CN114292189A - Continuous preparation method of alcohol ether acetate - Google Patents
Continuous preparation method of alcohol ether acetate Download PDFInfo
- Publication number
- CN114292189A CN114292189A CN202111656870.0A CN202111656870A CN114292189A CN 114292189 A CN114292189 A CN 114292189A CN 202111656870 A CN202111656870 A CN 202111656870A CN 114292189 A CN114292189 A CN 114292189A
- Authority
- CN
- China
- Prior art keywords
- tower
- alcohol ether
- ether acetate
- water
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of alcohol ether acetate, in particular to a continuous preparation method of alcohol ether acetate. Pumping alcohol ether and acetic acid into a tubular reactor according to a ratio to perform catalytic reaction; feeding the material flowing out of the tubular reactor into a reaction rectifying tower; and the alcohol ether acetate and unreacted alcohol ether generated by the reaction flow out of the tower kettle and enter a next separation unit, and the alcohol ether acetate with high purity is obtained through separation and purification. The invention combines the tubular reaction and the reactive distillation, firstly converts most of acetic acid in the tubular reactor, and then converts the rest acetic acid in the reactive distillation tower, thereby realizing the continuous production of alcohol ether acetate and improving the production capacity, leading the acetic acid to be completely converted, and not influencing the quality of the alcohol ether acetate.
Description
Technical Field
The invention relates to a preparation method of alcohol ether acetate, in particular to a continuous preparation method of alcohol ether acetate.
Background
The alcohol ether acetate is an important industrial solvent with excellent performance, the dissolving performance of the alcohol ether acetate is superior to that of common solvents and alcohol ether solvents, the thermal stability is good, the viscosity change is small, the environmental protection performance is good, and the alcohol ether acetate is widely applied to the industries of synthetic resins, coatings, printing ink, detergents, textile printing and dyeing, pesticides and the like.
Chinese patent CN101239907B discloses a method for preparing ethylene glycol monomethyl ether acetate, which is carried out in a batch mode in a reaction kettle, and has low efficiency, and the catalyst needs to be separated by filtration subsequently. Chinese patent CN102206153A discloses a continuous synthesis method of propylene glycol methyl ether acetate, which can realize continuous production of first reaction and then rectification, but has low conversion per pass of acetic acid, and propylene glycol methyl ether and acetic acid continuously flow out from the top of the tower, thus having higher energy consumption. Chinese patent CN101693661A discloses a method for producing propylene glycol methyl ether acetate, wherein a reaction kettle and a reaction rectifying tower are combined for use, and unreacted raw materials rectified at the top of the reaction rectifying tower return to the reaction kettle to continue to react. The reaction kettle used in the operation method has low reaction efficiency, the one-way conversion rate of the acetic acid still cannot be improved, the acetic acid conversion rate is not improved, the acetic acid is easy to remain in the product, the unreacted acetic acid is easy to cause corrosion of equipment, and the equipment investment is increased.
Therefore, the existing production has the problems of low continuity of the production process, low production capacity, incomplete single-pass conversion of acetic acid and low product quality.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a process method for continuously producing alcohol ether acetate, which solves the problems of low continuous degree, low production capacity, incapability of completely converting acetic acid in a single pass and low product quality of the production process in the prior art.
In order to achieve the purpose, the invention is realized by the following technical scheme: a continuous preparation method of alcohol ether acetate comprises the following steps:
1) pumping alcohol ether and acetic acid into a tubular reactor according to a ratio to perform catalytic reaction, wherein the tubular reactor is filled with a catalyst;
2) the material flowing out of the tubular reactor enters a reactive distillation tower, a packing layer and a catalyst layer are sequentially and alternately arranged in the reactive distillation tower from top to bottom, and the reactive distillation tower is provided with a plurality of water-carrying agent feed inlets;
3) when the reaction starts, adding the water-carrying agent at one time from the top of the tower, condensing at the top of the tower, refluxing to each feed inlet in the tower, taking the water generated by esterification out of the tower in an azeotropic form by the water-carrying agent, condensing at the top of the tower, enriching in a reflux tank at the top of the tower, layering, refluxing cyclohexane to the tower, and discharging the water out of the tower;
4) and the alcohol ether acetate and unreacted alcohol ether generated by the reaction flow out of the tower kettle and enter a next separation unit, and the alcohol ether acetate with high purity is obtained through separation and purification.
