CN111675678B - Deep drying and water removing method for ionic liquid - Google Patents
Deep drying and water removing method for ionic liquid Download PDFInfo
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- CN111675678B CN111675678B CN202010611792.1A CN202010611792A CN111675678B CN 111675678 B CN111675678 B CN 111675678B CN 202010611792 A CN202010611792 A CN 202010611792A CN 111675678 B CN111675678 B CN 111675678B
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/36—Azeotropic distillation
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- C07C303/42—Separation; Purification; Stabilisation; Use of additives
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2202/00—Details concerning evaporation, distillation or condensation
- B01D2202/20—Use of an ionic liquid in the separation process
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a drying method of ionic liquid, in particular to a deep drying and water removing method for ionic liquid. The method comprises the following steps: mixing the ionic liquid to be dried with a water removal agent, and carrying out azeotropic water carrying; wherein the water removing agent is one of n-butyl acetate, isoamyl acetate, ethyl propionate and n-propyl propionate. According to the invention, the purpose of reducing the water content of the ionic liquid is realized by selecting the specific water removal agent and the specific water removal process, and the obtained ionic liquid with low water content has high purity and high yield. The deep drying and water removing method can reduce the water content of the ionic liquid to the maximum extent, can avoid the residue of a water removing agent to the maximum extent, and ensures the purity of the ionic liquid; meanwhile, the yield of the ionic liquid with low water content is extremely high. The deep drying and water removing method has the advantages of simple process, simple equipment, high drying efficiency, low cost and good application prospect.
Description
Technical Field
The invention relates to a drying method of ionic liquid, in particular to a deep drying and water removing method for ionic liquid.
Background
In the prior art, the water content of the lithium ion battery electrolyte is generally required to be lower than 20 ppm. The ionic liquid is used as a component of the lithium ion battery electrolyte, and has excellent performances such as high pressure resistance and flame retardance in the lithium ion battery electrolyte, so that the water content of the ionic liquid needs to be reduced to below 20ppm before the electrolyte is prepared. At present, the conventional industrial water removal method for ionic liquid mainly comprises the following two methods: firstly, mixing ionic liquid to be dried with dimethylbenzene, and carrying out azeotropic distillation to achieve the purpose of reducing the water content of the ionic liquid; however, the method is easy to cause xylene impurities to be doped in the ionic liquid, and the purity of the ionic liquid is influenced. Adding a molecular sieve into the ionic liquid to be dried so as to achieve the aim of removing water; however, the method can only process the ionic liquid with low water content, and the molecular sieve adsorbs a large amount of expensive ionic liquid, so that the recovery rate of the ionic liquid is low, and the cost is very high.
In summary, the following two problems exist in the deep drying and water removal method for ionic liquid: firstly, when the ionic liquid with high water content is used for removing water, a water removing agent pollutes the ionic liquid; ② when the ionic liquid with low water content is used for dewatering, the molecular sieve absorbs a large amount of expensive ionic liquid, thus leading to low recovery rate and high cost of the ionic liquid.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention provides a deep drying and water removing method for ionic liquid, which aims to solve the problems of low purity and low yield of the ionic liquid.
Specifically, the deep drying and water removing method comprises the following steps: mixing the ionic liquid to be dried with a water removal agent, and carrying out azeotropic water carrying;
wherein the water removal agent is one of n-butyl acetate, isoamyl acetate, ethyl propionate and n-propyl propionate.
In the prior art, the ionic liquid to be dried and a conventional water removal agent are adopted for azeotropic water carrying, so that the aim of reducing the water content of the ionic liquid is fulfilled. However, the ionic liquid after azeotropic water-carrying with a conventional water removal agent has the condition of water removal agent residue, and the purity of the ionic liquid is seriously influenced; in addition, the water removal agent can adsorb a part of ionic liquid in the process of azeotropic water carrying, so that the yield of the ionic liquid is low. The invention has the advantages that the specific water removal agent is beneficial to avoiding the situations of water removal agent residue and ionic liquid adsorption; specifically, the invention finds that the n-butyl acetate, the isoamyl acetate, the ethyl propionate or the n-propyl propionate are taken as the dehydrating agent, so that the residual of the dehydrating agent can be effectively prevented and the dehydrating agent is effectively prevented from adsorbing the ionic liquid under the condition of ensuring the low water content of the ionic liquid; namely, the dehydrating agent and the ionic liquid to be dried are adopted to carry out azeotropic water carrying and drying dehydration, so that the purity and the yield of the ionic liquid can be effectively improved.
