CN103073429A - Method for synthesizing diethyl carbonate through ester exchange - Google Patents
Method for synthesizing diethyl carbonate through ester exchange Download PDFInfo
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- CN103073429A CN103073429A CN2013100424860A CN201310042486A CN103073429A CN 103073429 A CN103073429 A CN 103073429A CN 2013100424860 A CN2013100424860 A CN 2013100424860A CN 201310042486 A CN201310042486 A CN 201310042486A CN 103073429 A CN103073429 A CN 103073429A
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- diethyl carbonate
- transesterify
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- synthesizing diethyl
- ethanol
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Abstract
The invention discloses a method for synthesizing diethyl carbonate through ester exchange. By using propylene carbonate or ethylene carbonate and alcohol as raw materials and selecting a solid acidic catalyst, diethyl carbonate and 1,2-propanediol or 1,2-glycol are generated through ester exchange. The method has the advantages of mild reaction conditions, short synthesis route, high reaction transformation rate and selectivity, and the like; and the catalyst can be repeatedly used.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of method of transesterify synthesizing diethyl carbonate.
Background technology
Diethyl carbonate is a kind of organic solvent of excellent property, also is synthetic intermediate and textiles auxiliary agent simultaneously, is widely used in the electrolyte solvent of battery at industrial circle; In addition, the oxygen rate that contains of diethyl carbonate is higher than the dimethyl tertbutyl ether, can be used as gasoline dope, improves the octane value of gasoline, reduces the quantity discharged of carbonic acid gas in the Extract from Gasoline-fueled Vehicle, is expected to become the wide gasoline dope of new generation of market outlook.
The preparation method of carbon current diethyl phthalate mainly contains oxidation of ethanol carbonyl process and ester-interchange method etc.The oxidation of ethanol carbonyl process comprises again two kinds of liquid-phase oxidation carbonyl process and gaseous oxidation carbonyl process.Liquid phase method adopts Cu-series catalyst, exists univalent copper ion unstable, equipment corrosion and product separation problem that the life-span is short, serious; The vapor phase process catalyzer mostly is precious metal salt, because reaction generates water byproduct, catalyzer is met the water capacity and easily decomposed, and causes poisoning of catalyst; It is large also to have simultaneously facility investment, and generative process operation control requires high weak point.
The transesterify of methylcarbonate and ethanol prepares diethyl carbonate under comparatively gentle condition, simultaneously by-product methyl alcohol.This reaction was divided into for two steps, and namely under catalyst action, ethanol at first generates Methyl ethyl carbonate and methyl alcohol with dimethyl carbonate; Methyl ethyl carbonate continues and ethanol synthesis Formed diethyl phthalate and methyl alcohol.This circuit by-product Methyl ethyl carbonate, the yield of diethyl carbonate is low; The material carbon dimethyl phthalate is synthetic by propylene carbonate and methyl alcohol transesterify simultaneously, and synthetic line is long, cost is high.
Summary of the invention
The object of the present invention is to provide a kind of method of transesterify synthesizing diethyl carbonate, the method has that reaction conditions gentleness, synthetic route are short, reaction conversion ratio and the advantage such as selectivity is high, catalyzer is reusable.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method of transesterify synthesizing diethyl carbonate take propylene carbonate or NSC 11801 and ethanol as raw material, is selected solid acid catalyst, transesterify synthesizing diethyl carbonate and 1,2 propylene glycol or 1,2 ethylene glycol.
Solid acid catalyst is a kind of or several mixture among ion exchange resin A36, A39, C68, D61,732, CT175D, NKC-9, D072, A35, the C115E, adopts directly joining method, reacts to be inhomogeneous reaction.
Processing parameter is as follows: the mol ratio of propylene carbonate or NSC 11801 and ethanol is 1:2 ~ 1:10; The consumption of catalyzer accounts for 8 ~ 20% of raw material total mass; Temperature of reaction is 50 ~ 85 ℃; Reaction pressure is 0.01～0.11MPa.
Distinguishing feature of the present invention is:
(1) the present invention is the transesterify synthesizing diethyl carbonate, and take propylene carbonate or NSC 11801 and ethanol as raw material, product is diethyl carbonate and 1,2 propylene glycol or 1,2 ethylene glycol, and wherein 1,2 propylene glycol and 1,2 ethylene glycol also are important industrial chemicals.
(2) the present invention has the remarkable advantages such as transformation efficiency height, reaction conditions is gentle, selectivity is high, little to the corrosion of equipment, catalyzer is reusable.The catalyzer that the present invention adopts, catalytic activity is high, and transformation efficiency reaches as high as 50% ~ 65%, and yield can reach 95% ~ 99%.The present invention can solve methylcarbonate and the ethanol transesterify prepares diethyl carbonate synthetic route length, transformation efficiency and the problems such as yield is low, the difficult recovery of catalyzer, investment is large, energy consumption is high.
Embodiment
The present invention will be further described below in conjunction with case study on implementation, and case study on implementation will help to understand better the present invention, but the present invention is not limited only to following embodiment.
Embodiment 1
Adopt tank reactor, the reactor specification is 100ml, take NKC-9 as catalyzer, the ratio of raw material propylene carbonate and ethanol is 1:2, and catalyst levels is 10% of stock liquid total mass, and temperature of reaction is 80 ℃, reaction pressure is 1atm, with being heated to temperature of reaction in 26.158g propylene carbonate and the catalyzer adding reactor, again 23.701g ethanol is preheating to temperature of reaction first, then ethanolic soln is added in the reactor and react.The transformation efficiency of propylene carbonate is 52.8%.The yield of diethyl carbonate is 96.3%.
Embodiment 2
Each operation steps and condition according to embodiment 1.Feed change is NSC 11801, with being heated to temperature of reaction in 24.431g propylene carbonate and the catalyzer adding reactor, again 25.569g ethanol is preheating to temperature of reaction, then ethanolic soln is added in the reactor and reacts.The transformation efficiency of NSC 11801 is 53.4%.The yield of diethyl carbonate is 96.7%.
Embodiment 3
Each operation steps and condition according to embodiment 1.The ratio that changes propylene carbonate and ethanol is 1:6, and take A36 as catalyzer, catalyst levels is 14% of stock liquid total mass, and temperature of reaction is 70 ℃.With being heated to temperature of reaction in 13.484g propylene carbonate and the catalyzer adding reactor, again 36.516g ethanol is preheating to temperature of reaction first, then ethanolic soln is added in the reactor and react.The transformation efficiency of propylene carbonate is 63.5%.The yield of diethyl carbonate is 98.8%.
Embodiment 4
Each operation steps and condition according to embodiment 3.Feed change is NSC 11801, with being heated to temperature of reaction in 12.078g propylene carbonate and the catalyzer adding reactor, again 37.922g ethanol is preheating to temperature of reaction, then ethanolic soln is added in the reactor and reacts.The transformation efficiency of NSC 11801 is 62.7%.The yield of diethyl carbonate is 97.5%.
Embodiment 5
Each operation steps and condition according to embodiment 1.The ratio that changes propylene carbonate and ethanol is 1:8, and take A39 as catalyzer, the proportion that catalyzer accounts for stock liquid is 18%, and temperature of reaction is 60 ℃.With being heated to temperature of reaction in 12.078g propylene carbonate and the catalyzer adding reactor, again 37.922g ethanol is preheating to temperature of reaction first, then ethanolic soln is added in the reactor and react.The transformation efficiency of propylene carbonate is 61.8%.The yield of diethyl carbonate is 98.5%.
Embodiment 6
Each operation steps and condition according to embodiment 5.Feed change is NSC 11801, with being heated to temperature of reaction in 8.286g propylene carbonate and the catalyzer adding reactor, again 41.714g ethanol is preheating to temperature of reaction, then ethanolic soln is added in the reactor and reacts.The transformation efficiency of NSC 11801 is 62.0%.The yield of diethyl carbonate is 97.8%.
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. the method for a transesterify synthesizing diethyl carbonate is characterized in that: take propylene carbonate or NSC 11801 and ethanol as raw material, select solid acid catalyst, the transesterify synthesizing diethyl carbonate.
2. the method for described transesterify synthesizing diethyl carbonate according to claim 1, it is characterized in that: solid acid catalyst is a kind of or several mixture among ion exchange resin A36, A39, C68, D61,732, CT175D, NKC-9, D072, A35, the C115E, adopts directly joining method.
3. the method for described transesterify synthesizing diethyl carbonate according to claim 1, it is characterized in that: the mol ratio of propylene carbonate or NSC 11801 and ethanol is 1:2 ~ 1:10.
4. the method for transesterify synthesizing diethyl carbonate according to claim 1, it is characterized in that: the consumption of catalyzer accounts for 8 ~ 20% of raw material total mass.
5. the method for transesterify synthesizing diethyl carbonate according to claim 1, it is characterized in that: temperature of reaction is 50 ~ 85 ℃.
6. the method for described transesterify synthesizing diethyl carbonate according to claim 1, it is characterized in that: reaction pressure is 0.01～0.11MPa.
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| CN2013100424860A CN103073429A (en) | 2013-02-04 | 2013-02-04 | Method for synthesizing diethyl carbonate through ester exchange |
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| CN2013100424860A CN103073429A (en) | 2013-02-04 | 2013-02-04 | Method for synthesizing diethyl carbonate through ester exchange |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641720A (en) * | 2013-12-17 | 2014-03-19 | 福州大学 | Method of synthesizing diethyl carbonate by basic ionic liquid as catalyst |
| CN105646219A (en) * | 2016-01-24 | 2016-06-08 | 辽宁会福化工有限公司 | Method for catalytically synthesizing diethyl carbonate by means of strong acidic cationic resin |
| CN109180490A (en) * | 2018-10-15 | 2019-01-11 | 沈阳化工大学 | The lithium electricity homogeneous production technology of high-purity diethyl carbonate |
| CN114341099A (en) * | 2019-08-30 | 2022-04-12 | 国际壳牌研究有限公司 | Process for producing organic carbonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06343870A (en) * | 1993-06-02 | 1994-12-20 | Mitsui Toatsu Chem Inc | Simultaneous production of dialkyl carbonate and glycol |
| JPH07112134A (en) * | 1993-10-20 | 1995-05-02 | Mitsui Toatsu Chem Inc | Simultaneous production of dialkyl carbonate and glycol |
-
2013
- 2013-02-04 CN CN2013100424860A patent/CN103073429A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06343870A (en) * | 1993-06-02 | 1994-12-20 | Mitsui Toatsu Chem Inc | Simultaneous production of dialkyl carbonate and glycol |
| JPH07112134A (en) * | 1993-10-20 | 1995-05-02 | Mitsui Toatsu Chem Inc | Simultaneous production of dialkyl carbonate and glycol |
Non-Patent Citations (2)
| Title |
|---|
| 王默等: "碳酸钾催化碳酸丙烯酯与乙醇酯交换合成碳酸二乙酯", 《高校化学工程学报》 * |
| 马新宾等: "碳酸二乙酯的合成方法", 《化学通报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641720A (en) * | 2013-12-17 | 2014-03-19 | 福州大学 | Method of synthesizing diethyl carbonate by basic ionic liquid as catalyst |
| CN105646219A (en) * | 2016-01-24 | 2016-06-08 | 辽宁会福化工有限公司 | Method for catalytically synthesizing diethyl carbonate by means of strong acidic cationic resin |
| CN109180490A (en) * | 2018-10-15 | 2019-01-11 | 沈阳化工大学 | The lithium electricity homogeneous production technology of high-purity diethyl carbonate |
| CN114341099A (en) * | 2019-08-30 | 2022-04-12 | 国际壳牌研究有限公司 | Process for producing organic carbonate |
| US11807599B2 (en) | 2019-08-30 | 2023-11-07 | Shell Usa, Inc. | Organic carbonate production process |
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Application publication date: 20130501 |