Preferably, the alcohol ether comprises ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether and dipropylene glycol methyl ether.
Preferably, the reaction pressure in the tubular reactor is normal pressure, the reaction temperature is 90-140 ℃, and the molar ratio of the alcohol ether to the acetic acid is 1.1:1-2.0: 1.
Preferably, the catalyst in the tubular reactor and the reactive distillation tower is strong-acid macroporous cation resin.
Preferably, the packing in the reaction rectifying tower is any one of pall ring, stainless steel wire mesh packing and magnetic ring.
Preferably, the water-carrying agent in the reactive distillation column is any one of cyclohexane, benzene and toluene. The water carrying agent takes the water generated in the reaction away from the tower top in an azeotropic mode, the water carrying agent and the water are layered in a reflux tank at the tower top, the water flows out of the tower and flows into the tower, and the circulating water carrying agent can flow in from a plurality of feed inlets of the tower.
Compared with the prior art, the invention has the following outstanding advantages and positive effects:
1. the tubular reaction and the reactive distillation are combined, most of acetic acid is converted in the tubular reactor, and then the rest of acetic acid is converted in the reactive distillation tower, so that the continuous production of alcohol ether acetate can be realized, the production capacity can be improved, the acetic acid is completely converted, and the quality of the alcohol ether acetate is not influenced.
2. The filling material and the catalyst layer are alternately filled in the rectifying tower, and the water generated by the reaction is continuously removed from the top of the tower by adding the water-carrying agent, so that the esterification reaction is balanced and moved rightwards, and the separation, purification and conversion of the acetic acid can be continuously realized.
Drawings
FIG. 1 is a flow chart of the continuous production process of alcohol ether acetate.
Detailed Description
The technical scheme of the invention is further specifically described by the following embodiments and the accompanying drawings of the specification.
A continuous preparation method of alcohol ether acetate, which comprises the following steps,
1) pumping alcohol ether and acetic acid into a tubular reactor according to a ratio to perform catalytic reaction, wherein the tubular reactor is filled with a strong-acid macroporous cationic resin catalyst;
2) the material flowing out of the tubular reactor enters a reactive distillation tower, a packing layer and a catalyst layer (the catalyst is macroporous cation resin) are alternately arranged in the reactive distillation tower from top to bottom in sequence, and the reactive distillation tower is provided with a plurality of water-carrying agent feed inlets;
3) when the reaction starts, adding the water-carrying agent at one time from the top of the tower, condensing at the top of the tower, refluxing to each feed inlet in the tower, taking the water generated by esterification out of the tower in an azeotropic form by the water-carrying agent, condensing at the top of the tower, enriching in a reflux tank at the top of the tower, layering, refluxing cyclohexane to the tower, and discharging the water out of the tower;
4) and the alcohol ether acetate and unreacted alcohol ether generated by the reaction flow out of the tower kettle and enter a next separation unit, and the alcohol ether acetate with high purity is obtained through separation and purification.
Example 1
The molar ratio of ethylene glycol monomethyl ether to acetic acid is 1.5:1, the treatment capacity of the catalyst in the tubular reactor to the feed liquid is 500 g/(lcat.h), and the reaction temperature is 100 ℃. The rectifying tower is filled with filler and catalyst from top to bottom in turn, two sections are respectively filled, the height of each section is 0.5m, the filler is a stainless steel wire net, and a reaction material feed inlet is a first section catalyst layer. When the reaction is started, a certain amount of cyclohexane is added from the top of the reaction rectifying tower as a water-carrying agent, the molar ratio of the water-carrying agent to acetic acid is 1.44:1, the water-carrying agent condensed at the top of the tower circulates in the tower, and the feeding positions of the circulating water-carrying agent are respectively a first section of packing and a second section of packing. The reflux ratio at the top of the tower is 0.8, the temperature at the top of the reactive distillation tower is 56.6 ℃, and the temperature at the bottom of the tower is 138 ℃.
The tower top product of the reactive distillation tower comprises the following components: 12.52 percent of water, 84.28 percent of cyclohexane and 3.20 percent of ethylene glycol monomethyl ether.
