CN115286612A - Production method of chloroethylene carbonate - Google Patents
Production method of chloroethylene carbonate Download PDFInfo
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- CN115286612A CN115286612A CN202210894072.XA CN202210894072A CN115286612A CN 115286612 A CN115286612 A CN 115286612A CN 202210894072 A CN202210894072 A CN 202210894072A CN 115286612 A CN115286612 A CN 115286612A
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- 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
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Abstract
The invention belongs to the technical field of chemical industry, and discloses a production method of chlorinated ethylene carbonate. The production method comprises the following steps: placing ethylene carbonate into a reaction container, introducing chlorine gas from the bottom of the reaction container, placing an LED lamp on the upper part of the reaction container, and performing light irradiation catalytic reaction to obtain a product, wherein chlorinated ethylene carbonate is contained in the product; 4-6 20-30W LED lamps are arranged in each 100L ethylene carbonate in the reaction container. The specific amount of reactants is matched with the specific amount of LED lamps for catalytic reaction, so that the generation of black byproducts can be greatly reduced, and the yield of the chloroethylene carbonate in the prepared product is over 85 percent after the reaction is finished. The method is necessary for the industrial application of the chloroethylene carbonate, and is particularly beneficial to the industrial mass production of the fluoroethylene carbonate.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a production method of chlorinated ethylene carbonate.
Background
The chloroethylene carbonate (CEC) is a main raw material for preparing fluoroethylene carbonate (FEC), and the fluoroethylene carbonate can be used for preparing electrolyte and is used in the field of lithium ion batteries. In recent years, the market demand of lithium ion batteries is remarkably increased, so that the demand of fluoroethylene carbonate is remarkably increased, and the demand of chloroethylene carbonate is also remarkably increased.
The industrial method for producing fluoroethylene carbonate in the prior art mainly comprises the following three types: in the first category, ethylene Carbonate (EC) and sulfonyl chloride are adopted for chlorination reaction, but the method generates a lot of acid gases and has great pollution to the environment; and secondly, ethylene carbonate and chlorine gas are catalyzed to react under the irradiation of a high-pressure mercury lamp, the high-pressure mercury lamp is a heat light source, the reaction temperature is gradually increased in the catalysis process, the generation amount of dichloroethylene carbonate (DCEC) and some black byproducts is increased, the yield of the target product chloroethylene carbonate (CEC) is low (not more than 82%), the content of dichloroethylene carbonate (DCEC) in the product exceeds 5% and even reaches 10%, and the energy consumption of the production process is high. The generated black by-products can further block the irradiation of the light of a high-pressure mercury lamp in the actual industrial mass production process, the reaction of the ethylene carbonate and chlorine is not facilitated to be carried out, and the rate of generating chloroethylene carbonate is slower and slower as the reaction time is prolonged and the black by-products are increased; and thirdly, azodiisobutyronitrile is used as an initiator to initiate the reaction of ethylene carbonate and chlorine to generate chloroethylene carbonate (CEC), after the reaction is finished, the yield of the chloroethylene carbonate (CEC) in the product after the reaction is not more than 83%, and the content of dichloroethylene carbonate (DCEC) in the product is more than 5% and even reaches 10%, so that the low target product yield is not beneficial to large-scale industrial production of the chloroethylene carbonate (CEC).
Therefore, it is highly desirable to provide a new method for industrially mass-producing Chlorinated Ethylene Carbonate (CEC), which avoids the use of a heat source such as a high-pressure mercury lamp, does not require azobisisobutyronitrile as an initiator, has few black byproducts in the reaction process, and has a high yield of Chlorinated Ethylene Carbonate (CEC) in the product, and thus is essential for industrial application of Chlorinated Ethylene Carbonate (CEC).
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a production method of chloroethylene carbonate, which avoids using a heat light source such as a high-pressure mercury lamp and does not need to use azobisisobutyronitrile as an initiator, has few black byproducts (no obvious black byproducts visible to the naked eye) in the reaction process, has high yield of chloroethylene carbonate (CEC) in the product, has the yield of the chloroethylene carbonate exceeding 85 percent, is necessary for industrial application of the chloroethylene carbonate (CEC), and is particularly beneficial to industrial mass production of fluoroethylene carbonate (FEC).
