CN108707095A - The continuous method for preparing sulfuric acid vinyl ester - Google Patents
The continuous method for preparing sulfuric acid vinyl ester Download PDFInfo
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- CN108707095A CN108707095A CN201810783141.3A CN201810783141A CN108707095A CN 108707095 A CN108707095 A CN 108707095A CN 201810783141 A CN201810783141 A CN 201810783141A CN 108707095 A CN108707095 A CN 108707095A
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- sulfuric acid
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- vinyl ester
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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Abstract
The present invention provides a kind of continuous method for preparing sulfuric acid vinyl ester, includes the following steps：(1) ethylene sulfite is diluted with carbonate-based solvent and is dissolved, is configured to A liquid by the preparation steps of material liquid, and sodium hypochlorite and catalyst are mixedly configured into B liquid；(2) the A liquid and the B liquid are simultaneously and continuously imported tubular reactor by successive reaction step, reaction temperature is 5~15 DEG C, the molar ratio of ethylene sulfite and sodium hypochlorite is 1:1.2~1:Successive reaction is carried out under conditions of 2.5, is collected simultaneously solution after reaction；(3) processing step of solution after reacting, solution natural layering after reaction recycle organic phase, and evaporated under reduced pressure after being neutralized obtains sulfuric acid vinyl ester.Through the invention, the sulfuric acid vinyl ester of high-purity can be can be obtained by simple method, and effectively improves the mass-and heat-transfer effect of reaction, reduce wastewater discharge, in addition, the organic solvent used in reaction can recycle, be conducive to cost-effective.
Description
Technical field
The present invention relates to a kind of continuous methods for preparing sulfuric acid vinyl ester.
Background technology
Sulfuric acid vinyl ester is the very important additive in secondary lithium battery nonaqueous electrolytic solution, can be in secondary lithium
The cathode of ion battery forms SEI films, can especially improve and improve the performance of secondary lithium battery, can inhibit carbonic acid third
The interaction of enester solvent and natural graphite improves the cycle performance of battery core, while can improve lithium battery electric core in high temperature
When capacity restoration, expand the temperature in use of lithium battery.
Currently, the synthetic method as sulfuric acid vinyl ester, main use makes ethylene sulfite, sodium hypochlorite and tri-chlorination
The method that ruthenium is reacted at low temperature.In the method, sodium hypochlorite carries out usually in the form of 10~13% aqueous solution
It uses, releases a large amount of heat during the reaction, can lead to react generated sulfuric acid vinyl ester fast hydrolyzing, therefore, anti-
Reaction temperature must be controlled in low temperature during answering.In order to control temperature, usually used when using common still reaction method
Blender is constantly stirred, but is still not sufficient to ensure that above-mentioned raw materials i.e. sulfuric acid Asia ethylene fat, sodium hypochlorite, tri-chlorination
Ruthenium equably mixes in container, there are in reaction kettle actual temperature be distributed non-uniformity the case where, so as to cause product
Sulfuric acid vinyl ester is hydrolyzed in part because of overheat.Often production 1kg sulfuric acid vinyl esters about generates 20kg contain a large amount of chlorine with
The waste water of COD (organic matter), causes environmental pressure to aggravate, while considerably increasing cost for wastewater treatment.
In addition, be solid under sulfuric acid vinyl ester room temperature, and it is not soluble in water, so when continuously preparing sulfuric acid vinyl ester, as
The sulfuric acid vinyl ester of final product is very easy to be precipitated, to block flow path, therefore, to there is no continuous preparation at present in reacting flow path
The technique of sulfuric acid vinyl ester.
Invention content
Problems to be solved by the invention
Project present in for the above-mentioned prior art, the purpose of the present invention is to provide one kind can continuously preparing sulfuric acid second
The method of enester.
Technological means for solving project
The present invention provides a kind of continuous method for preparing sulfuric acid vinyl ester, which is characterized in that includes the following steps：
(1) ethylene sulfite is diluted with carbonate-based solvent and is dissolved, is configured to A liquid by the preparation steps of material liquid, will
Sodium hypochlorite is mixedly configured into B liquid with catalyst；
(2) the A liquid and the B liquid are simultaneously and continuously imported tubular reactor by successive reaction step, in reaction temperature
Degree is 5~15 DEG C, the molar ratio of ethylene sulfite and sodium hypochlorite is 1:1.2~1:Successive reaction is carried out under conditions of 2.5,
It is collected simultaneously solution after reacting；
(3) processing step of solution after reacting, solution natural layering after reaction recycle organic phase, are depressurized after being neutralized
It is evaporated, obtains sulfuric acid vinyl ester.
