CN104328455A - Preparation method for fluoroethylene carbonate - Google Patents
Preparation method for fluoroethylene carbonate Download PDFInfo
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- CN104328455A CN104328455A CN201410538078.9A CN201410538078A CN104328455A CN 104328455 A CN104328455 A CN 104328455A CN 201410538078 A CN201410538078 A CN 201410538078A CN 104328455 A CN104328455 A CN 104328455A
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- ethylene carbonate
- fluorinated ethylene
- hydrogen fluoride
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Abstract
The invention provides a preparation method for fluoroethylene carbonate. The preparation method comprises: performing electrolysis fluorination on an anhydrous hydrogen fluoride solution of ethylene carbonate, controlling the current density to be 10-30 mA/cm<2>, the electrolysis voltage to be 5-8 V, the electrolysis temperature to be 0-15 DEG C and the reaction time to be 3-6 h, after the reaction is finished, standing the electrolysis solution for layering, so as to obtain a fluoroethylene carbonate crude product, and performing reduced-pressure distillation and drying on the fluoroethylene carbonate crude product, so as to obtain the fluoroethylene carbonate product. The preparation method has the advantages of mild reaction conditions, good reaction conversion rate and selection rate and purification easiness for the product.
Description
Technical field
The present invention relates to the preparation method of lithium battery electrolytes additive, be specifically related to a kind of preparation of fluorinated ethylene carbonate.
Background technology
As the fluorinated ethylene carbonate of lithium-ion battery electrolytes additive, it can maintain excellent performance and the security of battery, but its quality specification is high, purity requirement more than 99.8%, moisture are less than 19ppm, metal ion content is less than 50ppm lower than 1ppm, free acid content, thus it is large to cause fluorinated ethylene carbonate to prepare difficulty.
At present, the direct fluorine gas method of the many employings of fluorinated ethylene carbonate suitability for industrialized production and chlorine method of substitution.It is raw material that Japanese Patent JP2000-309583 discloses with NSC 11801, the method preparing fluorinated ethylene carbonate is directly fluoridized with F2/N2 mixed gas, wash removing HF with water, and then use 10%NaHCO3 solution washing, then prepare fluorinated ethylene carbonate finished product with distilling refining, crystallization etc. after MgSO4 drying.Because the chemically reactive of fluorine gas is higher, the selectivity ratios of partially fluorinated product is poor, can form the byproduct of multiple fluoro.Therefore, direct fluorine gas method is difficult to the carrying out controlling reaction, requires very high to equipment and process.And fluorine gas toxicity is large, big for environment pollution, aftertreatment is also very difficult.
And for example International Patent Publication No. W WO9815024 discloses chlorocarbonic acid vinyl acetate and KF reacts, and is prepared the method for fluorinated ethylene carbonate by fluoro-reaction.The temperature of this reaction is higher, long reaction time, and selection rate is lower, and the use of KF easily produces the residues such as KCl, HCl, and this residue has a strong impact on the performance of battery.In order to remove these by products, obtaining highly purified fluorinated ethylene carbonate, needing complicated treating process.
As can be seen here, adopt direct fluorine gas method and chlorine method of substitution synthesizing fluoroethylene carbonate, all there is very large defect.
Summary of the invention
Instant invention overcomes the defect of prior art, provide that a kind of technique is simple, reaction conversion ratio and selectivity is high, the preparation method of the fluorinated ethylene carbonate of good product quality.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of preparation method of fluorinated ethylene carbonate, the anhydrous hydrogen fluoride solution of NSC 11801 is carried out electrofluorination, electrofluorination condition is: current density is 10-30mA/cm2, electrolysis voltage is 5-8V, electrolysis temperature is 0-15 DEG C, reaction times 3-6h, after reaction terminates, electrolytic solution stratification is obtained fluorinated ethylene carbonate crude product, obtain fluorinated ethylene carbonate product by after the underpressure distillation of fluorinated ethylene carbonate crude product, drying.
Further:
As the preferred embodiments of the invention, the mass percentage concentration of the anhydrous hydrogen fluoride solution of described NSC 11801 is preferably 10-25%.
As the preferred embodiments of the invention, described underpressure distillation is for being first 60-120 DEG C in temperature, distilling under pressure 40-140mmHg, removing anhydrous hydrogen fluoride; Be 100-160 DEG C in temperature, distill under pressure 30-100mmHg again, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace.
As the preferred embodiments of the invention, described electrofluorination reacts in a cell, and described anode electrolytic cell is preferably Graphite Electrodes, and electric tank cathode is preferably nickel electrode or platinum electrode or iron electrode.
