CN110041299A - A kind of method that the continuous gas phase catalytic fluorination of fixed bed prepares fluorinated ethylene carbonate - Google Patents
A kind of method that the continuous gas phase catalytic fluorination of fixed bed prepares fluorinated ethylene carbonate Download PDFInfo
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- CN110041299A CN110041299A CN201910281711.3A CN201910281711A CN110041299A CN 110041299 A CN110041299 A CN 110041299A CN 201910281711 A CN201910281711 A CN 201910281711A CN 110041299 A CN110041299 A CN 110041299A
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- ethylene carbonate
- fluorinated ethylene
- fixed bed
- gas phase
- catalytic fluorination
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro radicals
Abstract
The invention discloses the methods that a kind of continuous gas phase catalytic fluorination of fixed bed prepares fluorinated ethylene carbonate, the following steps are included: using chlorocarbonic acid vinyl acetate as raw material, in the case where being fluorinated hydrogen atmosphere, in the presence of fluorination catalyst, the fluoro- chlorine exchange reaction of gas phase occurs and obtains fluorinated ethylene carbonate or/and vinylene carbonate；Catalytic fluorination reaction, after nitrogen is replaced, the vaporization of chlorocarbonic acid vinyl acetate is each led into the fixed bed reactors for being placed with catalyst with anhydrous hydrogen fluoride gas, catalytic fluorination reaction is carried out at a certain temperature, fixed bed reactors progress gas phase reaction, which is continuously passed through, with the gas after anhydrous hydrogen fluoride gas and the vaporization of chlorocarbonic acid vinyl acetate prepares fluorinated ethylene carbonate, shorten the reaction time, significantly improve reaction efficiency, the tail gas for reacting last institute's output is handled by condensing tower can be achieved hydrofluoric acid condensation reuse, hydrogen chloride can make by-product use by lye absorption, safety and environmental protection, it is particularly suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of fluorinated ethylene carbonate, urge more particularly, to a kind of continuous gas phase of fixed bed
Change the method that fluorination prepares fluorinated ethylene carbonate.
Background technique
In recent years, with the fast development of lithium ion battery, electric car, smart phone, pen are increasingly used in
Remember the fields such as this computer, other digital products.It experienced the safe things such as a series of battery of mobile phone explosion, electric car spontaneous combustion
Therefore and battery durable ability is insufficient, the awkward scene such as service life cycle is short, improve lithium ion battery security and stability, improve
Cruising ability and prolong the service life as major issue urgently to be resolved in lithium ion battery development process.Electrolysis additive
Because its additive amount is small, significant effect becomes one of the main method for improving performance of lithium ion battery.
Existing Chinese patent CN201810357667.5 proposes that gas phase continuously prepares fluorinated ethylene carbonate and carbonic acid is sub-
Vinyl acetate, used consersion unit are tubular reactor, and product separately need to be separated off HF and HCl, reaction time by heating
Extension, reaction efficiency are low, for this purpose, proposing that a kind of continuous gas phase catalytic fluorination of fixed bed prepares the side of fluorinated ethylene carbonate
Method.
Summary of the invention
The purpose of the present invention is to provide the sides that a kind of continuous gas phase catalytic fluorination of fixed bed prepares fluorinated ethylene carbonate
Method shortens the reaction time, improves reaction efficiency, and prepares and be simply easily achieved product separating-purifying, remarkable in economical benefits.
To achieve the above object, present invention employs following technical solutions:
A kind of method that the continuous gas phase catalytic fluorination of fixed bed prepares fluorinated ethylene carbonate, comprising the following steps:
S1, using chlorocarbonic acid vinyl acetate as raw material, in the case where being fluorinated hydrogen atmosphere, in the presence of fluorination catalyst, occur the fluoro- chlorine of gas phase
Exchange reaction obtains fluorinated ethylene carbonate or/and vinylene carbonate；
Chlorocarbonic acid vinyl acetate is vaporized and is each led into anhydrous hydrogen fluoride gas after nitrogen is replaced by S2, catalytic fluorination reaction
The fixed bed reactors of catalyst are placed with, carry out catalytic fluorination reaction at a certain temperature；
S3, generation fluorinated ethylene carbonate liquid product pass through from flowing to discharge port and be collected；
S4, last institute's output tail gas by condensing tower carry out condensing recovery utilization, fixed gas by absorption plant absorb disposition.
As the technical program further preferred that in the S1, fluorination catalyst is active carbon or metal fluoride,
The metal fluoride is at least one of aluminum fluoride, magnesium fluoride, ferric flouride, cobaltous fluoride, nickel fluoride, charomic fluoride, zinc fluoride
Or it is several.