The invention further researches the selection of the ionic liquid and discovers that when the water content of the ionic liquid is not more than 1 wt%, the water removal agent can be fully mixed with residual water in the ionic liquid, and the water removal agent is not easy to remain in the process of carrying water by azeotropy and is not easy to adsorb the ionic liquid. Further, when the water content of the ionic liquid is 0.3-1 wt%, the drying and dewatering efficiency is high, the ionic liquid is less affected by a dewatering agent, and the purity is higher.
Preferably, the ionic liquid is a solvent or additive of the lithium ion battery electrolyte;
further, the ionic liquid is one of imidazole ionic liquid, pyridine ionic liquid, piperidine ionic liquid and pyrrolidine ionic liquid;
further, the ionic liquid is one of 1-ethyl-3-methylimidazole trifluoromethanesulfonate, N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt and N-ethylpyridine bis (trifluoromethanesulfonyl) imide salt.
Preferably, when the ionic liquid is 1-ethyl-3-methylimidazole trifluoromethanesulfonate, the water removal agent is n-butyl acetate, isoamyl acetate, ethyl propionate or n-propyl propionate;
preferably, when the ionic liquid is N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, the water removal agent is N-butyl acetate, isoamyl acetate, ethyl propionate or N-propyl propionate;
preferably, when the ionic liquid is N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, the water scavenger is N-butyl acetate, isoamyl acetate, ethyl propionate or N-propyl propionate;
preferably, when the ionic liquid is N-ethylpyridine bis (trifluoromethanesulfonyl) imide salt, the water scavenger is N-butyl acetate, isoamyl acetate, ethyl propionate or N-propyl propionate.
In addition, the invention further researches the ratio of the ionic liquid to the water removing agent, and discovers that when the mass ratio of the ionic liquid to the water removing agent is 20-100: 1 hour (at this time, the water content of the ionic liquid is preferably 0.3-1 wt%), so that the ionic liquid can be prevented from being polluted by the dehydrating agent.
Preferably, when the mass ratio of the ionic liquid to the water removing agent is 20-50: 1, it is particularly preferable.
In order to further improve the purity and yield of the ionic liquid, the invention simultaneously provides the following preferred schemes:
preferably, the deep drying and water removing method comprises the following steps:
1) adding an ionic liquid to be dried and a water removing agent into a reactor, heating under an inert atmosphere condition, and collecting the water removing agent and an azeotrope thereof by a condensing tube after the temperature of the top of the reactor is stabilized at 50-90 ℃; when no obvious liquid falls in the condensing tube and the gas phase temperature begins to decrease, reducing the pressure to the relative vacuum degree of 80000-100000 Pa, and continuously collecting the water removal agent and the azeotrope thereof until the water content of the ionic liquid is lower than 100 ppm;
2) and continuously introducing inert gas into the ionic liquid, heating until the temperature at the top of the reactor is stabilized at 50-90 ℃, then decompressing and discharging the inert gas in the reactor, and continuously collecting the water removing agent and the azeotrope thereof until the water content of the ionic liquid is lower than 20 ppm.
In the invention, the ionic liquid is deeply dried and dehydrated by adopting the process, no dehydrating agent residue exists in the obtained ionic liquid with low water content, and the yield is very high.
In the technical scheme, the azeotrope consists of a water removal agent and water.
In order to avoid the residual of the dehydrating agent to the maximum extent and improve the yield of the ionic liquid, the deep drying and dehydrating method is optimized; the method comprises the following specific steps:
preferably, the inert atmosphere and the inert gas are the same or different and are respectively and independently selected from one or more of nitrogen, helium and argon.
Preferably, in the step 1), when no liquid drops down in the condensing tube within 1 minute and the gas phase temperature starts to decrease, the pressure is reduced to a relative vacuum degree of 80000 to 100000 Pa.
Preferably, in the step 2), the introduction amount of the inert gas is 0.5-2.0L/min based on 1 kg of the ionic liquid.
