CN110724041B - Separation method of glycerol monomethyl ether reaction mixed liquid - Google Patents
Separation method of glycerol monomethyl ether reaction mixed liquid Download PDFInfo
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/58—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention relates to a separation method of a reaction mixed solution of glycerol monomethyl ether. The separation method comprises the steps of rectifying the reaction mixed liquid in a first rectifying tower, a second rectifying tower, a third rectifying tower and a fourth rectifying tower in sequence, thereby separating out the required product and recovering valuable compounds. The separation method can save reaction raw materials and reduce production cost, and the production process is environment-friendly, and the obtained products can reach qualified products.
Description
Technical Field
The invention relates to the technical field of chemical reaction post-treatment, in particular to a separation method of a reaction mixed solution of glycerol monomethyl ether.
Background
Glyceryl monomethyl ether, scientific name 3-methoxy-1, 2-propanediol, molecular formula C4H10O3The molecular weight of 106.12 is a clean chemical raw material, has no toxicity, good hygroscopicity, and no color and transparency, and can be used as solvent and synthetic raw material of unsaturated polyester.
Glycerol monomethyl ether can be synthesized by reacting methanol with glycerol under certain conditions. The reaction mixture produced by the reaction contains glycerol monomethyl ether, methanol, glycerol, water, glycerol dimethyl ether, glycerol monomethyl ether, dimethyl ether, and the like. How to separate the desired product from the reaction mixture and recover the valuable compound becomes a problem to be investigated.
Disclosure of Invention
[ problem ] to
In order to solve the above problems, an object of the present invention is to provide a method for separating a reaction mixture of monomethyl ether of glycerin.
[ solution ]
According to an embodiment of the present invention, there is provided a method for separating a reaction mixture of monomethyl ether of glycerin, the method including:
(1) introducing the reaction mixed solution into a first rectifying tower, and rectifying under the conditions of normal pressure, tower top temperature of 55-70 ℃ and tower bottom temperature of 108-120 ℃ so as to lead out methanol from the tower top and tower bottom;
(2) introducing the tower bottom liquid obtained in the step (1) into a second rectifying tower, and rectifying under the conditions of vacuum degree of-90 kPa to-80 kPa, tower top temperature of 42 ℃ to 57 ℃ and tower bottom temperature of 140 ℃ to 150 ℃, so as to lead out water from the tower top and tower bottom liquid;
(3) introducing the tower bottoms obtained in the step (2) into a third rectifying tower, and rectifying under the conditions of vacuum degree of-100 kPa to-98 kPa, tower top temperature of 25 ℃ to 37 ℃ and tower bottom temperature of 140 ℃ to 155 ℃, so as to lead out polyether from the tower top and tower bottoms from the tower bottom; and
(4) introducing the tower bottom liquid obtained in the step (3) into a fourth rectifying tower, rectifying under the conditions of vacuum degree of-101 kPa to-100 kPa, tower top temperature of 80 ℃ to 95 ℃ and tower bottom temperature of 160 ℃ to 170 ℃, so as to lead out the glycerol monomethyl ether from the tower top,
in the step (1), preferably, the reaction mixture of monomethyl ether of glycerol is produced by reacting methanol and glycerol in the presence of a catalyst.
Preferably, the conditions for the reaction of methanol and glycerol are: the reaction temperature is 150 ℃ to 170 ℃, the reaction pressure is 1.8MPa to 3.5MPa, and the reaction time is 4 to 10 hours.
The catalyst may be a catalyst commonly used in the art, preferably a solid acid catalyst, for example, a cation exchange resin. The dosage of the catalyst is 3-10% of the total weight of the methanol, the glycerol and the catalyst.
The weight ratio of methanol to glycerol is from 1:1 to 1:3, preferably from 1:1.2 to 1: 1.8.
In the step (3), the polyether is dimethyl glycerol or trimethyl glycerol.
Preferably, the rectification conditions in step (1) may be: normal pressure, tower top temperature of 62-67 ℃ and tower kettle temperature of 112-117 ℃; preferably, the rectification conditions in step (2) may be: the vacuum degree is between 87kPa and 82kPa, the tower top temperature is between 47 and 53 ℃, and the tower kettle temperature is between 142 and 147 ℃; preferably, the rectification conditions in step (3) may be: the vacuum degree is-99.4 kPa to-98.5 kPa, the tower top temperature is 30 ℃ to 35 ℃, and the tower kettle temperature is 142 ℃ to 147 ℃; and preferably, the rectification conditions in step (4) may be: the vacuum degree is between minus 101kPa and minus 100.5kPa, the tower top temperature is between 87 ℃ and 92 ℃, and the tower kettle temperature is between 162 ℃ and 167 ℃.