The tower bottom product of the reactive distillation tower comprises the following components: ethylene glycol methyl ether acetate: 77.93%, ethylene glycol methyl ether: 22.07 percent.
Example 2
The molar ratio of propylene glycol methyl ether to acetic acid is 1.5:1, the treatment capacity of the catalyst in the tubular reactor to the feed liquid is 500 g/(lcat.h), and the reaction temperature is 110 ℃. The rectifying tower is filled with the filler and the catalyst in turn from top to bottom, three sections with the height of 0.5m are respectively filled, the filler is a stainless steel wire mesh, and a reaction material feed inlet is a second section of catalyst layer. When the reaction is started, a certain amount of cyclohexane is added from the top of the reaction rectifying tower as a water-carrying agent, the molar ratio of the water-carrying agent to acetic acid is 1.44:1, the water-carrying agent condensed at the top of the tower circulates in the tower, and the feeding positions of the circulating water-carrying agent are respectively a first section of packing and a third section of packing. The overhead reflux ratio was 1. The tower top temperature of the reactive distillation tower is 56.2 ℃, and the tower kettle temperature is 134.4 ℃.
The tower top product of the reactive distillation tower comprises the following components: 13 percent of water and 87 percent of cyclohexane.
The tower bottom product of the reactive distillation tower comprises the following components: propylene glycol methyl ether acetate: 74.6%, propylene glycol methyl ether: 25.4 percent.
Example 3
The molar ratio of the ethylene glycol ether to the acetic acid is 1.5:1, the treatment capacity of the catalyst in the tubular reactor to the feed liquid is 400 g/(lcat.h), and the reaction temperature is 110 ℃. The packing and the catalyst are sequentially and alternately filled in the rectifying tower from top to bottom, two sections are respectively filled, the height of each section is 0.5m, the packing is a magnetic ring, and a reaction material feeding hole is a first section catalyst layer. When the reaction is started, a certain amount of cyclohexane is added from the top of the reaction rectifying tower as a water-carrying agent, the molar ratio of the water-carrying agent to acetic acid is 1.44:1, the water-carrying agent condensed at the top of the tower circulates in the tower, and the feeding positions of the circulating water-carrying agent are respectively a first section of packing and a second section of packing. The overhead reflux ratio was 1. The tower top temperature of the reactive distillation tower is 56.2 ℃, and the tower bottom temperature is 142.9 ℃.
The tower top product of the reactive distillation tower comprises the following components: 13 percent of water and 87 percent of cyclohexane.
The tower bottom product of the reactive distillation tower comprises the following components: ethylene glycol monoethyl ether acetate: 75.8%, ethylene glycol ethyl ether: 23.6%, water: 0.4 percent.
Example 4
The mol ratio of the diethylene glycol ethyl ether to the acetic acid is 1.8:1, the treatment capacity of the catalyst in the tubular reactor to the feed liquid is 400 g/(lcat.h), and the reaction temperature is 120 ℃. The rectifying tower is filled with five sections of stainless steel wire meshes, the height of each section of the five sections of the rectifying tower. When the reaction is started, a certain amount of cyclohexane is added from the top of the reaction rectifying tower as a water-carrying agent, the molar ratio of the water-carrying agent to acetic acid is 1.44:1, the water-carrying agent condensed at the top of the tower circulates in the tower, and the feeding positions of the circulating water-carrying agent are respectively a first section of packing and a fourth section of packing. The overhead reflux ratio was 1. The tower top temperature of the reactive distillation tower is 56.2 ℃, and the tower kettle temperature is 209.2 ℃.
The tower top product of the reactive distillation tower comprises the following components: 12.9 percent of water and 87.1 percent of cyclohexane.
The tower bottom product of the reactive distillation tower comprises the following components: diethylene glycol monoethyl ether acetate: 62.1%, diethylene glycol ethyl ether: 37.9 percent.
