WO2024065156A1 - 一种双氟磺酰亚胺锂的生产方法及生产系统 - Google Patents

一种双氟磺酰亚胺锂的生产方法及生产系统 Download PDF

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WO2024065156A1
WO2024065156A1 PCT/CN2022/121603 CN2022121603W WO2024065156A1 WO 2024065156 A1 WO2024065156 A1 WO 2024065156A1 CN 2022121603 W CN2022121603 W CN 2022121603W WO 2024065156 A1 WO2024065156 A1 WO 2024065156A1
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reactor
triethylamine
distillation tower
imide
outlet
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PCT/CN2022/121603
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English (en)
French (fr)
Inventor
丁永良
张飞
李明全
钟显威
邓建伟
高毅
肖佳
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上海东庚化工技术有限公司
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Priority to PCT/CN2022/121603 priority Critical patent/WO2024065156A1/zh
Publication of WO2024065156A1 publication Critical patent/WO2024065156A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms

Definitions

  • the invention belongs to the technical field of chemical industry, and specifically discloses a production method and a production system of lithium bis(fluorosulfonyl)imide.
  • Lithium-ion batteries are widely used in industries such as mobile phones, electric vehicles, power tools, and digital products. Under the environmental protection theme of "green, low-carbon, energy saving first", lithium batteries are particularly important as energy storage devices for new energy vehicles.
  • the key materials of lithium batteries include positive electrodes, negative electrodes, electrolytes, and separators.
  • lithium hexafluorophosphate LiPF6
  • LiPF6 lithium hexafluorophosphate
  • lithium hexafluorophosphate has problems such as poor thermal stability and easy hydrolysis, which can easily cause rapid decay of battery capacity and bring great safety hazards.
  • lithium bis(fluorosulfonyl)imide LiFSI
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiFSI has better low temperature resistance, high temperature performance, conductivity, safety, compatibility and other performance.
  • Lithium bis(fluorosulfonyl)imide has physical and chemical properties far superior to lithium hexafluorophosphate, and is the next generation of lithium ion battery electrolyte lithium salt that can replace lithium hexafluorophosphate.
  • the main method at home and abroad is to use bis(chlorosulfonyl)imide as raw material, fluorinate with a fluorinating agent to obtain bis(fluorosulfonyl)imide, and then use alkali metal salt for lithiumation to generate lithium bis(fluorosulfonyl)imide.
  • the preparation methods of lithium bis(fluorosulfonyl)imide can be divided into the following three categories:
  • Sulfonamide, thionyl chloride and chlorosulfonic acid are used as raw materials to react to generate bischlorosulfonyl imide, and then hydrofluoric acid is used as a fluorinating agent to react bischlorosulfonyl imide with alkali metal fluoride to generate bisfluorosulfonyl imide alkali metal salt, and then bisfluorosulfonyl imide lithium is obtained by lithiation, such as CN103935970A.
  • lithiation such as CN103935970A
  • Sulfonyl chloride or sulfuryl fluoride and ammonia are used as raw materials, HF fluorinating agent is used to react with sulfuryl chloride and ammonia to obtain bischlorosulfonyl imide, followed by fluorination reaction to obtain alkali salt of lithium bisfluorosulfonyl imide, which is then mixed with an alkaline substance to obtain alkali metal salt of bisfluorosulfonyl imide, and the alkali metal salt is subjected to replacement reaction with a lithiation agent to obtain lithium bisfluorosulfonyl imide, such as CN104495767A.
  • a lithiation agent to obtain lithium bisfluorosulfonyl imide, such as CN104495767A.
  • the preparation of lithium bisfluorosulfonyl imide by this method needs to be carried out under high pressure conditions, the equipment investment cost is high, and there is a great safety hazard due to the violent heat release during the
  • Fluorosulfonic acid and urea are used as raw materials, and fluorosulfonic acid and urea react to generate bisfluorosulfonyl imide, and bisfluorosulfonyl imide and lithium fluoride are subjected to lithiation reaction to generate lithium bisfluorosulfonyl imide, such as US5916475A.
  • the raw material fluorosulfonic acid used in the preparation of lithium bisfluorosulfonyl imide is expensive and has certain corrosiveness, and the hydrogen fluoride generated in the reaction process is also highly corrosive, which not only easily causes damage to the equipment, but also may cause the performance of the lithium ion secondary battery to decrease during the application process.
  • the traditional synthesis process of lithium bis(fluorosulfonyl)imide has the disadvantages of many side reactions, many wastes, high energy consumption, high cost, and low safety performance.
  • the obtained lithium bis(fluorosulfonyl)imide has low purity and high content of impurities such as water, which makes it difficult to meet battery-grade standards and is not conducive to large-scale commercial production of lithium bis(fluorosulfonyl)imide.
  • a large amount of water will be produced in the above reaction process and the material circulation rate is low.
  • Lithium bis(fluorosulfonyl imide) is easily decomposed in a water environment under heat or high temperature conditions.
  • lithium bis(fluorosulfonyl imide) has strict regulations on water ( ⁇ 0.005wt%, see “YS/T 1302-2019 Power Battery Electrolyte Bis(fluorosulfonyl imide) Lithium Salt"), metal ions (such as K, Fe, Ca, Cu, Mg, Ni, etc. are required to be ⁇ 0.0005wt%, Cr, Zn, As, Cd, Pb, etc. are required to be ⁇ 0.0002wt%, Na is required to be ⁇ 0.001wt%, see “YS/T 1302-2019 Power Battery Electrolyte Bis(fluorosulfonyl imide) Lithium Salt”) and other indicators.
  • the object of the present invention is to provide a production method and production system for lithium bis(fluorosulfonyl)imide, which is used to solve the technical problems of using existing equipment and methods to produce lithium bis(fluorosulfonyl)imide, such as many side reactions, many wastes, high energy consumption, high cost, low safety performance, high content of impurities such as water in the obtained product, and low purity.
  • the present application provides a method for producing lithium bis(fluorosulfonyl)imide, comprising:
  • Triethylamine hydrofluoride and sulfuryl chloride undergo a sulfuryl fluoride synthesis reaction in the presence of a solvent to obtain sulfuryl fluoride gas;
  • Sulfuryl fluoride gas reacts with triethylamine and ammonium fluoride in the presence of a solvent to produce bis(fluorosulfonyl)imide triethylamine salt;
  • Bisfluorosulfonyl imide triethylamine salt and lithium fluoride undergo lithiation reaction in a protective gas atmosphere and in the presence of a solvent to obtain lithium bisfluorosulfonyl imide.
  • protecting gas includes nitrogen, helium, argon, neon and the like.
  • the temperature of the sulfuryl fluoride synthesis reaction is 20-45°C, preferably 30-45°C; the time of the sulfuryl fluoride synthesis reaction is 1-2h, preferably 1.5-2h.
  • the molar ratio of triethylamine hydrofluoride to sulfuryl chloride is 1-3:1, preferably 2-3:1.
  • the molar ratio of triethylamine hydrofluoride to the solvent is 1-3:1, preferably 2-3:1.
  • the molar ratio of triethylamine to ammonium fluoride is 3-5:1, preferably 4-5:1.
  • 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.
  • the temperature of the fluorination reaction is 20-60°C, preferably 30-60°C; the pressure of the fluorination reaction is 0.1-0.4MPa, preferably 0.2-0.4MPa; and the time of the fluorination reaction is 4-12h, preferably 5-12h.
  • the molar ratio of the bis(fluorosulfonyl)imide triethylamine salt to lithium fluoride is 1:1-3, preferably 1:2-3.
  • the temperature of the lithiation reaction is 20-40° C., preferably 30-40° C.; the time of the lithiation reaction is 8-12 h, preferably 10-12 h.
  • a purification step is also included.
  • the purification comprises distillation, falling film crystallization, recrystallization and drying steps.
  • the crystallization temperature during the falling film crystallization process is 115-120°C, preferably 118-120°C.
  • the distillation temperature is 85-95°C, preferably 90-95°C.
  • the production method further comprises: recovering triethylamine hydrochloride in the solvent obtained during the drying process.
  • the present application provides a production system adopted by the production method of lithium bis(fluorosulfonyl)imide as described above, comprising a sulfuryl fluoride synthesis reactor, a loop reactor, an evaporator and a lithiation reactor connected in sequence, wherein the sulfuryl fluoride synthesis reactor is provided with a liquid discharge port, the loop reactor comprises a plurality of differential baffled reactors connected in series and connected, the lithiation reactor is provided with a liquid outlet, a first gas outlet is provided at the top of the evaporator, a second gas outlet is provided at the top of the evaporator, and a centrifugal pump is provided on the connecting pipe between the differential baffled reactors.
  • the production system further comprises a first filtering mechanism, a first distillation tower, a falling film crystallizer and a crystallization kettle which are sequentially connected, the first filtering mechanism being provided with a feed inlet and a liquid outlet, the feed inlet of the first filtering mechanism being connected to the liquid outlet of the lithiation reaction kettle, the liquid outlet of the first filtering mechanism being connected to the first end of the first distillation tower, the crystallization kettle being provided with a gas outlet, the first distillation tower being provided with a gas outlet, and the gas outlet of the first distillation tower being connected to the lithiation reaction kettle.
  • the first filtering mechanism being provided with a feed inlet and a liquid outlet
  • the feed inlet of the first filtering mechanism being connected to the liquid outlet of the lithiation reaction kettle
  • the liquid outlet of the first filtering mechanism being connected to the first end of the first distillation tower
  • the crystallization kettle being provided with a gas outlet
  • the first distillation tower being provided with a gas outlet
  • the production system further comprises a second distillation tower, which is arranged on a connecting pipe between the first distillation tower and the falling film crystallizer, and the second distillation tower is provided with a gas outlet, and the gas outlet of the second distillation tower is connected to the sulfuryl fluoride synthesis reactor and/or the differential baffle reactor and/or the lithiation reactor.
