile discharged from the top of the second distillation tower 10 is condensed by a condenser 20 and then is sent into a sulfuryl fluoride synthesis reaction kettle 1 and/or a differential baffling reactor (i.e., a DSR reactor) 31 and/or a lithiation reaction kettle 6 to be used as a solvent for continuous use; the second distillation column 10 yields relatively pure lithium bis-fluorosulfonyl imide;
the purer lithium bis (fluorosulfonyl) imide is sent to a falling film crystallizer 11, and is melted, crystallized, sweated and melted to obtain liquid, and the crystallization temperature in the falling film crystallization process is 115-120 ℃; delivering the liquid to a crystallization kettle 12 for crystallization, and then delivering the liquid to a drying kettle 13 for drying at the temperature of 80 ℃ to obtain lithium bis (fluorosulfonyl) imide;
s4, recovering triethylamine hydrofluoric acid salt: the triethylamine hydrofluoric acid salt obtained after the drying treatment of the drying kettle 13 is sent to a neutralization kettle 14, potassium hydroxide solution with the excessive concentration of 20 to 40 weight percent is added into the neutralization kettle 14, and the potassium hydroxide and the triethylamine hydrofluoric acid salt undergo neutralization reaction at normal temperature to generate potassium chloride and triethylamine;
the phase separation treatment is carried out through a first phase separation mechanism 15 to obtain a water phase and an oil phase, the water phase is subjected to three-effect concentration (sent to a three-effect concentration evaporator) to obtain a potassium fluoride byproduct, the oil phase is sent to a drying kettle 16, potassium hydroxide is added to the drying kettle 16, the temperature of the drying kettle 16 is controlled to be 60 ℃, the oil phase is subjected to drying treatment, the oil phase after the drying treatment is sent to a rectifying tower 17, the oil phase after the drying treatment is rectified at normal temperature and normal pressure, and pure triethylamine gas phase discharged from the top of the rectifying tower 17 is sent to a differential baffling reactor (namely a DSR reactor) 31 after being condensed to continuously participate in the reaction.
The above embodiments are merely illustrative of the principles of the present utility model and its effectiveness, and are not intended to limit the utility model. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the utility model. Accordingly, it is intended that all equivalent modifications and variations of the utility model be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (9)
1. The utility model provides a production system of difluoro sulfonyl imide lithium, its characterized in that, including sulfuryl fluoride synthetic reaction cauldron, circulation reactor, evaporimeter and the lithiation reation kettle that communicate in proper order, sulfuryl fluoride synthetic reaction cauldron is provided with the leakage fluid dram, circulation reactor includes a plurality of differential baffling reactors of establishing ties and intercommunication, lithiation reation kettle is provided with out the liquid end, evaporimeter upper portion is provided with first gas outlet, the evaporimeter top is provided with the second gas outlet.
2. The production system of claim 1, further comprising a first filtering mechanism, a first distillation tower, a falling film crystallizer and a crystallization kettle which are sequentially communicated, wherein the first filtering mechanism is provided with a feed inlet and a liquid outlet, the feed inlet of the first filtering mechanism is communicated with the liquid outlet of the lithiation reaction kettle, the liquid outlet of the first filtering mechanism is communicated with the first end of the first distillation tower, the crystallization kettle is provided with an air outlet, the first distillation tower is provided with an air outlet, and the air outlet of the first distillation tower is communicated with the lithiation reaction kettle.
3. The production system according to claim 2, further comprising a second distillation column disposed on a communication pipe between the first distillation column and the falling film crystallizer, the second distillation column being provided with an air outlet communicating with the sulfuryl fluoride synthesis reactor and/or the differential baffled reactor and/or the lithiation reactor.
4. The production system of claim 2, further comprising a neutralization kettle and a first phase separation mechanism, wherein the neutralization kettle is communicated with an air outlet of the crystallization kettle, the first phase separation mechanism is provided with a water phase outlet and an oil phase outlet, the oil phase outlet of the first phase separation mechanism is communicated with a rectifying tower, a drying mechanism and a second phase separation mechanism are sequentially arranged on a communication pipeline between the oil phase outlet and the rectifying tower, the second phase separation mechanism is provided with an oil phase outlet, the oil phase outlet of the second phase separation mechanism is communicated with the rectifying tower, and the rectifying tower is provided with an air outlet.
5. The production system of claim 4, wherein the gas outlet communicates with the differential deflection reactor.
6. The production system of claim 1, further comprising a gas collection mechanism disposed on a communication conduit between the sulfuryl fluoride synthesis reactor and the loop reactor.
7. The production system of claim 1, further comprising a second filter mechanism, wherein the second filter mechanism is in communication with a liquid outlet of the sulfuryl fluoride synthesis reaction kettle, the second filter mechanism is provided with a filtrate outlet, and the filtrate outlet of the second filter mechanism is in communication with the sulfuryl fluoride synthesis reaction kettle via a circulation pipeline.
8. The production system of claim 1, wherein the first gas outlet communicates with the differential deflection reactor.
9. The production system of claim 1, wherein the second gas outlet is communicated with a sulfuryl fluoride synthesis reaction kettle, and a condenser is arranged on a communication pipeline between the second gas outlet and the sulfuryl fluoride synthesis reaction kettle.
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| Publication number | Priority date | Publication date | Assignee | Title |
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