CN109384654A - The method for producing ethylene glycol mono-tert-butyl ether - Google Patents
The method for producing ethylene glycol mono-tert-butyl ether Download PDFInfo
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- CN109384654A CN109384654A CN201710652493.0A CN201710652493A CN109384654A CN 109384654 A CN109384654 A CN 109384654A CN 201710652493 A CN201710652493 A CN 201710652493A CN 109384654 A CN109384654 A CN 109384654A
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- ethylene glycol
- butyl 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
- C07C41/14—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 field of chemical technology, and in particular to a method of produce ethylene glycol mono-tert-butyl ether.The method of production ethylene glycol mono-tert-butyl ether of the present invention, solid catalyst, ethylene glycol are added in reaction kettle with methyl tertiary butyl ether(MTBE) and reacted, end of reaction is filtered to remove solid catalyst, obtains ethylene glycol mono-tert-butyl ether product.The present invention provides a kind of efficient and rational, environmentally protective ethylene glycol mono-tert-butyl ether production methods, pass through the adjusting of the mol ratio to reaction temperature, reaction pressure and raw material, the ethylene glycol mono-tert-butyl ether of generation selectivity with higher, reach 95% or more, MTBE has higher conversion ratio, and the conversion ratio of MTBE reaches 93% or more.
Description
Technical field
The invention belongs to field of chemical technology, and in particular to a method of produce ethylene glycol mono-tert-butyl ether.
Background technique
Ethylene glycol mono-tert-butyl ether has the advantages that the various aspects such as flash-point is high, nonflammable, toxicity is low, it is molten to be important industry
Agent and chemically synthesized intermediate, with its excellent performance, are widely used as water base since its intramolecular contains ehter bond and hydroxyl
The industries such as surface coating, jet fuel anti-freezing agent, brake-fluid, ink, dyestuff, medicine, fragrance and cleaning agent, are alternatively arranged as automobile
The basal liquid of industry synthesis brake-fluid.
Currently, ethylene glycol mono-tert-butyl ether mainly uses isobutene with glycol reaction to prepare.CN106397137A is situated between
Continued a kind of method for preparing glycol ChanShuDing ether, which is that gas isobutene and liquid phase dihydric alcohol are passed through in reactor
The catalyst bed in portion, glycol ChanShuDing ether are steamed under the gas stripping of gas isobutene by bed after generating, can
Avoid its continue with isobutene the reaction was continued generate ethylene glycol di-tert-butyl ether.Boiling point of the method due to glycol ChanShuDing ether
Higher, specific heat is larger, and with isobutene air lift glycol ChanShuDing ether, the isobutene used is more, causes the temperature of isobutene
It is excessively high, it is easy to happen the dimerization reaction etc. of isobutene.
Ethylene glycol is reacted with methyl tertiary butyl ether(MTBE) (MTBE) can also prepare ethylene glycol mono-tert-butyl ether.JP57114543A is public
The method that ethylene glycol reacts synthesizing glycol list tertbutyl ether with MTBE is opened, which is in 5kg/cm2Nitrogen protection under, with
Sulfuric acid etc. is catalyst, is reacted under conditions of 80 DEG C of temperature, and ethylene glycol mono-tert-butyl ether is generated.During the reaction, ethylene glycol
It is excessively high with the molar ratio of MTBE, due to there is the presence of sulfuric acid, cause to react that local acid concentration is excessively high, causes more by-product
It generates, the generation of spent acid causes the difficulty of post-processing to increase.
In conclusion the prior art has the disadvantage that (1) due to making catalyst using inorganic acid, generates spent acid, deposits
The problem of handling spent acid, (2) cause isobutene and ethylene glycol molar ratio excessive since a large amount of isobutene participates in air lift, and two
The impurity contents such as polyisobutene are high, influence product purity.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of method for producing ethylene glycol mono-tert-butyl ether,
Efficient and rational, environmentally protective, the selectivity of the ethylene glycol mono-tert-butyl ether of generation is high, the high conversion rate of MTBE.
The method of production ethylene glycol mono-tert-butyl ether of the present invention, by solid catalyst, ethylene glycol and methyl- tert fourth
Base ether, which is added in reaction kettle, to react, and end of reaction is filtered to remove solid catalyst, obtains ethylene glycol mono-tert-butyl ether product.
Wherein:
The dosage of the solid catalyst is the 5~30% of ethylene glycol and methyl tertiary butyl ether(MTBE) gross mass.
The solid catalyst is one of resin catalyst or heteropolyacid catalyst.
Preferably, the solid catalyst is macropore sulfonic acid cation resin catalyst.The aperture of catalyst is with energy
Subject to enough permission ethylene glycol, methyl tertiary butyl ether(MTBE), ethylene glycol mono-tert-butyl ether molecule pass freely through.
It is highly preferred that the partial size of the macropore sulfonic acid cation resin catalyst is 0.1~1.3mm.
The reaction temperature is 40~100 DEG C, and reaction pressure is 0.1~0.6MPa, and the reaction time is 0.5~3h.
Preferably, the reaction temperature be 55~70 DEG C, reaction pressure be 0.1~0.3MPa, the reaction time be 1~
1.5h。
The molar ratio of the ethylene glycol and methyl tertiary butyl ether(MTBE) is 6:1~1:6.
