CN109384654B - Method for producing ethylene glycol mono-tert-butyl ether - Google Patents
Method for producing ethylene glycol mono-tert-butyl ether Download PDFInfo
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- CN109384654B CN109384654B CN201710652493.0A CN201710652493A CN109384654B CN 109384654 B CN109384654 B CN 109384654B CN 201710652493 A CN201710652493 A CN 201710652493A CN 109384654 B CN109384654 B CN 109384654B
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/14—Preparation of ethers by exchange of organic parts on the ether-oxygen for other organic parts, e.g. by trans-etherification
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Abstract
The invention belongs to the technical field of organic chemical industry, and particularly relates to a method for producing ethylene glycol mono-tert-butyl ether. The method for producing the ethylene glycol mono-tert-butyl ether comprises the steps of adding a solid catalyst, the ethylene glycol and the methyl tert-butyl ether into a reaction kettle for reaction, and filtering to remove the solid catalyst after the reaction is finished to obtain the ethylene glycol mono-tert-butyl ether product. The invention provides a high-efficiency, reasonable, green and environment-friendly method for producing ethylene glycol mono-tert-butyl ether, which is characterized in that the produced ethylene glycol mono-tert-butyl ether has high selectivity which is more than 95 percent, MTBE has high conversion rate which is more than 93 percent by adjusting the reaction temperature, the reaction pressure and the molar ratio of raw materials.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and particularly relates to a method for producing ethylene glycol mono-tert-butyl ether.
Background
Ethylene glycol mono-tert-butyl ether has the advantages of high flash point, nonflammability, low toxicity and the like, is an important industrial solvent and a chemically synthesized intermediate, and is widely used in the industries of water-based surface coatings, jet fuel anti-icing agents, brake fluids, printing inks, dyes, medicines, spices, cleaning agents and the like due to the excellent performance of the ethylene glycol mono-tert-butyl ether because the molecule of the ethylene glycol mono-tert-butyl ether contains ether bonds and hydroxyl groups, and can also be used as a base fluid for synthesizing the brake fluids in the automobile industry.
Currently, ethylene glycol mono-t-butyl ether is mainly prepared by reacting isobutylene with ethylene glycol. CN106397137A describes a method for preparing glycol mono-tertiary butyl ether, which comprises introducing gaseous isobutylene and liquid phase glycol into a catalyst bed layer in the middle of a reactor, and evaporating the glycol mono-tertiary butyl ether generated from the catalyst bed layer under the stripping action of the gaseous isobutylene to avoid the glycol di-tertiary butyl ether from continuously reacting with the isobutylene to generate glycol di-tertiary butyl ether. In the method, because the boiling point of the dihydric alcohol mono-tertiary butyl ether is higher and the specific heat is higher, the glycol mono-tertiary butyl ether is stripped by isobutene, and more isobutene is used, so that the temperature of the isobutene is overhigh, the dimerization reaction of the isobutene is easy to occur, and the like.
Ethylene glycol may also be prepared by reacting ethylene glycol with methyl tert-butyl ether (MTBE). JP57114543A discloses a process for synthesizing ethylene glycol mono-tert-butyl ether by reacting ethylene glycol with MTBE at 5kg/cm2Under the protection of the nitrogen gas, the nitrogen gas is introduced into the reactor,the reaction is carried out at the temperature of 80 ℃ by taking sulfuric acid and the like as catalysts to generate the ethylene glycol mono-tert-butyl ether. In the reaction process, the molar ratio of the ethylene glycol to the MTBE is too high, and the existence of sulfuric acid causes the local acid concentration of the reaction to be too high, so that more byproducts are generated, and the difficulty of post-treatment is increased due to the generation of waste acid.
In summary, the prior art has the following disadvantages: (1) the method has the advantages that (1) inorganic acid is used as a catalyst, waste acid is generated, and the problem of waste acid treatment exists, (2) a large amount of isobutene participates in gas stripping, so that the molar ratio of isobutene to glycol is too large, the content of impurities such as diisobutylene is high, and the product purity is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for producing ethylene glycol mono-tert-butyl ether, which is high-efficiency, reasonable, green and environment-friendly, and has high selectivity of the produced ethylene glycol mono-tert-butyl ether and high conversion rate of MTBE.
The method for producing the ethylene glycol mono-tert-butyl ether comprises the steps of adding a solid catalyst, the ethylene glycol and the methyl tert-butyl ether into a reaction kettle for reaction, and filtering to remove the solid catalyst after the reaction is finished to obtain the ethylene glycol mono-tert-butyl ether product.
Wherein:
the dosage of the solid catalyst is 5-30% of the total mass of the ethylene glycol and the methyl tert-butyl ether.
The solid catalyst is one of a resin catalyst or a heteropoly acid catalyst.
Preferably, the solid catalyst is a macroporous sulfonic acid type cationic resin catalyst. The pore diameter of the catalyst is based on the fact that the catalyst can allow ethylene glycol, methyl tert-butyl ether and ethylene glycol tert-butyl ether molecules to freely pass through.
More preferably, the particle size of the macroporous sulfonic acid type cationic resin catalyst is 0.1-1.3 mm.
The reaction temperature is 40-100 ℃, the reaction pressure is 0.1-0.6 MPa, and the reaction time is 0.5-3 h.
Preferably, the reaction temperature is 55-70 ℃, the reaction pressure is 0.1-0.3 MPa, and the reaction time is 1-1.5 h.
The molar ratio of the ethylene glycol to the methyl tert-butyl ether is 6: 1-1: 6.
preferably, the molar ratio of ethylene glycol to methyl tert-butyl ether is 3: 1-1: 1.
the filtration is carried out at normal temperature and under slight positive pressure.
The reaction product is filtered and collected at normal temperature and slight positive pressure for reuse.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the macroporous sulfonic acid type cationic resin catalyst is adopted, and the reaction temperature, the reaction pressure and the molar ratio of the raw materials are regulated, so that the generated ethylene glycol mono-tert-butyl ether has high selectivity which is up to more than 95%, MTBE has high conversion rate, and the conversion rate of MTBE is up to more than 93%.
2. The invention overcomes the problems of over high molar ratio of isobutene to ethylene glycol, backward production process, serious environmental pollution, poor selectivity of ethylene glycol tert-butyl ether and the like in the prior art, and provides a high-efficiency, reasonable, green and environment-friendly production method of the ethylene glycol tert-butyl ether.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 379.8g of ethylene glycol (with the mass content of 99.0%) and 88.9g of MTBE (with the mass content of 99.0%) are added into a 1L reaction kettle with a stirrer, the reaction temperature is controlled at 60 ℃, the reaction pressure is controlled at 0.2MPa, and after stirring for 1h, the catalyst is cooled and filtered; the reaction product was analyzed, and the selectivity of ethylene glycol mono-t-butyl ether was 98.8% and the conversion of MTBE was 94.87%.
Example 2
Adding 50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 126.6g of ethylene glycol (with the mass content of 99.0%) and 88.9g of MTBE (with the mass content of 99.0%) into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 60 ℃ and the reaction pressure at 0.2MPa, stirring for 1h, cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity to ethylene glycol mono-t-butyl ether was 97.8% and the conversion of MTBE was 93.6%.
Example 3
Adding 100g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 379.8g of ethylene glycol (with the mass content of 99.0%) and 88.9g of MTBE (with the mass content of 99.0%) into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 60 ℃ and the reaction pressure at 0.2MPa, stirring for 1h, cooling and filtering the catalyst; the reaction product was analyzed for ethylene glycol mono-t-butyl ether selectivity of 98.9% and MTBE conversion of 94.78%.
Example 4
Adding 50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 126.6g of ethylene glycol (with the mass content of 99.0%) and 88.9g of MTBE (with the mass content of 99.0%) which are recovered by reaction into a 1L reaction kettle with stirring, controlling the reaction temperature at 60 ℃ and the reaction pressure at 0.2MPa, stirring for 1h, cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity of ethylene glycol mono-t-butyl ether was 98.2% and the conversion of MTBE was 93.6%.
Example 5
50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 379.8g of ethylene glycol (with the mass content of 99.0%) and 88.9g of MTBE (with the mass content of 99.0%) are added into a 1L reaction kettle with a stirrer, the reaction temperature is controlled at 60 ℃, the reaction pressure is controlled at 0.2MPa, and after stirring for 2 hours, the catalyst is cooled and filtered; the reaction product was analyzed, and the selectivity of ethylene glycol mono-t-butyl ether was 98.7% and the conversion of MTBE was 94.79%.
Example 6
Adding 50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 126.6g of ethylene glycol (with the mass content of 99.0%) and 88.9g of MTBE (with the mass content of 99.0%) into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 75 ℃ and the reaction pressure at 0.2MPa, stirring for 1h, cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity to ethylene glycol mono-t-butyl ether was 97.4% and the conversion of MTBE was 93.7%.
Example 7
Adding 50g of heteropolyacid catalyst, 126.6g of ethylene glycol (with the mass content of 99.0%) and 88.9g of MTBE (with the mass content of 99.0%) into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 90 ℃ and the reaction pressure at 0.3MPa, stirring for 1h, and cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity to ethylene glycol mono-t-butyl ether was 97.5% and the conversion of MTBE was 93.6%.