  • a second distillation tower which is arranged on a connecting pipe between the first distillation tower and the falling film crystallizer, and the second distillation tower is provided with a gas outlet, and the gas outlet of the second distillation tower is connected to the sulfuryl fluoride synthesis reactor and/or the differential baffle reactor and/or the lithiation reactor.
  • the production system also includes a connected neutralization kettle and a first phase-separation mechanism, the neutralization kettle is connected to the gas 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 connected to a distillation tower, and a drying mechanism and a second phase-separation mechanism are sequentially arranged on the connecting pipeline between the oil phase outlet and the distillation tower, the second phase-separation mechanism is provided with an oil phase outlet, and the oil phase outlet of the second phase-separation mechanism is connected to the distillation tower.
  • the production system further comprises a gas collecting mechanism, and the gas collecting mechanism is arranged on a connecting pipeline between the sulfuryl fluoride synthesis reactor and the loop reactor.
  • the production system further comprises a second filtering mechanism, the second filtering mechanism is connected to the liquid discharge port of the sulfuryl fluoride synthesis reactor, the second filtering mechanism is provided with a filtrate outlet, and the filtrate outlet of the second filtering mechanism is connected to the sulfuryl fluoride synthesis reactor via a circulation pipeline.
  • the first gas outlet is connected to the differential baffled flow reactor.
  • the second gas outlet is connected to a sulfuryl fluoride synthesis reactor, and a condenser is provided on the connecting pipe between the second gas outlet and the sulfuryl fluoride synthesis reactor.
  • the present invention prepares lithium bis(fluorosulfonyl)imide by a new synthetic route, and no additional water is generated during the entire reaction process.
  • the content of impurities such as water in the prepared lithium bis(fluorosulfonyl)imide is reduced.
  • the present application does not introduce chlorine-containing raw materials during the entire reaction process, thereby improving the purity of the product.
  • the purity of the prepared lithium bis(fluorosulfonyl)imide can reach more than 99.95%.
  • the intermediate product triethylamine hydrochloride can be recovered and reused after being treated with potassium hydroxide, and the recovery rate can reach more than 90%, thus realizing circular economic production.
  • the method of the present application is used to prepare lithium bis(fluorosulfonyl)imide, and the product yield is high, which can reach more than 90%, and the production cost is greatly reduced. Compared with lithium hexafluorophosphate, the cost of the present application has a significant advantage. After the product is mass-produced, it can gradually replace the lithium hexafluorophosphate market.
  • lithium bis(fluorosulfonyl)imide When lithium bis(fluorosulfonyl)imide is prepared by the method of the present application, the byproduct potassium chloride can be directly sold to the outside, the raw materials can be fully converted into economic products, and the industrial value is high.
  • the method of the present application does not involve any hazardous waste that is difficult to treat, has a small amount of wastewater, is easy to treat, and basically achieves clean production.
  • FIG. 1 is a schematic structural diagram of a production system for lithium bis(fluorosulfonyl)imide of Example 1.
  • the diagram provided in the present embodiment only illustrates the basic concept of the present invention in a schematic manner, so the diagram only shows the components related to the present invention rather than drawing according to the number, shape and size of the components during actual implementation.
  • the type, quantity and ratio of each component during actual implementation can be a random change, and the component layout type may also be more complicated.
  • the structure, ratio, size, etc. illustrated in the drawings of the present specification are only used to match the content disclosed in the specification for people familiar with this technology to understand and read, and are not used to limit the limiting conditions that the present invention can implement, so they have no technical substantive significance.
  • the present application provides a method for producing lithium bis(fluorosulfonyl)imide, comprising:
  • triethylamine hydrofluoride and sulfuryl chloride undergo sulfuryl fluoride synthesis reaction in the presence of a solvent at a temperature of 20-45°C for 1-2 hours to obtain sulfuryl fluoride gas, wherein the solvent is selected from ethyl acetate, dimethyl carbonate, ethyl ether, isopropyl ether, acetonitrile, ethanol, acetone or a combination thereof; the molar ratio of triethylamine hydrofluoride to sulfuryl chloride is 1-3:1, and the molar ratio of triethylamine hydrofluoride to solvent is 1-3:1;
  • Sulfuryl fluoride gas, triethylamine and ammonium fluoride undergo fluorination reaction in the presence of a solvent at a temperature of 20-60° C. and a pressure of 0.1-0.4 MPa for 4-12 hours to obtain bis(fluorosulfonyl)imide triethylamine salt, wherein the molar ratio of triethylamine to ammonium fluoride is 3-5:1;
  • the solvent is selected from ethyl acetate or dimethyl carbonate or ethyl ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof;
  • Bis(fluorosulfonyl)imide triethylamine salt and lithium fluoride are subjected to a lithiation reaction at a temperature of 20-40°C for 8-12 hours in a protective gas atmosphere and in the presence of a solvent to obtain bis(fluorosulfonyl)imide lithium.
  • the solvent is selected from ethyl acetate, dimethyl carbonate, ethyl ether, isopropyl ether, acetonitrile, ethanol, acetone or a combination thereof.
  • the molar ratio of the bis(fluorosulfonyl)imide triethylamine salt to the lithium fluoride is 1:1-3.
  • distillation is carried out at a temperature of 85-95° C., followed by falling film crystallization, recrystallization and drying.
  • the crystallization temperature during the falling film crystallization is 115-120° C., and triethylamine hydrochloride in the solvent obtained during the drying process is recovered.
  • the present application provides a production system used in the production method as described above, comprising a sulfuryl fluoride synthesis reactor, a loop reactor, an evaporator and a lithiation reactor, a first filtration 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 connected in sequence;
  • the sulfuryl fluoride synthesis reactor is provided with a liquid discharge port
  • the loop reactor comprises a plurality of differential baffled flow reactors connected in series and in communication, and a centrifugal pump is arranged on the communication pipelines between the differential baffled flow reactors;
  • the lithiation reactor is provided with a liquid outlet
  • a first gas outlet is provided on the upper part of the evaporator, a second gas outlet is provided on the top of the evaporator, the first gas outlet is connected to the differential baffle reactor, the second gas outlet is connected to the sulfuryl fluoride synthesis reactor, and a condenser is provided on the connecting pipeline between the second gas outlet and the sulfuryl fluoride synthesis reactor;
  • the first filtering mechanism is provided with a feed inlet and a liquid outlet, the feed inlet of the first filtering mechanism is connected to the liquid outlet of the lithiation reaction kettle, and the liquid outlet of the first filtering mechanism is connected to the first end of the first distillation tower;
  • the crystallization kettle is provided with a gas outlet
  • the first distillation tower is provided with a gas outlet, and the gas outlet of the first distillation tower is connected to the lithiation reaction kettle;
  • the second distillation tower is provided with a gas outlet, and the gas outlet of the second distillation tower is connected to the sulfuryl fluoride synthesis reactor and/or the differential baffle reactor and/or the lithiation reactor;
  • the neutralization kettle is connected to the gas 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 connected to a distillation tower, a drying mechanism and a second phase separation mechanism are sequentially provided on the connecting pipeline between the oil phase outlet and the distillation tower, the second phase separation mechanism is provided with an oil phase outlet, and the oil phase outlet of the second phase separation mechanism is connected to the distillation tower;
  • a gas collecting mechanism is provided on the connecting pipeline between the sulfuryl fluoride synthesis reactor and the loop reactor;
  • the liquid discharge port connected to the sulfuryl fluoride synthesis reactor is connected to a second filtering mechanism, the second filtering mechanism is provided with a filtrate outlet, and the filtrate outlet of the second filtering mechanism is connected to the sulfuryl fluoride synthesis reactor via a circulation pipeline.
  • FIG. 1 is a schematic diagram of the structure of a production system of lithium bis(fluorosulfonyl)imide according to this embodiment.
  • the production system is used to prepare high-purity lithium bis(fluorosulfonyl)imide.
  • the production system of lithium bis(fluorosulfonyl)imide of this embodiment includes a sulfuryl fluoride synthesis reactor 1, a gas collecting mechanism 2, a loop reactor, an evaporator 4, a first liquid collecting tank 5, a lithiation reactor 6 and a first filtering mechanism 7 which are connected in sequence.
  • the sulfuryl fluoride synthesis reactor 1 is used as a reaction vessel for synthesizing sulfuryl fluoride.
  • triethylamine hydrofluoride and sulfuryl chloride undergo a sulfuryl fluoride synthesis reaction in the presence of a solvent (the solvent is selected from ethyl acetate or dimethyl carbonate or ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof) to generate sulfuryl fluoride gas and triethylamine hydrochloride, and obtain a mixture of sulfuryl fluoride gas, triethylamine hydrochloride, triethylamine hydrofluoric acid that is not fully reacted, and solvent.
  • a solvent the solvent is selected from ethyl acetate or dimethyl carbonate or ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof
  • the sulfuryl fluoride synthesis reactor 1 is provided with a temperature regulating component (not shown), a feed port (not shown) and a first stirring component 11, and the first stirring component 11 is used to mix the reaction raw materials evenly, and the first stirring component 11 can use a stirring rod, etc.
  • the sulfuryl fluoride synthesis reactor 1 can use a comprehensive stirring reactor, etc.
  • the comprehensive stirring reactor, etc. are prior art and will not be repeated here.
  • the gas collection mechanism 2 is used to collect the sulfuryl fluoride gas obtained by the sulfuryl fluoride synthesis reaction to prepare for the subsequent fluorination reaction, and the gas collection mechanism 2 can be a gas collection tank, etc.
  • the gas collection tank is a prior art and will not be described here.
  • the loop reactor includes a plurality of differential baffled flow reactors (i.e., DSR reactors) 31 connected in series and connected.
