CN104328455B - A kind of preparation method of fluorinated ethylene carbonate - Google Patents
A kind of preparation method of fluorinated ethylene carbonate Download PDFInfo
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- CN104328455B CN104328455B CN201410538078.9A CN201410538078A CN104328455B CN 104328455 B CN104328455 B CN 104328455B CN 201410538078 A CN201410538078 A CN 201410538078A CN 104328455 B CN104328455 B CN 104328455B
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- ethylene carbonate
- fluorinated ethylene
- hydrogen fluoride
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Abstract
The invention provides a kind of preparation method of fluorinated ethylene carbonate, the anhydrous hydrogen fluoride solution of ethylene carbonate is subjected to electrofluorination, electrofluorination condition is：Current density is 10 30mA/cm2, decomposition voltage is 5 8V, and electrolysis temperature is 0 15 DEG C, the 6h of reaction time 3, electrolyte stratification is obtained into fluorinated ethylene carbonate crude product after the completion of reaction, fluorinated ethylene carbonate product will be obtained after the vacuum distillation of fluorinated ethylene carbonate crude product, drying.The present invention has reaction condition gentle, and reaction conversion ratio and selection rate are good, and product purifies easy advantage.
Description
Technical field
The present invention relates to the preparation method of lithium battery electrolytes additive, and in particular to a kind of system of fluorinated ethylene carbonate
It is standby.
Background technology
As the fluorinated ethylene carbonate of lithium-ion battery electrolytes additive, it can maintain the excellent performance of battery
And security, but its quality specification is high, purity requirement more than 99.8%, moisture are less than 19ppm, metal ion content and are less than
1ppm, free acid content are less than 50ppm, so that it is big to cause fluorinated ethylene carbonate to prepare difficulty.
At present, direct fluorine gas method and chlorine method of substitution are used fluorinated ethylene carbonate industrialized production more.Japan Patent
JP2000-309583 is disclosed using ethylene carbonate as raw material, and fluoro ethylene carbonate is prepared with the direct fluorination of F2/N2 mixed gas
The method of ester, is washed with water removing HF, then wash again with the 10%NaHCO3 aqueous solution, then after being dried with MgSO4 distillation refine,
Crystallization etc. prepares fluorinated ethylene carbonate finished product.Because the chemism of fluorine gas is higher, the selectivity ratios of partially fluorinated product
It is poor, the byproduct of a variety of fluoro can be formed.Therefore, direct fluorine gas method is difficult the progress of control reaction, will to equipment and technique
Ask very high.It is big for environment pollution and fluorine gas toxicity is big, post-process also highly difficult.
And for example International Patent Publication No. W WO9815024 discloses chlorocarbonic acid vinyl acetate and reacted with KF, passes through fluoro-reaction
The method for preparing fluorinated ethylene carbonate.The temperature of the reaction is higher, the reaction time is long, and selection rate is than relatively low, and KF makes
The residues such as KCl, HCl are produced with easy, this residue has a strong impact on the performance of battery.In order to remove these accessory substances, obtain
Fluorinated ethylene carbonate to high-purity is, it is necessary to the subtractive process of complexity.
As can be seen here, using direct fluorine gas method and chlorine method of substitution synthesizing fluoroethylene carbonate, all in the presence of very big defect.
The content of the invention
Instant invention overcomes the defect of prior art, there is provided a kind of technique is simple, reaction conversion ratio and selectivity are high, produce
The preparation method of the measured fluorinated ethylene carbonate of quality.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions：A kind of fluoro ethylene carbonate
The preparation method of ester, electrofluorination is carried out by the anhydrous hydrogen fluoride solution of ethylene carbonate, and electrofluorination condition is：Current density
For 10-30mA/cm2, decomposition voltage is 5-8V, and electrolysis temperature is 0-15 DEG C, and reaction time 3-6h is reacted electrolyte after terminating
Stratification obtains fluorinated ethylene carbonate crude product, will obtain fluoro carbon after the vacuum distillation of fluorinated ethylene carbonate crude product, drying
Vinyl acetate product.
Further：
As the preferred embodiments of the invention, the quality percentage of the anhydrous hydrogen fluoride solution of described ethylene carbonate is dense
Degree is preferably 10-25%.
As the preferred embodiments of the invention, it is first 60-120 DEG C, pressure 40- in temperature that described vacuum distillation, which is,
Distilled under 140mmHg, remove anhydrous hydrogen fluoride；It is 100-160 DEG C, steamed under pressure 30-100mmHg in temperature again
Evaporate, remove difluorinated ethylene carbonate and micro anhydrous fluoride.
