CN101863761B - Method for preparing dipropylene glycol methyl ether acetate - Google Patents
Method for preparing dipropylene glycol methyl ether acetate Download PDFInfo
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- CN101863761B CN101863761B CN201010213655.9A CN201010213655A CN101863761B CN 101863761 B CN101863761 B CN 101863761B CN 201010213655 A CN201010213655 A CN 201010213655A CN 101863761 B CN101863761 B CN 101863761B
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- dipropylene glycol
- methyl ether
- glycol methyl
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Abstract
The invention discloses a process for preparing dipropylene glycol methyl ether acetate, which uses dipropylene glycol monomethyl ether and acetic acid as raw materials. The process is characterized in that: performing a fixed bed continuous esterification reaction in the presence of a solid acid catalyst at an esterification temperature of 70 to 150 DEG and removing the water generated by the esterification reaction by azeotropic distillation; distilling the product of the esterification reaction, removing and recovering unreacted dipropylene glycol monomethyl ether and acetic acid, and obtaining the dipropylene glycol methyl ether acetate. The method of the invention realizes the continuous production of the dipropylene glycol methyl ether acetate, is simple in operation mode, obviouslyimproves the production efficiency of the dipropylene glycol methyl ether acetate, reduces the production cost of the dipropylene glycol methyl ether acetate, can reduce solid pollutants and waste water discharge and has high scale industrial application values.
Description
Technical field
The present invention relates to a kind of preparation method of dipropylene glycol methyl ether acetate, especially be particularly related to the method that a kind of continuous esterification prepares dipropylene glycol methyl ether acetate.
Background technology
Dipropylene glycol methyl ether acetate (DPMA) is the important industrial solvent of a class, this solvent molecule structure is unique, with existing nonpolar part in a part, polar group is arranged again, therefore it all has preferably dissolving power to polarity and apolar substance, its solubility property is much higher than common solvent and propylene glycol ethers and glycol ethers solvent.Because the characteristics such as dipropylene glycol methyl ether acetate has that solvent nature is high, Heat stability is good, viscosity changes little and corrodibility is little are widely used in the industry such as coating, washing composition, printing and dyeing, agricultural chemicals and pluronic polymer.
By dipropylene glycol methyl ether and acetic acid through esterification dipropylene glycol methyl ether acetate processed, though be general technological line, but the at present industrial method that generally adopts is intermittent type esterification dehydration reaction technique, 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 by removing employed catalyzer in the alkali, and the 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.The heteropllyacids of employing solid acid catalyst (Wang Xi is also arranged, Liaoning Journal of Teachers College: natural science edition, the 1st phase of the 2nd volume in 2000) is used for the synthetic report of propylene-glycol ether acetate, but the factors such as the complicacy from the Nomenclature Composition and Structure of Complexes of heteropolyacid own and work-ing life are considered, are larger in industrial practical application difficulty.The employing modified molecular screen class composite solid-acid catalysts such as Chen Yuandong also add auxiliary agent (the 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 larger toxicity and easily runs off, and apparent, its actual application and popularization value can be subject to larger restriction undoubtedly.
Summary of the invention
The object of the invention is to provide a kind of preparation method of dipropylene glycol methyl ether acetate, the method can overcome the existing product of existing batch production technique to be needed through neutralizing treatment, and complex technical process, production efficiency low, produce the shortcomings such as a large amount of solid waste and waste water, realize the serialization production of dipropylene glycol methyl ether acetate, improve the production efficiency of dipropylene glycol methyl ether acetate, reduce its production cost.
