CN111233635A - Synthesis method of diethylene glycol monoethyl ether - Google Patents
Synthesis method of diethylene glycol monoethyl ether Download PDFInfo
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- CN111233635A CN111233635A CN201811446633.XA CN201811446633A CN111233635A CN 111233635 A CN111233635 A CN 111233635A CN 201811446633 A CN201811446633 A CN 201811446633A CN 111233635 A CN111233635 A CN 111233635A
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- diethylene glycol
- monoethyl ether
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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Abstract
The application discloses a synthesis method of diethylene glycol monoethyl ether, which is characterized in that a raw material containing diethylene glycol and ethanol is in contact reaction with a solid acid catalyst to obtain the diethylene glycol monoethyl ether. The method overcomes the defects of a strong-corrosivity inorganic acid catalyst in the prior art, adopts an environment-friendly acid catalyst to catalyze the catalytic etherification reaction of the diethylene glycol and the ethanol, and thus provides a green synthetic route for preparing the diethylene glycol monoethyl ether, which reduces the environmental pollution and the production cost.
Description
Technical Field
The application relates to a synthesis method of diethylene glycol monoethyl ether, belonging to the technical field of chemical industry.
Background
Diethylene glycol monoethyl ether is an important glycol ether, has a higher boiling point and is an excellent high-boiling-point solvent; in addition, the structure of the compound contains hydroxyl, ether bond, alkyl and other groups, and the compound has good solubility in water and various organic matters and polymers, is used as a solvent of nitrocellulose, resin, lacquer, dye, ink and the like, and has important application in various fields.
The synthesis route of diethylene glycol monoethyl ether mainly adopts an ethylene oxide method and a diethylene glycol method. The ethylene oxide process is the use of ethanolAnd ethylene oxide in BF3Under the catalytic action of an ether complex, the ethylene glycol ethyl ether is prepared by addition reaction, and the diethylene glycol ethyl ether is coproduced. The route uses ethylene oxide, and has poor safety and high cost. The diethylene glycol method is to prepare diethylene glycol ethyl ether by dehydrating diethylene glycol and ethanol under the action of sulfuric acid, but the catalyst adopts inorganic acid such as sulfuric acid and the like, so that the catalyst has high corrosivity, high equipment requirement and high environmental protection pressure. The method has great advantages, namely, the diethylene glycol is a byproduct in the process of synthesizing the ethylene glycol, the raw material source is rich, and the cost is low, so that the development of an environment-friendly acid catalyst for preparing diethylene glycol monoethyl ether by catalytic conversion of the diethylene glycol has important significance.
Disclosure of Invention
According to one aspect of the application, a synthesis method of diethylene glycol monoethyl ether is provided, which overcomes the defects that in the prior art, an inorganic acid catalyst with strong corrosivity is adopted, and an environment-friendly acid catalyst is adopted to catalyze diethylene glycol and ethanol to carry out catalytic etherification reaction, so that a green synthesis route for preparing diethylene glycol monoethyl ether is provided, the environmental pollution is reduced, and the production cost is reduced.
The synthesis method of diethylene glycol monoethyl ether comprises the step of enabling a raw material containing diethylene glycol and ethanol to be in reaction contact with a solid acid catalyst to obtain diethylene glycol monoethyl ether.
Optionally, the feedstock is diethylene glycol and ethanol.
Optionally, the solid acid catalyst comprises at least one of an acidic ion exchange resin, an H-beta molecular sieve, an HZSM-5 molecular sieve, an HY molecular sieve.
Alternatively, the acidic ion exchange resin is divinylbenzene crosslinked sulfonated polystyrene Amberlyst-15.
Optionally, the solid acid catalyst is selected from at least one of Amberlyst-15, H-beta molecular sieve, HZSM-5 molecular sieve, HY molecular sieve.
Optionally, the addition amount of the solid acid catalyst is 0.5-20% by mass of the raw material.
