CN104355996A - Method for synthesizing ethylene glycol diacetate by adopting transesterification method - Google Patents
Method for synthesizing ethylene glycol diacetate by adopting transesterification method Download PDFInfo
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- CN104355996A CN104355996A CN201410519550.4A CN201410519550A CN104355996A CN 104355996 A CN104355996 A CN 104355996A CN 201410519550 A CN201410519550 A CN 201410519550A CN 104355996 A CN104355996 A CN 104355996A
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- butyl acetate
- ethylene glycol
- glycol diacetate
- butyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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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
- Y02P20/10—Process efficiency
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Abstract
The invention relates to a method for synthesizing ethylene glycol diacetate by adopting a reactive distillation technology. Sec-butyl acetate and ethylene glycol are used as raw materials, ethylene glycol diacetate is produced by transesterification on the presence of a basic catalyst, and a byproduct is ethylene glycol monoethyl acetate. According to the method, the yield of the ethylene glycol diacetate can reach over 90 percent, and the method has the advantages of high conversion rate, mild reaction conditions, high yield, no corrosion, no environmental pollution and the like.
Description
Technical field
The invention belongs to organic compound synthesis field, particularly relate to a kind of method adopting ester-interchange method synthesizing glycol diacetate esters.
Background technology
Glycol diacetate (EGDA), has another name called glycol diacetate, diacetate glycol ester, is colourless liquid, boiling point 190.2 DEG C, is environment-friendly type organic solvent that is efficient, safety non-toxic.Be widely used in pharmaceutical industry; Foundry resin organic ester curing agent; Also as various organic resin particularly nitrocellulosic fine solvent, and the raw material of leather gloss agent; Spray paint as nitro in paint, the solvent of printing-ink, cellulose ester, fluorescent coating.
The traditional method of glycol diacetate synthesis has acetate esterification process, oxyethane and acetic acid catalysis additive process, ethylene glycol and acetic acid direct esterification.Acetate esterification process adopts glycol dibromide and potassium acetate to react, with pyridine, second acid as catalyst.This reaction esterification yied is 55% ~ 61%, long reaction time, and cost of material is high, and toxicity is large, is unfavorable for suitability for industrialized production.Oxyethane and acetic acid catalysis additive process, reaction mixture composition is simple, and product separation and control are also easier to, but severe reaction conditions, oxyethane is dangerous large, and acetic acid is serious to equipment corrosion.Ethylene glycol and acetic acid direct esterification are the industrial methods generally adopted at present, and it take toluene as dewatering agent, adopt Lewis acid catalyst, and the shortcoming of the method produces acid-bearing wastewater, to equipment corrosion and environmental pollution serious.For the defect that the traditional method of EDGA synthesis exists, Chinese patent CN 103183609 proposes transesterify synthesis method, that is: with sec-butyl acetate and ethylene glycol for raw material, under the effect of basic catalyst, synthesizing glycol monoacetate and glycol diacetate.This technique comprises preliminary transesterify, breaks transesterify chemical reaction equilibrium, latter stage transesterification reaction and the step such as product separation purification.The method cost of material is low, and reaction conditions is gentle, and the another kind of product sec-butyl alcohol of reaction is also a kind of important industrial chemicals, and production process does not produce waste water, and equipment is corrosion-free, is eco-friendly green synthesis process.But the method is in preliminary Exchange Ester Process, the timely sec-butyl alcohol that generates of removal system, thus make that reaction conversion ratio is low, long reaction time; Break the transesterify chemical equilibrium stage, the amount of the sec-butyl acetate of overhead product will detected in batch, and add quantity of distillate 1-4 sec-butyl acetate doubly.This behaviour makes production process complicated operation, and adds sec-butyl acetate off and on, makes temperature of reaction system unstable, and production process difficulty controls; In the sepn process of ethylene glycol acetate and glycol diacetate, adopt one or more in benzene, toluene or dimethylbenzene as extraction agent, extraction agent toxicity is large; In the separating-purifying process of sec-butyl alcohol, do not consider the azeotropic of sec-butyl alcohol and 2-butyl acetate.Because sec-butyl alcohol and 2-butyl acetate exist azeotropism, so adopt conventional rectification to can not get the sec-butyl alcohol product of 99% when sec-butyl alcohol content 86.3% (wt).
Summary of the invention
The present invention is directed to the defect that prior art exists, kind of the method adopting ester-interchange method synthesizing glycol diacetate esters is provided, cost of material of the present invention is low, reaction conditions is gentle, speed of response is fast, product yield is high, simple to operate, production unit can realize control automatically, equipment is corrosion-free, the green synthesis process of environmentally safe.
For achieving the above object, the present invention is by the following technical solutions:
A kind of method adopting reaction rectification technique synthesizing glycol diacetate esters, with sec-butyl acetate and ethylene glycol for raw material, under basic catalyst exists, produce glycol diacetate by transesterify, by product is ethylene glycol acetate, specifically comprises the following steps:
(1) basic catalyst, ethylene glycol and sec-butyl acetate are added to still kettle with rectifying tower and agitator according to mol ratio 0.003-0.015:1:0.5-1.2, be heated to tower top temperature stable after, with the azeotrope of reflux ratio 5-12:1 extraction sec-butyl alcohol and sec-butyl acetate, add remaining sec-butyl acetate continuously simultaneously.