Example 5
The molar ratio of the propylene glycol ether to the acetic acid is 2:1, the treatment capacity of the catalyst in the tubular reactor to the feed liquid is 400g/(Lcat h), and the reaction temperature is 120 ℃. The rectifying tower is filled with five sections of 0.5m height respectively from top to bottom in turn, the filler is a pall ring, and the reaction material feed inlet is a third section of catalyst layer. When the reaction is started, a certain amount of cyclohexane is added from the top of the reaction rectifying tower as a water-carrying agent, the molar ratio of the water-carrying agent to acetic acid is 1.44:1, the water-carrying agent condensed at the top of the tower circulates in the tower, and the feeding positions of the circulating water-carrying agent are respectively a first section of packing and a fourth section of packing. The overhead reflux ratio was 1. The tower top temperature of the reactive distillation tower is 56.2 ℃, and the tower bottom temperature is 144.1 ℃.
The tower top product of the reactive distillation tower comprises the following components: 12.9 percent of water and 87.1 percent of cyclohexane.
The tower bottom product of the reactive distillation tower comprises the following components: propylene glycol ethyl ether acetate: 58.4%, propylene glycol ethyl ether: 41.6 percent.
Example 6
The molar ratio of ethylene glycol monobutyl ether to acetic acid is 1.1:1, the treatment capacity of the catalyst in the tubular reactor to the feed liquid is 400 g/(lcat.h), and the reaction temperature is 120 ℃. The rectifying tower is filled with five sections of fillers and catalysts from top to bottom in turn, the heights of the five sections are 0.5m respectively, the fillers are magnetic rings, and a reaction material feed inlet is a third section of catalyst layer. When the reaction is started, a certain amount of cyclohexane is added from the top of the reaction rectifying tower as a water-carrying agent, the molar ratio of the water-carrying agent to acetic acid is 1.44:1, the water-carrying agent condensed at the top of the tower circulates in the tower, and the feeding positions of the circulating water-carrying agent are respectively a first section of packing and a fourth section of packing. The overhead reflux ratio was 1. The tower top temperature of the reactive distillation tower is 56.6 ℃, and the tower bottom temperature is 178.2 ℃.
The tower top product of the reactive distillation tower comprises the following components: 11.9 percent of water, 85.8 percent of cyclohexane and 2.3 percent of ethylene glycol monobutyl ether.
The tower bottom product of the reactive distillation tower comprises the following components: ethylene glycol butyl ether acetate: 94.6%, propylene glycol ethyl ether: ethylene glycol butyl ether: 5.04%, water: 0.3 percent.
Claims (6)
1. The continuous preparation method of the alcohol ether acetate is characterized by comprising the following steps:
1) pumping alcohol ether and acetic acid into a tubular reactor according to a ratio to perform catalytic reaction, wherein the tubular reactor is filled with a catalyst;
2) the material flowing out of the tubular reactor enters a reactive distillation tower, a packing layer and a catalyst layer are sequentially and alternately arranged in the reactive distillation tower from top to bottom, and the reactive distillation tower is provided with a plurality of water-carrying agent feed inlets;
3) when the reaction starts, adding the water-carrying agent at one time from the top of the tower, condensing at the top of the tower, refluxing to each feed inlet in the tower, taking the water generated by esterification out of the tower in an azeotropic form by the water-carrying agent, condensing at the top of the tower, enriching in a reflux tank at the top of the tower, layering, refluxing cyclohexane to the tower, and discharging the water out of the tower;
4) and the alcohol ether acetate and unreacted alcohol ether generated by the reaction flow out of the tower kettle and enter a next separation unit, and the alcohol ether acetate with high purity is obtained through separation and purification.
2. The continuous process for preparing alcohol ether acetate according to claim 1, wherein the alcohol ether comprises ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether.
3. The continuous preparation method of alcohol ether acetate according to claim 1, wherein the reaction pressure in the tubular reactor is normal pressure, the reaction temperature is 90 ℃ to 140 ℃, and the molar ratio of the alcohol ether to the acetic acid is 1.1:1 to 2.0: 1.
4. The continuous preparation method of alcohol ether acetate according to claim 1, wherein the catalyst in the tubular reactor and the reactive distillation column is a strong acid macroporous cation resin.
5. The continuous preparation method of alcohol ether acetate according to claim 1, wherein the packing in the reactive distillation column is any one of pall ring, stainless steel wire mesh packing and magnetic ring.