As the technical program further preferred that in the S2, the chlorocarbonic acid vinyl acetate that is passed into reactor
It is 1:1~15, preferably 1:5~10 with the ratio between the mole of anhydrous hydrogen fluoride.
As the technical program further preferred that in the S2, catalyst is chromium base, magnesium-based, nickel-based aluminum oxide are negative
The mixture of load and/or silicon dioxide carried fluorination catalyst catalyst one or more of them.
As the technical program further preferred that the catalyst is divided into three layers of upper, middle and lower, wherein lower layer's partial size is
20-50mm, intermediate 5-20mm, upper layer partial size are less than 5mm.
As the technical program further preferred that in the S2, certain temperature is 135~185 DEG C, preferably 135~
165℃。
As the technical program further preferred that in the S3, the fluorinated ethylene carbonate liquid product of generation is certainly
Discharge port is flow to be collected.
As the technical program further preferred that in the S4, condensing tower condensation temperature is controlled at 7 DEG C or less.
As the technical program further preferred that in the S4, condensing gas is hydrogen fluoride, and fixed gas is hydrogen chloride,
Fixed gas is absorbed using lye.
Technical effect and advantage of the invention: a kind of continuous gas phase catalytic fluorination of fixed bed proposed by the present invention prepares fluoro
The method of ethylene carbonate, compared with prior art, the present invention are vaporized with anhydrous hydrogen fluoride gas and chlorocarbonic acid vinyl acetate
Gas afterwards, which is continuously passed through fixed bed reactors, to carry out gas phase reaction and prepares fluorinated ethylene carbonate, shortens reaction time, significant
Reaction efficiency is improved, and contained hydrogen fluoride and chlorination hydrogen amount are few in liquid product, does not need in addition to heat removing sour gas, receive
Collection is simple；The tail gas for reacting last institute's output is handled by condensing tower can be achieved hydrofluoric acid condensation reuse, and hydrogen chloride passes through lye
Absorption can make by-product use, and safety and environmental protection is particularly suitable for industrialized production.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Tool described herein
Body embodiment is only used to explain the present invention, is not intended to limit the present invention.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
In specific embodiment, fixed bed reactors used are gas phase flow reactor, and equipment material is nichrome,
Feeding manner used by chlorocarbonic acid vinyl acetate after anhydrous hydrogen fluoride and vaporization is nitrogen pressurization.
Embodiment 1
The method that a kind of continuous gas phase catalytic fluorination of fixed bed of the present embodiment prepares fluorinated ethylene carbonate, including following step
It is rapid:
By chromium base/SiO 2 catalyst by lower layer's particle size be 20mm, intermediate 5mm, upper layer partial size 3mm and by lower layer, in
Layer, upper thickness 2:2:1 are completed, with the replacement fixed bed inside reactor gas of high pure nitrogen, using nitrogen pressure method by nothing
1:5 is added chlorocarbonic acid vinyl acetate after water hydrogen fluoride and vaporization by volume, controls 135 DEG C of reaction temperature, mixes solid/liquid/gas reactions
Residence time 25 seconds, liquid product was received from exit, and tail gas initially enters condensing tower recycling hydrofluoric acid, and then not solidifying gas enters
+ 1 grade of absorbing by liquid caustic soda tower processing of 2 grades of water；
Analysis is sampled to gained liquid, the mass content of chlorocarbonic acid vinyl acetate is 0.76%, the matter of fluorinated ethylene carbonate
Measuring content is 93.8%；
By gained liquid through rectification under vacuum, the fraction that negative pressure -0.09Mpa collects 92-98 DEG C is controlled, fluoro ethylene carbonate is obtained
Ester；
Through detecting, the purity of fluorinated ethylene carbonate obtained by the implementation case is 99.45%, yield 96.2%.
Embodiment 2
The present invention provides the methods that a kind of continuous gas phase catalytic fluorination of fixed bed prepares fluorinated ethylene carbonate, including following step
It is rapid:
By magnesium-based/SiO 2 catalyst by lower layer's particle size be 50mm, intermediate 20mm, upper layer partial size 5mm and by lower layer, in
Layer, upper thickness 2:2:1 are completed, with the replacement fixed bed inside reactor gas of high pure nitrogen, using nitrogen pressure method by nothing
1:10 is added chlorocarbonic acid vinyl acetate after water hydrogen fluoride and vaporization by volume, controls 165 DEG C of reaction temperature, mixes solid/liquid/gas reactions
Residence time 15 seconds, liquid product was received from exit, and tail gas initially enters condensing tower recycling hydrofluoric acid, and then not solidifying gas enters
+ 1 grade of absorbing by liquid caustic soda tower processing of 2 grades of water；
Analysis is sampled to gained liquid, the mass content of chlorocarbonic acid vinyl acetate is 0.54%, the matter of fluorinated ethylene carbonate
Measuring content is 94.6%；
By gained liquid through rectification under vacuum, the fraction that negative pressure -0.09Mpa collects 92-98 DEG C is controlled, fluoro ethylene carbonate is obtained
Ester；
Through detecting, the purity of fluorinated ethylene carbonate obtained by the implementation case is 99.3%, yield 96.6%.
Embodiment 3
The present invention provides the methods that a kind of continuous gas phase catalytic fluorination of fixed bed prepares fluorinated ethylene carbonate, including following step
It is rapid:
Chromium base/silica is laid on lower layer and middle layer by particle size for 50mm and 20mm respectively, with chromium base/aluminum oxide
Catalyst is layered on upper layer by partial size 3mm, and thickness 2:2:1 is completed, and with the replacement fixed bed inside reactor gas of high pure nitrogen, uses
By the chlorocarbonic acid vinyl acetate after anhydrous hydrogen fluoride and vaporization, 1:15 is added nitrogen pressure method by volume, controls reaction temperature
185 DEG C, gaseous mixture reaction time 10 seconds, liquid product was received from exit, and tail gas initially enters condensing tower recycling hydrogen fluorine
Acid, then not solidifying gas enters+1 grade of absorbing by liquid caustic soda tower processing of 2 grades of water；
Analysis is sampled to gained liquid, the mass content of chlorocarbonic acid vinyl acetate is 0.49%, the matter of fluorinated ethylene carbonate
Measuring content is 90.2%；
By gained liquid through rectification under vacuum, the fraction that negative pressure -0.09Mpa collects 92-98 DEG C is controlled, fluoro ethylene carbonate is obtained
Ester；
Through detecting, the purity of fluorinated ethylene carbonate obtained by the implementation case is 98.36%, yield 93.1%.
The embodiment of this patent is explained in detail above, it is those skilled in the art that place is not described in detail by the present invention
The well-known technique of member.
The method that the continuous gas phase catalytic fluorination of a kind of fixed bed proposed by the present invention prepares fluorinated ethylene carbonate, and it is existing
Technology is compared, and the method for the present invention step is simple, with short production cycle, is vaporized with anhydrous hydrogen fluoride gas and chlorocarbonic acid vinyl acetate
Gas afterwards, which is continuously passed through fixed bed reactors, to carry out gas phase reaction and prepares fluorinated ethylene carbonate, shortens reaction time, significant
Reaction efficiency is improved, and contained hydrogen fluoride and chlorination hydrogen amount are few in liquid product, does not need in addition to heat removing sour gas, receive
Collection is simple；The tail gas for reacting last institute's output is handled by condensing tower can be achieved hydrofluoric acid condensation reuse, and hydrogen chloride passes through lye
Absorption can make by-product use, and safety and environmental protection is particularly suitable for industrialized production.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features,
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (9)
1. a kind of method that the continuous gas phase catalytic fluorination of fixed bed prepares fluorinated ethylene carbonate, it is characterised in that: including following
Step:
S1, using chlorocarbonic acid vinyl acetate as raw material, in the case where being fluorinated hydrogen atmosphere, in the presence of fluorination catalyst, occur the fluoro- chlorine of gas phase
Exchange reaction obtains fluorinated ethylene carbonate or/and vinylene carbonate；
Chlorocarbonic acid vinyl acetate is vaporized and is each led into anhydrous hydrogen fluoride gas after nitrogen is replaced by S2, catalytic fluorination reaction
The fixed bed reactors of catalyst are placed with, carry out catalytic fluorination reaction at a certain temperature；
S3, generation fluorinated ethylene carbonate liquid product pass through from flowing to discharge port and be collected；
S4, last institute's output tail gas by condensing tower carry out condensing recovery utilization, fixed gas by absorption plant absorb disposition.
2. the method that the continuous gas phase catalytic fluorination of a kind of fixed bed according to claim 1 prepares fluorinated ethylene carbonate,
It is characterized by: fluorination catalyst is active carbon or metal fluoride in the S1, the metal fluoride is aluminum fluoride, fluorine
Change at least one of magnesium, ferric flouride, cobaltous fluoride, nickel fluoride, charomic fluoride, zinc fluoride or several.