(2) total add-on of sec-butyl acetate is 3-5 times (mol ratio) of ethylene glycol, in the reinforced process of sec-butyl acetate, make bottom temperature keep 120-140 DEG C, the speed that adds of sec-butyl acetate is controlled by bottom temperature, and feed time continues 1-2 hour.
(3), after having fed in raw material, continuation reaction and extraction are until bottom temperature rises to 180 DEG C, and the time length is 3-5 hour, and tower reactor is the ethylene glycol of glycol diacetate, ethylene glycol acetate and non-complete reaction, and wherein the content of glycol diacetate is greater than 90%.
(4) kettle material is separated the glycol diacetate that can obtain content more than 98% through rectification under vacuum, and the sec-butyl alcohol of overhead extraction and the azeotrope of sec-butyl acetate, through extracting rectifying, can obtain sec-butyl acetate and the sec-butyl alcohol of content more than 99%.
And described basic catalyst is: Na
2cO
3, K
2cO
3, CH
3oNa, C2H
5oNa, CaO, MgO, KOH and NaOH of load on Al2O3.
And preferred basic catalyst is CH
3oNa.
Advantage of the present invention and positively effect are:
Glycol diacetate yield of the present invention can reach more than 90%, has that transformation efficiency is high, reaction conditions is gentle, yield is high, an advantage such as corrosion-free, non-environmental-pollution.
Embodiment
Below in conjunction with embodiment, the present invention is further described; Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1
Adopt a method for ester-interchange method synthesizing glycol diacetate esters, step is as follows:
(1) by K
2cO
3, ethylene glycol and sec-butyl acetate be added to the still kettle with rectifying tower and agitator according to mol ratio 0.003:1:0.5, be heated to tower top temperature stable after, with the azeotrope of reflux ratio 5:1 extraction sec-butyl alcohol and sec-butyl acetate, add remaining sec-butyl acetate continuously simultaneously.
(2) total add-on of sec-butyl acetate is 3 times (mol ratios) of ethylene glycol, in the reinforced process of sec-butyl acetate, makes bottom temperature keep 120 DEG C, and the speed that adds of sec-butyl acetate is controlled by bottom temperature, and feed time continues 1 hour.
(3), after having fed in raw material, continuation reaction and extraction are until bottom temperature rises to 180 DEG C, and the time length is 5 hours, and tower reactor is the ethylene glycol of glycol diacetate, ethylene glycol acetate and non-complete reaction, and wherein the content of glycol diacetate is 90%.
(4) kettle material is separated the glycol diacetate that can obtain content more than 98% through rectification under vacuum, and the sec-butyl alcohol of overhead extraction and the azeotrope of sec-butyl acetate, through extracting rectifying, can obtain sec-butyl acetate and the sec-butyl alcohol of content more than 99%.
Embodiment 2
Adopt a method for ester-interchange method synthesizing glycol diacetate esters, step is as follows:
(1) by CH
3oNa, ethylene glycol and sec-butyl acetate are added to the still kettle with rectifying tower and agitator according to mol ratio 0.01:1:0.85, be heated to tower top temperature stable after, with the azeotrope of reflux ratio 8:1 extraction sec-butyl alcohol and sec-butyl acetate, add remaining sec-butyl acetate continuously simultaneously.
(2) total add-on of sec-butyl acetate is 4 times (mol ratios) of ethylene glycol, in the reinforced process of sec-butyl acetate, makes bottom temperature keep 130 DEG C, and the speed that adds of sec-butyl acetate is controlled by bottom temperature, and feed time continues 1.5 hours.
(3), after having fed in raw material, continuation reaction and extraction are until bottom temperature rises to 180 DEG C, and the time length is 3 hours, and tower reactor is the ethylene glycol of glycol diacetate, ethylene glycol acetate and non-complete reaction, and wherein the content of glycol diacetate is 92%.
(4) kettle material is separated the glycol diacetate that can obtain content more than 98% through rectification under vacuum, and the sec-butyl alcohol of overhead extraction and the azeotrope of sec-butyl acetate, through extracting rectifying, can obtain sec-butyl acetate and the sec-butyl alcohol of content more than 99%.
Embodiment 3
Adopt a method for ester-interchange method synthesizing glycol diacetate esters, step is as follows:
(1) the KOH of load on Al2O3, ethylene glycol and sec-butyl acetate are added to still kettle with rectifying tower and agitator according to mol ratio 0.015:1:1.2, be heated to tower top temperature stable after, with the azeotrope of reflux ratio 12:1 extraction sec-butyl alcohol and sec-butyl acetate, add remaining sec-butyl acetate continuously simultaneously.
(2) total add-on of sec-butyl acetate is 5 times (mol ratios) of ethylene glycol, in the reinforced process of sec-butyl acetate, makes bottom temperature keep 140 DEG C, and the speed that adds of sec-butyl acetate is controlled by bottom temperature, and feed time continues 2 hours.