  • a centrifugal pump 19 is provided on the connecting pipes between the differential baffled flow reactors (i.e., DSR reactors) 31.
  • the differential baffled flow reactor 31 is used as a container for fluorination reaction.
  • sulfuryl fluoride gas, triethylamine and ammonium fluoride undergo fluorination reaction in the presence of a solvent (the solvent is selected from ethyl acetate or dimethyl carbonate or ethyl ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof) to generate bisfluorosulfonyl imide triethylamine salt and triethylamine hydrofluoride, thereby obtaining a mixed solution containing bisfluorosulfonyl imide, triethylamine hydrofluoride, triethylamine and acetonitrile.
  • a solvent the solvent is selected from ethyl acetate or dimethyl carbonate or ethyl ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof
  • the unreacted sulfuryl fluoride gas, triethylamine, and ammonium fluoride can continue to undergo fluorination reaction in the presence of a solvent (the solvent is selected from ethyl acetate, dimethyl carbonate, ethyl ether, isopropyl ether, acetonitrile, ethanol, acetone, or a combination thereof), so that the fluorination reaction can be more thorough.
  • the differential baffled flow reactor i.e., DSR reactor
  • DSR reactor is a prior art and will not be described in detail herein.
  • the first end of the evaporator 4 is connected to the connecting pipe between the differential baffle reactor (i.e., DSR reactor) 31, and the second end of the evaporator 4 is connected to the first end of the first liquid collecting tank 5.
  • the evaporator 4 is used to separate the triethylamine, solvent, and triethylamine hydrofluoride in the mixed solution from the mixed solution.
  • a first gas outlet is provided on the upper part of the evaporator 4, and a second gas outlet is provided on the top of the evaporator 4.
  • the first gas outlet is connected to the differential baffle reactor (i.e., DSR reactor) 31, and the second gas outlet is connected to the sulfuryl fluoride synthesis reactor 1.
  • a condenser 20 is provided on the connecting pipe between the second gas outlet and the sulfuryl fluoride synthesis reactor 1.
  • the evaporator 4 can adopt a multi-effect plate evaporator, etc.
  • the multi-effect plate evaporator is a prior art and will not be repeated here.
  • the triethylamine and the solvent discharged from the first gas outlet can be re-entered into the differential baffled flow reactor (i.e., DSR reactor) 31, thereby realizing the recycling of the triethylamine and the solvent, and the triethylamine hydrofluoride discharged from the second gas outlet can be sent to the sulfuryl fluoride synthesis reactor 1 again, so that the triethylamine hydrofluoride that has not reacted completely can participate in the sulfuryl fluoride synthesis reaction again, thereby improving the utilization rate of the triethylamine hydrofluoride.
  • the second end of the first liquid collecting tank 5 is connected to the first end of the lithiation reactor 6 .
  • a centrifugal pump 19 is disposed on the connecting pipe between the first liquid collecting tank 5 and the lithiation reactor 6 .
  • the first end of the lithiation reactor 6 is connected to the second end of the first liquid collecting tank 5, and the second end of the lithiation reactor 6 is connected to the liquid inlet of the first filtering mechanism 7.
  • the lithiation reactor 6 is used as a reaction vessel for lithiation reaction.
  • lithiation reactor 6 bis(fluorosulfonyl)imide triethylamine salt and lithium fluoride undergo lithiation reaction in the presence of a protective gas (such as nitrogen, helium, argon, neon, etc.) atmosphere and a solvent (the solvent is selected from ethyl acetate or dimethyl carbonate or ether or isopropyl ether or acetonitrile or ethanol or acetone or a combination thereof) to obtain bis(fluorosulfonyl)imide lithium.
  • the lithiation reactor 6 is provided with a temperature regulating component (not shown) and a second stirring component 61.
  • the second stirring component 61 is used to mix the reaction raw materials evenly.
  • the second stirring component 61 can use a stirring rod, etc.
  • the lithiation reactor 6 can use a comprehensive stirring reactor, etc.
  • the comprehensive stirring reactor is a prior art and will not be described here.
  • the first filtering mechanism 7 is used to remove unreacted lithium fluoride.
  • the first filtering mechanism 7 is located below the lithiation reaction kettle 6, and the first filtering mechanism 7 is provided with a liquid outlet and a solid outlet.
  • the first filtering mechanism 7 can be a filter, etc.
  • the filter is a prior art and will not be described in detail here.
  • the production system of this embodiment further includes a first distillation tower 8 , a second liquid collecting tank 9 , a second distillation tower 10 , a falling film crystallizer 11 and a crystallization kettle 12 .
  • the first end of the first distillation tower 8 is connected to the liquid outlet end of the first filtering mechanism 7.
  • the top of the first distillation tower 8 is provided with a gas outlet, and the bottom of the first distillation tower 8 is provided with a liquid outlet.
  • the gas outlet of the first distillation tower 8 is connected to the sulfuryl fluoride synthesis reactor 1, and the liquid outlet of the first distillation tower 8 is connected to the first end of the second liquid collecting tank 9.
  • the unreacted bis(fluorosulfonyl)imide triethylamine salt separated from the crude bis(fluorosulfonyl)imide lithium product can be sent back to the lithiation reactor 6 to continue to participate in the reaction, thereby realizing the recycling of raw materials.
  • the second distillation tower 10 is used to separate the solvent from the crude lithium bis(fluorosulfonyl)imide.
  • the feed port of the second distillation tower 10 is connected to the second end of the second liquid collecting tank 9.
  • the top of the second distillation tower 10 is provided with a gas outlet.
  • the bottom of the second distillation tower 10 is provided with a liquid outlet.
  • the gas outlet of the second distillation tower 10 is connected to the sulfuryl fluoride synthesis reactor 1 and/or the differential baffle reactor (i.e., DSR reactor) 31 and/or the lithiation reactor 6.
  • the liquid outlet of the second distillation tower 10 is connected to the falling film crystallizer 11.
  • a condenser 20 and a centrifugal pump 19 are provided on the connecting pipeline between the gas outlet of the second distillation tower 10 and the sulfuryl fluoride synthesis reactor 1 and/or the differential baffle reactor (i.e., DSR reactor) 31 and/or the lithiation reactor 6.
  • the solvent in the reaction system can be sent back to the sulfuryl fluoride synthesis reactor 1 and/or the differential baffle reactor (i.e., DSR reactor) 31 and/or the lithiation reactor 6 for continued use, thereby realizing the recycling of the solvent.
  • the falling film crystallizer 11 is used to perform melt falling film crystallization on the crude lithium bis(fluorosulfonyl)imide product after the solvent is removed to obtain the fine lithium bis(fluorosulfonyl)imide product (liquid state).
  • the feed end of the falling film crystallizer 11 is connected to the liquid outlet of the second distillation tower 10, and the discharge end of the falling film crystallizer 11 is connected to the first end of the crystallization kettle 12.
  • the falling film crystallizer is a prior art and will not be described in detail here.
  • the first end of the crystallization kettle 12 is connected to the discharge end of the falling film crystallizer 11.
  • the crystallization kettle 12 is provided with a gas outlet, and the crystallization kettle 12 is used to crystallize the lithium bis(fluorosulfonyl)imide fine product obtained by melt falling film crystallization.
  • the crystallization kettle is prior art and will not be described in detail here.
  • the production system of this embodiment further includes a neutralization kettle 13 , a first phase separation mechanism 14 , a drying mechanism 15 , a second phase separation mechanism 16 and a distillation tower 17 .
  • the first end of the neutralization kettle 13 is connected to the gas outlet of the crystallization kettle 12, and the neutralization kettle 13 is used as a neutralization reaction container.
  • the neutralization kettle 13 triethylamine hydrochloride and an alkali solution (potassium hydroxide solution and/or sodium hydroxide solution) undergo a neutralization reaction to generate potassium chloride and triethylamine.
  • the neutralization kettle is a prior art and will not be described in detail here.
  • the intermediate product triethylamine hydrochloride can be recovered to obtain potassium chloride and triethylamine. While the recovery rate of triethylamine is improved, the byproduct potassium chloride can be sold directly, thereby improving the economic benefits.
  • the first end of the first phase-separation mechanism 14 is connected to the second end of the neutralization kettle 13.
  • the first phase-separation mechanism 14 is used to separate the mixed liquid obtained after the neutralization reaction into an oil phase (the main component is triethylamine) and a water phase (the main component is a potassium fluoride aqueous solution).
  • the first phase-separation mechanism 14 adopts an automatic 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.
  • the oil phase outlet of the first phase-separation mechanism 14 is connected to the first end of the drying mechanism 15.
  • the drying mechanism 15 is used as a drying container for the oil phase.
  • the drying mechanism 15 is provided with a feed inlet, through which a material desiccant (such as potassium hydroxide and/or sodium hydroxide, etc.) can be added into the drying mechanism 15 .
  • a material desiccant such as potassium hydroxide and/or sodium hydroxide, etc.
  • the first end of the second phase-separation mechanism 16 is connected to the second end of the drying mechanism 15.
  • the second phase-separation mechanism 16 is used to separate the oil phase after drying.
  • the second phase-separation mechanism 16 adopts an automatic 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.
  • the oil phase outlet of the second phase-separation mechanism 16 is connected to the first end of the distillation tower.
  • the distillation tower 17 is used to separate and purify the triethylamine oil phase and remove impurities in the triethylamine oil phase.
  • a gas outlet is set at the top of the distillation tower 17.
  • the gas outlet of the distillation tower 17 is connected to the differential baffle reactor (i.e., DSR reactor) 31.
  • a condenser 20 and a centrifugal pump 19 are set on the connecting pipeline between the gas outlet of the distillation tower 17 and the differential baffle reactor (i.e., DSR reactor) 31.
  • the triethylamine after separation and purification can be condensed and pumped into the differential baffle reactor (i.e., DSR reactor) 31 by the centrifugal pump 19, thereby realizing the recovery and reuse of the triethylamine.
