CN104744423B - A kind of process of continuous prodution vinylene carbonate - Google Patents
A kind of process of continuous prodution vinylene carbonate Download PDFInfo
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- CN104744423B CN104744423B CN201510114056.4A CN201510114056A CN104744423B CN 104744423 B CN104744423 B CN 104744423B CN 201510114056 A CN201510114056 A CN 201510114056A CN 104744423 B CN104744423 B CN 104744423B
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- vinylene carbonate
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- triethylamine
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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
- C07D317/34—Oxygen atoms
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of continuous prodution vinylene carbonate, including process units and production method.Process units includes tubular reactor（1）, equipment for separating liquid from solid（2）, knockout tower（3）, fractional condenser（4）, condenser（5）, two grades of equipment for separating liquid from solid（6）, equipment room connecting pipeline, display with control instrument and adnexa；Production method is raw material monochloroethylene carbonate and triethylamine continuously enters tubular reactor in proportion（1）；Reactant liquor is through equipment for separating liquid from solid（2）Knockout tower is entered after the solid phase that removing generates（3）；Tower top distillates unreacted triethylamine and the vinylene carbonate mixing gas of reaction generation enters fractional condenser（4）；Once condense to obtain vinylene carbonate, a part returns knockout tower as backflow（3）, another part is product；Triethylamine enters condenser（5）Condensation Posterior circle return system participates in reacting again；Knockout tower（3）Tower bottoms is recycled back into system and participates in again reacting.
Description
Technical field
The present invention relates to a kind of preparation method of chemical products, more particularly to a kind of continuous prodution vinylene carbonate
Process.
Background technology
Vinylene carbonate is a kind of important lithium-ion battery electrolytes additive.The same triithylamine of chlorocarbonic acid vinyl acetate
Occur elimination reaction can generate vinylene carbonate；In this course of reaction, the hydrogen chloride of generation can be with the three of a large amount of presence
Ethamine reaction generates triethylamine hydrochloride, and vinylene carbonate is a kind of strong esters of activity, and polyreaction can occur under high temperature
The triethylamine hydrochloride being generated with dehydrochlorination reaction is mixed to form one kind and is difficult to detached dark thick shape material, so that purpose is produced
Thing vinylene carbonate is surrounded by sticky mass, is unfavorable for that later separation is more and acquires high-purity product.For as many as possible
Ground obtains high-purity vinylene carbonate, and people add solvent so that product is easily isolated in reaction system；Add polymerization inhibitor
To suppress product to be polymerized.
At present, chlorocarbonic acid vinyl acetate is autoclave Deca with the production process that triethylamine react produces methyl ethyl carbonate alkene ester
Reaction intermittently operated, low production efficiency, product quality is difficult to ensure, raw material availability is not high.Develop a kind of continuous prodution carbon
The process of sour vinylene, improve production efficiency, improve product quality, improves raw material availability significant.
Content of the invention
It is an object of the invention to provide one kind is sub- for raw material continuous prodution carbonic acid with chlorocarbonic acid vinyl acetate and triethylamine
The method of vinyl acetate, using the tubular reactor setting turbulent element in peripheral hardware chuck, mass-and heat-transfer effect is good, reactant for the method
Fully, response speed is fast, good product quality for material contact；Can make to produce carbonic acid Asia second with chlorocarbonic acid vinyl acetate and triethylamine react
The process of alkene ester realizes continuous prodution.
Technical scheme is as follows：
A kind of process of continuous prodution vinylene carbonate, including following process units and production method：
Process units includes：Tubular reactor, equipment for separating liquid from solid, knockout tower, fractional condenser, condenser, equipment room connect
Pipeline, display and control instrument and adnexa；Tubular reactor 1 is to set pipe in or without the blank pipe of chuck or continuously or discontinuously
Put the dynamic and static hybrid element that material is risen with perturbation action；
B. production method includes：a）Raw material chlorocarbonic acid vinyl acetate and triethylamine and polymerization inhibitor are continuously entered by regulation mol ratio
Enter tubular reactor, the Axial Temperature Distribution in heat control reactor is transmitted by tubular reactor chuck, makes reactor
Outlet temperature is less than the boiling point of triethylamine（When containing unconverted triethylamine in tubular reactor outlet material）Or it is sub- less than carbonic acid
Vinyl acetate boiling temperature；b）The reactant liquor going out tubular reactor enters equipment for separating liquid from solid, isolates the reactant liquor after solid phase and enters to divide
From tower；c）Separate column overhead and distillate vinylene carbonate and triethylamine mixed vapour, through once condensing to obtain vinylene carbonate, one
Part makees backflow, and another part does product；Knockout tower overhead vapours time condensation obtains triethylamine return system and participates in again instead
Should；d）Knockout tower tower bottoms is recycled back into system and continues to participate in reaction.