As the preferred embodiments of the invention, described electrofluorination is reacted in a cell, the electrolytic cell
Anode is preferably graphite electrode, and electric tank cathode is preferably nickel electrode or platinum electrode or iron electrode.
The present invention is electrolysed hydrogen fluoride using making ethylene carbonate carry out electrofluorination in anhydrous hydrogen fluoride solution,
Negative electrode produces fluoro free radical, and ethylene carbonate is fluorinated into fluorinated ethylene carbonate.By electrolyte sufficient standing after the completion of reaction
Afterwards, the fluorinated ethylene carbonate crude product deposited is released from bottom of electrolytic tank, anhydrous hydrogen fluoride is removed with vacuum distillation method,
The further vacuum distillation of fluorinated ethylene carbonate crude product of anhydrous hydrogen fluoride will be removed, remove difluorinated ethylene carbonate and micro
Anhydrous fluoride, distillation that vacuum distillation is obtained obtains fluorinated ethylene carbonate finished product after drying.
Compared with prior art, the present invention has advantages below：
1st, technique is simple, and product is easily purified, straight relative to what is commonly used at present using electrolysis synthesizing fluoroethylene carbonate
Fluorine gas method and chlorine displacement method are connect, simple with technique, reaction condition is gentle, the advantage that product is easily purified；
2nd, reaction conversion ratio is high, and selectivity is good, and reaction conversion ratio is more than 95%, and product selectivity is more than 93%；
3rd, good product quality, the content of fluorinated ethylene carbonate product is more than 99.98%, moisture 0.5ppm with
Under, metal ion content is below 0.05ppm, and free acid content is below 1ppm, can be widely applied to manufacture lithium ion battery.
Embodiment
The present invention is described in further detail with reference to embodiments, but the present invention is not limited to described embodiment.
Embodiment 1
First anhydrous hydrogen fluoride is pressed into electrolytic cell with nitrogen, then ethylene carbonate is added in electrolytic cell, makes ethylene
The concentration of the anhydrous hydrogen fluoride solution of alkene ester is beginning electrofluorination reaction after 10wt%, and electrofluorination condition is：Current density
For 10mA/cm2, decomposition voltage is 5V, and electrolysis temperature is 0 DEG C, and reaction time 3h, anode electrolytic cell is graphite electrode, and negative electrode is
Nickel electrode.By after electrolyte sufficient standing after the completion of reaction, the fluorinated ethylene carbonate deposited is released from bottom of electrolytic tank
Crude product, removes anhydrous hydrogen fluoride, vapo(u)rizing temperature is 60 DEG C, pressure is 40mmHg with vacuum distillation method.Anhydrous fluorination will be removed
The further vacuum distillation of fluorinated ethylene carbonate crude product of hydrogen, removes difluorinated ethylene carbonate and micro anhydrous fluoride,
Vapo(u)rizing temperature is 100 DEG C, pressure is 20mmHg, and the distillation that further vacuum distillation is obtained obtains fluoro ethylene after drying
Alkene ester product.
The result of the embodiment：Conversion ratio is 95.5%, and selection rate is 94.5%；The content of fluorinated ethylene carbonate is
99.99%, moisture is 0.3ppm, and metal ion content is 0.03ppm, and free acid content is 0.8ppm.
Embodiment 2
First anhydrous hydrogen fluoride is pressed into electrolytic cell with nitrogen, then ethylene carbonate is added in electrolytic cell, makes ethylene
The concentration of the anhydrous hydrogen fluoride solution of alkene ester is beginning electrofluorination reaction after 12wt%, and electrofluorination condition is：Current density
For 13mA/cm2, decomposition voltage is 5.5V, and electrolysis temperature is 2 DEG C, and reaction time 3.5h, anode electrolytic cell is graphite electrode, cloudy
Extremely platinum.By after electrolyte sufficient standing after the completion of reaction, the fluoro ethylene carbonate deposited is released from bottom of electrolytic tank
Ester crude product, removes anhydrous hydrogen fluoride, vapo(u)rizing temperature is 70 DEG C, pressure is 60mmHg with vacuum distillation method.Anhydrous fluorine will be removed
Change the further vacuum distillation of fluorinated ethylene carbonate crude product of hydrogen, remove difluorinated ethylene carbonate and micro anhydrous fluorination
Thing, vapo(u)rizing temperature is 110 DEG C, pressure is 70mmHg, and the distillation that further vacuum distillation is obtained obtains fluoro carbon after drying
Vinyl acetate product.