  • the bottom of the sulfuryl fluoride synthesis reactor 1 is connected to a second filtering mechanism 18.
  • the second filtering mechanism 18 is used to filter the mixture formed by triethylamine hydrochloride obtained after the sulfuryl fluoride reaction, triethylamine hydrofluoric acid that has not fully reacted, and the solvent.
  • the second filtering mechanism 18 is located below the sulfuryl fluoride synthesis reactor 1, and 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 connected to the sulfuryl fluoride synthesis reactor 1 through a circulation pipeline, and a centrifugal pump 19 is provided on the circulation pipeline.
  • the second filtering mechanism 18 can adopt a filter.
  • the filter is a prior art and will not be repeated here.
  • Example 1 The production system of Example 1 is used to prepare high-purity lithium bis(fluorosulfonyl)imide, and the specific steps are as follows:
  • the sulfuryl fluoride gas is processed by the gas collecting mechanism 2 and then flows to the differential baffle reactor (i.e., DSR reactor) 31 through a pipeline;
  • DSR reactor differential baffle reactor
  • the mixture of triethylamine hydrochloride and triethylamine hydrofluoric acid and acetonitrile which have not fully reacted is filtered by the second filtering mechanism 18 to obtain triethylamine hydrochloride solid and a filtrate containing triethylamine hydrofluoric acid and acetonitrile.
  • the triethylamine hydrochloride solid is manually recovered and the filtrate is pumped by a centrifugal pump 19 to the sulfuryl fluoride synthesis reactor 1 to continue to participate in the reaction;
  • reaction pressure drops to 0.2 MPa
  • sulfuryl fluoride is continuously added to 0.3 MPa, and the cycle is continued until the pressure drops very slowly or not obviously, indicating that sulfuryl fluoride no longer participates in the reaction, indicating that the reaction is over, and the reaction time is 4 h to obtain a mixed solution containing bis(fluorosulfonyl)imide, triethylamine hydrofluoride, triethylamine, and acetonitrile;
  • a mixed solution containing bis(fluorosulfonyl)imide, triethylamine hydrofluoride, triethylamine and acetonitrile is pumped into the dispenser 4 by a centrifugal pump 19;
  • the temperature of the evaporator 4 is controlled to be 90° C.
  • the triethylamine and acetonitrile separated in the evaporator 4 are circulated to the differential baffle reactor (i.e., DSR reactor) 31.
  • the triethylamine hydrofluoride separated at the top of the evaporator 4 is circulated to the sulfuryl fluoride synthesis reactor 1 to continue to participate in the reaction.
  • 702 g (about 2.5 mol) of pure bis(fluorosulfonyl)imide triethylamine salt is obtained at the bottom of the evaporator 4.
  • the pure bis(fluorosulfonyl)imide triethylamine salt is pumped into the lithiation reactor 6.
  • 205 g (5 mol) of acetonitrile and 65 g (2.5 mol) of lithium fluoride are added into the lithiation reactor 6.
  • the temperature in the lithiation reactor 6 is adjusted to 20° C.
  • the bis(fluorosulfonyl)imide triethylamine salt reacts with lithium fluoride. After 12 hours, lithium bis(fluorosulfonyl)imide is obtained.
  • the crude lithium bis(fluorosulfonyl)imide product is sent to the first filtering mechanism 7; the first filtering mechanism 7 filters and removes the unreacted lithium fluoride solid in the crude lithium bis(fluorosulfonyl)imide product to obtain the lithium fluoride solid and the filtrate containing lithium bis(fluorosulfonyl)imide, triethylamine hydrofluoride and acetonitrile;
  • the filtrate is sent to the first distillation tower 8, and the temperature of the first distillation tower is controlled to be 90° C.
  • the bis(fluorosulfonyl)imide triethylamine salt in the filtrate is discharged from the first distillation tower 8 and sent to the lithiation reactor 6 to continue to participate in the reaction, and 460 g (about 2.5 mol) of crude bis(fluorosulfonyl)imide lithium is obtained at the bottom of the first distillation tower 8;
  • the crude lithium bis(fluorosulfonyl)imide is treated in the second liquid collecting tank 9 and then sent to the second distillation tower 10.
  • the temperature of the second distillation tower 10 is controlled to be 90° C.
  • the acetonitrile of the crude lithium bis(fluorosulfonyl)imide is evaporated.
  • the acetonitrile discharged from the top of the second distillation tower 10 is condensed in the condenser 20 and then sent to the sulfuryl fluoride synthesis reactor 1 and/or the differential baffle reactor (i.e., DSR reactor) 31 and/or the lithiation reactor 6 for continued use as a solvent.
  • the second distillation tower 10 obtains relatively pure lithium bis(fluorosulfonyl)imide.
  • the relatively pure lithium bis(fluorosulfonyl)imide was sent to a falling film crystallizer 11, and obtained a liquid through melt crystallization, sweating, and melting.
  • the crystallization temperature during the falling film crystallization process was 115°C.
  • the liquid was sent to a crystallization kettle 12 for crystallization, and then sent to a drying kettle 13 for drying.
  • the drying temperature was 80°C, and 438g (about 2.34mol) of lithium bis(fluorosulfonyl)imide was obtained.
  • the purity of lithium bis(fluorosulfonyl)imide was 99.98% after testing, and the yield was 93.7%.
  • triethylamine hydrofluoride obtained after drying in drying kettle 13 is sent to neutralization kettle 14, and potassium hydroxide solution having an excess concentration of 20wt% is added to neutralization kettle 14, and potassium hydroxide and triethylamine hydrochloride are neutralized at room temperature to generate potassium chloride and triethylamine;
  • Phase separation is performed through the first phase separation mechanism 15 to obtain a water phase and an oil phase.
  • the water phase is subjected to triple-effect concentration (sent to a triple-effect concentration evaporator) to obtain potassium fluoride by-product, and 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°C, and the oil phase is dried.
  • the oil phase is sent to a distillation tower 17. After the drying treatment, the oil phase is distilled at normal temperature and pressure.
  • the pure triethylamine gas phase discharged from the top of the distillation tower 17 is condensed and sent to a differential baffle reactor (i.e., a DSR reactor) 31 to continue to participate in the reaction.
  • a differential baffle reactor i.e., a DSR reactor
  • the amount of triethylamine hydrofluoride used was 1512 g (12.5 mol), and the temperature of sulfuryl fluoride synthesis reactor 1 was controlled at 30°C;
  • the pressure in the differential baffled flow reactor (i.e., DSR reactor) 31 is evacuated to 0 MPa, 93 g (2.5 mol) of ammonium fluoride, 1262.5 g (12.5 mol) of triethylamine, and 205 g (5 mol) of acetonitrile are added, and sulfuryl fluoride gas is slowly introduced to ensure that the pressure of the differential baffled flow reactor (i.e., DSR reactor) 31 is about 0.2 MPa, and the temperature is controlled at about 30° C.
  • reaction pressure drops to 0.1 MPa
  • sulfuryl fluoride is continuously added to 0.2 MPa, and the cycle is continued until the pressure drops very slowly or not obviously, indicating that sulfuryl fluoride no longer participates in the reaction, indicating that the reaction is finished, and the reaction time is 5 h, to obtain a mixed solution containing bis(fluorosulfonyl)imide, triethylamine hydrofluoride, triethylamine, and acetonitrile;
  • the temperature in the lithiation reaction kettle 6 is adjusted to 30° C., and after 10 hours, lithium bis(fluorosulfonyl)imide is obtained;
  • the concentration of potassium hydroxide solution is 30wt%
  • lithium bis(fluorosulfonyl)imide 422 g (about 2.25 mol) of lithium bis(fluorosulfonyl)imide was obtained.
  • the purity of lithium bis(fluorosulfonyl)imide was 99.98% after testing, and the yield was 90.26%.
  • the amount of triethylamine hydrofluoride used was 1361 g (11.25 mol), and the temperature of sulfuryl fluoride synthesis reactor 1 was controlled at 40°C;
  • the pressure in the differential baffled flow reactor (i.e., DSR reactor) 31 is evacuated to 0 MPa, 93 g (2.5 mol) of ammonium fluoride, 1262.5 g (12.5 mol) of triethylamine, and 205 g (5 mol) of acetonitrile are added, and sulfuryl fluoride gas is slowly introduced to ensure that the pressure of the differential baffled flow reactor (i.e., DSR reactor) 31 is about 0.2 MPa, and the temperature is controlled at about 30° C.
  • reaction pressure drops to 0.1 MPa
  • sulfuryl fluoride is continuously added to 0.2 MPa, and the cycle is continued until the pressure drops very slowly or not obviously, indicating that sulfuryl fluoride no longer participates in the reaction, indicating that the reaction is finished, and the reaction time is 12 h, to obtain a mixed solution containing bis(fluorosulfonyl)imide, triethylamine hydrofluoride, triethylamine, and acetonitrile;
  • the temperature in the lithiation reaction kettle 6 is adjusted to 30° C., and after 10 hours, lithium bis(fluorosulfonyl)imide is obtained;
  • the concentration of potassium hydroxide solution is 40wt%
  • lithium bis(fluorosulfonyl)imide 415 g (about 2.22 mol) of lithium bis(fluorosulfonyl)imide was obtained.
  • the purity of lithium bis(fluorosulfonyl)imide was 99.98% after testing, and the yield was 88.87%.