Preferably, above-mentioned tubular reactor is microchannel continuous flow reaction unit.
Preferably, above-mentioned carbonate-based solvent is dimethyl carbonate, methyl ethyl carbonate or diethyl carbonate.
Preferably, above-mentioned catalyst is ruthenium based compound, for example, can be ruthenic chloride or ruthenium-oxide.
Preferably, in above-mentioned successive reaction step, continuous reaction time is 100~300 seconds.
Preferably, above-mentioned carbonate based organic solvent be dimethyl carbonate, and above-mentioned ethylene sulfite with time
The molar ratio of sodium chlorate is 1/2.
Invention effect
The present invention can be obtained the sulfuric acid vinyl ester of high-purity by simple preparation method, and method of the invention is effectively
The mass-and heat-transfer effect of reaction is improved, wastewater discharge is reduced, a large amount of waste water of yield in existing commercial synthesis is greatly reduced
Drawback.In addition, the organic solvent used in reaction can recycle, be conducive to cost-effective.
Specific implementation mode
Microchannel continuous flow reaction unit or other tubular type/flow path formula reactors with mixed function are general to have spy
The heat and mass of different combination construction, reactant improves hundreds times compared with common still reaction device, can greatly promote
Into the mixed effect between raw material, while microchannel continuous flow reaction unit can realize sufficient temperature control, can be effectively
Ensure uniform low temperature environment in reaction system, the generation of waste water can be substantially reduced.One of the characteristics of preparation method of the present invention
It is, above-mentioned apparatus is applied to the preparation of sulfuric acid vinyl ester for the first time.
But inventor has found under study for action, the fusing point of the sulfuric acid vinyl ester generated is less than 0 DEG C, that is, in normal low temp
Reaction system in be solid, so, when according to reaction condition identical with still reaction, utilize microchannel reaction unit prepare
When sulfuric acid vinyl ester, there is generated sulfuric acid vinyl ester solid and block the flow path of tubular reactor, cause system jams superpressure
The problem of, cause reaction to can not be successfully progress.In view of the above problems, inventor has found after numerous studies, specific by setting
Reaction condition can efficiently solve the problems caused by blocking.
The preparation method of the present invention includes following process.
(1) dilution of ethylene sulfite carbonate based organic solvent is configured to A liquid, sodium hypochlorite and catalyst is mixed
Conjunction is configured to B liquid.
The carbonate based organic solvent selected in the present invention can dissolve raw material ethylene sulfite and final product sulfuric acid second
Enester, is a kind of solvent larger to final product sulfuric acid vinyl ester solubility, and the product generated in reaction process can be dissolved in
In the solvent, and the solvent is not soluble in water, is layered with self-assembling formation with sodium hypochlorite, can be readily available and be contained by liquid separation
There is the solution of final product crude product.The solution is washed, is recrystallized, you can obtain the sterling of sulfuric ester.
Above-mentioned organic solvent can dissolve ethylene sulfite and final products sulfuric acid vinyl ester so that sulfurous acid ethylene
Ester and final products sulfuric acid vinyl ester exist with the state of liquid always in the reaction system, so as to prevent sulfuric acid ethylene
Ester solid blocks the flow path of microchannel continuous flow reactor.In addition, above-mentioned organic solvent and water are immiscible, so as to subsequent point
From extraction.
Organic solvent should select the solvent larger to product sulfuric acid vinyl ester solubility, and choosing the larger solvent of solubility can
To be effectively reduced the usage amount of organic solvent, the energy consumption of the following solvent recovery is reduced, choosing the relatively low solvent of solubility can make
It is big and raw material is excessively diluted at the usage amount of solvent, cause the reduction of reaction efficiency.From the above considerations, of the invention
In specific selection carbonate based organic solvent, it is preferable to use dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate
(DEC) etc..
In addition, above-mentioned catalyst can be common catalyst, not special restriction, example when preparing sulfuric acid vinyl ester
Such as can be ruthenium system chemicals, such as ruthenic chloride, ruthenium-oxide etc.