According to an embodiment of the present invention, the separation method may further include: and rectifying the gas phase generated by the reaction of the methanol and the glycerol so as to lead out dimethyl ether gas from the top of the tower, lead out tower bottom liquid from the bottom of the tower, and lead the tower bottom liquid into the first rectifying tower.
The method utilizes the different boiling points of methanol, water, polyether and glycerol monomethyl ether to separate by heating and rectifying in turn. The first, second, third and fourth rectifying towers are respectively a methanol separation tower, a water separation tower, a polyether separation tower and a glycerol monomethyl ether separation tower, and the tower top temperatures of the four towers are 55-70 ℃, 42-57 ℃, 25-37 ℃ and 80-95 ℃ in sequence; and the temperature of the tower kettle is 108-120 ℃, 140-150 ℃, 140-155 ℃ and 160-170 ℃ in sequence.
The rectification adopts negative pressure operation, can reduce the boiling point of the material under the negative pressure operation condition, reduce energy consumption and reduce cost. The vacuum degrees of the methanol separation tower, the water separation tower, the polyether separation tower and the glycerol monomethyl ether separation tower are respectively normal pressure, -90kPa to-80 kPa, -100kPa to-98 kPa and-101 kPa to-100 kPa.
The feed rate of the first rectification column for separating methanol, the second rectification column for separating water, the third rectification column for separating polyether and the fourth rectification column for separating glycerol monomethyl ether may be 0.6g/min to 1.3g/min, preferably 1.0g/min to 1.3 g/min.
The feed rate may be controlled by a pump, preferably a plunger pump.
The reflux ratio of the first, second, third and fourth rectification columns is 1:1 to 1:5, preferably 1:1 to 1: 2.
According to the method, the purity of the obtained methanol, water, polyether and glycerol monomethyl ether is more than or equal to 99 percent, and the chroma is 5 to 20, so that the methanol and the water can be recycled, the product glycerol monomethyl ether can be obtained, and valuable polyether and the like can also be obtained.
[ technical effects ]
In the separation method, the pressure in each rectifying tower is normal pressure or negative pressure, so that the energy consumption can be effectively reduced, and the efficiency is improved. In addition, the rectifying towers of the invention are connected in series, and the material is discharged from the upper tower and directly enters the lower tower, so the material loss can be reduced to the minimum.
Therefore, the separation method can save reaction raw materials and reduce production cost, the production process is environment-friendly, and the obtained products can reach qualified products.
Drawings
Fig. 1 is a schematic view showing a synthesis and separation apparatus of glycerol monomethyl ether according to an embodiment of the present invention.
Detailed Description
The invention will be further illustrated by reference to the following examples, which are intended to describe the invention by way of example only. These examples are not meant to impose any limitation on the invention. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention within the scope and spirit of the invention. It is to be understood that the invention may also include other equivalent techniques or modifications within the scope of the description and claims of the invention.
Sources of reagents
Glycerol: from Asahi Yang chemical industry of Tangshang, the purity is 99.5%;
methanol: technical grade, from aigrette, texas, 99.5% pure.
Example 1
(1) 1785g of methanol, 2500g of glycerol and 245g of cation exchange resin are added into a reaction kettle (R101) and reacted at the reaction temperature of 155 ℃, the reaction time of 4 hours and the reaction pressure of 2.8MPa to generate a reaction mixed solution, wherein the reaction mixed solution comprises 23.5 weight percent of methanol, 2 weight percent of polyether, 45.3 weight percent of glycerol and 8.5 weight percent of water, and the balance is glycerol monomethyl ether.
(2) Introducing the reaction mixture into a first rectifying tower (methanol separation tower) (T101), rectifying under the conditions of normal pressure, tower top temperature of 65 ℃ and tower bottom temperature of 115 ℃ so as to lead out methanol from the tower top, and leading out tower bottom liquid from the tower bottom to a second rectifying tower (water separation tower) (T102);
(3) rectifying in a water separation column (T102) under the conditions of vacuum degree of-85 kPa, tower top temperature of 50 ℃ and tower bottom temperature of 145 ℃ so as to lead out water from the tower top, and leading out tower bottom liquid (water content is less than or equal to 0.02%) from the tower bottom to a third rectifying column (polyether separation column) (T103);
(4) rectifying in a polyether separation column (T103) under vacuum of-99 kPa, at an overhead temperature of 32 ℃ and a column bottom temperature of 145 ℃ to thereby take out polyether (dimethyl and/or tri-methyl glycerol, and in most cases, a mixture thereof) from the top of the column and take out the column bottom to a fourth rectification column (monomethyl glycerol separation column) (T104); and
(5) in a glycerol monomethyl ether separation column (T104), rectification was carried out under conditions of a vacuum degree of-101 kPa, a column top temperature of 90 ℃ and a column bottom temperature of 165 ℃ to remove glycerol monomethyl ether from the column top.
Further, the top gas of the reaction tank (R101) is introduced into a rectifying column (T105) and rectified, whereby dimethyl ether gas is taken out from the top of the column, and the bottom liquid is taken out from the bottom of the column to a first rectifying column (methanol separation column) (T101).
The purity of the obtained methanol, water, polyether and glycerol monomethyl ether is more than or equal to 99 percent through detection.
Example 2
(1) 432g of methanol, 605g of glycerol and 57g of cation exchange resin are added into a reaction kettle (R101) and reacted at the reaction temperature of 155 ℃, the reaction time of 4 hours and the reaction pressure of 3.0MPa to generate a reaction mixed solution, wherein the reaction mixed solution comprises 26.5 weight percent of methanol, 3 weight percent of polyether, 42.3 weight percent of glycerol and 8.5 weight percent of water, and the balance is glycerol monomethyl ether.
(2) Introducing the reaction mixture into a first rectifying column (methanol separation column) (T101), rectifying at normal pressure at a column top temperature of 63 ℃ and a column bottom temperature of 117 ℃ to thereby lead out methanol from the column top and to lead out column bottom liquid from the column bottom to a second rectifying column (water separation column) (T102);
(3) rectifying in a water separation column (T102) under the conditions of vacuum degree of-86 kPa, tower top temperature of 52 ℃ and tower bottom temperature of 145 ℃ so as to lead out water from the tower top, and leading out tower bottom liquid (water content is less than or equal to 0.02%) from the tower bottom to a third rectifying column (polyether separation column) (T103);
(4) rectifying in a polyether separation column (T103) under vacuum of-99.5 kPa, at an overhead temperature of 35 ℃ and a column bottom temperature of 145 ℃ to thereby take out polyether (dimethyl and/or tri-methyl glycerol ether, and in most cases, a mixture thereof) from the top of the column and take out the column bottom to a fourth rectifying column (monomethyl glycerol separation column) (T104);
(5) in the separation column (T104), the distillation was carried out under conditions of a vacuum degree of-101 kPa, a column top temperature of 92 ℃ and a column bottom temperature of 160 ℃ to remove monomethyl ether from the column top.
Further, the top gas of the reaction tank (R101) is introduced into a rectifying column (T105) and rectified, whereby dimethyl ether gas is taken out from the top of the column, and the bottom liquid is taken out from the bottom of the column to a first rectifying column (methanol separation column) (T101).
The purity of the obtained methanol, water, polyether and glycerol monomethyl ether is more than or equal to 99 percent through detection.
Although specific embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that such detailed description is merely a preferred embodiment, and the scope of the present invention is not limited thereto. Therefore, the true scope of the invention should be defined by the following claims and their equivalents.
Claims (13)
1. A separation method of a reaction mixed solution of glycerol monomethyl ether comprises the following steps:
(1) introducing the reaction mixed solution into a first rectifying tower, and rectifying under the conditions of normal pressure, tower top temperature of 55-70 ℃ and tower bottom temperature of 108-120 ℃ so as to lead out methanol from the tower top and lead out tower bottom liquid from the tower bottom;
(2) introducing the tower bottom liquid obtained in the step (1) into a second rectifying tower, and rectifying under the conditions of vacuum degree of-90 kPa to-80 kPa, tower top temperature of 42 ℃ to 57 ℃ and tower bottom temperature of 140 ℃ to 150 ℃, so as to lead out water from the tower top and tower bottom liquid;
(3) introducing the tower bottoms obtained in the step (2) into a third rectifying tower, and rectifying under the conditions of vacuum degree of-100 kPa to-98 kPa, tower top temperature of 25 ℃ to 37 ℃ and tower bottom temperature of 140 ℃ to 155 ℃, so as to lead out polyether from the tower top and tower bottoms from the tower bottom; and
(4) introducing the tower bottom liquid obtained in the step (3) into a fourth rectifying tower, rectifying under the conditions of vacuum degree of-101 kPa to-100 kPa, tower top temperature of 80 ℃ to 95 ℃ and tower bottom temperature of 160 ℃ to 170 ℃, so as to lead out the glycerol monomethyl ether from the tower top,
wherein, in the step (3), the polyether is glycerol dimethyl ether and glycerol tri-methyl ether;
in the step (1), the glycerol monomethyl ether reaction mixture is generated by the reaction of methanol and glycerol in the presence of a catalyst, wherein the reaction conditions of the methanol and the glycerol are as follows: the reaction temperature is 150 ℃ to 170 ℃, the reaction pressure is 1.8MPa to 3.5MPa, and the reaction time is 4 to 10 hours.