The invention conception of the invention is as follows: according to the invention, 4-6 20-30W LED lamps are configured for every 100L of ethylene carbonate, the LED lamps are ordinary cold light source LED lamps, a specific amount of reactants are matched with a specific amount of LED lamps for catalytic reaction, the generation of black byproducts can be greatly reduced, and the yield of Chlorinated Ethylene Carbonate (CEC) in the prepared product exceeds 85% after the reaction is finished.
The invention provides a production method of chlorinated ethylene carbonate, which comprises the following steps:
placing ethylene carbonate into a reaction container, introducing chlorine gas from the bottom of the reaction container, placing an LED lamp on the upper part of the reaction container, and performing light-catalyzed reaction to obtain a product, wherein chlorinated ethylene carbonate is contained in the product;
4-6 20-30W LED lamps are arranged in the reaction container according to every 100L ethylene carbonate.
Preferably, the reaction time is 12 to 18 hours; further preferably, the reaction time is 14 to 17 hours.
Preferably, the temperature of the reaction is 60-90 ℃; further preferably, the temperature of the reaction is 65-85 ℃.
Preferably, the reaction vessel is a reaction kettle.
Preferably, the LED lamp is a 25W LED lamp, and the wavelength of light emitted by the LED lamp is 200-600nm, preferably 270-470nm.
Preferably, the distance between the LED lamps is 0.2-0.3m.
Preferably, the molar ratio of the ethylene carbonate to the chlorine gas is 1.0-1.3; further preferably, the molar ratio of ethylene carbonate to chlorine is 1.1 to 1.2.
Preferably, the pressure in the reaction kettle is 0-50KPa higher than the atmospheric pressure; further preferably, the pressure in the reaction kettle is 0-40KPa higher than the atmospheric pressure.
Preferably, the pH of the reaction system is 2 to 3 during the reaction.
Preferably, the water content in the ethylene carbonate does not exceed 30ppm; further preferably, the water content in the ethylene carbonate does not exceed 20ppm.
After the reaction is finished, the molar content of each component in the product can be detected by adopting gas chromatography.
Preferably, the mole fraction of the chloroethylene carbonate in the product is more than 85%; it is further preferred that the mole fraction of vinyl chlorocarbonate exceeds 86%. In the present invention, the mole fraction of chloroethylene carbonate in the product after the reaction is finished can be regarded as the yield of chloroethylene carbonate.
Preferably, the mole fraction of ethylene Dichlorocarbonate (DCEC) in the product does not exceed 5%; it is further preferred that the mole fraction of ethylene Dichlorocarbonate (DCEC) does not exceed 4%.
Preferably, the mole fraction of unreacted Ethylene Carbonate (EC) in the product does not exceed 5%; it is further preferred that the mole fraction of unreacted Ethylene Carbonate (EC) does not exceed 4%.
Preferably, the molar fraction of substances other than vinyl chlorocarbonate, vinyl dichlorocarbonate and vinyl carbonate in the product amounts to not more than 5%.
The application of the production method in preparing fluoroethylene carbonate.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, 4-6 20-30W LED lamps are configured for every 100L of ethylene carbonate, the LED lamps are ordinary cold light source LED lamps, a specific amount of reactants are matched with a specific amount of LED lamps for catalytic reaction, the generation of black byproducts can be greatly reduced, and the yield of Chlorinated Ethylene Carbonate (CEC) in the prepared product exceeds 85% after the reaction is finished. This is necessary for the industrial application of chloroethylene carbonate (CEC), and is particularly advantageous for the industrial mass production of fluoroethylene carbonate (FEC).
Detailed Description
In order to make the technical solutions of the present invention more clearly apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1: production method of chlorinated ethylene carbonate
A method for producing chloroethylene carbonate comprises the following steps:
placing 100L of ethylene carbonate into a reaction kettle, introducing chlorine gas (the molar ratio of the ethylene carbonate to the chlorine gas is 1.1) from the bottom of the reaction kettle, placing an LED lamp on the upper part of the reaction kettle for carrying out illumination catalytic reaction to obtain a product, wherein the product contains chlorinated ethylene carbonate;
5 25W LED lamps are arranged in each 100L ethylene carbonate in the reaction kettle, and the distance between the LED lamps is 0.3m; the reaction time is 17 hours, and the reaction temperature is 75 ℃; the pressure in the reaction kettle is 0.5KPa higher than the atmospheric pressure.
The water content in the ethylene carbonate is about 25ppm.
After the reaction is finished, the molar content of each component in the product is detected by adopting gas chromatography.
The mole fraction of the chloroethylene carbonate in the product is 86%, and the mole fraction of the chloroethylene carbonate in the product after the reaction is finished can be regarded as the yield of the chloroethylene carbonate, namely the yield of the chloroethylene carbonate is 87%.
The molar fraction of ethylene Dichlorocarbonate (DCEC) in the product was 4%.
The molar fraction of unreacted Ethylene Carbonate (EC) in the product was 5%.
The molar fraction of the materials other than vinyl chlorocarbonate, vinyl dichlorocarbonate and vinyl carbonate in the product amounted to 4% and there were no visible black by-products in the product.
Example 2: production method of chloroethylene carbonate
A production method of chlorinated ethylene carbonate comprises the following steps:
placing 100L of ethylene carbonate into a reaction kettle, introducing chlorine gas (the molar ratio of the ethylene carbonate to the chlorine gas is 1.05) from the bottom of the reaction kettle, placing an LED lamp on the upper part of the reaction kettle for carrying out illumination catalytic reaction to obtain a product, wherein the product contains chlorinated ethylene carbonate;
4 25W LED lamps are arranged in each 100L ethylene carbonate in the reaction kettle, and the distance between the LED lamps is 0.3m; the reaction time is 18 hours, and the reaction temperature is 80 ℃; the pressure in the reaction kettle is 1KPa higher than the atmospheric pressure.
The water content in the ethylene carbonate is about 30ppm.
After the reaction is finished, detecting the molar content of each component in the product by adopting gas chromatography.
The mole fraction of the chloroethylene carbonate in the product is 86%, and the mole fraction of the chloroethylene carbonate in the product after the reaction is finished can be regarded as the yield of the chloroethylene carbonate, namely the yield of the chloroethylene carbonate is 86%.
The molar fraction of ethylene Dichlorocarbonate (DCEC) in the product was 5%.
The molar fraction of unreacted Ethylene Carbonate (EC) in the product was 5%.
The molar fraction of the materials other than vinyl chlorocarbonate, vinyl dichlorocarbonate and vinyl carbonate in the product amounted to 4% and there were no visible black by-products in the product.
Example 3: production method of chloroethylene carbonate
A production method of chlorinated ethylene carbonate comprises the following steps:
placing 100L of ethylene carbonate into a reaction kettle, introducing chlorine gas (the molar ratio of the ethylene carbonate to the chlorine gas is 1.2) from the bottom of the reaction kettle, placing an LED lamp on the upper part of the reaction kettle, and carrying out illumination catalytic reaction to obtain a product, wherein the product contains chlorinated ethylene carbonate;
6 25W LED lamps are arranged in each 100L of ethylene carbonate in the reaction kettle, and the distance between the LED lamps is 0.3m; the reaction time is 18 hours, and the reaction temperature is 85 ℃; the pressure in the reaction kettle is 1.5KPa higher than the atmospheric pressure.
The water content in the ethylene carbonate is about 25ppm.
After the reaction is finished, the molar content of each component in the product is detected by adopting gas chromatography.
The mole fraction of the chloroethylene carbonate in the product is 88%, and the mole fraction of the chloroethylene carbonate in the product after the reaction is finished can be regarded as the yield of the chloroethylene carbonate, namely the yield of the chloroethylene carbonate is 88%.
The molar fraction of ethylene Dichlorocarbonate (DCEC) in the product was 4%.
The molar fraction of unreacted Ethylene Carbonate (EC) in the product was 4%.
The mole fraction of the product was 4% except for chloroethylene carbonate, dichloroethylene carbonate and ethylene carbonate, and there was no visible black by-product in the product.
Comparative example 1
Compared with example 1, in comparative example 1, 4 25W LED lamps per 100L ethylene carbonate in the reaction kettle were replaced by 1KW high-pressure mercury lamp, and the reaction kettle was water-cooled, and the components in the product obtained after the reaction were completed were as follows:
the mole fraction of the chloroethylene carbonate is 82 percent;
the molar fraction of dichloroethylene carbonate (DCEC) was 8%;
the molar fraction of unreacted Ethylene Carbonate (EC) is 5%;
after the reaction, the mole fraction of other substances except the chloroethylene carbonate, dichloroethylene carbonate and ethylene carbonate is 5%, and the product has a black by-product which is obviously visible to naked eyes.