6. The continuous preparation method of alcohol ether acetate according to claim 1, wherein the water-carrying agent in the reactive distillation column is any one of cyclohexane, benzene and toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111656870.0A CN114292189A (en) | 2021-12-30 | 2021-12-30 | Continuous preparation method of alcohol ether acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111656870.0A CN114292189A (en) | 2021-12-30 | 2021-12-30 | Continuous preparation method of alcohol ether acetate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114292189A true CN114292189A (en) | 2022-04-08 |
Family
ID=80973919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111656870.0A Pending CN114292189A (en) | 2021-12-30 | 2021-12-30 | Continuous preparation method of alcohol ether acetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114292189A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260813A (en) * | 1978-02-02 | 1981-04-07 | Showa Denko K.K. | Process for the continuous production of ethylene glycol monoethyl ether acetate |
| CN109456190A (en) * | 2018-10-18 | 2019-03-12 | 天津大学 | A kind of method of the continuous synthesizing propylene glycol monomethyl ether acetate of the highly selective catalytic distillation of low temperature |
| CN112194580A (en) * | 2020-11-04 | 2021-01-08 | 中建安装集团有限公司 | Device and process for producing propylene glycol monomethyl ether acetate by reactive distillation coupled pervaporation |
-
2021
- 2021-12-30 CN CN202111656870.0A patent/CN114292189A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260813A (en) * | 1978-02-02 | 1981-04-07 | Showa Denko K.K. | Process for the continuous production of ethylene glycol monoethyl ether acetate |
| CN109456190A (en) * | 2018-10-18 | 2019-03-12 | 天津大学 | A kind of method of the continuous synthesizing propylene glycol monomethyl ether acetate of the highly selective catalytic distillation of low temperature |
| CN112194580A (en) * | 2020-11-04 | 2021-01-08 | 中建安装集团有限公司 | Device and process for producing propylene glycol monomethyl ether acetate by reactive distillation coupled pervaporation |
Non-Patent Citations (1)
| Title |
|---|
| 韩玉墀等: "化工工人岗位培训读本", 化学工业出版社, pages: 311 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475472B (en) | Method for preparing oxalate by coupling reaction of CO in gaseous phase | |
| CN109369396A (en) | A kind of method that direct esterification prepares high-purity ethylene acetate | |
| CN101367724B (en) | Method and apparatus for synthesis of isopropyl acetate | |
| CN108276257B (en) | Azeotropic distillation thermal coupling methoxy dimethyl ether synthesis reaction system | |
| CN102206153A (en) | Method for continuously synthesizing propylene glycol methyl ether acetate | |
| CN112279762B (en) | Process method for synthesizing methyl ethyl oxalate by heterogeneous catalysis transesterification | |
| CN103772147A (en) | Separating method for ethylene-glycol and 1,2-butanediol | |
| CN111889059B (en) | Reaction device and process for preparing DOTP | |
| CN101774886B (en) | Method for preparing dichlorohydrin and reaction device | |
| CN109748791B (en) | Energy-saving method for producing dimethyl adipate | |
| CN103342642B (en) | Process for continuously producing dimethyl adipate through reaction-rectification method | |
| CN110613946B (en) | Backpack reaction rectification equipment for synthesizing diethyl oxalate and process thereof | |
| CN102452934A (en) | Preparation method of sec-butyl acetate | |
| CN109796406B (en) | Br nsted-Lewis double-acid ionic liquid and method for catalytically synthesizing succinate by using Br nsted-Lewis double-acid ionic liquid | |
| CN110981721A (en) | Method for continuously producing n-propyl acetate | |
| CN111574378B (en) | Method for efficiently synthesizing dihydroxy ethyl terephthalate without catalysis | |
| CN108774100B (en) | Combined method for preparing methyl tert-butyl ether and isobutene from tert-butyl alcohol and methanol | |
| CN101979365B (en) | Method for continuously preparing dichlorohydrin | |
| CN101993350B (en) | Production method of glycol | |
| CN114292189A (en) | Continuous preparation method of alcohol ether acetate | |
| CN114984866B (en) | System and method for preparing dimethyl maleate | |
| CN114749121B (en) | System and process for preparing epichlorohydrin by glycerol method | |
| CN115282913A (en) | Reaction system and method for preparing methyl propionate | |
| CN106187754B (en) | A kind of method of catalytic distillation production aromatic esters | |
| CN114192086A (en) | Device and process for producing propylene glycol monomethyl ether acetate by partition plate reaction rectification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |