CN114573542B - Preparation method of ethylene carbonate - Google Patents
Preparation method of ethylene carbonate Download PDFInfo
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- CN114573542B CN114573542B CN202210129347.0A CN202210129347A CN114573542B CN 114573542 B CN114573542 B CN 114573542B CN 202210129347 A CN202210129347 A CN 202210129347A CN 114573542 B CN114573542 B CN 114573542B
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- ethylene carbonate
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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
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to the technical field of organic synthesis, in particular to a preparation method of ethylene carbonate. The preparation method of the ethylene carbonate takes the ethylene carbonate and the ethylene glycol as raw materials, and the eutectic solvent is taken as a catalyst to react and synthesize the ethylene carbonate; the carbonic ester is dimethyl carbonate or diethyl carbonate; the eutectic solvent is prepared from choline chloride and urea according to a molar ratio of 1:2. The preparation method of the ethylene carbonate has the advantages of low-cost and easily-obtained raw materials, simple and convenient preparation method, low toxicity and easy biodegradation, the eutectic solvent is easy to separate from the product, the activity is not obviously reduced after the 10 times of cyclic utilization, the development requirements of green chemical industry and clean production are met, and good economic, social and environmental benefits are achieved.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of ethylene carbonate.
Background
Ethylene Carbonate (EC) is an excellent high-boiling point solvent and an organic synthesis intermediate, has the advantages of low toxicity, low corrosiveness and the like, is widely applied to the fields of material synthesis, plastics, textiles, electrochemistry and the like, and has wide market application prospect, and is called a 21 st century green basic chemical raw material.
The synthesis method of ethylene carbonate mainly comprises phosgene method, transesterification method, halohydrin method, ethylene oxide and CO 2 Synthesis method, urea alcoholysis method. The phosgene method is a traditional production method of ethylene carbonate, but has the defects of complex process, low yield, high cost and the like, and the phosgene has high toxicity and serious pollution and is gradually eliminated. Ethylene oxide and CO 2 The synthesis method is a main production method in the industry at present, and has the advantages of fixed greenhouse gas carbon dioxide, short process flow and the like; however, the reaction is a volume reduction reaction, and high pressure conditions are favorable for the progress of the reaction, so that more severe conditions are required and the selection and subsequent separation of the catalyst are difficult to influence the reaction. In the urea alcoholysis method, urea and glycol are used as raw materials, su et al firstly propose that the urea and glycol are used for preparing ethylene carbonate in the presence of a tin-containing catalyst in 1991, and the conversion rate of the urea is less than 66%. In recent years, research on synthesis of EC by alcoholysis of urea has been greatly advanced, and Bhadaluri et al uses ZnO-Cr 2 O 3 As a catalyst, the EC yield reaches 85.75% under the condition of reduced pressure at 150 ℃. Zhou et al, found PbCO by catalyzing urea alcoholysis with Zn-Pb mixed carbonate to synthesize Propylene Carbonate (PC) 3 And Zn 5 (CO 3 ) 2 (OH) 6 Obviously improves the activity of the catalyst, ensures that the PC yield reaches 96.3 percent, and is more favorable for improving the synergistic effect due to weak alkalinityHigh.
In view of the present research situation, how to provide a preparation method of ethylene carbonate, which has low raw material and process cost, and simple preparation method, the prepared ethylene carbonate is convenient to store, and the adopted eutectic solvent is biodegradable and has good biocompatibility and non-toxicity, which is a subject worthy of research by those skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of ethylene carbonate, which has the advantages of low-cost and easily-obtained raw materials, simple and convenient preparation method, low toxicity and easy biodegradation, and the eutectic solvent can be recycled, meets the development requirements of green chemical industry and clean production, and has good economic, social and environmental benefits.