The present invention adopts in anhydrous hydrogen fluoride solution, makes NSC 11801 carry out electrofluorination, makes hydrogen fluoride electrolysis, produces fluoro free radical, NSC 11801 is fluoridized into fluorinated ethylene carbonate at negative electrode.By after electrolytic solution sufficient standing after having reacted, the fluorinated ethylene carbonate crude product deposited is released from bottom of electrolytic tank, anhydrous hydrogen fluoride is removed with vacuum distillation method, by the further underpressure distillation of fluorinated ethylene carbonate crude product of removing anhydrous hydrogen fluoride, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace, obtains fluorinated ethylene carbonate finished product after the distillment drying that underpressure distillation obtains.
Compared with prior art, the present invention has the following advantages:
1, technique is simple, and product is easily purified, and adopts electrolytic process synthesizing fluoroethylene carbonate, and relative to direct fluorine gas method conventional at present and chlorine substitution method, have technique simple, reaction conditions is gentle, the advantage that product is easily purified;
2, reaction conversion ratio is high, and selectivity is good, and reaction conversion ratio is more than 95%, and product selectivity is more than 93%;
3, good product quality, the content of fluorinated ethylene carbonate product is more than 99.98%, and moisture content is at below 0.5ppm, and metal ion content is below 0.05ppm, and free acid content is below 1ppm, can be widely used in manufacturing lithium ion battery.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not limited to described embodiment.
Embodiment 1
First anhydrous hydrogen fluoride nitrogen is pressed in electrolyzer, again NSC 11801 is added in electrolyzer, the concentration of the anhydrous hydrogen fluoride solution of NSC 11801 is made to be after 10wt%, start electrofluorination reaction, electrofluorination condition is: current density is 10mA/cm2, electrolysis voltage is 5V, and electrolysis temperature is 0 DEG C, reaction times 3h, anode electrolytic cell is Graphite Electrodes, and negative electrode is nickel electrode.By after electrolytic solution sufficient standing after having reacted, release the fluorinated ethylene carbonate crude product deposited from bottom of electrolytic tank, remove anhydrous hydrogen fluoride with vacuum distillation method, distillation temperature has been 60 DEG C, pressure is 40mmHg.By the further underpressure distillation of fluorinated ethylene carbonate crude product of removing anhydrous hydrogen fluoride, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace, distillation temperature is 100 DEG C, pressure is 20mmHg, obtains fluorinated ethylene carbonate product after the distillment drying further underpressure distillation obtained.
The result of this embodiment: transformation efficiency is 95.5%, selection rate is 94.5%; The content of fluorinated ethylene carbonate is 99.99%, and moisture content is 0.3ppm, and metal ion content is 0.03ppm, and free acid content is 0.8ppm.
Embodiment 2
First anhydrous hydrogen fluoride nitrogen is pressed in electrolyzer, again NSC 11801 is added in electrolyzer, the concentration of the anhydrous hydrogen fluoride solution of NSC 11801 is made to be after 12wt%, start electrofluorination reaction, electrofluorination condition is: current density is 13mA/cm2, electrolysis voltage is 5.5V, and electrolysis temperature is 2 DEG C, reaction times 3.5h, anode electrolytic cell is Graphite Electrodes, and negative electrode is platinum.By after electrolytic solution sufficient standing after having reacted, release the fluorinated ethylene carbonate crude product deposited from bottom of electrolytic tank, remove anhydrous hydrogen fluoride with vacuum distillation method, distillation temperature has been 70 DEG C, pressure is 60mmHg.By the further underpressure distillation of fluorinated ethylene carbonate crude product of removing anhydrous hydrogen fluoride, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace, distillation temperature is 110 DEG C, pressure is 70mmHg, obtains fluorinated ethylene carbonate product after the distillment drying further underpressure distillation obtained.
The result of this embodiment: transformation efficiency is 95%, selection rate is 96.5%; The content of fluorinated ethylene carbonate is 99.98%, and moisture content is 0.4ppm, and metal ion content is 0.01ppm, and free acid content is 0.4ppm.
Embodiment 3
First anhydrous hydrogen fluoride nitrogen is pressed in electrolyzer, again NSC 11801 is added in electrolyzer, the concentration of the anhydrous hydrogen fluoride solution of NSC 11801 is made to be after 15wt%, start electrofluorination reaction, electrofluorination condition is: current density is 16mA/cm2, electrolysis voltage is 6V, and electrolysis temperature is 4 DEG C, reaction times 4h, wherein anode electrolytic cell is Graphite Electrodes, and negative electrode is iron electrode.By after electrolytic solution sufficient standing after having reacted, release the fluorinated ethylene carbonate crude product deposited from bottom of electrolytic tank, remove anhydrous hydrogen fluoride with vacuum distillation method, distillation temperature has been 80 DEG C, pressure is 80mmHg.By the further underpressure distillation of fluorinated ethylene carbonate crude product of removing anhydrous hydrogen fluoride, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace, distillation temperature is 120 DEG C, pressure is 40mmHg, obtains fluorinated ethylene carbonate product after the distillment drying further underpressure distillation obtained.