(2) successive reaction step
Above-mentioned A liquid and B liquid are simultaneously and continuously imported into tubular reactor, are 5~15 DEG C, sulfurous acid second in reaction temperature
Enester and the molar ratio of sodium hypochlorite are 1:1.2~1:Successive reaction is carried out under conditions of 2.5, is collected simultaneously solution after reaction
In the present invention by the reaction temperature of successive reaction be set as 5~15 DEG C, which is because, if temperature be less than 5 degree,
The water being be easy to cause in flow path when especially close to 0 degree can freeze, volume expansion, and blocking reveals or even reactor can be caused broken
Damage.It should be noted that reaction temperature cannot be below the molten point of selected solvent simultaneously, otherwise can equally cause passage blockage and reactor
Damage.When temperature is higher than 15 DEG C, because there is water in reaction system, temperature, which increases, will gradually cause the hydrolysis of sulfuric acid vinyl ester, drop
Low crude product purity.
In above-mentioned reaction, the time of successive reaction is preferably set to 100~300 seconds.
(3) processing step of solution after reacting
Natural layering after solution left standstill after reaction recycles water phase, and sodium hydrogensulfite is added and neutralizes.Organic phase is recycled, is carried out
Neutrality is washed and be neutralized to, organic phase evaporated under reduced pressure is obtained to the crude product and organic solvent recovered liquid of sulfuric acid vinyl ester respectively.Have
Solvent recovered liquid carries out molecular sieve dehydration processing, can be recycled later, is re-used for the preparation of ethylene sulfite.
Embodiment
Hereinafter, the present invention is illustrated by embodiment in further detail, but the present invention is not limited thereto.
Microchannel reaction unit (the healthy and free from worry SiC reactors of France) used in embodiment includes 5 reaction modules, each
The volume of flow path is 10ml in module, and use temperature range is 5~200 DEG C.The temperature that each flow path is arranged is 5-20 DEG C.
Embodiment 1
100g ethylene sulfites are mixed with 400g dimethyl carbonates, are configured to A liquid, by sodium hypochlorite 1000g with urge
The 2g mixing of agent solution of ruthenium trichloride, is configured to B liquid, as reaction solution.
It is imported in the reaction unit of microchannel with the flow velocity of 20ml/min using dimethyl carbonate solution, is rinsed 5min
(that is, the amount using three times flow rate volume is rinsed).PTFE pumps (Corning Incorporated's system) are used to import A with overall flow rate 60ml/min later
Liquid and B liquid, it is 1/1.5 to make the molar ratio of ethylene sulfite and sodium hypochlorite, and reaction temperature is 10 degree, and the reaction time is
100s after reaction carries out 5min, picks up suitable sample with this condition.Sodium hydrogensulfite is added and is neutralized to neutrality, sample is quiet
Layering is postponed, the organic phase of lower layer is taken out, is washed according to organic phase using pure water, GC is in washing afterwards three times, can be obtained pure
The sulfuric acid vinyl ester of degree 93.39%.
Embodiment 2-9
According to reaction condition shown in table 1, operate same as Example 1ly, acquired results are as shown in table 1.
Table 1
Comparative Examples 1 and 2
According to condition shown in table 2, operated same as Example 1ly, acquired results are as shown in table 2.
Comparative example 3
100g ethylene sulfites and 1000g dichloromethane are uniformly mixed, A liquid is configured to, by sodium hypochlorite 1000g with
The 2g mixing of catalyst solution of ruthenium trichloride, is configured to B liquid.Next, being led with the flow velocity of 20ml/min using dichloromethane solution
In a subtle way in pathway reaction device, it is rinsed 5min (that is, the amount using three times flow rate volume is rinsed).It is pumped later using PTFE
(Corning Incorporated's system) imports A liquid and B liquid, the molar ratio of ethylene sulfite and sodium hypochlorite with the flow velocity of overall flow rate 40ml/min
It is 1/2, reaction temperature is 10 degree.With this condition, after reaction carries out 5min, suitable sample is picked up.Sodium hydrogensulfite is added
It is neutralized to neutrality, sample is layered after standing, takes out the organic phase of lower layer, washed using pure water, and GC is in washing afterwards three times,
The sulfuric acid vinyl ester of purity 74.39% can be obtained.
Table 2
Comparative example 4 (discontinuous still reaction)
Taking the ethylene sulfite crude product (laboratory synthesis) of 95% or more purity, 100g is in beaker, by beaker as ice
In bath, catalyst solution 2g is added, control material temperature is 0 DEG C.Prepare the aqueous sodium hypochlorite solution of 10% concentration simultaneously
1000g controls its temperature at 0 DEG C.Then 0 DEG C of liquor natrii hypochloritis is added dropwise to 0 DEG C of ethylene sulfite and catalysis
The mixing of agent, while opening stirring (mixing speed 500rpm), and controlled at 0 DEG C, be added dropwise to complete after 1 lab scale.Kept for 0 DEG C
The reaction was continued 1h, is obtained by filtration white solid, and weight is 85g after being dried using Rotary Evaporators；A small amount of solid is taken, dichloromethane is used
After alkane solution, GC chromatographies are done, it is 79.82% to obtain sulfuric acid vinyl ester purity.