3. the method that the continuous gas phase catalytic fluorination of a kind of fixed bed according to claim 1 prepares fluorinated ethylene carbonate,
It is characterized by: in the S2, the ratio between the mole of the chlorocarbonic acid vinyl acetate and anhydrous hydrogen fluoride that are passed into reactor is
1:1~15.
4. the method that the continuous gas phase catalytic fluorination of a kind of fixed bed according to claim 1 prepares fluorinated ethylene carbonate,
It is characterized by: catalyst is chromium base, magnesium-based, nickel-based aluminum oxide load and/or silicon dioxide carried fluorination catalyst in the S2
The mixture of catalyst one or more of them.
5. the method that the continuous gas phase catalytic fluorination of a kind of fixed bed according to claim 4 prepares fluorinated ethylene carbonate,
It is characterized by: the catalyst is divided into three layers of upper, middle and lower, wherein lower layer's partial size is 20-50mm, intermediate 5-20mm, upper layer partial size
Less than 5mm.
6. the method that the continuous gas phase catalytic fluorination of a kind of fixed bed according to claim 1 prepares fluorinated ethylene carbonate,
It is characterized by: certain temperature is 135~185 DEG C in the S2.
7. the method that the continuous gas phase catalytic fluorination of a kind of fixed bed according to claim 1 prepares fluorinated ethylene carbonate,
It is characterized by: the fluorinated ethylene carbonate liquid product of generation flow to discharge port certainly and is collected in the S3.
8. the method that the continuous gas phase catalytic fluorination of a kind of fixed bed according to claim 1 prepares fluorinated ethylene carbonate,
It is characterized by: condensing tower condensation temperature is controlled at 7 DEG C or less in the S4.
9. the method that the continuous gas phase catalytic fluorination of a kind of fixed bed according to claim 1 prepares fluorinated ethylene carbonate,
It is characterized by: condensing gas is hydrogen fluoride in the S4, fixed gas is hydrogen chloride, and fixed gas is absorbed using lye.
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| CN201910281711.3A CN110041299A (en) | 2019-04-09 | 2019-04-09 | A kind of method that the continuous gas phase catalytic fluorination of fixed bed prepares fluorinated ethylene carbonate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876450A (en) * | 2021-01-19 | 2021-06-01 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Preparation method and application of cyclic carbonate |
| CN114315785A (en) * | 2021-12-29 | 2022-04-12 | 浙江工业大学 | Method for preparing fluoroethylene carbonate by continuous gas-phase fluorine-chlorine exchange of fixed bed |
| CN115043812A (en) * | 2022-08-16 | 2022-09-13 | 北京宇极科技发展有限公司 | Method for preparing vinylene carbonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513158A (en) * | 2011-12-05 | 2012-06-27 | 上海师范大学 | Method for preparing ethylene carbonate through continuous heterogeneous catalysis and catalyst |
| CN108329293A (en) * | 2018-04-20 | 2018-07-27 | 北京宇极科技发展有限公司 | The method that gas phase continuously prepares fluorinated ethylene carbonate or/and vinylene carbonate |
| CN109336859A (en) * | 2018-09-29 | 2019-02-15 | 南通新宙邦电子材料有限公司 | A kind of preparation method of fluorinated ethylene carbonate |
-
2019
- 2019-04-09 CN CN201910281711.3A patent/CN110041299A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513158A (en) * | 2011-12-05 | 2012-06-27 | 上海师范大学 | Method for preparing ethylene carbonate through continuous heterogeneous catalysis and catalyst |
| CN108329293A (en) * | 2018-04-20 | 2018-07-27 | 北京宇极科技发展有限公司 | The method that gas phase continuously prepares fluorinated ethylene carbonate or/and vinylene carbonate |
| CN109336859A (en) * | 2018-09-29 | 2019-02-15 | 南通新宙邦电子材料有限公司 | A kind of preparation method of fluorinated ethylene carbonate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876450A (en) * | 2021-01-19 | 2021-06-01 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Preparation method and application of cyclic carbonate |
| CN114315785A (en) * | 2021-12-29 | 2022-04-12 | 浙江工业大学 | Method for preparing fluoroethylene carbonate by continuous gas-phase fluorine-chlorine exchange of fixed bed |
| CN115043812A (en) * | 2022-08-16 | 2022-09-13 | 北京宇极科技发展有限公司 | Method for preparing vinylene carbonate |
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Application publication date: 20190723 |
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