CN101985419A - Method for preparing ethylene glycol ethyl ether acetate - Google Patents
Method for preparing ethylene glycol ethyl ether acetate Download PDFInfo
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- CN101985419A CN101985419A CN2010102543076A CN201010254307A CN101985419A CN 101985419 A CN101985419 A CN 101985419A CN 2010102543076 A CN2010102543076 A CN 2010102543076A CN 201010254307 A CN201010254307 A CN 201010254307A CN 101985419 A CN101985419 A CN 101985419A
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- ethylene glycol
- ether acetate
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- glycol ether
- ethyl ether
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Abstract
The invention discloses a method for preparing ethylene glycol ethyl ether acetate. Ethylene glycol ethyl ether and acetic acid are used as raw materials. The method is characterized by comprising the following steps of: performing fixed bed continuous esterification reaction by adopting a solid acid catalyst at the esterification temperature of between 70 and 150 DEG C, and removing the water generated in the esterification reaction by azeotropic distillation; and rectifying the esterification reaction product, and removing and reclaiming the un-reacted ethylene glycol ethyl ether and acetic acid to obtain the ethylene glycol ethyl ether acetate. The method realizes continuous production of the ethylene glycol ethyl ether acetate, has simple operating mode, remarkably improves the production efficiency of the ethylene glycol ethyl ether acetate, reduces the production cost, can reduce the discharge of solid pollutants and wastewater, and has extremely good scale industrial application value.
Description
Technical field
The present invention relates to a kind of preparation method of ethylene glycol ether acetate, especially be particularly related to the method that a kind of continuous esterification prepares ethylene glycol ether acetate.
Background technology
Ethylene glycol ether acetate (CAC) is the important industrial solvent of a class, this solvent molecule structure uniqueness, with existing nonpolar part in a part, polar group is arranged again, so it all has dissolving power preferably to polarity and apolar substance, its solubility property is much higher than common solvent and gylcol ether and propylene glycol kind solvent.Change little and characteristics such as corrodibility is little because ethylene glycol ether acetate has solubility property height, Heat stability is good, viscosity, be widely used in industry such as coating, washing composition, printing and dyeing, agricultural chemicals and pluronic polymer.
By ethylene glycol ethyl ether and acetic acid through esterification preparing ethylene glycol ethyl ether acetate ester, though be general technological line, but the at present industrial method that generally adopts is an intermittent type esterification dehydration reaction technology, the catalyzer that uses in the reaction process is generally mineral acid or organic acid, and mineral acid is mainly: phosphoric acid, hydrochloric acid, the vitriol oil and chlorsulfonic acid; Organic acid is mainly: oxalic acid, citric acid, methylsulfonic acid and tosic acid, take homogeneous reaction (Liu Zhun etc., Chinese patent CN1515537A, on July 28th, 2004; Zhu Xinbao etc., CN101475469A, on July 8th, 2009).The problem that aforesaid method exists is, need after reaction finishes remove employed catalyzer by the alkali neutralization, and this method side reaction is many, corrodibility strong, complex technical process, production efficiency is low, generation is a large amount of solid waste and contaminated wastewater environment.Employing modified molecular screen class composite solid-acid catalysts such as Chen Yuandong also add auxiliary agent (Chinese patent CN1048990A such as metallic tin compound, on February 6th, 1991) carry out esterification, it is said and to reduce esterification reaction temperature, react 2-3 hour transformation efficiency near 100%.But the contained tin compound auxiliary agent of this type of solid acid catalyst has big toxicity and runs off easily, and apparent, its actual application and popularization value can be subjected to bigger restriction undoubtedly.
Summary of the invention
The object of the invention is to provide a kind of preparation method of ethylene glycol ether acetate, this method can overcome the existing product of existing batch production technology to be needed through neutralizing treatment, and complex technical process, production efficiency low, produce shortcomings such as a large amount of solid waste and waste water, realize the serialization production of ethylene glycol ether acetate, improve the production efficiency of ethylene glycol ether acetate, reduce its production cost.