(3), after having fed in raw material, continuation reaction and extraction are until bottom temperature rises to 180 DEG C, and the time length is 4 hours, and tower reactor is the ethylene glycol of glycol diacetate, ethylene glycol acetate and non-complete reaction, and wherein the content of glycol diacetate is 91%.
(4) kettle material is separated the glycol diacetate that can obtain content more than 98% through rectification under vacuum, and the sec-butyl alcohol of overhead extraction and the azeotrope of sec-butyl acetate, through extracting rectifying, can obtain sec-butyl acetate and the sec-butyl alcohol of content more than 99%.
Claims (3)
1. adopt a method for reaction rectification technique synthesizing glycol diacetate esters, it is characterized in that: specifically comprise the following steps:
(1) basic catalyst, ethylene glycol and sec-butyl acetate are added to still kettle with rectifying tower and agitator according to mol ratio 0.003-0.015:1:0.5-1.2, be heated to tower top temperature stable after, with the azeotrope of reflux ratio 5-12:1 extraction sec-butyl alcohol and sec-butyl acetate, add remaining sec-butyl acetate continuously simultaneously;
(2) total add-on of sec-butyl acetate is 3-5 times of mol ratio of ethylene glycol, and in the reinforced process of sec-butyl acetate, make bottom temperature keep 120-140 DEG C, the speed that adds of sec-butyl acetate is controlled by bottom temperature, and feed time continues 1-2 hour;
(3), after having fed in raw material, continuation reaction and extraction are until bottom temperature rises to 180 DEG C, and the time length is 3-5 hour, and tower reactor is the ethylene glycol of glycol diacetate, ethylene glycol acetate and non-complete reaction, and wherein the content of glycol diacetate is greater than 90%;
(4) kettle material is separated the glycol diacetate that can obtain content more than 98% through rectification under vacuum, and the sec-butyl alcohol of overhead extraction and the azeotrope of sec-butyl acetate, through extracting rectifying, can obtain sec-butyl acetate and the sec-butyl alcohol of content more than 99%.
2. the method for employing reaction rectification technique synthesizing glycol diacetate esters according to claim 1, is characterized in that: described basic catalyst is: Na
2cO
3, K
2cO
3, CH
3oNa, C2H
5oNa, CaO, MgO, KOH and NaOH of load on Al2O3.
3. the method for employing reaction rectification technique synthesizing glycol diacetate esters according to claim 1, is characterized in that: preferably basic catalyst is CH
3oNa.
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| CN201410519550.4A CN104355996A (en) | 2014-09-30 | 2014-09-30 | Method for synthesizing ethylene glycol diacetate by adopting transesterification method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876037A (en) * | 2017-12-08 | 2018-04-06 | 湖南长岭石化科技开发有限公司 | Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis |
| CN109956849A (en) * | 2017-12-22 | 2019-07-02 | 湖南中创化工股份有限公司 | A kind of method preparing ethylene acetate and sec-butyl alcohol and catalyst system and device |
| CN110423197A (en) * | 2019-09-17 | 2019-11-08 | 凯瑞环保科技股份有限公司 | A kind of device and method using low concentration ethylene glycol production glycol acetate |
| CN112642485A (en) * | 2020-12-23 | 2021-04-13 | 深圳市普利凯新材料股份有限公司 | Acetoacetic acid tert-butyl ester catalyst and preparation method thereof |
| CN112996766A (en) * | 2018-11-13 | 2021-06-18 | 伊士曼化工公司 | Synthesis of triethylene glycol bis (2-ethylhexanoate) |
-
2014
- 2014-09-30 CN CN201410519550.4A patent/CN104355996A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876037A (en) * | 2017-12-08 | 2018-04-06 | 湖南长岭石化科技开发有限公司 | Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis |
| CN109956849A (en) * | 2017-12-22 | 2019-07-02 | 湖南中创化工股份有限公司 | A kind of method preparing ethylene acetate and sec-butyl alcohol and catalyst system and device |
| CN109956849B (en) * | 2017-12-22 | 2022-01-25 | 湖南中创化工股份有限公司 | Method for preparing ethylene glycol diacetate and sec-butyl alcohol, catalytic system and device |
| CN112996766A (en) * | 2018-11-13 | 2021-06-18 | 伊士曼化工公司 | Synthesis of triethylene glycol bis (2-ethylhexanoate) |
| CN112996766B (en) * | 2018-11-13 | 2024-07-05 | 伊士曼化工公司 | Synthesis of triethylene glycol bis (2-ethylhexanoate) |
| CN110423197A (en) * | 2019-09-17 | 2019-11-08 | 凯瑞环保科技股份有限公司 | A kind of device and method using low concentration ethylene glycol production glycol acetate |
| CN110423197B (en) * | 2019-09-17 | 2023-11-14 | 凯瑞环保科技股份有限公司 | Device and method for producing ethylene glycol diacetate by using low-concentration ethylene glycol |
| CN112642485A (en) * | 2020-12-23 | 2021-04-13 | 深圳市普利凯新材料股份有限公司 | Acetoacetic acid tert-butyl ester catalyst and preparation method thereof |
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