The result of the embodiment：Conversion ratio is 95%, and selection rate is 96.5%；The content of fluorinated ethylene carbonate is
99.98%, moisture is 0.4ppm, and metal ion content is 0.01ppm, and free acid content is 0.4ppm.
Embodiment 3
First anhydrous hydrogen fluoride is pressed into electrolytic cell with nitrogen, then ethylene carbonate is added in electrolytic cell, makes ethylene
The concentration of the anhydrous hydrogen fluoride solution of alkene ester is beginning electrofluorination reaction after 15wt%, and electrofluorination condition is：Current density
For 16mA/cm2, decomposition voltage is 6V, and electrolysis temperature is 4 DEG C, and reaction time 4h, wherein anode electrolytic cell are graphite electrode, cloudy
Extremely iron electrode.By after electrolyte sufficient standing after the completion of reaction, the fluoro ethylene deposited is released from bottom of electrolytic tank
Alkene ester crude product, removes anhydrous hydrogen fluoride, vapo(u)rizing temperature is 80 DEG C, pressure is 80mmHg with vacuum distillation method.It will remove anhydrous
The further vacuum distillation of fluorinated ethylene carbonate crude product of hydrogen fluoride, removes difluorinated ethylene carbonate and micro anhydrous fluorination
Thing, vapo(u)rizing temperature is 120 DEG C, pressure is 40mmHg, and the distillation that further vacuum distillation is obtained obtains fluoro carbon after drying
Vinyl acetate product.
The result of the embodiment：Conversion ratio is 96%, and selection rate is 93%；The content of fluorinated ethylene carbonate is
99.99%, moisture is 0.5ppm, and metal ion content is 0.02ppm, and free acid content is 0.5ppm.
Embodiment 4
First anhydrous hydrogen fluoride is pressed into electrolytic cell with nitrogen, then ethylene carbonate is added in electrolytic cell, makes ethylene
The concentration of the anhydrous hydrogen fluoride solution of alkene ester is beginning electrofluorination reaction after 17wt%, and electrofluorination condition is：Current density
For 20mA/cm2, decomposition voltage is 6.5V, and electrolysis temperature is 6 DEG C, and reaction time 4.5h, wherein anode electrolytic cell are graphite electricity
Pole, negative electrode is iron electrode.By after electrolyte sufficient standing after the completion of reaction, the fluoro carbon deposited is released from bottom of electrolytic tank
Vinyl acetate crude product, removes anhydrous hydrogen fluoride, vapo(u)rizing temperature is 70 DEG C, pressure is 60mmHg with vacuum distillation method.It will remove
The further vacuum distillation of fluorinated ethylene carbonate crude product of anhydrous hydrogen fluoride, removes difluorinated ethylene carbonate and micro anhydrous
Fluoride, vapo(u)rizing temperature is 110 DEG C, pressure is 55mmHg, and the distillation that further vacuum distillation is obtained obtains fluorine after drying
For ethylene carbonate product.
The result of the embodiment：Conversion ratio is 95.8%, and selection rate is 93%；The content of fluorinated ethylene carbonate is
99.98%, moisture is 0.1ppm, and metal ion content is 0.03ppm, and free acid content is 1ppm.
Embodiment 5
First anhydrous hydrogen fluoride is pressed into electrolytic cell with nitrogen, then ethylene carbonate is added in electrolytic cell, makes ethylene
The concentration of the anhydrous hydrogen fluoride solution of alkene ester is beginning electrofluorination reaction after 20wt%, and electrofluorination condition is：Current density
For 23mA/cm2, decomposition voltage is 7V, and electrolysis temperature is 9 DEG C, and reaction time 5h, wherein anode electrolytic cell are graphite electrode, cloudy
Extremely iron electrode.By after electrolyte sufficient standing after the completion of reaction, the fluoro ethylene deposited is released from bottom of electrolytic tank
Alkene ester crude product, removes anhydrous hydrogen fluoride, vapo(u)rizing temperature is 80 DEG C, pressure is 80mmHg with vacuum distillation method.It will remove anhydrous
The further vacuum distillation of fluorinated ethylene carbonate crude product of hydrogen fluoride, removes difluorinated ethylene carbonate and micro anhydrous fluorination
Thing, vapo(u)rizing temperature is 140 DEG C, pressure is 70mmHg, and the distillation that further vacuum distillation is obtained obtains fluoro carbon after drying
Vinyl acetate product.
The result of the embodiment：Conversion ratio is 96.3%, and selection rate is 96%；The content of fluorinated ethylene carbonate is
99.99%, moisture is 0.2ppm, and metal ion content is 0.01ppm, and free acid content is 0.2ppm.