The technical solution adopted in the present invention is as follows:
A kind of method for preparing ethylene glycol ether acetate is a raw material with ethylene glycol ethyl ether and acetic acid, it is characterized in that: adopt solid acid catalyst to carry out the fixed bed continuous esterification, esterification temperature 70-150 ℃, the water that generates in the esterification removes through component distillation; With esterification reaction product rectifying, remove and reclaim unreacted ethylene glycol ethyl ether and acetic acid, obtain ethylene glycol ether acetate.
Described solid acid catalyst is a kind of composite enhanced macroporous polystyrene sulfonic acid type storng-acid cation exchange resin.Described Zeo-karb polymkeric substance can adopt the common synthetic method of polystyrolsulfon acid type storng-acid cation exchange resin, and soon sulfonation makes behind vinylbenzene and the Vinylstyrene monomer polymerization.The mole number of Vinylstyrene accounts for 20～35% in its polymerization single polymerization monomer of described Zeo-karb, and adding weight accounts for the micron order graphite whisker of polymerization single polymerization monomer total amount 1～3%(wt/wt) and the pore-creating agent of polymerization single polymerization monomer total amount 40～70%(wt/wt).Described pore-creating agent comprises toluene, dimethylbenzene, gasoline, normal heptane, octane-iso, isooctyl alcohol or 2-ethyl butanol etc., or their mixture.Add composite pore-forming, can make the ion exchange resin that obtains have the equally distributed basically aperture of macropore, mesopore, aperture, thereby improve intensity, thermostability and the specific surface area of catalyst backbone greatly.Through the actual trial run that investigate and carry out on full scale plant the work-ing life on the pilot plant, the work-ing life of described solid acid catalyst is at least more than 1 year.
Described fixed bed continuous esterification can adopt the two-part fixed bed to carry out continuous esterification, promptly carries out two sections esterifications continuously in two fixed-bed reactor that all are filled with described solid acid catalyst.In view of esterification is the reversible reaction that is subjected to thermodynamics equilibrium limit, carry out to the direction of expectation for helping esterification, after first section esterification reaction product removes the water of reaction generation, carry out second section esterification again, to obtain higher transformation efficiency.Specific practice is, earlier raw material ethylene glycol ethyl ether and acetic acid mixed by certain mole proportioning, carries out esterification through entering first section fixed-bed reactor that solid acid catalyst is housed continuously after the preheating, and reaction product enters the distillation tower dehydration; Material after the dehydration is extracted out continuously in distillation tower stripping section bottom, and delivers in second section fixed-bed reactor as the charging of second section esterification and to proceed esterification.Entering the raw material ethylene glycol ethyl ether of first section fixed-bed reactor and the mol ratio of acetic acid is 0.7-2:1, and preferable range is 0.9-1.2:1; The mass flow of extracting and be input to second section fixed-bed reactor out at the distillation tower stripping section be first section fixed-bed reactor inlet amount 1-5 doubly, preferable range be 2-3 doubly.Equally, the product of second section esterification enters the distillation tower dehydration again after the reaction product with first section esterification merges.
In described two fixed-bed reactor, esterification reaction temperature is 70-150 ℃, and preferable range is 90-120 ℃; Air speed is 1-10 h
-1, preferable range is 2-6 h
-1
The water that esterification generated removes in the component distillation mode in distillation tower, and the band aqua that is adopted is benzene or hexanaphthene.First section reaction product with second section esterification enters distillation tower and carries out component distillation from top, forming water steams from the distillation tower cat head with the azeotrope of being with aqua, after condenser condenses, enter the layering jar, and in the layering jar, be divided into organic phase and water, lower floor's water is drawn, and upper organic phase is back to distillation tower and uses for the band aqua.
Unreacted ethylene glycol ethyl ether, acetic acid and with object esterification products ethylene glycol ether acetate by discharging at the bottom of the distillation tower still, enter lightness-removing column rectifying, the lighting end that cat head steams is ethylene glycol ethyl ether and acetic acid, with its recovery.The ethylene glycol ethyl ether and the acetic acid that reclaim can be used as the reaction raw materials cycling and reutilization.Lightness-removing column bottoms material is the object ethylene glycol ether acetate.