Optionally, the solid acid catalyst is added in an amount with the upper limit of the mass percent of the raw material selected from 0.6%, 0.8%, 1%, 2%, 5%, 8%, 10%, 15%, 18% or 20%; the lower limit is selected from 0.5%, 0.6%, 0.8%, 1%, 2%, 5%, 8%, 10%, 15% or 18%.
Optionally, the molar ratio of diethylene glycol to ethanol is 1:1 to 1: 20.
Optionally, the upper limit of the molar ratio of diethylene glycol to ethanol is selected from 1:1.5, 1:2, 1:4, 1:5, 1:6, 1:8, 1:10, 1:12, 1:15, 1:18, or 1: 20; the lower limit is selected from 1:1, 1:1.5, 1:2, 1:4, 1:5, 1:6, 1:8, 1:10, 1:12, 1:15 or 1: 18.
Optionally, the reaction is carried out under protection of a reactive atmosphere.
Optionally, the inert atmosphere is selected from at least one of nitrogen, helium, and argon
Alternatively, nitrogen gas replaces the air atmosphere in the reaction.
Alternatively, the reaction is an etherification reaction.
Optionally, the temperature of the reaction is 100-250 ℃.
Optionally, the temperature of the reaction is 110-220 ℃.
Optionally, the upper temperature limit of the reaction is selected from 110 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃ or 250 ℃; the lower limit is selected from 100 deg.C, 110 deg.C, 120 deg.C, 150 deg.C, 180 deg.C, 200 deg.C, 220 deg.C or 240 deg.C.
Optionally, the reaction time is 2-10 h.
Optionally, the reaction time is 2-6 h.
Alternatively, the reaction time is selected from 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10 h; the lower limit is selected from 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9 h.
Optionally, in any of the above processes, the conversion of diethylene glycol is greater than 30%; the selectivity of diethylene glycol monoethyl ether is higher than 60%.
The beneficial effects that this application can produce include:
1) according to the synthesis method of diethylene glycol monoethyl ether, the diethylene glycol used in the route is a byproduct in the process of synthesizing ethylene glycol, so that the raw material source is rich, and the cost is low; the transformation of the diethylene glycol monoethyl ether is used for improving the high-efficiency utilization of the by-product of the synthesis of ethylene glycol.
2) Compared with the prior art, the method for preparing diethylene glycol monoethyl ether by adopting the catalytic synthesis method has the advantages that the environment-friendly catalyst is adopted, the using amount of the catalyst is less, the use of strong corrosive inorganic acid is avoided, and the catalytic etherification of diethylene glycol and ethanol by green and efficient catalysis is realized.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were purchased commercially, and the instruments used were those recommended by the manufacturer.
The molecular sieves used were purchased from south-opening catalyst factories, Amberlyst-15 from south-China synthetic chemical Co., Ltd.
The analysis method in the examples of the present application is as follows:
the product analysis was performed by gas chromatography using an agilent gas 7890 gas chromatograph.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, the conversion of diethylene glycol and the selectivity of diethylene glycol monoethyl ether were calculated based on carbon moles.
According to one embodiment of the present application, the method for synthesizing diethylene glycol monoethyl ether is characterized in that diethylene glycol and ethanol are used as raw materials, and the diethylene glycol monoethyl ether is generated under the action of a solid acid catalyst.
Optionally, the catalyst is selected from one or more of Amberlyst-15, H-beta, HZSM-5 and HY.
Optionally, the molar ratio of diethylene glycol to ethanol is 1:1 to 1: 20.
Optionally, the addition amount of the acidic catalyst is 0.5-20% by mass of the raw material.
Alternatively, the etherification reaction conditions are: the reaction temperature is 100-250 ℃, and the reaction time is 2-10 h.
Alternatively, the etherification reaction conditions are: the reaction temperature is 110-220 ℃, and the reaction time is 2-6 h.