Abstract

本发明属于化工技术领域，具体涉及一种双氟磺酰亚胺锂的生产方法及生产系统，该生产方法包括三乙胺氢氟酸盐与硫酰氯在溶剂存在下发生硫酰氟合成反应得到硫酰氟气体，硫酰氟气体与三乙胺和氟化铵在溶剂存在下发生氟化反应，得到双氟磺酰亚胺三乙胺盐，双氟磺酰亚胺三乙胺盐与氟化锂在保护气体气氛且溶剂存在下发生锂化反应，得到双氟磺酰亚胺锂，本申请通过新的合成路线制备双氟磺酰亚胺锂，在整个反应过程中不产生额外的水分，降低了制得的双氟磺酰亚胺锂中水分等杂质的含量。

Description

一种双氟磺酰亚胺锂的生产方法及生产系统 技术领域
本发明属于化工技术领域，具体涉及公开一种双氟磺酰亚胺锂的生产方法及生产系统。
 背景技术
锂离子电池广泛应用于移动电话、电动汽车、电动工具、数码产品等行业，且在“绿色低碳，节能先行”的环保主题下，锂电池作为新能源汽车的储能设备显得尤为重要。锂电池的关键材料包括正极、负极、电解液、隔膜等。目前，六氟磷酸锂(LiPF6)是商业化应用最广泛的锂电池溶质锂盐，然而在使用过程中，六氟磷酸锂存在热稳定性差、易水解等问题，易造成电池容量的快速衰减，并带来极大的安全隐患。双氟磺酰亚胺锂（LiFSI）中的氟离子具有很强的吸电子性，使锂盐的阴阳离子间配位作用减弱，锂离子的活动性增强，故与六氟磷酸锂相较而言，双氟磺酰亚胺锂（LiFSI）具备更佳的耐低温性能、高温性能、电导率、安全性、相容性等方面性能，双氟磺酰亚胺锂具有远超于六氟磷酸锂的物化性能，是能够替代六氟磷酸锂的下一代锂离子电池电解质锂盐。
目前，国内外主要以双氯磺酰亚胺为原料，经氟化剂氟化得到双氟磺酰亚胺，再利用碱金属盐进行锂化，生成双氟磺酰亚胺锂。按照合成原料的不同，可将双氟磺酰亚胺锂的制备方法分为以下三类：
以磺酰胺、二氯亚砜和氯磺酸为原料，反应生成双氯磺酰亚胺，然后以氢氟酸为氟化剂，将双氯磺酰亚胺与碱金属氟化物反应生成双氟磺酰亚胺碱金属盐，再通过锂化得到双氟磺酰亚胺锂，如CN103935970A，但采用该方法制备双氟磺酰亚胺碱金属，制备过程中会生成大量水，且存在工艺繁琐、收率低等缺陷。
以磺酰氯或硫酰氟和氨气为原料，利用HF氟化剂与硫酰氯和氨气反应得到双氯磺酰亚胺，接着进行氟化反应得到双氟磺酰亚胺锂的碱盐，再使其与碱性物质混合，得到双氟磺酰亚胺碱金属盐，碱金属盐与锂化试剂进行置换反应，得到双氟磺酰亚胺锂，如CN104495767A,但采用该方法制备双氟磺酰亚胺锂，需在高压条件下进行，设备投资成本高，且反应过程中会剧烈放热，存在极大安全隐患。
以氟磺酸与尿素为原料，氟磺酸与尿素反应生成双氟磺酰亚胺，双氟磺酰亚胺与氟化锂进行锂化反应生成双氟磺酰亚胺锂，如US5916475A，但采用该方法制备双氟磺酰亚胺锂，所采用的原料氟磺酸的成本较高且具有一定腐蚀性，反应过程中生成的氟化氢也具有强腐蚀性，不仅易造成设备的损坏，同时可能会导致在应用过程中锂离子二次电池的性能降低。
综上所述，传统的双氟磺酰亚胺锂合成工艺存在副反应多、三废多、能耗高、成本高、安全性能低等缺点，且制得的双氟磺酰亚胺锂纯度低，水分等杂质的含量较高，难以达到电池级的标准，不利于双氟磺酰亚胺锂的大规模商业化生产。且上述反应过程中均会产生大量水且物料循环率低，而双氟磺酰亚胺锂在有水环境中在受热或者高温条件下易分解，且生产过程中若引入其他金属离子会给双氟磺酰亚胺锂的性能带来不良影响，因此，为满足电解液的使用要求，双氟磺酰亚胺锂对于水分（≤0.005wt%，详见《YS/T 1302-2019 动力电池电解质双氟磺酰亚胺锂盐》）、金属离子（如K、Fe、Ca、Cu、Mg、Ni等均要求≤0.0005wt%，Cr、Zn、As、Cd、Pb等均要求≤0.0002wt%，Na要求≤0.001wt%，详见《YS/T 1302-2019 动力电池电解质双氟磺酰亚胺锂盐》）等指标有严格规定。
 技术解决方案
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种双氟磺酰亚胺锂的生产方法及生产系统，用于解决采用现有的设备及方法生产双氟磺酰亚胺锂，副反应多、三废多、能耗高、成本高、安全性能低，制得的产品中水分等杂质含量高，纯度低等技术问题。
第一个方面，本申请提供一种双氟磺酰亚胺锂的生产方法，包括：
三乙胺氢氟酸盐与硫酰氯在溶剂存在下发生硫酰氟合成反应得到硫酰氟气体；
硫酰氟气体与三乙胺和氟化铵在溶剂存在下发生氟化反应，得到双氟磺酰亚胺三乙胺盐；
双氟磺酰亚胺三乙胺盐与氟化锂在保护气体气氛且溶剂存在下发生锂化反应，得到双氟磺酰亚胺锂。
反应原理如下：
本申请中，术语“保护气体”包括氮气、氦气、氩气和氖气等。
可选地，所述硫酰氟合成反应的温度为20-45℃，优选为30-45℃；硫酰氟合成反应的时间为1-2h，优选为1.5-2h。
可选地，所述三乙胺氢氟酸盐与硫酰氯的摩尔比为1-3：1，优选为2-3：1。
可选地，所述三乙胺氢氟酸盐与溶剂的摩尔比为1-3：1，优选为2-3：1。
可选地，所述三乙胺与氟化铵的摩尔比为3-5：1，优选为4-5：1。
可选地，所述溶剂选自乙酸乙酯或碳酸二甲酯或乙醚或异丙醚或乙腈或乙醇或丙酮或组合物。
可选地，所述氟化反应的温度为20-60℃，优选为30-60℃；氟化反应的压力为0.1-0.4MPa，优选为0.2-0.4MPa；氟化反应的时间为4-12h，优选为5-12h。
可选地，所述双氟磺酰亚胺三乙胺盐与氟化锂的摩尔比为1：1-3，优选为1：2-3。
可选地，所述锂化反应的温度为20-40℃，优选为30-40℃；锂化反应的时间为8-12h，优选为10-12h。
可选地，所述锂化反应后，还包括提纯步骤。
可选地，所述提纯包括蒸馏、降膜结晶、重结晶和干燥步骤。
可选地，所述降膜结晶过程中结晶温度为115-120℃，优选为118-120℃。
可选地，所述蒸馏的温度为85-95℃，优选为90-95℃。
可选地，所述生产方法还包括：回收干燥过程中得到的溶剂中的三乙胺盐酸盐。
另一个方面，本申请提供如上所述的双氟磺酰亚胺锂的生产方法所采用的生产系统，包括依次连通的硫酰氟合成反应釜、环流反应器、蒸发器和锂化反应釜，所述硫酰氟合成反应釜设置有排液口，所述环流反应器包括若干串联且连通的微分折流反应器，所述锂化反应釜设置有出液端，所述蒸发器上部设置有第一气体出口，所述蒸发器顶部设置有第二气体出口，所述微分折流反应器之间的连通管道上设置有离心泵。
可选地，所述生产系统还包括依次连通的第一过滤机构、第一蒸馏塔、降膜结晶器和结晶釜，所述第一过滤机构设置有进料口和出液端，所述第一过滤机构的进料口连通锂化反应釜的出液端，所述第一过滤机构的出液端连通所述第一蒸馏塔的第一端，所述结晶釜设置有出气口，所述第一蒸馏塔设置有出气口，所述第一蒸馏塔的出气口连通所述锂化反应釜。
可选地，所述生产系统还包括第二蒸馏塔，所述第二蒸馏塔设置于所述第一蒸馏塔与降膜结晶器之间的连通管道上，所述第二蒸馏塔设置有出气口，所述第二蒸馏塔的出气口连通所述硫酰氟合成反应釜和/或微分折流反应器和/或锂化反应釜。
可选地，所述生产系统还包括连通的中和釜和第一分相机构、所述中和釜连通所述结晶釜的出气口，所述第一分相机构设置有水相出口和油相出口，所述第一分相机构的油相出口连通有精馏塔，油相出口与精馏塔之间的连通管道上设置依次有干燥机构和第二分相机构，所述第二分相机构设置有油相出口，所述第二分相机构的油相出口连通所述精馏塔。
可选地，所述生产系统还包括集气机构，所述集气机构设置于硫酰氟合成反应釜与环流反应器之间的连通管道上。
可选地，所述生产系统还包括第二过滤机构，所述第二过滤机构连通所述硫酰氟合成反应釜的排液口，所述第二过滤机构设置有滤液出口，所述第二过滤机构的滤液出口经循环管道连通所述硫酰氟合成反应釜。
可选地，所述第一气体出口连通所述微分折流反应器。
可选地，所述第二气体出口连通硫酰氟合成反应釜，所述第二气体出口与硫酰氟合成反应釜之间的连通管道上设置有冷凝器。
 有益效果
本发明的有益效果为：
本申请通过新的合成路线制备双氟磺酰亚胺锂，在整个反应过程中不产生额外的水分，
降低了制得的双氟磺酰亚胺锂中水分等杂质的含量。
本申请在整个反应过程中未引入含氯原料，提高了产品纯度，制得的双氟磺酰亚胺锂的纯度可达99.95%以上。