Embodiment 6
First anhydrous hydrogen fluoride is pressed into electrolytic cell with nitrogen, then ethylene carbonate is added in electrolytic cell, makes ethylene
The concentration of the anhydrous hydrogen fluoride solution of alkene ester is beginning electrofluorination reaction after 22wt%, and electrofluorination condition is：Current density
For 26mA/cm2, decomposition voltage is 7.5V, and electrolysis temperature is 12 DEG C, and reaction time 5.5h, wherein anode electrolytic cell are graphite electricity
Pole, negative electrode is iron electrode.By after electrolyte sufficient standing after the completion of reaction, the fluoro carbon deposited is released from bottom of electrolytic tank
Vinyl acetate crude product, removes anhydrous hydrogen fluoride, vapo(u)rizing temperature is 110 DEG C, pressure is 110mmHg with vacuum distillation method.It will remove
The further vacuum distillation of fluorinated ethylene carbonate crude product of anhydrous hydrogen fluoride is gone, difluorinated ethylene carbonate and micro nothing is removed
Water fluoride, vapo(u)rizing temperature is 150 DEG C, pressure is 85mmHg, and the distillation that further vacuum distillation is obtained is obtained after drying
Fluorinated ethylene carbonate product.
The result of the embodiment：Conversion ratio is 95.2%, and selection rate is 95%；The content of fluorinated ethylene carbonate is
99.995%, moisture is 0.1ppm, and metal ion content is 0.05ppm, and free acid content is 0.8ppm.
Embodiment 7
First anhydrous hydrogen fluoride is pressed into electrolytic cell with nitrogen, then ethylene carbonate is added in electrolytic cell, makes ethylene
The concentration of the anhydrous hydrogen fluoride solution of alkene ester is beginning electrofluorination reaction after 25wt%, and electrofluorination condition is：Current density
For 30mA/cm2, decomposition voltage is 8V, and electrolysis temperature is 15 DEG C, and reaction time 6h, wherein anode electrolytic cell are graphite electrode, cloudy
Extremely iron electrode.By after electrolyte sufficient standing after the completion of reaction, the fluoro ethylene deposited is released from bottom of electrolytic tank
Alkene ester crude product, removes anhydrous hydrogen fluoride, vapo(u)rizing temperature is 120 DEG C, pressure is 120mmHg with vacuum distillation method.Nothing will be removed
The further vacuum distillation of fluorinated ethylene carbonate crude product of water hydrogen fluoride, removes difluorinated ethylene carbonate and micro anhydrous fluorine
Compound, vapo(u)rizing temperature is 160 DEG C, pressure is 100mmHg, and the distillation that further vacuum distillation is obtained obtains fluoro after drying
Ethylene carbonate product.
The result of the embodiment：Conversion ratio is 96%, and selection rate is 94%；The content of fluorinated ethylene carbonate is
99.98%, moisture is 0.5ppm, and metal ion content is 0.02ppm, and free acid content is 1ppm.
Claims (1)
1. a kind of preparation method of fluorinated ethylene carbonate, it is characterised in that anhydrous hydrogen fluoride is first pressed into electrolytic cell with nitrogen
In, then will ethylene carbonate add electrolytic cell in, make ethylene carbonate anhydrous hydrogen fluoride solution concentration be 20wt% after open
Beginning electrofluorination reacts, and electrofluorination condition is：Current density is 23mA/cm2, decomposition voltage is 7V, and electrolysis temperature is 9 DEG C,
Reaction time 5h, wherein anode electrolytic cell are graphite electrode, and negative electrode is iron electrode, by electrolyte sufficient standing after the completion of reaction
Afterwards, the fluorinated ethylene carbonate crude product deposited is released from bottom of electrolytic tank, anhydrous hydrogen fluoride is removed with vacuum distillation method,
Vapo(u)rizing temperature is 80 DEG C, pressure is 80mmHg, and the fluorinated ethylene carbonate crude product for removing anhydrous hydrogen fluoride is further depressurized into steaming
Evaporate, remove difluorinated ethylene carbonate and micro anhydrous fluoride, vapo(u)rizing temperature is 140 DEG C, pressure is 70mmHg, will enter one
The distillation that step vacuum distillation is obtained obtains fluorinated ethylene carbonate product after drying.
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| CN111155141B (en) * | 2020-01-20 | 2022-01-11 | 中国科学技术大学 | Method for electrochemically synthesizing gem-difluoroolefin |
| CN115323412B (en) * | 2022-10-11 | 2023-03-24 | 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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