The result of this embodiment: transformation efficiency is 96%, selection rate is 93%; The content of fluorinated ethylene carbonate is 99.99%, and moisture content is 0.5ppm, and metal ion content is 0.02ppm, and free acid content is 0.5ppm.
Embodiment 4
First anhydrous hydrogen fluoride nitrogen is pressed in electrolyzer, again NSC 11801 is added in electrolyzer, the concentration of the anhydrous hydrogen fluoride solution of NSC 11801 is made to be after 17wt%, start electrofluorination reaction, electrofluorination condition is: current density is 20mA/cm2, electrolysis voltage is 6.5V, and electrolysis temperature is 6 DEG C, reaction times 4.5h, wherein anode electrolytic cell is Graphite Electrodes, and negative electrode is iron electrode.By after electrolytic solution sufficient standing after having reacted, release the fluorinated ethylene carbonate crude product deposited from bottom of electrolytic tank, remove anhydrous hydrogen fluoride with vacuum distillation method, distillation temperature has been 70 DEG C, pressure is 60mmHg.By the further underpressure distillation of fluorinated ethylene carbonate crude product of removing anhydrous hydrogen fluoride, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace, distillation temperature is 110 DEG C, pressure is 55mmHg, obtains fluorinated ethylene carbonate product after the distillment drying further underpressure distillation obtained.
The result of this embodiment: transformation efficiency is 95.8%, selection rate is 93%; The content of fluorinated ethylene carbonate is 99.98%, and moisture content is 0.1ppm, and metal ion content is 0.03ppm, and free acid content is 1ppm.
Embodiment 5
First anhydrous hydrogen fluoride nitrogen is pressed in electrolyzer, again NSC 11801 is added in electrolyzer, the concentration of the anhydrous hydrogen fluoride solution of NSC 11801 is made to be after 20wt%, start electrofluorination reaction, electrofluorination condition is: current density is 23mA/cm2, electrolysis voltage is 7V, and electrolysis temperature is 9 DEG C, reaction times 5h, wherein anode electrolytic cell is Graphite Electrodes, and negative electrode is iron electrode.By after electrolytic solution sufficient standing after having reacted, release the fluorinated ethylene carbonate crude product deposited from bottom of electrolytic tank, remove anhydrous hydrogen fluoride with vacuum distillation method, distillation temperature has been 80 DEG C, pressure is 80mmHg.By the further underpressure distillation of fluorinated ethylene carbonate crude product of removing anhydrous hydrogen fluoride, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace, distillation temperature is 140 DEG C, pressure is 70mmHg, obtains fluorinated ethylene carbonate product after the distillment drying further underpressure distillation obtained.
The result of this embodiment: transformation efficiency is 96.3%, selection rate is 96%; The content of fluorinated ethylene carbonate is 99.99%, and moisture content is 0.2ppm, and metal ion content is 0.01ppm, and free acid content is 0.2ppm.
Embodiment 6
First anhydrous hydrogen fluoride nitrogen is pressed in electrolyzer, again NSC 11801 is added in electrolyzer, the concentration of the anhydrous hydrogen fluoride solution of NSC 11801 is made to be after 22wt%, start electrofluorination reaction, electrofluorination condition is: current density is 26mA/cm2, electrolysis voltage is 7.5V, and electrolysis temperature is 12 DEG C, reaction times 5.5h, wherein anode electrolytic cell is Graphite Electrodes, and negative electrode is iron electrode.By after electrolytic solution sufficient standing after having reacted, release the fluorinated ethylene carbonate crude product deposited from bottom of electrolytic tank, remove anhydrous hydrogen fluoride with vacuum distillation method, distillation temperature has been 110 DEG C, pressure is 110mmHg.By the further underpressure distillation of fluorinated ethylene carbonate crude product of removing anhydrous hydrogen fluoride, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace, distillation temperature is 150 DEG C, pressure is 85mmHg, obtains fluorinated ethylene carbonate product after the distillment drying further underpressure distillation obtained.