Through the prepared product of aforesaid method is the ethylene glycol ether acetate crude product.The lightness-removing column bottom product is delivered to the rectifying of product rectifying tower, can obtain the pure product of ethylene glycol ether acetate.
Fig. 1 prepares the schema of the main part of ethylene glycol ether acetate technology for two sections fixed bed continuous esterifications that adopt solid acid catalyst.
In Fig. 1,
1For first section fixed-bed reactor of solid acid catalyst are housed,
2For second section fixed-bed reactor of solid acid catalyst are housed,
3Be distillation tower,
4Be condenser,
5Be the layering jar,
6Be first section fixed-bed reactor feeding pipe position,
7Be second section fixed-bed reactor feeding pipe position,
8For the esterification material enters distillation tower pipeline position,
9Be the water outlet,
10Be the band aqua into distillation tower pipeline position of refluxing,
11For distillation Tata still material is sent to the lightness-removing column pipeline.
Ethylene glycol ethyl ether and acetic acid raw material after preheating by
6Enter first section fixed-bed reactor that solid acid catalyst is housed
1, ethylene glycol ethyl ether and acetic acid generation esterification under catalyst action are carried out for helping the esterification forward direction, improve transformation efficiency, with the reaction mass of first section fixed-bed reactor by
8Send distillation tower to
3Dehydration.At distillation tower
3In, the water that esterification generates is constantly gone out from cat head is separated in 68-71 ℃ of formation azeotrope in the presence of band aqua of the present invention.The esterification material is drawn out of in distillation tower stripping section bottom continuously through the dehydration back, by
7Deliver to second section fixed-bed reactor
2Proceed esterification.The mass flow of extracting and be input to second section fixed-bed reactor out at the distillation tower stripping section be first section fixed-bed reactor inlet amount 1-5 doubly, preferable range be 2-3 doubly.Through the material of second section fixed-bed reactor reaction equally by
8Enter distillation tower
3Separation removal moisture.Distillation tower
3Cat head steams thing through condenser
4After the condensation, enter the layering jar
5, and at the layering jar
5In be divided into organic phase and water, lower floor's water from
9Draw, upper organic phase is the band aqua, by
10Be back to distillation tower
3Ethylene glycol ether acetate and unreacted ethylene glycol ethyl ether and acetic acid that esterification generates are by distillation tower
3Discharging warp at the bottom of the still
11Enter lightness-removing column (not marking among Fig. 1) rectifying of other outfit, ethylene glycol ethyl ether and acetic acid that the lightness-removing column top steams reclaim Recycling, the thick product of ethylene glycol ether acetate at the bottom of the lightness-removing column still is delivered to product rectifying tower (not marking among Fig. 1) rectifying, obtains the pure product of ethylene glycol ether acetate.
In sum, the production method of ethylene glycol ether acetate of the present invention by the novel process that serialization is produced, can realize the suitability for industrialized production of ethylene glycol ether acetate product expeditiously, and operating method is simple, production efficiency is high, reduces the discharging of slag and effluent in production process; Reaction product need not a large amount of alkali and neutralizes, the long service life of catalyzer, and the products production cost reduces.Continuous esterification of the present invention prepares the method for ethylene glycol ether acetate, and good economic benefit and environmental benefit are arranged.
Describe the present invention below in conjunction with specific embodiment.Scope of the present invention is not exceeded with embodiment, but is limited by the scope of claim.
Description of drawings
Fig. 1 continuous esterification prepares the process flow diagram of ethylene glycol ether acetate.