Example 1
This example provides a method for synthesizing diethylene glycol monoethyl ether. 20g of diethylene glycol and ethanol with the molar ratio of 1:4 are added into a 50ml high-pressure reaction kettle, after the mixture is stirred uniformly, 0.2g of H-beta (the ratio of silicon to aluminum is 40) is added, the mixture is stirred and mixed uniformly at room temperature, and then the kettle is sealed. The air was replaced with nitrogen gas for 5 times, the temperature was raised to 200 ℃ and the reaction pressure was autogenous pressure, and the reaction was carried out for 2 hours. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid, and analyzing by gas chromatography. As a result, the conversion of diethylene glycol was 40.7%, and the selectivity of diethylene glycol monoethyl ether was 71.8%.
Example 2
This example provides a method for synthesizing diethylene glycol monoethyl ether. 20g of diethylene glycol and ethanol with a molar ratio of 1:4 are added into a 50ml high-pressure reaction kettle, and after uniform stirring, 0.2g of HZSM-5 (silicon-aluminum ratio of 25) catalyst is added, and after uniform stirring and mixing at room temperature, the kettle is sealed. The air is replaced by nitrogen for 5 times, the temperature is raised to 220 ℃, the reaction pressure is autogenous pressure, and the reaction lasts for 2 hours. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid, and analyzing by gas chromatography. As a result, the conversion of diethylene glycol was 30.3%, and the selectivity of diethylene glycol monoethyl ether was 78.6%.
Example 3
This example provides a method for synthesizing diethylene glycol monoethyl ether. 20g of diethylene glycol and ethanol with the molar ratio of 1:2 are added into a 50ml high-pressure reaction kettle, after uniform stirring, 0.4g of H-beta (silicon-aluminum ratio of 25) catalyst is added, and after uniform stirring and mixing at room temperature, the kettle is sealed. The air was replaced with nitrogen for 4 times, the temperature was raised to 200 ℃ and the reaction pressure was autogenous pressure, and the reaction was carried out for 2 hours. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid, and analyzing by gas chromatography. As a result, the conversion of diethylene glycol was 36.8%, and the selectivity of diethylene glycol monoethyl ether was 75.4%.
Example 4
This example provides a method for synthesizing diethylene glycol monoethyl ether. 20g of diethylene glycol and ethanol with a molar ratio of 1:10 and 1g of HY (silicon-aluminum ratio of 11) catalyst are added into a 50ml high-pressure reaction kettle, the mixture is stirred and mixed uniformly at room temperature, the kettle is sealed, air is replaced by nitrogen, the temperature is increased to 240 ℃, the reaction pressure is self-pressure, and the reaction is carried out for 2 hours. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid, and analyzing by gas chromatography. As a result, the conversion of diethylene glycol was 46.8%, and the selectivity of diethylene glycol monoethyl ether was 75.2%.
Example 5
This example provides a method for synthesizing diethylene glycol monoethyl ether. 20g of diethylene glycol and ethanol in a molar ratio of 1:6 are added into a 50ml high-pressure reaction kettle, 2g of Amberlyst-15 catalyst is added, and the kettle is sealed after stirring and mixing uniformly at room temperature. Replacing air with nitrogen for 3-5 times, heating to 150 deg.C, reacting for 2 hr under autogenous pressure. The stirring was stopped. The reaction kettle was cooled to room temperature. Taking a proper amount of reaction liquid, and analyzing by gas chromatography. As a result, the conversion of diethylene glycol was 67.1%, and the selectivity of diethylene glycol monoethyl ether was 66.1%.
Example 6
This example provides a method for synthesizing diethylene glycol monoethyl ether. The reaction temperature was 100 ℃ and the reaction time was 10 hours, and the other operating conditions were the same as in example 1.
Example 7
This example provides a method for synthesizing diethylene glycol monoethyl ether. The reaction temperature was 110 ℃ and the reaction time was 6 hours, and the other operating conditions were the same as in example 1.
Example 8
This example provides a method for synthesizing diethylene glycol monoethyl ether. The reaction temperature was 250 ℃ and the reaction time was 3 hours, and the remaining operating conditions were the same as in example 1.
Example 9
This example provides a method for synthesizing diethylene glycol monoethyl ether. The molar ratio of diethylene glycol to ethanol was 1:1, and the remaining operating conditions were the same as in example 2.