Example 8
Adding 50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 63.3g of ethylene glycol (with the mass content of 99.0%) and 177.8g of MTBE (with the mass content of 99.0%) into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 60 ℃ and the reaction pressure at 0.2MPa, stirring for 1h, cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity to ethylene glycol mono-t-butyl ether was 92.9% and the conversion of MTBE was 48.6%.
Example 9
Adding 50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 63.3g of ethylene glycol (with the mass content of 99.0%) and 177.8g of MTBE (with the mass content of 99.0%) which are recovered by reaction into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 60 ℃ and the reaction pressure at 0.2MPa, stirring for 1h, cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity to ethylene glycol mono-t-butyl ether was 92.6% and the conversion of MTBE was 48.5%.
Example 10
50g of heteropolyacid catalyst, 63.3g of ethylene glycol (with the mass content of 99.0%) and 533.4g of MTBE (with the mass content of 99.0%) are added into a 1L reaction kettle with a stirrer, the reaction temperature is controlled at 90 ℃, the reaction pressure is controlled at 0.3MPa, and after stirring for 1h, the catalyst is cooled and filtered; the reaction product was analyzed, and the selectivity of ethylene glycol mono-tert-butyl ether was 92.9% and the conversion of MTBE was 14.3%.
Example 11
Adding 50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 63.3g of ethylene glycol (with the mass content of 99.0%) and 177.8g of MTBE (with the mass content of 99.0%) into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 60 ℃ and the reaction pressure at 0.2MPa, stirring for 3 hours, cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity to ethylene glycol mono-t-butyl ether was 93.6% and the conversion of MTBE was 48.2%.
Example 12
Adding 50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 63.3g of ethylene glycol (with the mass content of 99.0%) and 177.8g of MTBE (with the mass content of 99.0%) into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 60 ℃ and the reaction pressure at 0.2MPa, stirring for 0.5h, cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity of ethylene glycol mono-t-butyl ether was 90.7% and the conversion of MTBE was 47.9%.
Example 13
Adding 50g of macroporous sulfonic acid type cationic resin catalyst with the particle size of 0.1-1.3 mm, 126.6g of ethylene glycol (with the mass content of 99.0%) and 88.9g of MTBE (with the mass content of 99.0%) into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 40 ℃ and the reaction pressure at 0.1MPa, stirring for 3 hours, cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity to ethylene glycol mono-t-butyl ether was 88.9% and the conversion of MTBE was 92.1%.
Example 14
Adding 50g of heteropolyacid catalyst, 126.6g of ethylene glycol (with the mass content of 99.0%) and 88.9g of MTBE (with the mass content of 99.0%) into a 1L reaction kettle with a stirrer, controlling the reaction temperature at 100 ℃ and the reaction pressure at 0.6MPa, stirring for 0.5h, cooling and filtering the catalyst; the reaction product was analyzed, and the selectivity to ethylene glycol mono-t-butyl ether was 88.2% and the conversion of MTBE was 91.7%.
Claims (8)
1. A method for producing ethylene glycol mono-tert-butyl ether is characterized in that: adding a solid catalyst, ethylene glycol and methyl tert-butyl ether into a reaction kettle for reaction, and filtering to remove the solid catalyst after the reaction is finished to obtain an ethylene glycol mono tert-butyl ether product;
the solid catalyst is a macroporous sulfonic acid type cationic resin catalyst.
2. The method for producing ethylene glycol mono-t-butyl ether according to claim 1, characterized in that: the dosage of the solid catalyst is 5-30% of the total mass of the ethylene glycol and the methyl tert-butyl ether.
3. The method for producing ethylene glycol mono-t-butyl ether according to claim 1, characterized in that: the particle size of the macroporous sulfonic acid type cationic resin catalyst is 0.1-1.3 mm.
4. The method for producing ethylene glycol mono-t-butyl ether according to claim 1, characterized in that: the reaction temperature is 40-100 ℃, the reaction pressure is 0.1-0.6 MPa, and the reaction time is 0.5-3 h.
5. The method of producing ethylene glycol mono-t-butyl ether according to claim 4, characterized in that: the reaction temperature is 55-70 ℃, the reaction pressure is 0.1-0.3 MPa, and the reaction time is 1-1.5 h.
6. The method for producing ethylene glycol mono-t-butyl ether according to claim 1, characterized in that: the molar ratio of the ethylene glycol to the methyl tert-butyl ether is 6: 1-1: 6.
7. the method of producing ethylene glycol mono-t-butyl ether according to claim 6, characterized in that: the molar ratio of the ethylene glycol to the methyl tert-butyl ether is 3: 1-1: 1.
8. the method for producing ethylene glycol mono-t-butyl ether according to claim 1, characterized in that: the filtration is carried out at normal temperature and under slight positive pressure.
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