Embodiment
Be preheated to 110 ℃ raw material ethylene glycol ethyl ether and acetic acid in molar ratio 1:1, with 15 L/h flows continuously input first section fixed-bed reactor of the composite enhanced macroporous polystyrene sulfonic acid type of 5 L storng-acid cation exchange resin solid acid catalyst are housed, 110 ℃ of esterification reaction temperatures, air speed are 3 h
-1Material through the reaction of first section fixed-bed reactor enters distillation tower, and in distillation tower, the water that esterification generates is in the presence of water liquid benzene, in 68-71 ℃ of formation azeotrope and constantly separated.The material that is removed moisture is drawn out of and is transported to second section fixed-bed reactor that the above-mentioned solid acid catalyst of 5 L is housed at the stripping section of distillation tower continuously with 30 L/h flows and proceeds esterification, and 120 ℃ of temperature of reaction, air speed are 6 h
-1The mass flow that is input to second section fixed-bed reactor is 2 times of first section fixed-bed reactor inlet amount.Material through second section fixed-bed reactor reaction enters distillation tower separation removal moisture equally, the distillation tower cat head steams thing after condenser condenses, enters the layering jar, and is divided into organic phase and water in the layering jar, water is drawn, and organic phase is that water liquid benzene is back to distillation tower and uses.The discharging of distillation Tata still is formed mass ratio and is: ethylene glycol ether acetate 57.6%, acetic acid 17.2%, ethylene glycol ethyl ether 25.2%.The discharging of distillation Tata still enters the lightness-removing column rectifying of other outfit, and ethylene glycol ethyl ether that cat head steams and acetic acid reclaim Recycling, and tower still material is delivered to product rectifying tower purifying, but output ethylene glycol ether acetate product 7.6 kg per hour.
Be preheated to 90 ℃ raw material ethylene glycol ethyl ether and acetic acid in molar ratio 1.5:1, with 10 L/h flows continuously input be equipped with the composite enhanced macroporous polystyrene sulfonic acid type of 5 L storng-acid cation exchange resin solid acid catalyst first section fixed-bed reactor, 90 ℃ of esterification reaction temperatures, air speed are 2 h
-1Material through the reaction of first section fixed-bed reactor enters distillation tower, and in distillation tower, the water that esterification generates is in the presence of hexanaphthene band aqua, in 69-71 ℃ of formation azeotrope and constantly separated.The esterification material that removes moisture is extracted and is transported to out second section fixed-bed reactor that the above-mentioned solid acid catalyst of 5 L is housed at the stripping section of distillation tower continuously with 10 L/h flows, 100 ℃ of esterification reaction temperatures, and air speed is 2 h
-1The mass flow that is input to second section fixed-bed reactor is 1 times of first section fixed-bed reactor inlet amount.Material through second section fixed-bed reactor reaction enters distillation tower separation removal moisture equally, and the distillation tower cat head steams thing after condenser condenses, enters the layering jar, and in the layering jar, be divided into organic phase and water, water is drawn, and organic phase is a hexanaphthene, turns back to distillation tower.The discharging of distillation Tata still consists of: ethylene glycol ether acetate 44.2%, acetic acid 12.7%, ethylene glycol ethyl ether 43.1%.The discharging of distillation Tata still enters the lightness-removing column fractionation of other outfit, and ethylene glycol ethyl ether that cat head steams and acetic acid reclaim Recycling, the rectifying of tower still material input product rectifying tower, but output ethylene glycol ether acetate product 3.9 kg per hour.
Claims (10)
1.
A kind of method for preparing ethylene glycol ether acetate is a raw material with ethylene glycol ethyl ether and acetic acid, it is characterized in that: adopt solid acid catalyst to carry out the fixed bed continuous esterification, esterification temperature 70-150 ℃, the water that generates in the esterification removes through component distillation; With esterification reaction product rectifying, remove and reclaim unreacted ethylene glycol ethyl ether and acetic acid, obtain ethylene glycol ether acetate.
2.
The method for preparing ethylene glycol ether acetate according to claim 1 is characterized in that: described solid acid catalyst is composite enhanced macroporous polystyrene sulfonic acid type storng-acid cation exchange resin.
3.
The method for preparing ethylene glycol ether acetate according to claim 2, it is characterized in that: described ion exchange resin by vinylbenzene and Vinylstyrene monomer polymerization after sulfonation make, the mole number of Vinylstyrene accounts for 20～35% in its polymerization single polymerization monomer, and adding weight accounts for the micron order graphite whisker of polymerization single polymerization monomer total amount 1～3%(wt/wt) and the pore-creating agent of monomer total amount 40～70%(wt/wt).