By Examples 1 to 3 it is found that the molar ratio in ethylene sulfite/sodium hypochlorite is 1/1.5,10 DEG C of reaction temperature
When, sulfuric acid vinyl ester crude product purity is up to 90~95%.Reaction time can lead to partial hydrolysis when long, and purity is caused to have decline
Trend.
By embodiment 4,6 it is found that the molar ratio when ethylene sulfite/sodium hypochlorite is less than 1/1.2 compared with comparative example 1
When, sulfuric acid vinyl ester crude product purity is substantially reduced.Since raw material is diluted by solvent, when reaction, greatly reduces intermolecular collision
Probability, so need improve a mole Bizet be conducive to reaction carry out.
Embodiment 6~8 can be obtained compared with comparative example 2 it is found that by the way that reaction temperature is specific at 5~15 DEG C
Higher crude product purity.In addition, using embodiment 6~8 it is found that when using dimethyl carbonate as organic compared with other embodiments
Solvent makes the molar ratio of ethylene sulfite/sodium hypochlorite be 1/2, when temperature is 5~15 DEG C, and gained crude product purity is reachable
95% or more, obtain superior effect.
By by embodiment compared with comparative example 3 it is found that since dichloromethane is at normal temperatures to the dissolving of sulfuric acid vinyl ester
Spend for 10% hereinafter, and dimethyl carbonate to the solubility of sulfuric acid vinyl ester 30%, therefore used quantity of solvent is to use
3 times or so when dimethyl carbonate.In addition, by using dichloromethane as organic solvent, the product of gained sulfuric acid vinyl ester
Purity is relatively low.
Organic solvent purity used in above-mentioned continuous preparation method is organic by gained after reaction 98% or more
Mix, organic solvent recycled using Rotary Evaporators, is dehydrated using molecular sieve column, the purity for being GC be 95% with
On, which can recycle, and organic solvent recovery utilization rate is 90% or more.
In the discontinuous reaction as comparative example 5, sodium hypochlorite is used in the form of 10% aqueous solution, anti-
A large amount of heat should be released in the process, in order to prevent because a large amount of thermal conductivity released causes the generated quick water of sulfuric acid vinyl ester
Solution, it is necessary to constantly be stirred, but uneven due to container for stirring, so must control temperature at 0 DEG C.And micro-
Since heat exchange is rapid and uniformly, temperature need not be controlled in 5 DEG C or so by special means in pathway reaction container.
In addition, since reactant is diluted, need to maintain higher sodium hypochlorite ratio, to promote to carry out to product.From
Economy and actual effect consider that the molar ratio of ethylene sulfite and sodium hypochlorite is most preferably controlled 1：2.
The limited volume of tubular reactor device when overall flow rate is fast, can increase mixed effect, promote reaction efficiency, but
Retention time in reactor shortens, it is also possible to which reaction is not enough, so the suitable reaction time is critically important.This reaction is most
The preferred reaction time is in 100-300S.
Industrial availability
Established in the present invention can continuous sulphuric acid production vinyl acetate technique, method is simple and efficient, and obtains the purity of crude product
Height, the solvent used in reaction can be recycled effectively, greatly reduce the wastewater flow rate in discontinuous reaction, be conducive to industrial metaplasia
Production.
Claims (7)
1. a kind of continuous method for preparing sulfuric acid vinyl ester, which is characterized in that include the following steps：
(1) ethylene sulfite is diluted with carbonate based organic solvent and is dissolved, is configured to A liquid by the preparation steps of material liquid, will
Sodium hypochlorite is mixedly configured into B liquid with catalyst；
(2) the A liquid and the B liquid are simultaneously and continuously imported tubular reactor, are in reaction temperature by successive reaction step
5~15 DEG C, the molar ratio of ethylene sulfite and sodium hypochlorite be 1:1.2~1:Successive reaction is carried out under conditions of 2.5, simultaneously
Collect solution after reacting；
(3) processing step of solution after reacting, solution natural layering after reaction, recycling organic phase, evaporated under reduced pressure after being neutralized,
Obtain sulfuric acid vinyl ester.