2. The separation process of claim 1, wherein the catalyst is a solid acid catalyst.
3. The separation process of claim 2, wherein the catalyst is a cation exchange resin.
4. The separation process according to claim 1, wherein the catalyst is used in an amount of 3 to 10% by weight based on the total weight of methanol, glycerol and catalyst.
5. The separation process according to claim 1, wherein the weight ratio of methanol to glycerol is from 1:1 to 1: 3.
6. The separation process according to claim 5, wherein the weight ratio of methanol to glycerol is from 1:1.2 to 1: 1.8.
7. The separation method according to claim 1, wherein the rectification conditions in step (1) are: atmospheric pressure, overhead temperature of 62 ℃ to 67 ℃ and column kettle temperature of 112 ℃ to 117 ℃; the rectification conditions in the step (2) are as follows: the vacuum degree is between 87kPa and 82kPa, the tower top temperature is between 47 and 53 ℃, and the tower kettle temperature is between 142 and 147 ℃; the rectification conditions in the step (3) are as follows: the vacuum degree is-99.4 kPa to-98.5 kPa, the tower top temperature is 30 ℃ to 35 ℃, and the tower kettle temperature is 142 ℃ to 147 ℃; and the rectification conditions in the step (4) are as follows: the vacuum degree is between minus 101kPa and minus 100.5kPa, the tower top temperature is between 87 ℃ and 92 ℃, and the tower kettle temperature is between 162 ℃ and 167 ℃.
8. The separation method according to claim 1, characterized in that the separation method further comprises: and rectifying the gas phase generated by the reaction of the methanol and the glycerol so as to lead out dimethyl ether gas from the top of the tower, lead out tower bottom liquid from the bottom of the tower, and lead the tower bottom liquid into the first rectifying tower.
9. The separation method according to claim 1, wherein the feed rates of the first, second, third and fourth rectification columns are 0.6g/min to 1.3 g/min.
10. The separation method according to claim 9, wherein the feed rates of the first, second, third and fourth rectification columns are 1.0g/min to 1.3 g/min.
11. The separation method according to claim 1, wherein the reflux ratio of each of the first, second, third and fourth rectification columns is 1:1 to 1: 5.
12. The separation method according to claim 11, wherein the reflux ratio of each of the first, second, third and fourth rectification columns is 1:1 to 1: 2.
13. The separation method according to claim 1, wherein the purity of the obtained methanol, water, polyether and glycerol monomethyl ether is equal to or more than 99%, and the chroma is 5-20.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101151235A (en) * | 2005-04-01 | 2008-03-26 | 花王株式会社 | Process for producing glyceryl ether |
| CN102276430A (en) * | 2010-06-14 | 2011-12-14 | 大林产业株式会社 | Separation of glycol mono-tertiary-butyl ether and glycol di-tertiary-butyl ether |
| CN102391076A (en) * | 2011-10-08 | 2012-03-28 | 中国科学院山西煤炭化学研究所 | Method for preparing glycerol single methanol ether by utilizing glycerol and methanol |
| CN103270011A (en) * | 2010-12-16 | 2013-08-28 | 罗地亚管理公司 | Process for making polyglycerol ethers of fatty alcohols |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101151235A (en) * | 2005-04-01 | 2008-03-26 | 花王株式会社 | Process for producing glyceryl ether |
| CN102276430A (en) * | 2010-06-14 | 2011-12-14 | 大林产业株式会社 | Separation of glycol mono-tertiary-butyl ether and glycol di-tertiary-butyl ether |
| CN103270011A (en) * | 2010-12-16 | 2013-08-28 | 罗地亚管理公司 | Process for making polyglycerol ethers of fatty alcohols |
| CN102391076A (en) * | 2011-10-08 | 2012-03-28 | 中国科学院山西煤炭化学研究所 | Method for preparing glycerol single methanol ether by utilizing glycerol and methanol |
Non-Patent Citations (1)
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| 酸催化甘油醚化合成烷基甘油醚反应的研究进展;董超琦等;《化学通报》;20121231;第75卷(第11期);第988-993页 * |
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