4.
The method for preparing ethylene glycol ether acetate according to claim 1, it is characterized in that: described fixed bed continuous esterification, be all to be filled with two sections esterifications of carrying out continuously in the fixed-bed reactor of solid acid catalyst at two, first section esterification reaction product carries out second section esterification after removing and reacting the water that generates.
5.
The method for preparing ethylene glycol ether acetate according to claim 4, it is characterized in that: described fixed bed continuous esterification comprises, after raw material ethylene glycol ethyl ether and acetic acid mix also preheating, enter first section fixed-bed reactor that solid acid catalyst is housed continuously and carry out esterification, reaction product enters the distillation tower dehydration; Material after the dehydration is extracted out continuously in distillation tower stripping section bottom, and delivers in second section fixed-bed reactor as the charging of second section esterification and to proceed esterification.
6.
The method for preparing ethylene glycol ether acetate according to claim 4 is characterized in that: entering the raw material ethylene glycol ethyl ether of first section fixed-bed reactor and the mol ratio of acetic acid is 0.7-2:1; The mass flow that enters into second section fixed-bed reactor is 1-5 a times of first section fixed-bed reactor inlet amount.
7.
According to claim 1, the 2 or 4 described methods that prepare ethylene glycol ether acetate, it is characterized in that: esterification reaction temperature is 90-120 ℃.
8.
According to claim 1, the 2 or 4 described methods that prepare ethylene glycol ether acetate, it is characterized in that: the esterification air speed of described fixed-bed reactor is 1-10 h
-1
9.
According to claim 1, the 2 or 4 described methods that prepare ethylene glycol ether acetate, it is characterized in that: the band aqua that described component distillation adopts is benzene or hexanaphthene.
10. according to claim 1, the 2 or 4 described methods that prepare ethylene glycol ether acetate, it is characterized in that: the ethylene glycol ether acetate that obtains obtains the pure product of ethylene glycol ether acetate through rectifying.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102267896A (en) * | 2011-06-09 | 2011-12-07 | 江苏天音化工有限公司 | Method for preparing 2,2,4-trimethyl-1,3-pentanediol diisobutyrate |
| CN106349064A (en) * | 2016-08-24 | 2017-01-25 | 安徽金邦医药化工有限公司 | Preparation process of glycol ether acetic ester |
| CN109535121A (en) * | 2019-01-17 | 2019-03-29 | 江苏天音化工有限公司 | A method of preparing 2- methyl -2- isobutyl group -4- methylol -1,3-dioxolane |
| CN110183326A (en) * | 2019-07-03 | 2019-08-30 | 上海中溶科技有限公司 | A kind of method of continuous preparation purification glycol dibenzoate only son ether-ether |
| CN112010754A (en) * | 2020-08-19 | 2020-12-01 | 江门谦信化工发展有限公司 | Refining method for esterification synthesis of ethylene glycol methyl ether acetate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267896A (en) * | 2011-06-09 | 2011-12-07 | 江苏天音化工有限公司 | Method for preparing 2,2,4-trimethyl-1,3-pentanediol diisobutyrate |
| CN106349064A (en) * | 2016-08-24 | 2017-01-25 | 安徽金邦医药化工有限公司 | Preparation process of glycol ether acetic ester |
| CN109535121A (en) * | 2019-01-17 | 2019-03-29 | 江苏天音化工有限公司 | A method of preparing 2- methyl -2- isobutyl group -4- methylol -1,3-dioxolane |
| CN110183326A (en) * | 2019-07-03 | 2019-08-30 | 上海中溶科技有限公司 | A kind of method of continuous preparation purification glycol dibenzoate only son ether-ether |
| CN112010754A (en) * | 2020-08-19 | 2020-12-01 | 江门谦信化工发展有限公司 | Refining method for esterification synthesis of ethylene glycol methyl ether acetate |
| CN112010754B (en) * | 2020-08-19 | 2023-02-28 | 江门谦信化工发展有限公司 | Refining method for esterification synthesis of ethylene glycol methyl ether acetate |
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Application publication date: 20110316 |