Example 10
This example provides a method for synthesizing diethylene glycol monoethyl ether. The molar ratio of diethylene glycol to ethanol was 1:20, and the remaining operating conditions were the same as in example 2.
Example 11
This example provides a method for synthesizing diethylene glycol monoethyl ether. The catalyst was added in an amount of 0.1g, and the remaining operating conditions were the same as in example 3.
Example 12
This example provides a method for synthesizing diethylene glycol monoethyl ether. The amount of catalyst added was 4g, and the remaining operating conditions were the same as in example 3.
In examples 6 to 12, the conversion of diethylene glycol in the process was above 30%; the selectivity of diethylene glycol monoethyl ether is higher than 60%.
The results show that the method for preparing diethylene glycol monoethyl ether has the advantages that diethylene glycol and ethanol are subjected to etherification reaction under the action of the environment-friendly solid acidic catalyst, and diethylene glycol monoethyl ether is efficiently prepared. The method provides a green synthesis method of diethylene glycol monoethyl ether with high efficiency and industrial prospect.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A synthesis method of diethylene glycol monoethyl ether is characterized in that a raw material containing diethylene glycol and ethanol is in contact reaction with a solid acid catalyst to obtain the diethylene glycol monoethyl ether.
2. The method of claim 1, wherein the solid acid catalyst comprises at least one of an acidic ion exchange resin, an H-beta molecular sieve, an HZSM-5 molecular sieve, an HY molecular sieve;
preferably, the acidic ion exchange resin is divinylbenzene crosslinked sulfonated polystyrene Amberlyst-15.
3. The method according to claim 1, wherein the solid acid catalyst is added in an amount of 0.5 to 20% by mass based on the raw material.
4. The method according to claim 1, wherein the molar ratio of diethylene glycol to ethanol is 1:1 to 1: 20.
5. The method of claim 1, wherein the reaction is carried out under a non-reactive atmosphere.
6. The method of claim 1, wherein the inert atmosphere is selected from at least one of nitrogen, helium, and argon.
7. The method according to claim 1, wherein the reaction temperature is 100-250 ℃;
preferably, the reaction temperature is 110-220 ℃.
8. The method according to claim 1, wherein the reaction time is 2-10 h.
9. The method according to claim 1, wherein the reaction time is 2-6 h.
10. The process of any one of claims 1 to 9, wherein the conversion of diethylene glycol is higher than 30%; the selectivity of diethylene glycol monoethyl ether is higher than 60%.
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Citations (4)
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| WO2004020378A2 (en) * | 2002-08-28 | 2004-03-11 | Ferro Corporation | Method of producing glycol ethers |
| CN104250206A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Preparation method of glycol ether |
| CN105585455A (en) * | 2014-11-17 | 2016-05-18 | 中国科学院大连化学物理研究所 | Method of preparing ethylene glycol monomethyl ether through continuous etherification method |
| CN105688881A (en) * | 2016-02-25 | 2016-06-22 | 洛阳市科创石化科技开发有限公司 | Catalyst for synthesizing alkylene propylene and preparation method and application of catalyst |
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2018
- 2018-11-29 CN CN201811446633.XA patent/CN111233635A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004020378A2 (en) * | 2002-08-28 | 2004-03-11 | Ferro Corporation | Method of producing glycol ethers |
| CN104250206A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Preparation method of glycol ether |
| CN105585455A (en) * | 2014-11-17 | 2016-05-18 | 中国科学院大连化学物理研究所 | Method of preparing ethylene glycol monomethyl ether through continuous etherification method |
| CN105688881A (en) * | 2016-02-25 | 2016-06-22 | 洛阳市科创石化科技开发有限公司 | Catalyst for synthesizing alkylene propylene and preparation method and application of catalyst |
Non-Patent Citations (1)
| Title |
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| PAULA M. VEIGA等: "Etherification of different glycols with ethanol or 1-octanol catalyzed by acid zeolites", 《MOLECULAR CATALYSIS》 * |
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Application publication date: 20200605 |