The technical solution adopted in the present invention is as follows:
A kind of method for preparing dipropylene glycol methyl ether acetate, take dipropylene glycol methyl ether and acetic acid as raw material, it is characterized in that: adopt solid acid catalyst to be fixed a 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 dipropylene glycol methyl ether and acetic acid, obtain dipropylene glycol methyl 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 basically equally distributed aperture of macropore, mesopore, aperture, thereby greatly improve intensity, thermostability and the specific surface area of catalyst backbone.Investigate the work-ing life on pilot plant and reach the actual trial run of carrying out at full scale 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, namely carries out continuously two sections esterifications in two fixed-bed reactor that all are filled with described solid acid catalyst.Be the reversible reaction that is subjected to thermodynamics equilibrium limit in view of esterification, carry out to the direction of expectation for being conducive to esterification, the first paragraph esterification reaction product carries out the second segment esterification, again to obtain higher transformation efficiency after removing the water that reaction generates.Specific practice is, first raw material dipropylene glycol methyl ether and acetic acid mixed by certain mole proportioning, carries out esterification through entering continuously the first paragraph fixed-bed reactor that solid acid catalyst is housed 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 the second segment fixed-bed reactor as the charging of second segment esterification and to proceed esterification.Entering the raw material dipropylene glycol methyl ether of first paragraph 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 the second segment fixed-bed reactor out at the distillation tower stripping section be first paragraph fixed-bed reactor inlet amount 1-5 doubly, preferable range be 2-3 doubly.Equally, the product of second segment esterification enters the distillation tower dehydration again after the reaction product with the first paragraph esterification merges.
In described two fixed-bed reactor, the first paragraph esterification reaction temperature is 70-150 ℃, and preferable range is 80-110 ℃; Air speed is 1-5h
-1, preferable range is 3-4h
-1The second segment esterification reaction temperature is 70-150 ℃, and preferable range is 105-140 ℃; Air speed is 5-10h
-1, preferable range is 6-8h
-1
The water that esterification generates removes in the component distillation mode in distillation tower, and the band aqua that adopts is benzene or hexanaphthene.The reaction product of first paragraph and second segment esterification enters distillation tower and carries out component distillation from top, forming water steams from the distillation tower cat head with azeotrope with aqua, after condenser condenses, enter the layering tank, and in the layering tank, 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 dipropylene glycol methyl ether, acetic acid and with object esterification products dipropylene glycol methyl ether acetate by the distillation tower reactor at the bottom of discharging, enter lightness-removing column rectifying, the lighting end that cat head steams is dipropylene glycol methyl ether and acetic acid, with its recovery.The dipropylene glycol methyl ether and the acetic acid that reclaim can be used as the reaction raw materials cycling and reutilization.The lightness-removing column materials at bottom of tower is the object dipropylene glycol methyl ether acetate.
Be the dipropylene glycol methyl ether acetate crude product through the prepared product of aforesaid method.The lightness-removing column bottom product is delivered to the rectifying of product rectifying tower, can obtain the dipropylene glycol methyl ether acetate sterling.
Fig. 1 prepares the schema of the main part of dipropylene glycol methyl ether acetate technique for two sections fixed bed continuous esterifications that adopt solid acid catalyst.
In Fig. 1,
1For the first paragraph fixed-bed reactor of solid acid catalyst are housed,
2For the second segment fixed-bed reactor of solid acid catalyst are housed,
3Be distillation tower,
4Be condenser,
5Be the layering tank,
6Be first paragraph fixed-bed reactor feeding pipe position,
7Be second segment fixed-bed reactor feeding pipe position,
8For the esterification material enters distillation tower pipeline position,
9Be the water outlet,
10For the band aqua refluxes into distillation tower pipeline position,
11For distillation tower tower reactor material is sent to the lightness-removing column pipeline.
Dipropylene glycol methyl ether and acetic acid raw material after preheating by
6Enter the first paragraph fixed-bed reactor that solid acid catalyst is housed
1, propylene glycol monomethyl ether and acetic acid generation esterification under catalyst action are carried out for being conducive to the esterification forward direction, improve transformation efficiency, with the reaction mass of first paragraph fixed-bed reactor by
8Send distillation tower to
3Dehydration.At distillation tower
3In, the water that esterification generates constantly is separated from cat head in 68-71 ℃ of formation azeotrope in the presence of band aqua of the present invention.The esterification material is drawn out of continuously in distillation tower stripping section bottom after dewatering, by
7Deliver to the second segment fixed-bed reactor
2Proceed esterification.The mass flow of extracting and be input to the second segment fixed-bed reactor out at the distillation tower stripping section be first paragraph fixed-bed reactor inlet amount 1-5 doubly, preferable range be 2-3 doubly.Through the material of second segment 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 tank
5, and at the layering tank
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
3Dipropylene glycol methyl ether acetate and unreacted dipropylene glycol methyl 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, dipropylene glycol methyl ether and acetic acid recovery Recycling that the lightness-removing column top steams, the thick product of dipropylene glycol methyl 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 dipropylene glycol methyl ether acetate sterling.
In sum, the production method of dipropylene glycol methyl ether acetate of the present invention, novel process by serialization production, can realize expeditiously the suitability for industrialized production of dipropylene glycol methyl ether acetate product, 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, products production cost.Continuous esterification of the present invention prepares the method for dipropylene glycol methyl 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 limited with embodiment, but is limited by the scope of claim.
Description of drawings
Fig. 1 continuous esterification prepares the process flow diagram of dipropylene glycol methyl ether acetate
Technical process as shown in Figure 1, to be preheated to 110 ℃ raw material dipropylene glycol methyl ether and acetic acid 1: 1 in molar ratio, input continuously the first paragraph fixed-bed reactor 1 that 5L macroporous polystyrene sulfonic acid type storng-acid cation exchange resin solid acid catalyst is housed with the 15L/h flow, 110 ℃ of esterification reaction temperatures, air speed are 3h
-1Material through first paragraph fixed-bed reactor 1 reaction enters distillation tower 3, and in distillation tower 3, 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 continuously and is transported to the second segment fixed-bed reactor 2 that the above-mentioned solid acid catalyst of 5L is housed at the stripping section of distillation tower 3 and proceeds esterification with the 30L/h flow, 120 ℃ of temperature of reaction, air speed are 6h
-1The mass flow that is input to the second segment fixed-bed reactor is 2 times of first paragraph fixed-bed reactor 1 inlet amount.Material through 2 reactions of second segment fixed-bed reactor enters distillation tower 3 separation removal moisture equally, distillation tower 3 cats head steam thing after condenser 4 condensations, enter layering tank 5, and in layering tank 5, be divided into organic phase and water, water is drawn, and organic phase is that water liquid benzene is back to distillation tower 3 and uses.Distillation tower 3 tower reactor dischargings form mass ratio: dipropylene glycol methyl ether acetate 57.8%, acetic acid 12.2%, dipropylene glycol methyl ether 30.0%.Distillation tower 3 tower reactor dischargings enter the lightness-removing column rectifying of other outfit, the dipropylene glycol methyl ether that cat head steams and acetic acid recovery Recycling, and the tower reactor material is delivered to product rectifying tower purifying, but output dipropylene glycol methyl ether acetate product 8kg per hour.
Technical process as shown in Figure 1, to be preheated to 95 ℃ raw material dipropylene glycol methyl ether and acetic acid 1.5: 1 in molar ratio, input continuously the first paragraph fixed-bed reactor 1 that 5L macroporous polystyrene sulfonic acid type storng-acid cation exchange resin solid acid catalyst is housed with the 20L/h flow, 95 ℃ of esterification reaction temperatures, air speed are 4h
-1Material through first paragraph fixed-bed reactor 1 reaction enters distillation tower 3, and in distillation tower 3, the water that esterification generates is in the presence of cyclohexane, in 69-71 ℃ of formation azeotrope and constantly separated.The esterification material that removes moisture is extracted and is transported to out the second segment fixed-bed reactor 2 that the above-mentioned solid acid catalyst of 5L is housed continuously at the stripping section of distillation tower 3 with the 40L/h flow, 105 ℃ of esterification reaction temperatures, and air speed is 8h
-1The mass flow that is input to second segment fixed-bed reactor 2 is 2 times of first paragraph fixed-bed reactor 1 inlet amount.Material through 2 reactions of second segment fixed-bed reactor enters distillation tower 3 separation removal moisture equally, and distillation tower 3 cats head steam thing after condenser 4 condensations, enter layering tank 5, and in layering tank 5, be divided into organic phase and water, water is drawn, and organic phase is hexanaphthene, turns back to distillation tower 3.Distillation tower 3 tower reactor dischargings consist of: dipropylene glycol methyl ether acetate 49.5%, acetic acid 6.7%, dipropylene glycol methyl ether 43.8%.Distillation tower 3 tower reactor dischargings enter the lightness-removing column fractionation of other outfit, the dipropylene glycol methyl ether that cat head steams and acetic acid recovery Recycling, and the tower reactor material is got to the rectifying of product rectifying tower, but output dipropylene glycol methyl ether acetate product 9.2kg per hour.
Claims (6)
1. method for preparing dipropylene glycol methyl ether acetate, take dipropylene glycol methyl ether and acetic acid as raw material, it is characterized in that: adopt solid acid catalyst to be fixed a 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 dipropylene glycol methyl ether and acetic acid, obtain dipropylene glycol methyl ether acetate;
Described solid acid catalyst is composite enhanced macroporous polystyrene sulfonic acid type storng-acid cation exchange resin, made by sulfonation behind vinylbenzene and the Vinylstyrene monomer polymerization, 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% and the pore-creating agent of monomer total amount 40～70%;
Described fixed bed continuous esterification is all to be filled with two sections esterifications of carrying out continuously in the fixed-bed reactor of solid acid catalyst at two, and the first paragraph esterification reaction product carries out the second segment esterification after removing and reacting the water that generates; Its concrete steps comprise, after raw material dipropylene glycol methyl ether and acetic acid mixing and the preheating, enter continuously the first paragraph fixed-bed reactor that solid acid catalyst is housed and carry out esterification, 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 the second segment fixed-bed reactor as the charging of second segment esterification and to proceed esterification.
2. the method for preparing dipropylene glycol methyl ether acetate according to claim 1, it is characterized in that: entering the raw material dipropylene glycol methyl ether of first paragraph fixed-bed reactor and the mol ratio of acetic acid is 0.7-2:1; The mass flow that enters into the second segment fixed-bed reactor is 1-5 times of first paragraph fixed-bed reactor inlet amount.
3. the method for preparing dipropylene glycol methyl ether acetate according to claim 1, it is characterized in that: the first paragraph esterification reaction temperature is 80-110 ℃; The second segment esterification reaction temperature is 105-140 ℃.
4. the method for preparing dipropylene glycol methyl ether acetate according to claim 1, it is characterized in that: the esterification air speed of described first paragraph fixed-bed reactor is 1-5 h
-1The esterification air speed of second segment fixed-bed reactor is 5-10 h
-1
5. the method for preparing dipropylene glycol methyl ether acetate according to claim 1 is characterized in that: the band aqua that described component distillation adopts is benzene or hexanaphthene.
6. the method for preparing dipropylene glycol methyl ether acetate according to claim 1, it is characterized in that: the dipropylene glycol methyl ether acetate that obtains obtains the dipropylene glycol methyl ether acetate sterling through rectifying.
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| CN103483191A (en) * | 2013-09-13 | 2014-01-01 | 江苏华伦化工有限公司 | Method for producing DPMA |
| CN103435481A (en) * | 2013-09-13 | 2013-12-11 | 江苏华伦化工有限公司 | Production method of ethylene glycol diacetate (EGDA) |
| CN106966898B (en) * | 2017-04-21 | 2019-11-15 | 江苏天音化工有限公司 | A kind of method of presence of acidic ionic liquid catalyst synthesis dipropylene glycol methyl ether acetate |
| CN107098810B (en) * | 2017-05-16 | 2021-04-30 | 天津大学 | Separation and purification method for preparing electronic-grade propylene glycol monomethyl 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 |
| CN115215745A (en) * | 2022-09-07 | 2022-10-21 | 成都中金黎阳新材料科技有限公司 | Synthesis of diethylene glycol phenyl ether acetate and application of diethylene glycol phenyl ether acetate in high-temperature and low-temperature slurry |
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| CN101722027A (en) * | 2009-11-26 | 2010-06-09 | 沈阳工业大学 | Esterification catalyst for synthesizing ethylene/propylene glycol ether carboxylate, and preparation method thereof |
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| CN101722027A (en) * | 2009-11-26 | 2010-06-09 | 沈阳工业大学 | Esterification catalyst for synthesizing ethylene/propylene glycol ether carboxylate, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 不同结构的磺酸型阳离子交换树脂在酯化反应中的催化作用;伍征华等;《成都科技大学学报》;19811231;19-24 * |
| 伍征华等.不同结构的磺酸型阳离子交换树脂在酯化反应中的催化作用.《成都科技大学学报》.1981,19-24. |
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