The technical scheme adopted for solving the technical problems is as follows:
a method for preparing ethylene carbonate, comprising the following preparation steps:
(1) Ethylene glycol and carbonic ester are used as raw materials, and a eutectic solvent (ChCl/urea DES) composed of choline chloride-urea ((0.8-1.2): (1.7-2.2)) is used as a catalyst to react and synthesize the carbonic ester;
(2) And continuously distilling out byproduct alcohol in the reaction process, and continuously distilling to obtain ethylene carbonate after the reaction is finished, wherein the residual DES can be recycled.
The reaction route is as follows:
wherein: r is methyl or ethyl.
Preferably, the eutectic solvent preparation method in the step (1) is as follows: adding choline chloride and urea (1.7-2.2) into a single-neck flask according to the molar ratio of (0.8-1.2), reacting for 25-35min at 70-100 ℃, cooling the system to room temperature after the reaction is finished, and vacuum drying to obtain the colorless transparent eutectic solvent.
Preferably, the carbonate in step (1) is dimethyl carbonate or diethyl carbonate, more preferably dimethyl carbonate.
Preferably, the molar ratio of ethylene glycol to carbonate in step (1) is 1: (2-10), more preferably in a molar ratio of 1:3.
Preferably, the amount of the eutectic solvent in the step (1) is 1 to 20% by mass of the ethylene glycol, and more preferably 10% by mass of the ethylene glycol.
Preferably, the reaction temperature in step (1) is 80-150 ℃, preferably 100 ℃.
Preferably, the judging mode of the reaction end point in the step (2) is that the content of glycol detected by gas chromatography is less than 0.5 percent (area normalization method);
the beneficial effects of the invention are as follows: compared with the prior art, the preparation method of the ethylene carbonate has the following advantages: the raw materials are cheap and easy to obtain, the preparation method is simple and convenient, the low toxicity is realized, the biodegradation is easy, the eutectic solvent is easy to separate from the product, the activity is not obviously reduced after the eutectic solvent is recycled for 10 times, the development requirements of green chemical industry and clean production are met, and good economic, social and environmental benefits are realized.
Detailed Description
EXAMPLE 1 preparation of eutectic solvent (DES)
Choline chloride (140.0 g,1.0 mol) and urea (120.0 g,2.0 mol) were added to a 500mL single neck flask, reacted at 80 ℃ for 30min, after the reaction was completed, the system was cooled to room temperature, and vacuum-dried to obtain colorless and transparent DES.
Example 2A method for preparing ethylene carbonate
Ethylene glycol (62.0 g,1.0 mol), dimethyl carbonate (270.0 g,3.0 mol) and DES (6.2 g) are added into a three-neck flask, and the mixture is reacted at 100 ℃ until the content of the ethylene glycol detected by gas chromatography is less than 0.5% (area normalization method), methanol is continuously distilled out in the reaction process, and after the reaction is finished, 84.0g of ethylene carbonate is obtained by continuous distillation, wherein the yield is 95.4% and the gas phase purity is 98%.
The fresh raw materials are directly added into a distilled reaction bottle for repeated reaction, and the experimental results are as follows:
example 3 preparation of ethylene carbonate
Ethylene glycol (62.0 g,1.0 mol), diethyl carbonate (354 g,3.0 mol) and DES (6.2 g) are added into a three-neck flask, and the mixture is reacted at 130 ℃ until the content of the ethylene glycol detected by gas chromatography is less than 0.5% (area normalization method), ethanol is continuously distilled in the reaction process, and after the reaction is finished, 83.0g of ethylene carbonate is obtained by continuous distillation, wherein the yield is 94.3% and the purity is 98%.
The fresh raw materials are directly added into a distilled reaction bottle for repeated reaction, and the experimental results are as follows:
example 4A method for preparing ethylene carbonate
Ethylene glycol (62.0 g,1.0 mol), dimethyl carbonate (180 g,2.0 mol) and DES (6.2 g) are added into a three-neck flask, the reaction is carried out at 100 ℃, gas phase tracking detection is carried out in the process, the ethylene glycol reaction is incomplete, analysis reasons are that the dimethyl carbonate and methanol are azeotroped out in the reaction process, the amount of the dimethyl carbonate in the bottle is insufficient, side reactions are increased, when the content of the dimethyl carbonate in the system is less than 1%, 57.5g of ethylene carbonate is obtained through distillation, the yield is 65.3%, and the purity is 95%.
Example 5A method for preparing ethylene carbonate
Ethylene glycol (62.0 g,1.0 mol), diethyl carbonate (236 g,2.0 mol) and DES (6.2 g) were added to a three-necked flask, and reacted at 130℃to give 60.5g of ethylene carbonate in a co-distillation yield of 68.4% and a purity of 95% when the diethyl carbonate content in the system was less than 1%, which had the same problems as those of the dimethyl carbonate in example 4.
The foregoing embodiments are merely examples of the present invention, and the scope of the present invention includes, but is not limited to, the forms and styles of the foregoing embodiments, and any suitable changes or modifications made by those skilled in the art, which are consistent with the claims of the present invention, shall fall within the scope of the present invention.
Claims (8)
1. A method for preparing ethylene carbonate, which is characterized in that: the method takes carbonic ester and ethylene glycol as raw materials, takes a eutectic solvent as a catalyst, and synthesizes the ethylene carbonate through reaction, wherein the chemical formula is as follows:
wherein: the carbonic ester is dimethyl carbonate or diethyl carbonate, and R in the chemical reaction formula is methyl or ethyl; the eutectic solvent is prepared from choline chloride and urea according to the molar ratio of (0.8-1.2) to (1.7-2.2).
2. The method for producing ethylene carbonate according to claim 1, characterized in that: the eutectic solvent is prepared from choline chloride and urea according to a molar ratio of 1:2.
3. A process for the preparation of ethylene carbonate according to claim 1 or 2, characterized in that: the preparation method of the eutectic solvent comprises the following steps: adding choline chloride and urea into a single-neck flask according to a specified molar ratio, reacting at 70-100 ℃ for 25-35min, cooling the system to room temperature after the reaction is finished, and vacuum drying to obtain the colorless transparent eutectic solvent.
4. The method for producing ethylene carbonate according to claim 1, characterized in that: the molar ratio of the ethylene glycol to the carbonic ester is 1: (1-10).
5. The method for producing ethylene carbonate according to claim 1, characterized in that: the dosage of the eutectic solvent is 1-20% of the mass of the glycol.
6. The method for producing ethylene carbonate according to claim 1, characterized in that: the reaction temperature is 80-150 ℃ in the process of synthesizing ethylene carbonate by reaction.
7. The method for producing ethylene carbonate according to claim 1, characterized in that: and in the process of synthesizing the ethylene carbonate by reaction, byproduct alcohol is continuously distilled out, and after the reaction is finished, the ethylene carbonate is obtained by continuous distillation, and the residual catalyst can be recycled.
8. The method for producing ethylene carbonate according to claim 7, wherein: the reaction end point judgment mode of synthesizing ethylene carbonate by reaction is as follows: the content of ethylene glycol detected by gas chromatography is less than 0.5%.
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| CN101985435B (en) * | 2010-10-28 | 2012-05-09 | 河北科技大学 | Novel eutectic ionic liquid and preparation method thereof |
| GB201704222D0 (en) * | 2017-03-16 | 2017-05-03 | Cambridge Entpr Ltd | Deep eutectic solvent compositions |
| CN107190282B (en) * | 2017-05-19 | 2019-07-30 | 东北大学 | A kind of room temperature molten salt and its preparation method and application |
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| CN112174873B (en) * | 2019-07-02 | 2021-12-21 | 河北寰烯科技有限公司 | Method for synthesizing phthalimide by means of urea choline chloride eutectic |
| CN110156742B (en) * | 2019-07-02 | 2020-12-04 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by catalyzing urea and dihydric alcohol with ionic liquid |
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| CN113816852B (en) * | 2021-09-30 | 2022-08-16 | 四川大学 | Method for synthesizing glycerol carbonate by catalyzing glycerol and carbon dioxide with organic amine halide salt |
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