As a better technical scheme, the deep drying and water removing method comprises the following steps:
1) adding an ionic liquid with the water content of not more than 1 wt% and a water removal agent into a reactor, heating under the inert atmosphere condition, and collecting the water removal agent and an azeotrope thereof by a condensation pipe after the temperature at the top of the reactor is stabilized at 50-90 ℃; when no obvious liquid falls in the condensation pipe within 1 minute and the gas phase temperature begins to drop, reducing the pressure to the relative vacuum degree of 80000-100000 Pa, and continuously collecting the water removal agent and the azeotrope thereof until the water content of the ionic liquid is lower than 100 ppm;
wherein the ionic liquid is one of 1-ethyl-3-methylimidazole trifluoromethanesulfonate, N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt and N-ethylpyridine bis (trifluoromethanesulfonyl) imide salt;
the water removal agent is one of n-butyl acetate, isoamyl acetate, ethyl propionate and n-propyl propionate;
the mass ratio of the ionic liquid to the water removing agent is 20-50: 1;
2) and (2) continuously introducing inert gas into the ionic liquid according to 0.5-2.0L/min by taking 1 kg of the ionic liquid, heating until the temperature at the top of the reactor is stabilized at 50-90 ℃, then reducing the pressure to the relative vacuum degree of 80000-100000 Pa, discharging the inert gas in the reactor by adopting a vacuumizing mode, and continuously collecting the water removing agent and the azeotrope thereof until the water content of the ionic liquid is lower than 20 ppm.
In a specific embodiment, the reactor is a batch distillation apparatus.
The invention has the beneficial effects that:
(1) according to the invention, the purpose of reducing the water content of the ionic liquid is realized by selecting a specific water removal agent and a specific water removal process, and the obtained ionic liquid with low water content has high purity and high yield; wherein the water content of the ionic liquid is lower than 20ppm, the yield is more than 97%, and the purity is more than 99.6%; the ionic liquid with the mass degree is applied to the lithium ion battery electrolyte, and the ionic conductivity is high and the cycle performance is excellent.
(2) The deep drying and dewatering method has the advantages of simple and convenient process, simple equipment, high drying efficiency and low cost.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
Example 1
The embodiment provides a deep drying and water removing method for ionic liquid, which comprises the following steps:
(1) adding 1000g of N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide ionic liquid with the water content of 0.5 wt% and 50g of N-propyl propionate into an intermittent rectification device, stirring under the protection of argon, heating to the temperature of 90 ℃ at the top of the tower, starting a cooling device at the same time, setting the cooling temperature to be 0 ℃, and collecting the N-propyl propionate and azeotrope thereof. When no liquid drops into the collecting bottle within 1 minute and the gas phase temperature begins to drop, connecting a vacuum pump, controlling the relative vacuum degree of 90000Pa, and continuously collecting n-propyl propionate and the azeotrope thereof until the water content of the ionic liquid is lower than 100 ppm;
2) introducing argon gas into the ionic liquid of the intermittent rectification device at the flow rate of 0.5L/min, heating to the temperature of 90 ℃ at the top of the tower, starting the cooling device at the same time, setting the cooling temperature to be 0 ℃, connecting the vacuum pump, controlling the relative vacuum degree to be 80000Pa, discharging gas in the rectification device, continuously collecting n-propyl propionate and an azeotrope thereof until the water content of the ionic liquid is lower than 20ppm, and obtaining 970.2g of the ionic liquid.
In this example, the yield of the ionic liquid obtained after drying was 97.02%, and the purity was 99.71%.
Example 2
The embodiment provides a deep drying and water removing method for ionic liquid, which comprises the following steps:
(1) adding 1000g of N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt ionic liquid with the water content of 0.8 wt% and 40g of N-butyl acetate into an intermittent rectification device, stirring under the protection of helium, heating to the temperature of 50 ℃ at the top of the tower, starting a cooling device at the same time, setting the cooling temperature to be 0 ℃, and collecting N-butyl acetate and azeotrope thereof. When no liquid drops into the collecting bottle within 1 minute and the gas phase temperature begins to drop, connecting a vacuum pump, controlling the relative vacuum degree of 80000Pa, and continuously collecting n-butyl acetate and an azeotrope thereof until the water content of the ionic liquid is lower than 100 ppm;
2) introducing helium into the ionic liquid of the intermittent rectification device at the flow rate of 1.0L/min, heating to the temperature of 50 ℃ at the top of the tower, starting the cooling device at the same time, setting the cooling temperature to 0 ℃, connecting the vacuum pump, controlling the relative vacuum degree to be 90000Pa, discharging gas in the rectification device, continuously collecting n-butyl acetate and azeotrope thereof until the water content of the ionic liquid is lower than 20ppm, and obtaining 978.0g of the ionic liquid.
In this example, the yield of the ionic liquid obtained after drying was 97.80%, and the purity was 99.66%.
Example 3
The embodiment provides a deep drying and water removing method for ionic liquid, which comprises the following steps:
1) adding 1000g of N-ethylpyridine bis (trifluoromethanesulfonyl) imide salt ionic liquid with the water content of 0.3 wt% and 30g of ethyl propionate into a batch rectification device, stirring under the protection of nitrogen, heating to the temperature of 80 ℃ at the top of the tower, starting a cooling device at the same time, setting the cooling temperature to be 0 ℃, and collecting the ethyl propionate and an azeotrope thereof. When no liquid drops into the collecting bottle within 1 minute and the gas phase temperature begins to drop, connecting a vacuum pump, controlling the relative vacuum degree to be 95000Pa, and continuously collecting ethyl propionate and the azeotrope thereof until the water content of the ionic liquid is lower than 100 ppm;
2) introducing argon gas into the ionic liquid of the intermittent rectification device at the flow rate of 0.9L/min, heating to the temperature of 85 ℃ at the top of the tower, starting the cooling device at the same time, setting the cooling temperature to 0 ℃, connecting a vacuum pump, controlling the relative vacuum degree to be 85000Pa, discharging gas in the rectification device, continuously collecting ethyl propionate and an azeotrope thereof until the water content of the ionic liquid is lower than 20ppm, and obtaining 979.6g of the ionic liquid.
In this example, the yield of the ionic liquid obtained after drying was 97.96%, and the purity was 99.60%.
Example 4
The embodiment provides a deep drying and water removing method for ionic liquid, which comprises the following steps:
1) adding 1000g of 1-ethyl-3-methylimidazole trifluoromethane sulfonate ionic liquid with the water content of 1 wt% and 20g of isoamyl acetate into a batch rectification device, stirring under the protection of nitrogen, heating to 70 ℃ at the tower top temperature, starting a cooling device at the same time, setting the cooling temperature to be 0 ℃, and collecting the isoamyl acetate and azeotrope thereof. When no liquid drops into the collecting bottle within 1 minute and the gas phase temperature begins to drop, reducing the temperature of the rectifying device, connecting a vacuum pump, controlling the relative vacuum degree to be 100000Pa, and continuously collecting isoamyl acetate and azeotrope thereof until the water content of the ionic liquid is lower than 100 ppm;
2) introducing nitrogen into the ionic liquid of the intermittent rectification device at the flow rate of 2.0L/min, heating to the tower top temperature of 70 ℃, simultaneously starting the cooling device, setting the cooling temperature to 0 ℃, connecting a vacuum pump, controlling the relative vacuum degree to be 100000Pa, discharging gas in the rectification device, continuously collecting isoamyl acetate and azeotrope thereof until the water content of the ionic liquid is lower than 20ppm, and obtaining 980.1g of the ionic liquid.
In this example, the yield of the ionic liquid obtained after drying was 98.01%, and the purity was 99.63%.
Comparative example 1
This comparative example provides a deep drying dehydration process for ionic liquids, differing from example 1 only in that: the n-propyl propionate was replaced with xylene.
In this comparative example, the yield of the ionic liquid obtained after drying was 96.18%, and the purity was 98.82%.
Comparative example 2
This comparative example provides a deep drying water removal process for ionic liquids, which differs from example 1 only in that: in the step 1), adding 1000g of N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide ionic liquid with the water content of 0.5 wt% and 50g of N-propyl propionate into an intermittent rectification device, stirring under the protection of argon, heating to the temperature of 90 ℃ at the top of the tower, starting a cooling device at the same time, setting the cooling temperature to be 0 ℃, and collecting the N-propyl propionate and an azeotrope thereof until the water content of the ionic liquid is lower than 100 ppm;
in this comparative example, the yield of the ionic liquid obtained after drying was 97.6%, and the purity was 99.40%.
Comparative example 3
This comparative example provides a deep drying water removal process for ionic liquids, which differs from example 1 only in that: and 2) introducing argon into the ionic liquid of the intermittent rectifying device at the flow rate of 0.5L/min, heating to raise the temperature to 90 ℃ at the top of the tower, starting the cooling device at the same time, setting the cooling temperature to be 0 ℃, connecting a vacuum pump, controlling the relative vacuum degree to be 50000Pa, discharging gas in the rectifying device, and continuously collecting n-propyl propionate and azeotrope thereof until the water content of the ionic liquid is lower than 20 ppm.
In this comparative example, the yield of the ionic liquid obtained after drying was 97.7% and the purity was 99.14%.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (7)
1. The deep drying and water removing method for the ionic liquid is characterized in that the ionic liquid to be dried and a water removing agent are mixed and then subjected to azeotropic water carrying;
wherein the water removing agent is one of n-butyl acetate, isoamyl acetate, ethyl propionate and n-propyl propionate;
the water content of the ionic liquid is 0.3-1 wt%; the ionic liquid is one of 1-ethyl-3-methylimidazole trifluoromethanesulfonate, N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt and N-ethylpyridine bis (trifluoromethanesulfonyl) imide salt;
the mass ratio of the ionic liquid to the water removing agent is 20-50: 1.
2. the deep drying water removal method of claim 1, wherein when the ionic liquid is 1-ethyl-3-methylimidazole trifluoromethanesulfonate, the water removal agent is n-butyl acetate, isoamyl acetate, ethyl propionate or n-propyl propionate;
or, when the ionic liquid is N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, the water removal agent is N-butyl acetate, isoamyl acetate, ethyl propionate or N-propyl propionate;
or, when the ionic liquid is N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, the water removal agent is N-butyl acetate, isoamyl acetate, ethyl propionate or N-propyl propionate;
or when the ionic liquid is N-ethylpyridine bis (trifluoromethanesulfonyl) imide salt, the water removal agent is N-butyl acetate, isoamyl acetate, ethyl propionate or N-propyl propionate.
3. The method of claim 1 or 2, comprising the steps of:
1) adding an ionic liquid to be dried and a water removing agent into a reactor, heating under an inert atmosphere condition, and collecting the water removing agent and an azeotrope thereof by a condensing tube after the temperature of the top of the reactor is stabilized at 50-90 ℃; when no obvious liquid falls in the condensation pipe and the gas phase temperature begins to drop, reducing the pressure to the relative vacuum degree of 80000-100000 Pa, and continuously collecting the water removal agent and the azeotrope thereof until the water content of the ionic liquid is lower than 100 ppm;
2) and continuously introducing inert gas into the ionic liquid, heating until the temperature at the top of the reactor is stabilized at 50-90 ℃, then decompressing and discharging the inert gas in the reactor, and continuously collecting the water removing agent and the azeotrope thereof until the water content of the ionic liquid is lower than 20 ppm.
4. The method for deep drying and water removal as claimed in claim 3, wherein the inert atmosphere and the inert gas are the same or different and are each independently selected from one or more of nitrogen, helium and argon.
5. The method for deeply drying and removing water as claimed in claim 3, wherein in the step 1), when no liquid is dropped down obviously in the condensing tube within 1 minute and the temperature of the gas phase begins to drop, the relative vacuum degree is reduced to 80000-100000 Pa.
6. The method of claim 3, wherein the inert gas is introduced at a rate of 0.5 to 2.0L/min per 1 kg of the ionic liquid in step 2).
7. The method of deep drying water removal as set forth in claim 1, comprising the steps of:
1) adding an ionic liquid with the water content of not more than 1 wt% and a water removal agent into a reactor, heating under the inert atmosphere condition, and collecting the water removal agent and an azeotrope thereof by a condensation pipe after the temperature at the top of the reactor is stabilized at 50-90 ℃; when no obvious liquid falls in the condensation pipe within 1 minute and the gas phase temperature begins to drop, reducing the pressure to the relative vacuum degree of 80000-100000 Pa, and continuously collecting the water removal agent and the azeotrope thereof until the water content of the ionic liquid is lower than 100 ppm;
wherein the ionic liquid is one of 1-ethyl-3-methylimidazole trifluoromethanesulfonate, N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt and N-ethylpyridine bis (trifluoromethanesulfonyl) imide salt;
the water removing agent is one of n-butyl acetate, isoamyl acetate, ethyl propionate and n-propyl propionate;
the mass ratio of the ionic liquid to the water removing agent is 20-50: 1;
2) and continuously introducing inert gas into the ionic liquid according to the ratio of 0.5-2.0L/min by taking 1 kg of the ionic liquid, heating until the temperature at the top of the reactor is stabilized at 50-90 ℃, reducing the pressure to the relative vacuum degree of 80000-100000 Pa, discharging the inert gas in the reactor by adopting a vacuumizing mode, and continuously collecting the water removing agent and the azeotrope thereof until the water content of the ionic liquid is lower than 20 ppm.
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