阅读说明：本技术 一种乙二醇单烯丙基醚的制备方法及系统 (Preparation method and system of ethylene glycol monoallyl ether ) 是由 马定连 金一丰 王新荣 路伯庭 赵兴军 于 2020-07-23 设计创作，主要内容包括：本发明提供一种乙二醇单烯丙基醚的制备方法及系统,制备方法是采用以下反应方程式：<Image he="80" wi="700" file="DDA0002598531580000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>包括：烯丙醇和环氧乙烷在催化剂作用下于所述反应釜主体内反应合成乙二醇单烯丙基醚粗品；粗品再在精馏塔内经减压精馏得到乙二醇单烯丙基醚成品。制备系统包括加成精馏一体化反应釜,加成精馏一体化反应釜包括反应釜主体,反应釜主体上方连接精馏塔；反应釜主体包括反应进料口、反应出料口和物料蒸汽出口,物料蒸汽出口连接精馏塔的精馏进口,精馏塔上设有精馏进口和精馏出口,精馏塔还连接真空装置。采用本发明方法制备的乙二醇单烯丙基醚,纯度高(≥99.8％),副产物少。(The invention provides a preparation method and a system of ethylene glycol monoallyl ether, wherein the preparation method adopts the following reaction equation: the method comprises the following steps: allyl alcohol and ethylene oxide react in the reaction kettle main body under the action of a catalyst to synthesize a crude product of ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the crude product in a rectifying tower to obtain a finished product of the ethylene glycol monoallyl ether. The preparation system comprises an addition and rectification integrated reaction kettle, the addition and rectification integrated reaction kettle comprises a reaction kettle main body, and a rectification tower is connected above the reaction kettle main body; the reaction kettle main body comprises a reaction feed inlet, a reaction discharge outlet and a material steam outlet, the material steam outlet is connected with a rectification inlet of a rectification tower, and the rectification tower is provided with a rectification inletAnd a rectification outlet, and the rectification tower is also connected with a vacuum device. The ethylene glycol monoallyl ether prepared by the method has high purity (more than or equal to 99.8 percent) and few byproducts.)

1. A preparation system of ethylene glycol monoallyl ether is characterized in that: the device comprises an addition and rectification integrated reaction kettle, wherein the addition and rectification integrated reaction kettle comprises a reaction kettle main body, and a rectification tower is connected above the reaction kettle main body; the reaction kettle main body comprises a reaction feed inlet, a reaction discharge outlet and a material steam outlet, and the material steam outlet is connected with a rectification inlet of the rectification tower; the rectifying tower is provided with the rectifying inlet and the rectifying outlet and is also connected with a vacuum device.

2. The system for preparing ethylene glycol monoallyl ether according to claim 1, wherein: the reaction discharge hole is also connected with the reaction feed hole through a material return pipeline, and a filter and a material conveying pump are arranged on the material return pipeline.

3. The system for preparing ethylene glycol monoallyl ether according to claim 1, wherein: the reaction kettle is provided with an interlayer, and the interlayer is used for introducing a temperature control medium.

4. The system for producing ethylene glycol monoallyl ether according to any one of claims 1 to 3, wherein: the preparation system also comprises a raw material storage tank and a product storage tank, wherein the raw material storage tank and the product storage tank are respectively connected with the addition rectification integrated reaction kettle.

5. A preparation method of ethylene glycol monoallyl ether is characterized by comprising the following steps: the following reaction equation is adopted:

the preparation method adopts the preparation system of any one of claims 1 to 4, and comprises the following steps: allyl alcohol and ethylene oxide react in the reaction kettle main body under the action of a catalyst to synthesize a crude product of ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the crude product in a rectifying tower to obtain a finished product of the ethylene glycol monoallyl ether.

6. The method for preparing ethylene glycol monopropyl ether according to claim 5, wherein: the preparation method comprises the following steps: mixing allyl alcohol and a catalyst in the reaction vessel body, N₂Heating to 90-160 ℃ under protection, adding ethylene oxide, and carrying out heat preservation reaction; separating out the catalyst after the reaction is finished to obtain a crude product of the ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the ethylene glycol monoallyl ether crude product in the rectifying tower, respectively collecting free allyl alcohol, an ethylene glycol monoallyl ether finished product and kettle bottom liquid, wherein the separated catalyst and free allyl alcohol can be recycled for the reaction process, and the kettle bottom liquid can be directly used for producing an allyl alcohol polyoxyethylene ether surfactant product.

7. The method for preparing ethylene glycol monopropyl ether according to claim 5 or 6, characterized in that: the catalyst is at least one of zinc methanesulfonate and zinc p-toluenesulfonate.

8. The method for preparing ethylene glycol monopropyl ether according to claim 5 or 6, characterized in that: the mass ratio of the allyl alcohol to the ethylene oxide is as follows: 58: (13.2-52.8), wherein the dosage of the catalyst is 0.3-5 per mill of the total weight of the allyl alcohol and the ethylene oxide.

9. The method for preparing ethylene glycol monopropyl ether according to claim 5 or 6, characterized in that: the reaction temperature of the allyl alcohol and the ethylene oxide under the catalysis of the catalyst is 95-150 ℃, and the reaction pressure is-0.05-0.60 MPa.

10. The method for preparing ethylene glycol monopropyl ether according to claim 5 or 6, characterized in that: the vacuum rectification specific process comprises the following steps: vacuumizing the addition rectification integrated reaction kettle to-0.05 MPa, and controlling the vacuum degree to be not higher thanHeating the crude ethylene glycol monoallyl ether in the reaction kettle main body, opening rectification and condensing, controlling the temperature of materials at the bottom of the kettle to be 65-80 ℃, controlling the temperature at the top of the kettle to be 50-65 ℃, carrying out total reflux for 30min, then starting to receive allyl alcohol, vacuumizing to improve the vacuum degree in the kettle to be more than or equal to-0.098 MPa when the temperature at the top of the kettle is reduced to normal temperature after the allyl alcohol is collected; heating the materials in the kettle again, controlling the temperature of the materials at the bottom of the kettle to be 80-100 ℃, controlling the temperature at the top of the kettle to be 50-65 ℃, carrying out total reflux for 30min, and then starting to receive the mixture of the ethylene glycol monoallyl ether and the allyl alcohol, wherein the reflux ratio is controlled to be 5: 1, taking liquid during the period to detect the content of the ethylene glycol monoallyl ether in the mixture, starting to receive the finished product of the ethylene glycol monoallyl ether independently when the content of the ethylene glycol monoallyl ether in the receiving liquid is more than or equal to 99.7 percent, stopping receiving when the purity of the ethylene glycol monoallyl ether in the fraction is less than or equal to 99.7 percent, and finishing rectification. Cooling the bottom liquid to 40 + -2 deg.C, charging N₂And (3) putting the kettle bottom liquid into a packaging barrel for producing other allyl alcohol polyoxyethylene ether until the pressure of the reaction kettle is 0.00-0.04 MPa.

Technical Field

The invention belongs to the technical field of organic compound preparation, and particularly relates to a preparation method and a system of ethylene glycol monoallyl ether.

Background

Ethylene glycol monoallyl ether, also known as 2-allyloxyethanol, propylene glycol, and the like, is a colorless transparent liquid, and is miscible with water and polar solvents. The double bonds are contained in the molecule, so that the polymer can be used as a monomer of a polymer; a side chain can be introduced because the molecule contains an ether bond and a hydroxyl bond; the alcohol is useful for synthesizing an ester, and is used as an additive monomer for ordinary-temperature curing in the production of a fluororesin soluble in an organic solvent. The acrylic acid/methacrylic acid copolymer has high boiling point and low odor, reacts with acrylic acid and methacrylic acid to prepare propenyl glycol ester, and can be used as a monomer diluent of UV (ultraviolet) coating. With the national advocated energy conservation and environmental protection, the UV coating is an advanced material surface treatment technology which is an industrial technology with the 5E characteristic: 1 efficiency, 2Enabling (wide adaptability), 3Economical (economy), 4Energy Saving and 5Environmental Friendly, is known as a new green industrial technology facing twenty-first century, and has good development prospect.

The current synthesis process routes of ethylene glycol monoallyl ether include two types:

1) an etherification end-capping method, which is disclosed in the article "development of ethylene glycol monoallyl ether" published in 2012, 1.A technical scheme is that allyl chloride and ethylene glycol are subjected to hydroxyl etherification under an alkaline condition, and then rectification purification is adopted.

2) Polymerization method: with alkeneTaking propylene alcohol and ethylene oxide as raw materials, synthesizing a coarse product of ethylene glycol monoallyl ether under the action of an alkaline catalyst, and then neutralizing, rectifying and purifying by acid to obtain a finished product. A scheme is disclosed in the article KF/A1203 preparation, characterization and catalytic synthesis of ethylene glycol propenyl ether published in the university of Changzhou journal, 2013, No. 1, which takes propylene alcohol and ethylene oxide as raw materials, and adopts KF/AI₂O₃Synthesizing a coarse product of ethylene glycol monoallyl ether by catalyzing with a solid base catalyst; a scheme is disclosed in an article, namely ethylene glycol allyl ether catalyzed and synthesized by attapulgite loaded KF (potassium fluoride) in the 2 nd publication of the chemical engineering journal of colleges and universities 2014, wherein propylene alcohol and ethylene oxide are used as raw materials, a crude product of ethylene glycol allyl ether is synthesized by catalysis of KF/ATP (potassium fluoride)/Al (aluminum phosphate) solid base catalyst, and KF/AI (potassium fluoride)/Al (aluminum chloride) is used as a catalyst₂O₃And KF/ATP catalyst is used in synthesizing glycol monoallyl ether, and has low catalytic selectivity, low product yield and high production cost. A scheme is disclosed in an article, namely synthesis of ethylene glycol monoallyl ether, published in No. 1 of 2017 of Fine and specialty Chemicals, propylene alcohol and ethylene oxide are used as raw materials, crude ethylene glycol monoallyl ether is synthesized by catalyzing sodium propylene alcohol, and the crude ethylene glycol monoallyl ether is rectified and purified to obtain a finished product, wherein the content of the finished product is more than or equal to 99.5%. Chinese patent CN 103435455B, a preparation method of ethylene glycol monoallyl ether, discloses a preparation method of ethylene glycol monoallyl ether, which takes propylene alcohol and ethylene oxide as raw materials, adopts KOH, NaOH and CH₃Synthesizing coarse product of ethylene glycol monoallyl ether by using ONa, Na or sodium allyl alcohol as catalyst, then adding H₃PO₄、H₂SO₄Or neutralizing by HAC, and rectifying to obtain the final product with content not less than 99.0%. KOH, sodium allyl alcohol and the like have poor catalytic selectivity, and KF/AI₂O₃Similar to KF/ATP catalysis, the method also has the disadvantages of high production yield and addition of H along with the generation of a large amount of byproducts such as diethylene glycol monoallyl ether, triethylene glycol monoallyl ether and the like₃PO₄、H₂SO₄Or HAC, resulting in a large amount of Na in the crude product₂SO₄And the impurities of inorganic and organic salts such as NaAC are difficult to removeSo that the residual kettle bottom liquid can not be directly utilized after the crude product is rectified, a large amount of waste liquid is generated, the treatment cost is high, the product is polluted by the environment and the like.

Disclosure of Invention

In order to solve the problems of low purity of synthesized crude products, high production cost, generation of a large amount of waste solids, environmental pollution caused by waste liquid and the like in the two synthesis process routes at present, the invention provides a method and a system for preparing ethylene glycol monoallyl ether, which have the advantages of high catalytic selectivity, low production cost, few byproducts and waste liquid and waste solids, easiness in operation and high efficiency. The technical scheme of the invention is as follows:

the invention provides a preparation system of ethylene glycol monoallyl ether, which comprises an addition and rectification integrated reaction kettle, wherein the addition and rectification integrated reaction kettle comprises a reaction kettle main body, and a rectification tower is connected above the reaction kettle main body; the reaction kettle main body comprises a reaction feed inlet, a reaction discharge outlet and a material steam outlet, and the material steam outlet is connected with a rectification inlet of the rectification tower; the rectifying tower is provided with the rectifying inlet and the rectifying outlet and is also connected with a vacuum device.

Furthermore, the reaction discharge hole is connected with the reaction feed hole through a material return pipeline, and a filter and a material conveying pump are arranged on the material return pipeline.

Further, a stirring device is also arranged in the reaction kettle main body.

Further, the reaction kettle is provided with an interlayer, and the interlayer is used for introducing a temperature control medium.

Further, the preparation system also comprises a raw material storage tank and a product storage tank, wherein the raw material storage tank and the product storage tank are respectively connected with the addition rectification integrated reaction kettle.

In a second aspect, the present invention provides a method for preparing ethylene glycol monoallyl ether, which uses the following reaction equation:

the preparation method adopts the preparation system, and comprises the following steps: allyl alcohol and ethylene oxide react in the reaction kettle main body under the action of a catalyst to synthesize a crude product of ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the crude product in a rectifying tower to obtain a finished product of the ethylene glycol monoallyl ether.

Further, the preparation method comprises the following steps: mixing allyl alcohol and a catalyst in the reaction vessel body, N₂Heating to 90-160 ℃ under protection, adding ethylene oxide, and carrying out heat preservation reaction; separating out the catalyst after the reaction is finished to obtain a crude product of the ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the ethylene glycol monoallyl ether crude product in the rectifying tower, respectively collecting free allyl alcohol, an ethylene glycol monoallyl ether finished product and kettle bottom liquid, wherein the separated catalyst and free allyl alcohol can be recycled for the reaction process, and the kettle bottom liquid can be directly used for producing an allyl alcohol polyoxyethylene ether surfactant product.