2. the method as described in claim 1 for continuously preparing sulfuric acid vinyl ester, which is characterized in that the tubular reactor is micro-
Channel continuous flow reaction unit.
3. the method as described in claim 1 for continuously preparing sulfuric acid vinyl ester, which is characterized in that the carbonates are organic molten
Agent is dimethyl carbonate, methyl ethyl carbonate or diethyl carbonate.
4. the method as described in claim 1 for continuously preparing sulfuric acid vinyl ester, which is characterized in that the catalyst is ruthenium system
Close object.
5. the method as described in claim 1 for continuously preparing sulfuric acid vinyl ester, which is characterized in that the catalyst is ruthenic chloride
Or ruthenium-oxide.
6. the method as described in claim 1 for continuously preparing sulfuric acid vinyl ester, which is characterized in that in the successive reaction step
In, continuous reaction time is 100~300 seconds.
7. the method as described in claim 1 for continuously preparing sulfuric acid vinyl ester, which is characterized in that the carbonates are organic molten
Agent is dimethyl carbonate, and the molar ratio of the ethylene sulfite and sodium hypochlorite is 1/2.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456303A (en) * | 2018-11-20 | 2019-03-12 | 武汉联续流化学科技有限公司 | The method that micro passage reaction continuously synthesizes sulfuric acid vinyl ester and sulfuric acid 4- ethylene methacrylic ester |
| CN111825652A (en) * | 2019-04-17 | 2020-10-27 | 江苏长园华盛新能源材料有限公司 | Method for preparing vinyl sulfate |
| CN113683592A (en) * | 2021-08-27 | 2021-11-23 | 江苏瀚康新材料有限公司 | Preparation method of ethyl methyl carbonate solution containing ethylene sulfate |
| CN115611852A (en) * | 2022-11-01 | 2023-01-17 | 山东师范大学 | Method for synthesizing vinyl sulfate by in-situ catalytic oxidation |
| CN115745949A (en) * | 2022-10-21 | 2023-03-07 | 山东海科新源材料科技股份有限公司 | Vinyl sulfate production process |
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| CN107973774A (en) * | 2017-11-13 | 2018-05-01 | 张家港瀚康化工有限公司 | The method that sulfuric acid vinyl ester is prepared using micro passage reaction |
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| CN105481826A (en) * | 2016-01-11 | 2016-04-13 | 烟台海川化学制品有限公司 | Preparation method of ethylene sulfate |
| WO2018011062A2 (en) * | 2016-07-15 | 2018-01-18 | Solvay Sa | Nonaqueous electrolyte compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109456303A (en) * | 2018-11-20 | 2019-03-12 | 武汉联续流化学科技有限公司 | The method that micro passage reaction continuously synthesizes sulfuric acid vinyl ester and sulfuric acid 4- ethylene methacrylic ester |
| CN111825652A (en) * | 2019-04-17 | 2020-10-27 | 江苏长园华盛新能源材料有限公司 | Method for preparing vinyl sulfate |
| CN113683592A (en) * | 2021-08-27 | 2021-11-23 | 江苏瀚康新材料有限公司 | Preparation method of ethyl methyl carbonate solution containing ethylene sulfate |
| CN115745949A (en) * | 2022-10-21 | 2023-03-07 | 山东海科新源材料科技股份有限公司 | Vinyl sulfate production process |
| CN115611852A (en) * | 2022-11-01 | 2023-01-17 | 山东师范大学 | Method for synthesizing vinyl sulfate by in-situ catalytic oxidation |
| CN115611852B (en) * | 2022-11-01 | 2023-11-10 | 山东师范大学 | Method for synthesizing vinyl sulfate by in-situ catalytic oxidation |
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Address after: No. 198, Tongxing Road, Kenli District, Dongying, Shandong Province Patentee after: Shenghua New Material Group Co.,Ltd. Patentee after: FUJIAN XINCHEN CHEMICAL TECHNOLOGY Co.,Ltd. Patentee after: PMAT Co.,Ltd. Address before: No. 198, Tongxing Road, Kenli District, Dongying City, Shandong Province 257061 Patentee before: SHANDONG SHIDA SHENGHUA CHEMICAL GROUP Co.,Ltd. Patentee before: FUJIAN XINCHEN CHEMICAL TECHNOLOGY Co.,Ltd. Patentee before: PMAT Co.,Ltd. |