As can be seen from the results of the above examples and comparative examples, the process for producing chloroethylene carbonate of the present invention does not need to cool the reaction kettle with water, so as to simplify the production process and reduce the cost, and the yield of the prepared chloroethylene carbonate is 86-88%, and no obvious black by-product is visible to the naked eye. Namely, the yield of the target product chloroethylene carbonate in the production method of the embodiment of the invention is obviously higher than that of the prior art, and the capacity of industrial mass production of chloroethylene carbonate is greatly improved.
Claims (10)
1. The production method of chlorinated ethylene carbonate is characterized by comprising the following steps:
placing ethylene carbonate into a reaction container, introducing chlorine gas from the bottom of the reaction container, placing an LED lamp on the upper part of the reaction container, and performing light-catalyzed reaction to obtain a product, wherein chlorinated ethylene carbonate is contained in the product;
4-6 20-30W LED lamps are arranged in each 100L ethylene carbonate in the reaction container.
2. The production method according to claim 1, wherein the reaction time is 12 to 18 hours.
3. The production method according to claim 1, wherein the temperature of the reaction is 60 to 90 ℃.
4. The method of claim 1, wherein the LED lamp is a 25W LED lamp.
5. The method for manufacturing a lamp according to claim 1, wherein the LED lamps are spaced apart by 0.2 to 0.3m.
6. The production method according to claim 1, wherein the molar ratio of the ethylene carbonate to the chlorine gas is 1.0 to 1.3.
7. The production method according to claim 1, wherein the pressure in the reaction tank is 0 to 50KPa higher than atmospheric pressure.
8. The production method according to claim 1, wherein the water content in the ethylene carbonate is not more than 30ppm.
9. The process according to claim 1, wherein the product contains more than 85% of vinyl chlorocarbonate in mole fraction.
10. Use of the production process according to any one of claims 1 to 9 for the preparation of fluoroethylene carbonate.
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| CN202210894072.XA CN115286612A (en) | 2022-07-27 | 2022-07-27 | Production method of chloroethylene carbonate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894429A (en) * | 2022-12-16 | 2023-04-04 | 山东阳谷华泰化工股份有限公司 | Method for preparing vinylene carbonate |
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| CN103772344A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院理化技术研究所 | Method for photochemical synthesis of monochloroethylene carbonate and photochemical reactor |
| CN105503813A (en) * | 2015-12-17 | 2016-04-20 | 九江天赐高新材料有限公司 | Method for synthesizing fluoroethylene carbonate |
| CN110437202A (en) * | 2019-08-27 | 2019-11-12 | 许兆石 | A kind of chloridization process of ethylene carbonate |
| CN110483471A (en) * | 2019-09-08 | 2019-11-22 | 淮安瀚康新材料有限公司 | A kind of synthetic method of vinylene carbonate |
| CN114452916A (en) * | 2022-01-13 | 2022-05-10 | 宁夏天霖新材料科技有限公司 | Preparation equipment and method of monochloroethylene carbonate |
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- 2022-07-27 CN CN202210894072.XA patent/CN115286612A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772344A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院理化技术研究所 | Method for photochemical synthesis of monochloroethylene carbonate and photochemical reactor |
| CN105503813A (en) * | 2015-12-17 | 2016-04-20 | 九江天赐高新材料有限公司 | Method for synthesizing fluoroethylene carbonate |
| CN110437202A (en) * | 2019-08-27 | 2019-11-12 | 许兆石 | A kind of chloridization process of ethylene carbonate |
| CN110483471A (en) * | 2019-09-08 | 2019-11-22 | 淮安瀚康新材料有限公司 | A kind of synthetic method of vinylene carbonate |
| CN114452916A (en) * | 2022-01-13 | 2022-05-10 | 宁夏天霖新材料科技有限公司 | Preparation equipment and method of monochloroethylene carbonate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894429A (en) * | 2022-12-16 | 2023-04-04 | 山东阳谷华泰化工股份有限公司 | Method for preparing vinylene carbonate |
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