Further, the catalyst is at least one of zinc methanesulfonate or zinc toluenesulfonate.

Further, the mass ratio of the allyl alcohol to the ethylene oxide is: 58: (13.2-52.8), wherein the dosage of the catalyst is 0.3-5 per mill of the total weight of the allyl alcohol and the ethylene oxide.

Preferably, the reaction temperature of the allyl alcohol and the ethylene oxide under the catalysis of the catalyst is 95-150 ℃, and the reaction pressure is-0.05-0.60 MPa.

Further, the vacuum rectification specific process comprises the following steps: vacuumizing the addition rectification integrated reaction kettle to-0.05 MPa, controlling the vacuum degree to be constant, heating the crude ethylene glycol monoallyl ether in the reaction kettle main body, opening rectification and condensation, controlling the temperature of materials at the bottom of the kettle to be 65-80 ℃, controlling the temperature at the top of the kettle to be 50-65 ℃, carrying out total reflux for 30min, then starting to receive allyl alcohol, vacuumizing to improve the vacuum degree in the kettle to be more than or equal to-0.098 MPa after the allyl alcohol is collected and the temperature at the top of the kettle is reduced to normal temperature; heating the materials in the kettle again, controlling the temperature of the materials at the bottom of the kettle to be 80-100 ℃, controlling the temperature at the top of the kettle to be 50-65 ℃, carrying out total reflux for 30min, and then starting to receive the mixture of the ethylene glycol monoallyl ether and the allyl alcohol, wherein the reflux ratio is controlled to be 5: 1, during which the liquid is taken out and detected in the mixtureWhen the content of the ethylene glycol monoallyl ether in the receiving liquid is more than or equal to 99.7 percent, the finished product of the ethylene glycol monoallyl ether is independently received, and when the purity of the ethylene glycol monoallyl ether in the fraction is less than or equal to 99.7 percent, the receiving is stopped, and the rectification is finished. Cooling the bottom liquid to 40 + -2 deg.C, charging N₂And (3) putting the kettle bottom liquid into a packaging barrel for producing other allyl alcohol polyoxyethylene ether until the pressure of the reaction kettle is 0.00-0.04 MPa.

Compared with the prior art, the method has the following outstanding advantages and positive effects:

1. the ethylene glycol monoallyl ether prepared by the technical scheme of the invention has high purity (more than or equal to 99.8%) and few byproducts.

2. The preparation method has the advantages of simple process, mild reaction conditions, good selectivity, short production period, low energy consumption, repeated utilization of the catalyst and less three wastes.

3. The preparation system integrates the addition reaction and the rectification process, and the rectification step is directly carried out in the same reaction kettle after the addition reaction is finished, so that the equipment requirement is reduced, the cost is reduced, material transfer is not needed, the material pollution probability is avoided, and the product quality can be ensured.

Drawings

FIG. 1 is a schematic view of the structure of a production system of the present invention.

Fig. 2 is a schematic structural view of a rectifying column of the present invention.

In fig. 1 and 2, 1: ethylene oxide storage tank, 2: material transfer pump, 3: catalyst filter, 4: reaction kettle main body, 5: rectifying tower, 6: n-propanol storage tank, 7: ethylene glycol monopropyl ether reservoir, 8: vacuum pipeline, 9, branch pipeline, 10, reaction feed inlet, 11, reaction discharge outlet, 12, temperature-control steam outlet/cooling water inlet, 13, protective gas port, 14, rectification inlet, 15, rectification outlet, 16, stirring device, 17, interlayer, 18, control valve, 19, vacuumizing port on the storage tank, 20, protective gas port on the storage tank, 21, sampling port, 22, storage tank material outlet, 23, material return pipeline, 24, storage tank material inlet, 25 condenser, 26, temperature-control steam inlet/cooling water outlet, 27, check valve, 28 and vacuum device.

Detailed Description

In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The present invention will now be described in further detail with reference to the following figures and specific examples, which are intended to be illustrative, but not limiting, of the invention.

Preparation of the reaction kettle before implementation: washing the main body of the reaction kettle, the rectifying tower, the raw material storage tank and the product storage tank with distilled water for several times until the main body, the rectifying tower, the raw material storage tank and the product storage tank are clean, and heating N₂And blowing and drying the reaction kettle main body, the rectifying tower and the storage tank, and cooling to normal temperature for later use.