采用本申请的方法制备双氟磺酰亚胺锂，中间产物三乙胺盐酸盐能够通过氢氧化钾处理后回收再利用，回收率可达90%以上，实现了循环经济生产。
采用本申请的方法制备双氟磺酰亚胺锂，产品收率高，可达90%以上，生产成本大幅降低，与六氟磷酸锂相较而言，本申请的成本具有显著优势，产品放量生产后，可逐步替代六氟磷酸锂市场。
采用本申请的方法制备双氟磺酰亚胺锂，副产物氯化钾可直接对外销售，原料能够充分转化为经济产品，工业化价值高。
本申请的方法不涉及难处理的危险废弃物，废水量少，易于处理，基本实现了清洁生产。
 附图说明
图1为实施例1的双氟磺酰亚胺锂的生产系统的结构示意图。
附图标记
1-硫酰氟合成反应釜，11-搅拌组件；
2-集气机构；
31-干微分折流反应器；
4-蒸发器；
5-第一集液罐；
6-锂化反应釜，61-搅拌组件；
7-第一过滤机构；
8-第一蒸馏塔；
9-第二集液罐；
10-第二蒸馏塔；
11-降膜结晶器；
12-结晶釜；
13-中和釜；
14-第一分相机构；
15-干燥机构；
16-第二分相机构；
17-精馏塔；
18-第二过滤机构；
19-离心泵；
20-冷凝器。
 本发明的实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
需要说明的是，本实施例中所提供的图示仅以示意方式说明本发明的基本构想，遂图式中仅显示与本发明中有关的组件而非按照实际实施时的组件数目、形状及尺寸绘制，其实际实施时各组件的型态、数量及比例可为一种随意的改变，且其组件布局型态也可能更为复杂。本说明书所附图式所绘示的结构、比例、大小等，均仅用以配合说明书所揭示的内容，以供熟悉此技术的人士了解与阅读，并非用以限定本发明可实施的限定条件，故不具技术上的实质意义，任何结构的修饰、比例关系的改变或大小的调整，在不影响本发明所能产生的功效及所能达成的目的下，均应仍落在本发明所揭示的技术内容得能涵盖的范围内。同时，本说明书中所引用的如“上”、“下”、“顶”、“底”等的用语，亦仅为便于叙述的明了，而非用以限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容下，当亦视为本发明可实施的范畴。应理解的是，方位词“内、外”是指相对于各部件本身的轮廓的内外。
在本发明的描述中，需要理解的是，使用“第一”、“第二”等词语来限定零部件，仅仅是为了便于对相应零部件进行区别，如没有另行声明，上述词语并没有特殊含义，因此不能理解为对本发明保护范围的限制。
本申请提供一种双氟磺酰亚胺锂的生产方法，包括：
三乙胺氢氟酸盐与硫酰氯在溶剂存在且20-45℃温度下发生硫酰氟合成反应1-2h得到硫酰氟气体，溶剂选自乙酸乙酯或碳酸二甲酯或乙醚或异丙醚或乙腈或乙醇或丙酮或其组合物；三乙胺氢氟酸盐与硫酰氯的摩尔比为1-3：1，三乙胺氢氟酸盐与溶剂的摩尔比为1-3：1；
硫酰氟气体与三乙胺和氟化铵在溶剂存在且温度为20-60℃，压力为0.1-0.4MPa条件下发生氟化反应4-12h，得到双氟磺酰亚胺三乙胺盐，三乙胺与氟化铵的摩尔比为3-5：1；溶剂选自乙酸乙酯或碳酸二甲酯或乙醚或异丙醚或乙腈或乙醇或丙酮或其组合物；
双氟磺酰亚胺三乙胺盐与氟化锂在保护气体气氛且溶剂存在下于20-40℃温度下发生锂化反应8-12h，得到双氟磺酰亚胺锂，溶剂选自乙酸乙酯或碳酸二甲酯或乙醚或异丙醚或乙腈或乙醇或丙酮或其组合物；双氟磺酰亚胺三乙胺盐与氟化锂的摩尔比为1：1-3，锂化反应的。
随后于85-95℃温度下蒸馏，接着降膜结晶、重结晶和干燥，降膜结晶过程中结晶温度为115-120℃，回收干燥过程中得到的溶剂中的三乙胺盐酸盐。
另一个方面，本申请提供如上所述的生产方法所采用的生产系统，包括依次连通的硫酰氟合成反应釜、环流反应器、蒸发器和锂化反应釜、第一过滤机构、第一蒸馏塔、第二蒸馏塔、降膜结晶器、结晶釜、中和釜和第一分相机构；
硫酰氟合成反应釜设置有排液口；
环流反应器包括若干串联且连通的微分折流反应器，微分折流反应器之间的连通管道上设置有离心泵；
锂化反应釜设置有出液端；
蒸发器上部设置有第一气体出口，蒸发器顶部设置有第二气体出口，第一气体出口连通微分折流反应器，第二气体出口连通硫酰氟合成反应釜，第二气体出口与硫酰氟合成反应釜之间的连通管道上设置有冷凝器；
第一过滤机构设置有进料口和出液端，第一过滤机构的进料口连通锂化反应釜的出液端，第一过滤机构的出液端连通第一蒸馏塔的第一端；
结晶釜设置有出气口；
第一蒸馏塔设置有出气口，第一蒸馏塔的出气口连通锂化反应釜；
第二蒸馏塔设置有出气口，第二蒸馏塔的出气口连通硫酰氟合成反应釜和/或微分折流反应器和/或锂化反应釜；
中和釜连通结晶釜的出气口；
第一分相机构设置有水相出口和油相出口，第一分相机构的油相出口连通有精馏塔，油相出口与精馏塔之间的连通管道上设置依次有干燥机构和第二分相机构，第二分相机构设置有油相出口，第二分相机构的油相出口连通精馏塔；
硫酰氟合成反应釜与环流反应器之间的连通管道上设置有集气机构；
连通硫酰氟合成反应釜的排液口连通有第二过滤机构，第二过滤机构设置有滤液出口，第二过滤机构的滤液出口经循环管道连通硫酰氟合成反应釜。
下面通过具体的例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行具体的说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
本申请中，纯度按照《YS/T 1302-2019 动力电池电解质双氟磺酰亚胺锂盐》进行检测。
实施例1
请参阅图1，图1为本实施例的双氟磺酰亚胺锂的生产系统的结构示意图，该生产系统用于制备高纯双氟磺酰亚胺锂。
如图1所示，本实施例的双氟磺酰亚胺锂的生产系统包括依次连通的硫酰氟合成反应釜1、集气机构2、环流反应器、蒸发器4、第一集液罐5、锂化反应釜6及第一过滤机构7。
请继续参阅图1，硫酰氟合成反应釜1用于作为合成硫酰氟的反应容器。在硫酰氟合成反应釜1中，三乙胺氢氟酸盐与硫酰氯在溶剂（溶剂选自乙酸乙酯或碳酸二甲酯或乙醚或异丙醚或乙腈或乙醇或丙酮或其组合物）存在下发生硫酰氟合成反应生成硫酰氟气体和三乙胺盐酸盐，得到硫酰氟气体，三乙胺盐酸盐、未充分反应完的三乙胺氢氟酸和溶剂形成的混合物。硫酰氟合成反应釜1设置有温度调节组件（未画出）、进料口（未画出）和第一搅拌组件11，第一搅拌组件11用于使反应原料混合均匀，第一搅拌组件11可以采用搅拌棒等。硫酰氟合成反应釜1可以采用综合搅拌反应釜等。综合搅拌反应釜等为现有技术，此处不再赘述。
请继续参阅图1，集气机构2用于汇集硫酰氟合成反应得到的硫酰氟气体，为后续的氟化反应做准备，集气机构2可以采用集气罐等。集气罐为现有技术，此处不再赘述。
请继续参阅图1，环流反应器包括若干串联且连通的微分折流反应器（即DSR反应器）31，微分折流反应器（即DSR反应器）31之间的连通管道上设置有离心泵19。微分折流反应器31用于作为氟化反应的容器，在微分折流反应器31内，硫酰氟气体、三乙胺和氟化铵在溶剂（溶剂选自乙酸乙酯或碳酸二甲酯或乙醚或异丙醚或乙腈或乙醇或丙酮或其组合物）存在下发生氟化反应生成双氟磺酰亚胺三乙胺盐和三乙胺氢氟酸盐，得到含双氟磺酰亚胺、三乙胺氢氟酸盐、三乙胺及乙腈的混合溶液。
具体而言，通过将若干微分折流反应器（即DSR反应器）31串联且连通，能够使未反应完全的硫酰氟气体、三乙胺和氟化铵在溶剂（溶剂选自乙酸乙酯或碳酸二甲酯或乙醚或异丙醚或乙腈或乙醇或丙酮或其组合物）存在下继续发生氟化反应，能够使氟化反应更彻底。微分折流反应器（即DSR反应器）为现有技术，此处不再赘述。
请继续参阅图1，蒸发器4的第一端与微分折流反应器（即DSR反应器）31之间的连通管道相连通，蒸发器4的第二端连通第一集液罐5的第一端。蒸发器4用于将混合溶液中的三乙胺、溶剂、三乙胺氢氟酸盐自混合液中分离出去。蒸发器4上部设置有第一气体出口，蒸发器4顶部设置有第二气体出口。第一气体出口连通微分折流反应器（即DSR反应器）31，第二气体出口连通硫酰氟合成反应釜1，第二气体出口与硫酰氟合成反应釜1之间的连通管道上设置有冷凝器20。蒸发器4可以采用多效板式蒸发器等，多效板式蒸发器为现有技术，此处不再赘述。
具体而言，通过将蒸发器4的第一气体出口连通微分折流反应器（即DSR反应器）31，蒸发器4的第二气体出口连通硫酰氟合成反应釜1，能够使自第一气体出口排出的三乙胺和溶剂再次进入微分折流反应器（即DSR反应器）31中，实现三乙胺和溶剂的循环利用，使自第二气体出口排出的三乙胺氢氟酸盐再次被送入硫酰氟合成反应釜1中，以使未反应完全的三乙胺氢氟酸盐再次参与硫酰氟合成反应，提高三乙胺氢氟酸盐的利用率。
请继续参阅图1，第一集液罐5的第二端连通锂化反应釜6的第一端，第一集液罐5与锂化反应釜6之间的连通管道上设置有离心泵19。
请继续参阅图1，锂化反应釜6的第一端连通第一集液罐5的第二端，锂化反应釜6的第二端连通第一过滤机构7的进液口。锂化反应釜6用于作为锂化反应的反应容器。在锂化反应釜6中，双氟磺酰亚胺三乙胺盐与氟化锂在保护气体（如氮气、氦气、氩气、氖气等）气氛且溶剂（溶剂选自乙酸乙酯或碳酸二甲酯或乙醚或异丙醚或乙腈或乙醇或丙酮或其组合物）存在下发生锂化反应，得到双氟磺酰亚胺锂。锂化反应釜6设置有温度调节组件（未画出）和第二搅拌组件61，第二搅拌组件61用于使反应原料混合均匀，第二搅拌组件61可以采用搅拌棒等。锂化反应釜6可以采用综合搅拌反应釜等。综合搅拌反应釜为现有技术，此处不再赘述。
请继续参阅图1，第一过滤机构7用于除去未反应的氟化锂。第一过滤机构7位于锂化反应釜6的下方，第一过滤机构7设置有出液端和固体出口，第一过滤机构7可以采用过滤器等。过滤器为现有技术，此处不再赘述。
请继续参阅图1，本实施例的生产系统还包括第一蒸馏塔8、第二集液罐9、第二蒸馏塔10、降膜结晶器11和结晶釜12。
请继续参阅图1，第一蒸馏塔8的第一端连通第一过滤机构7的出液端，第一蒸馏塔8顶部设置有出气口，第一蒸馏塔8底部设置有液体出口，第一蒸馏塔8的气体出口连通硫酰氟合成反应釜1，第一蒸馏塔8的液体出口连通第二集液罐9的第一端。
具体而言，通过将第一蒸馏塔8的出气口连通锂化反应釜6，能够将自双氟磺酰亚胺锂粗品中分离出去的未反应完的双氟磺酰亚胺三乙胺盐送回锂化反应釜6继续参与反应，实现原料的循环利用。
请继续参阅图1，第二蒸馏塔10用于将双氟磺酰亚胺锂粗品中的溶剂分离出去。第二蒸馏塔10的进料口连通第二集液罐9的第二端，第二蒸馏塔10顶部设置有出气口，第二蒸馏塔10底部设置有出液口，第二蒸馏塔10的出气口连通硫酰氟合成反应釜1和/或微分折流反应器（即DSR反应器）31和/或锂化反应釜6，第二蒸馏塔10的出液口连通降膜结晶器11。第二蒸馏塔10的出气口与硫酰氟合成反应釜1和/或微分折流反应器（即DSR反应器）31和/或锂化反应釜6之间的连通管道上设置有冷凝器20和离心泵19。
具体而言，通过将第二蒸馏塔10的出气口连通硫酰氟合成反应釜1和/或微分折流反应器（即DSR反应器）31和/或锂化反应釜6，并在第二蒸馏塔10的出气口与硫酰氟合成反应釜1和/或微分折流反应器（即DSR反应器）31和/或锂化反应釜6之间的连通管道上设置冷凝器20和离心泵19，能够将反应体系中的溶剂送回硫酰氟合成反应釜1和/或微分折流反应器（即DSR反应器）31和/或锂化反应釜6继续使用，实现溶剂的循环利用。
请继续参阅图1，降膜结晶器11用于将去除溶剂后的双氟磺酰亚胺锂粗品进行熔融降膜结晶，得到双氟磺酰亚胺锂精品（液态）。降膜结晶器11的进料端连通第二蒸馏塔10的出液口，降膜结晶器11的出料端连通结晶釜12的第一端。降膜结晶器为现有技术，此处不再赘述。
请继续参阅图1，结晶釜12的第一端连通降膜结晶器11的出料端。结晶釜12设置有出气口，结晶釜12用于将经熔融降膜结晶处理得到的双氟磺酰亚胺锂精品进行结晶。结晶釜为现有技术，此处不再赘述。
请继续参阅图1，本实施例的生产系统还包括中和釜13、第一分相机构14、干燥机构15，第二分相机构16和精馏塔17。
请继续参阅图1，中和釜13的第一端连通结晶釜12的出气口，中和釜13用于作为中和反应容器。在中和釜13中，三乙胺盐酸盐和碱溶液（氢氧化钾溶液和/或氢氧化钠溶液）发生中和反应生成氯化钾和三乙胺。中和釜为现有技术，此处不再赘述。
具体而言，通过设置中和釜13，能够回收中间产品三乙胺盐酸盐，得到氯化钾和三乙胺，在提高三乙胺的回收利用率的同时，副产品氯化钾可直接售卖，提高了经济效益。
请继续参阅图1，第一分相机构14的第一端连通中和釜13的第二端，第一分相机构14用于将中和反应后得到的混合液分离成油相（主要成分为三乙胺）和水相（主要成分为氟化钾水溶液），第一分相机构14采用自动分相器或液液分相离心机，第一分相机构14设置有油相出口和水相出口，第一分相机构14的油相出口连通干燥机构15的第一端。
请继续参阅图1，干燥机构15用于作为油相的干燥容器，干燥机构15设置有进料口，通过进料口能够向干燥机构15内投放物料干燥剂（如氢氧化钾和/或氢氧化钠等）。
请继续参阅图1，第二分相机构16的第一端连通干燥机构15的第二端，第二分相机构16用于将经干燥处理后的油相进行分相处理，第二分相机构16采用自动分相器或液液分相离心机，第二分相机构16设置有油相出口和水相出口，第二分相机构16的油相出口连通精馏塔的第一端。
请继续参阅图1，精馏塔17用于对三乙胺油相进行分离提纯，去除三乙胺油相中的杂质，精馏塔17顶部设置有气体出口，精馏塔17的气体出口连通微分折流反应器（即DSR反应器）31，精馏塔17的气体出口与微分折流反应器（即DSR反应器）31之间的连通管道上设置有冷凝器20和离心泵19。
具体而言，通过将精馏塔17的气体出口连通微分折流反应器（即DSR反应器）31，并在精馏塔17的气体出口与微分折流反应器（即DSR反应器）31之间的连通管道上设置冷凝器20和离心泵19，能够将分离提纯后的三乙胺冷凝后被离心泵19泵送至微分折流反应器（即DSR反应器）31中，实现三乙胺的回收再利用。
请继续参阅图1，硫酰氟合成反应釜1的底部连通有第二过滤机构18。第二过滤机构18用于对硫酰氟反应后得到的三乙胺盐酸盐、未充分反应完的三乙胺氢氟酸和溶剂形成的混合物进行过滤处理。第二过滤机构18位于硫酰氟合成反应釜1的下方，第二过滤机构18设置有滤液出口和固体出口，第二过滤机构18的滤液出口经循环管道连通硫酰氟合成反应釜1，循环管道上设置有离心泵19。第二过滤机构18可以采用过滤器。过滤器为现有技术，此处不再赘述。
实施例2
采用实施例1的生产系统制备高纯双氟磺酰亚胺锂，具体步骤如下：
S1.在硫酰氟合成反应釜1中加入205g(5mol)乙腈和1210g（10mol）三乙胺氢氟酸盐，控制温度在20℃，加入675g（5mol）硫酰氯，充分搅拌反应1h后，得到硫酰氟气体、三乙胺盐酸盐和未充分反应完的三乙胺氢氟酸和乙腈的混合物；
硫酰氟气体经集气机构2处理后通过管道流向微分折流反应器（即DSR反应器）31；
三乙胺盐酸盐和未充分反应完的三乙胺氢氟酸和乙腈的混合物则经第二过滤机构18过滤处理，得到三乙胺盐酸盐固体和含三乙胺氢氟酸、乙腈的滤液，三乙胺盐酸盐固体进行人工回收处理，滤液被离心泵19泵送至硫酰氟合成反应釜1继续参与反应；
S2.将微分折流反应器（即DSR反应器）31内压力抽至-0.1Mpa后，加入93g（2.5mol）氟化铵，1010g（10mol）三乙胺、205g(5mol)乙腈，缓慢通入硫酰氟气体保证微分折流反应器（即DSR反应器）31的压力在0.3Mpa左右，控制温度在20℃左右，当反应压力降至0.2Mpa时，继续补加硫酰氟至0.3Mpa，一直循环，直至压力下降很慢或不明显表明硫酰氟不再参与反应，表明反应结束，反应时间为4h，得到含双氟磺酰亚胺、三乙胺氢氟酸盐、三乙胺、乙腈的混合溶液；
含双氟磺酰亚胺、三乙胺氢氟酸盐、三乙胺、乙腈的混合溶液被离心泵19泵送发器4中；
控制蒸发器4的温度为90℃，蒸发器4中分离出的三乙胺、乙腈循环至微分折流反应器（即DSR反应器）31中，蒸发器4的塔顶分离出的三乙胺氢氟酸盐循环至硫酰氟合成反应釜1继续参与反应，蒸发器4的塔底得到702g（约2.5mol）纯双氟磺酰亚胺三乙胺盐。
S3.纯双氟磺酰亚胺三乙胺盐经第一集液罐5处理后被泵送至锂化反应釜6中，在氮气保护下，向锂化反应釜6中加入205g(5mol)乙腈和65g（2.5mol）的氟化锂，调节锂化反应釜6内温度为20℃，双氟磺酰亚胺三乙胺盐和氟化锂发生反应，12h后，得到双氟磺酰亚胺锂；