A kind of process of described continuous prodution vinylene carbonate, feedstock mol ratio preferably employs chloro
Ethylene carbonate is excessive, makes in pipe reactor outlet material no triethylamine, and no raw material triethylamine is recycled back into system and again participates in
The operation of reaction；
A kind of process of described continuous prodution vinylene carbonate, isolate the reactant liquor of solid phase preferably by point
From the charging of tower tower reactor, both preferable separate tower only had rectifying section, did not set stripping section；
A kind of process of described continuous prodution vinylene carbonate, the unconverted chlorine of liquid storage in knockout tower tower reactor
Allow a certain proportion of vinylene carbonate for ethylene carbonate；
A kind of process of described continuous prodution vinylene carbonate, before equipment for separating liquid from solid is arranged on knockout tower
Or after, or before and after knockout tower, it is respectively provided with equipment for separating liquid from solid；
A kind of process of described continuous prodution vinylene carbonate, between tubular reactor and equipment for separating liquid from solid
Arrange or be not provided with reactant liquor pans；Arrange or be not provided with separating liquid pans between equipment for separating liquid from solid and knockout tower；
A kind of process of described continuous prodution vinylene carbonate, equipment for separating liquid from solid used can be centrifugation
Segregation apparatuss, filtering separation device, settling separation device are not limited to the combination of these devices and these devices；
A kind of process of described continuous prodution vinylene carbonate, can be using double tower operation from removing solid phase
Unconverted raw material triethylamine and product vinylene carbonate is isolated in reactant liquor；
A kind of process of described continuous prodution vinylene carbonate, the available solvent being not involved in reacting is to one
Raw material carries out premixing or two strands of raw materials is carried out continuously entering tubular reactor after premixing simultaneously；
It is an advantage of the invention that：
1. the process producing vinylene carbonate with chlorocarbonic acid vinyl acetate and triethylamine react can be made to realize continuous metaplasia
Produce；
2. do not pursue a conversion ratio of raw material, unconverted raw material return system participates in reacting again, and operating flexibility is big；
3. using the tubular reactor setting turbulent element in peripheral hardware chuck, mass-and heat-transfer effect is good, and reaction mass contact is filled
Point, response speed is fast, good product quality；
4. reactants separate adopts tower to feed, and the operation of only distillation operation, no stripping can preferentially ensure the pure of overhead product
Degree.
Brief description
Fig. 1 is with chlorocarbonic acid vinyl acetate and triethylamine for the letter of the process units of raw material continuous prodution vinylene carbonate
Figure.
Specific embodiment
The present invention is described in detail for embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Continuous prodution vinylene carbonate process units includes：Tubular reactor 1, equipment for separating liquid from solid 2, knockout tower 3,
Fractional condenser 4,5, two grades of equipment for separating liquid from solid 6 of condenser, equipment room connecting pipeline, control instrument and adnexa；Tubular reactor 1 is straight
Pipeline section is commercially available static mixer, and curved tube section is blank pipe.
Continuous prodution vinylene carbonate production method includes：Raw material chlorocarbonic acid vinyl acetate and triethylamine rub by theory
You than enter tubular reactor while flowing, while mix, while reacting, while conduct heat；The material going out tubular reactor enters solid-liquid separation
The triethylamine hydrochloride that device abjection generates, the liquid phase after taking off admittedly enters knockout tower by tower reactor；Tower top distillates unreacted three second
Amine and the vinylene carbonate mixed vapour of reaction generation, once condense to obtain vinylene carbonate, part conduct point in order
From column overhead backflow, another part is as crude product；Time condensation obtains triethylamine return system and participates in again reacting；Knockout tower tower
Kettle liquid is unconverted chlorocarbonic acid vinyl acetate and part vinylene carbonate and a small amount of triethylamine hydrochloride, and return system is again
Participate in reaction.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, and difference is in advance in raw material chlorocarbonic acid vinyl acetate（Or three second
Amine）Middle addition polymerization inhibitor, then with triethylamine（Or chlorocarbonic acid vinyl acetate）Converge entrance tubular reactor.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, and difference is that one raw material is first mixed into regulation before entering the reactor
The solvent of ratio, another strand of raw material is mixed into polymerization inhibitor before entering the reactor in advance, and two strands of raw materials enter warp after reactor reaction
After equipment for separating liquid from solid isolates solid phase, increase solvent recovery operation, take off the reactant liquor admittedly and after recycling design and enter knockout tower.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, and difference is all to fill in tubular reactor straight length and curved tube section
Chemical filler.