The result of this embodiment: transformation efficiency is 95.2%, selection rate is 95%; The content of fluorinated ethylene carbonate is 99.995%, and moisture content is 0.1ppm, and metal ion content is 0.05ppm, and free acid content is 0.8ppm.
Embodiment 7
First anhydrous hydrogen fluoride nitrogen is pressed in electrolyzer, again NSC 11801 is added in electrolyzer, the concentration of the anhydrous hydrogen fluoride solution of NSC 11801 is made to be after 25wt%, start electrofluorination reaction, electrofluorination condition is: current density is 30mA/cm2, electrolysis voltage is 8V, and electrolysis temperature is 15 DEG C, reaction times 6h, wherein anode electrolytic cell is Graphite Electrodes, and negative electrode is iron electrode.By after electrolytic solution sufficient standing after having reacted, release the fluorinated ethylene carbonate crude product deposited from bottom of electrolytic tank, remove anhydrous hydrogen fluoride with vacuum distillation method, distillation temperature has been 120 DEG C, pressure is 120mmHg.By the further underpressure distillation of fluorinated ethylene carbonate crude product of removing anhydrous hydrogen fluoride, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace, distillation temperature is 160 DEG C, pressure is 100mmHg, obtains fluorinated ethylene carbonate product after the distillment drying further underpressure distillation obtained.
The result of this embodiment: transformation efficiency is 96%, selection rate is 94%; The content of fluorinated ethylene carbonate is 99.98%, and moisture content is 0.5ppm, and metal ion content is 0.02ppm, and free acid content is 1ppm.
Claims (4)
1. the preparation method of a fluorinated ethylene carbonate, the anhydrous hydrogen fluoride solution of NSC 11801 is it is characterized in that to carry out electrofluorination, electrofluorination condition is: current density is 10-30mA/cm2, electrolysis voltage is 5-8V, electrolysis temperature is 0-15 DEG C, reaction times 3-6h, obtains fluorinated ethylene carbonate crude product by electrolytic solution stratification after reaction terminates, obtains fluorinated ethylene carbonate product by after the underpressure distillation of fluorinated ethylene carbonate crude product, drying.
2. the preparation method of fluorinated ethylene carbonate as claimed in claim 1, is characterized in that the mass percentage concentration of the anhydrous hydrogen fluoride solution of described NSC 11801 is 10-25%.
3. the preparation method of fluorinated ethylene carbonate as claimed in claim 1, is characterized in that described underpressure distillation is for being first 60-120 DEG C in temperature, distilling under pressure 40-140mmHg, removing anhydrous hydrogen fluoride; Be 100-160 DEG C in temperature, distill under pressure 30-100mmHg again, the anhydrous fluorochemical of removing difluorinated ethylene carbonate and trace.
4. the preparation method of fluorinated ethylene carbonate as claimed in claim 1, it is characterized in that described electrofluorination reacts in a cell, described anode electrolytic cell is Graphite Electrodes, and electric tank cathode is nickel electrode or platinum electrode or iron electrode.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111155141A (en) * | 2020-01-20 | 2020-05-15 | 中国科学技术大学 | Method for electrochemically synthesizing gem-difluoroolefin |
| CN113215600A (en) * | 2019-12-31 | 2021-08-06 | 浙江蓝天环保高科技股份有限公司 | Preparation method of fluoroethylene sulfate |
| CN115323412A (en) * | 2022-10-11 | 2022-11-11 | 山东海科创新研究院有限公司 | Preparation method of difluoroethylene carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261484A (en) * | 2010-12-15 | 2013-08-21 | 巴斯夫欧洲公司 | Process for the electrochemical fluorination of organic compounds |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261484A (en) * | 2010-12-15 | 2013-08-21 | 巴斯夫欧洲公司 | Process for the electrochemical fluorination of organic compounds |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113215600A (en) * | 2019-12-31 | 2021-08-06 | 浙江蓝天环保高科技股份有限公司 | Preparation method of fluoroethylene sulfate |
| CN113215600B (en) * | 2019-12-31 | 2022-09-16 | 浙江蓝天环保高科技股份有限公司 | Preparation method of fluoroethylene sulfate |
| CN111155141A (en) * | 2020-01-20 | 2020-05-15 | 中国科学技术大学 | Method for electrochemically synthesizing gem-difluoroolefin |
| CN115323412A (en) * | 2022-10-11 | 2022-11-11 | 山东海科创新研究院有限公司 | Preparation method of difluoroethylene carbonate |
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Inventor after: Zhou Mingjiong Inventor after: Wang Hai Inventor after: Li Sheng Inventor before: Zhou Mingjiong Inventor before: Wang Hai Inventor before: Li Sheng Inventor before: Xia Yonggao |
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