双氟磺酰亚胺锂粗品被送至第一过滤机构7；第一过滤机构7过滤除去双氟磺酰亚胺锂粗品中的未反应氟化锂固体，得到氟化锂固体和含双氟磺酰亚胺锂、三乙胺氢氟酸盐及乙腈的滤液；
人工回收氟化锂，并将氟化锂加入锂化反应釜6中继续参与反应；
滤液被送至第一蒸馏塔8中，控制第一蒸馏塔的温度为90℃，经第一蒸馏塔8分离提纯后，滤液中的双氟磺酰亚胺三乙胺盐自第一蒸馏塔8排出后被送至锂化反应釜6中继续参与反应，第一蒸馏塔8塔底得到460g（约2.5mol）双氟磺酰亚胺锂粗品；
双氟磺酰亚胺锂粗品经第二集液罐9处理后被送入第二蒸馏塔10中，控制第二蒸馏塔10的温度为90℃，双氟磺酰亚胺锂粗品的乙腈被蒸出，自第二蒸馏塔10塔顶排出的乙腈经冷凝器20冷凝后被送至硫酰氟合成反应釜1和/或微分折流反应器（即DSR反应器）31和/或锂化反应釜6中作为溶剂继续使用；第二蒸馏塔10得到较纯双氟磺酰亚胺锂；
较纯双氟磺酰亚胺锂被送至降膜结晶器11中，经熔融结晶、发汗、熔化，得到液体，降膜结晶过程中结晶温度为115℃；液体送至结晶釜12中进行结晶，接着被送至干燥釜13中进行干燥，干燥温度为80℃，得到438g(约2.34mol)双氟磺酰亚胺锂，经检测双氟磺酰亚胺锂的纯度为99.98%，收率为93.7%；
S4.三乙胺氢氟酸盐的回收：经干燥釜13干燥处理后得到的三乙胺氢氟酸盐被送至中和釜14中，向中和釜14中加入过量浓度为20wt%的氢氧化钾溶液，氢氧化钾与三乙胺盐酸盐在常温下发生中和反应生成氯化钾和三乙胺；
通过第一分相机构15进行分相处理，得到水相和油相，水相进行三效浓缩（送至三效浓缩蒸发器中）得到氟化钾副产品，油相被送至干燥釜16中，向干燥釜16中加入氢氧化钾，控制干燥釜16的温度为60℃，对油相进行干燥处理，干燥处理后油相被送至精馏塔17，干燥处理后油相在常温常压下进行精馏，自精馏塔17塔顶排出的纯三乙胺气相经冷凝后被送至微分折流反应器（即DSR反应器）31继续参与反应。
实施例3
本实施例与实施例2的区别在于：
三乙胺氢氟酸盐的用量为1512g（12.5mol），硫酰氟合成反应釜1的温度控制在30℃；
将微分折流反应器（即DSR反应器）31内压力抽至0Mpa后，加入93g（2.5mol）氟化铵，1262.5g（12.5mol）三乙胺、205g(5mol)乙腈，缓慢通入硫酰氟气体保证微分折流反应器（即DSR反应器）31的压力在0.2Mpa左右，控制温度在30℃左右，当反应压力降至0.1Mpa时，继续补加硫酰氟至0.2Mpa，一直循环，直至压力下降很慢或不明显表明硫酰氟不再参与反应，表明反应结束，反应时间为5h，得到含双氟磺酰亚胺、三乙胺氢氟酸盐、三乙胺、乙腈的混合溶液；
蒸发器4的塔底得到694g（约2.46mol）纯双氟磺酰亚胺三乙胺盐；
调节锂化反应釜6内温度为30℃，10h后，得到双氟磺酰亚胺锂；
第一蒸馏塔8塔底得到448g（约2.4mol）双氟磺酰亚胺锂粗品；
控制第二蒸馏塔10的温度为100℃；
氢氧化钾溶液的浓度为30wt%；
得到422g(约2.25mol)双氟磺酰亚胺锂，经检测双氟磺酰亚胺锂的纯度为99.98%，收率为90.26%。
实施例4
本实施例与实施例2的区别在于：
三乙胺氢氟酸盐的用量为1361g（11.25mol），硫酰氟合成反应釜1的温度控制在40℃；
将微分折流反应器（即DSR反应器）31内压力抽至0Mpa后，加入93g（2.5mol）氟化铵，1262.5g（12.5mol）三乙胺、205g(5mol)乙腈，缓慢通入硫酰氟气体保证微分折流反应器（即DSR反应器）31的压力在0.2Mpa左右，控制温度在30℃左右，当反应压力降至0.1Mpa时，继续补加硫酰氟至0.2Mpa，一直循环，直至压力下降很慢或不明显表明硫酰氟不再参与反应，表明反应结束，反应时间为12h，得到含双氟磺酰亚胺、三乙胺氢氟酸盐、三乙胺、乙腈的混合溶液；
蒸发器4的塔底得到688g（约2.46mol）纯双氟磺酰亚胺三乙胺盐；
调节锂化反应釜6内温度为30℃，10h后，得到双氟磺酰亚胺锂；
第一蒸馏塔8塔底得到436g（约2.33mol）双氟磺酰亚胺锂粗品；
控制第二蒸馏塔10的温度为95℃；
氢氧化钾溶液的浓度为40wt%；
得到415g(约2.22mol)双氟磺酰亚胺锂，经检测双氟磺酰亚胺锂的纯度为99.98%，收率为88.87%。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (10)

  1. 一种双氟磺酰亚胺锂的生产方法，其特征在于，包括：
    三乙胺氢氟酸盐与硫酰氯在溶剂存在下发生硫酰氟合成反应得到硫酰氟气体；
    硫酰氟气体与三乙胺和氟化铵在溶剂存在下发生氟化反应，得到双氟磺酰亚胺三乙胺盐；
    双氟磺酰亚胺三乙胺盐与氟化锂在保护气体气氛且溶剂存在下发生锂化反应，得到双氟磺酰亚胺锂。
  2. 根据权利要求1所述的生产方法，其特征在于，所述硫酰氟合成反应的温度为20-45℃，硫酰氟合成反应的时间为1-2h；
    和/或，所述三乙胺氢氟酸盐与硫酰氯的摩尔比为1-3：1；
    和/或，所述三乙胺氢氟酸盐与溶剂的摩尔比为1-3：1；
    和/或，所述三乙胺与氟化铵的摩尔比为3-5：1；
    和/或，所述溶剂选自乙酸乙酯或碳酸二甲酯或乙醚或异丙醚或乙腈或乙醇或丙酮或组合物；
    和/或，所述氟化反应的温度为20-60℃，氟化反应的压力为0.1-0.4MPa，氟化反应的时间为4-12h；
    和/或，所述双氟磺酰亚胺三乙胺盐与氟化锂的摩尔比为1：1-3；
    和/或，所述锂化反应的温度为20-40℃，锂化反应的时间为8-12h。
  3. 根据权利要求1所述的生产方法，其特征在于，所述锂化反应后，还包括提纯步骤。
  4. 根据权利要求3所述的生产方法，其特征在于，所述提纯包括蒸馏、降膜结晶、重结晶和干燥步骤。
  5. 根据权利要求4所述的生产方法，其特征在于，所述蒸馏的温度为85-95℃；
    和/或，所述降膜结晶过程中结晶温度为115-120℃；
    和/或，还包括：回收干燥过程中得到的溶剂中的三乙胺盐酸盐。
  6. 一种双氟磺酰亚胺锂的生产系统，其特征在于，包括依次连通的硫酰氟合成反应釜、环流反应器、蒸发器和锂化反应釜，所述硫酰氟合成反应釜设置有排液口，所述环流反应器包括若干串联且连通的微分折流反应器，所述锂化反应釜设置有出液端，所述蒸发器上部设置有第一气体出口，所述蒸发器顶部设置有第二气体出口，所述微分折流反应器之间的连通管道上设置有离心泵。
  7. 根据权利要求6所述的生产系统，其特征在于，还包括依次连通的第一过滤机构、第一蒸馏塔、降膜结晶器和结晶釜，所述第一过滤机构设置有进料口和出液端，所述第一过滤机构的进料口连通锂化反应釜的出液端，所述第一过滤机构的出液端连通所述第一蒸馏塔的第一端，所述结晶釜设置有出气口，所述第一蒸馏塔设置有出气口，所述第一蒸馏塔的出气口连通所述锂化反应釜。
  8. 根据权利要求7所述的生产系统，其特征在于，还包括第二蒸馏塔，所述第二蒸馏塔设置于所述第一蒸馏塔与降膜结晶器之间的连通管道上，所述第二蒸馏塔设置有出气口，所述第二蒸馏塔的出气口连通所述硫酰氟合成反应釜和/或微分折流反应器和/或锂化反应釜。
  9. 根据权利要求7所述的生产系统，其特征在于，还包括连通的中和釜和第一分相机构、所述中和釜连通所述结晶釜的出气口，所述第一分相机构设置有水相出口和油相出口，所述第一分相机构的油相出口连通有精馏塔，油相出口与精馏塔之间的连通管道上设置依次有干燥机构和第二分相机构，所述第二分相机构设置有油相出口，所述第二分相机构的油相出口连通所述精馏塔。
  10. 根据权利要求1所述的生产系统，其特征在于，还包括集气机构，所述集气机构设置于硫酰氟合成反应釜与环流反应器之间的连通管道上；
    和/或，还包括第二过滤机构，所述第二过滤机构连通所述硫酰氟合成反应釜的排液口，所述第二过滤机构设置有滤液出口，所述第二过滤机构的滤液出口经循环管道连通所述硫酰氟合成反应釜；
    和/或，所述第一气体出口连通所述微分折流反应器；
    和/或，所述第二气体出口连通硫酰氟合成反应釜，所述第二气体出口与硫酰氟合成反应釜之间的连通管道上设置有冷凝器。
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