Claims (5)
1. a kind of process of continuous prodution vinylene carbonate it is characterised in that methods described include process units and
Production method：
A. process units includes：Tubular reactor（1）, equipment for separating liquid from solid（2）, knockout tower（3）, fractional condenser（4）, condenser
（5）, two grades of equipment for separating liquid from solid（6）, equipment room connecting pipeline, control instrument and adnexa；Tubular reactor（1）Be with or without
The blank pipe of the chuck or dynamic and static perturbation element that material is risen with perturbation action is continuously or discontinuously set in pipe；
B. production method includes：a）Raw material chlorocarbonic acid vinyl acetate and triethylamine and polymerization inhibitor continuously enter pipe by regulation mol ratio
Formula reactor（1）, the Axial Temperature Distribution in heat control reactor is transmitted by tubular reactor chuck, makes going out of reactor
Mouth temperature is less than the boiling point of triethylamine or is less than vinylene carbonate boiling temperature；b）Go out tubular reactor（1）Reactant liquor enter
Equipment for separating liquid from solid（2）, isolate the reactant liquor after solid phase and enter knockout tower（3）；c）Knockout tower（3）Tower top distillates vinylene carbonate
Ester and triethylamine mixed vapour, through once condensing to obtain vinylene carbonate, a part makees backflow, and another part does product；Point
From tower（3）Overhead vapours time condensation obtains triethylamine return system and participates in again reacting；d）Knockout tower（3）Tower bottoms is recycled back into
System continues to participate in reaction；
The described reactant liquor isolating solid phase is by knockout tower（3）Tower reactor feeds, knockout tower（3）Only rectifying section, does not set stripping section；
Described equipment for separating liquid from solid（2）It is arranged on knockout tower（3）Front or rear, or knockout tower（3）It is respectively provided with solid-liquid separation dress in front and back
Put；
Described tubular reactor（1）And equipment for separating liquid from solid（2）Between arrange or be not provided with reactant liquor pans；Equipment for separating liquid from solid
（2）With knockout tower（3）Between arrange or be not provided with separating liquid pans；
Described equipment for separating liquid from solid is centrifugal separating device or filtering separation device or settling separation device and these devices
Combination.
2. a kind of process of continuous prodution vinylene carbonate according to claim 1 is it is characterised in that described
Feedstock mol ratio to preferably employ chlorocarbonic acid vinyl acetate excessive, make pipe reactor（1）No triethylamine in outlet material, no
Raw material triethylamine is recycled back into the operation that system participates in reacting again.
3. a kind of process of continuous prodution vinylene carbonate according to claim 1 is it is characterised in that described
Knockout tower（3）In tower reactor, liquid storage unconverted chlorocarbonic acid vinyl acetate has allowed a certain proportion of vinylene carbonate.
4. a kind of process of continuous prodution vinylene carbonate according to claim 1 is it is characterised in that described
Method can isolate unconverted raw material triethylamine and product carbonic acid using double tower operation from the reactant liquor of removing solid phase
Vinylene.
5. a kind of process of continuous prodution vinylene carbonate according to claim 1 is it is characterised in that described
Method can be carried out premixing or two strands of raw materials are carried out connecting after premixing simultaneously using the solvent being not involved in reacting to one raw material
Continuous entrance tubular reactor（2）.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510114056.4A CN104744423B (en) | 2015-03-17 | 2015-03-17 | A kind of process of continuous prodution vinylene carbonate |
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| CN201510114056.4A CN104744423B (en) | 2015-03-17 | 2015-03-17 | A kind of process of continuous prodution vinylene carbonate |
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| CN112174928A (en) * | 2020-11-02 | 2021-01-05 | 浙江天硕氟硅新材料科技有限公司 | Novel vinylene carbonate synthesis preparation method |
| CN112397781B (en) * | 2020-11-17 | 2022-06-07 | 徐文忠 | Preparation method of vinylene carbonate additive for lithium battery car electrolyte |
| CN112436187B (en) * | 2020-11-24 | 2022-12-02 | 徐文忠 | Gel electrolyte for lithium battery |
| CN114749136A (en) * | 2022-04-14 | 2022-07-15 | 山东惟普新能源有限公司 | Tubular reactor and system device for continuously preparing vinylene carbonate |
| CN116003374B (en) * | 2022-12-16 | 2024-03-29 | 山东惟普新能源有限公司 | Method for synthesizing immediately separated vinylene carbonate |
| CN115716815B (en) * | 2022-12-22 | 2024-03-29 | 青岛科技大学 | Method and system for continuously preparing vinylene carbonate |
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| CN200998645Y (en) * | 2006-09-29 | 2008-01-02 | 沈阳化工学院 | Pipe fluid destabilization device capable of reinforcing mass transfer and heat transfer |
| CN104327037A (en) * | 2014-10-16 | 2015-02-04 | 荣成青木高新材料有限公司 | Vinylene carbonate preparation method |
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