Preferably, the molar ratio of the ethylene glycol and methyl tertiary butyl ether(MTBE) is 3:1~1:1.
Described being filtered into is filtered under room temperature and micro-positive pressure.
Reaction product collects catalyst filtration under room temperature and micro-positive pressure, to reuse.
Compared with prior art, the present invention having the following beneficial effects:
1, the present invention uses macropore sulfonic acid cation resin catalyst, by reaction temperature, reaction pressure and original
The adjusting of the mol ratio of material, the ethylene glycol mono-tert-butyl ether of generation selectivity with higher, reaching 95% or more, MTBE has
The conversion ratio of higher conversion ratio, MTBE reaches 93% or more.
2, the present invention overcomes isobutene in the prior art and ethylene glycol molar ratio are excessively high, production technology falls behind, and environment is dirty
The problems such as contaminating serious and ethylene glycol mono-tert-butyl ether poor selectivity provides a kind of efficient and rational, environmentally protective ethylene glycol
Single tertbutyl ether production method.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of partial size of 50g, ethylene glycol (mass content
99.0%) 379.8g and MTBE (mass content 99.0%) 88.9g is added in the 1L reaction kettle with stirring, and reaction temperature is controlled
At 60 DEG C, reaction pressure control is in 0.2MPa, and after stirring 1h, cool down filtration catalytic agent；Reaction product is analyzed, ethylene glycol
The selectivity 98.8% of single tertbutyl ether, the conversion ratio of MTBE are 94.87%.
Embodiment 2
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of partial size of 50g, ethylene glycol (mass content
99.0%) 126.6g and MTBE (mass content 99.0%) 88.9g is added in the 1L reaction kettle with stirring, and reaction temperature is controlled
At 60 DEG C, reaction pressure control is in 0.2MPa, and after stirring 1h, cool down filtration catalytic agent；Reaction product is analyzed, ethylene glycol
The selectivity 97.8% of single tertbutyl ether, the conversion ratio of MTBE are 93.6%.
Embodiment 3
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of partial size of 100g, ethylene glycol (mass content
99.0%) 379.8g and MTBE (mass content 99.0%) 88.9g is added in the 1L reaction kettle with stirring, and reaction temperature is controlled
At 60 DEG C, reaction pressure control is in 0.2MPa, and after stirring 1h, cool down filtration catalytic agent；Reaction product is analyzed, ethylene glycol
The selectivity 98.9% of single tertbutyl ether, the conversion ratio of MTBE are 94.78%.
Embodiment 4
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of 50g partial size of reaction recycling, ethylene glycol (quality
Content 99.0%) 126.6g and MTBE (mass content 99.0%) 88.9g be added in the 1L reaction kettle that band stirs, by reaction temperature
Control is at 60 DEG C, and reaction pressure control is in 0.2MPa, and after stirring 1h, cool down filtration catalytic agent；Reaction product is analyzed, second
The selectivity 98.2% of glycol list tertbutyl ether, the conversion ratio of MTBE are 93.6%.
Embodiment 5
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of partial size of 50g, ethylene glycol (mass content
99.0%) 379.8g and MTBE (mass content 99.0%) 88.9g is added in the 1L reaction kettle with stirring, and reaction temperature is controlled
At 60 DEG C, reaction pressure control is in 0.2MPa, and after stirring 2h, cool down filtration catalytic agent；Reaction product is analyzed, ethylene glycol
The selectivity 98.7% of single tertbutyl ether, the conversion ratio of MTBE are 94.79%.
Embodiment 6
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of partial size of 50g, ethylene glycol (mass content
99.0%) 126.6g and MTBE (mass content 99.0%) 88.9g is added in the 1L reaction kettle with stirring, and reaction temperature is controlled
At 75 DEG C, reaction pressure control is in 0.2MPa, and after stirring 1h, cool down filtration catalytic agent；Reaction product is analyzed, ethylene glycol
The selectivity 97.4% of single tertbutyl ether, the conversion ratio of MTBE are 93.7%.
Embodiment 7
By the heteropolyacid catalyst of 50g, ethylene glycol (mass content 99.0%) 126.6g and MTBE (mass content
99.0%) 88.9g is added in the 1L reaction kettle with stirring, and by reaction temperature control at 90 DEG C, reaction pressure is controlled in 0.3MPa,
After stirring 1h, cool down filtration catalytic agent；Reaction product is analyzed, the selectivity 97.5% of ethylene glycol mono-tert-butyl ether,
The conversion ratio of MTBE is 93.6%.
Embodiment 8
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of partial size of 50g, ethylene glycol (mass content
99.0%) 63.3g and MTBE (mass content 99.0%) 177.8g is added in the 1L reaction kettle with stirring, and reaction temperature is controlled
At 60 DEG C, reaction pressure control is in 0.2MPa, and after stirring 1h, cool down filtration catalytic agent；Reaction product is analyzed, ethylene glycol
The selectivity 92.9% of single tertbutyl ether, the conversion ratio of MTBE are 48.6%.
Embodiment 9
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of 50g partial size of reaction recycling, ethylene glycol (quality
Content 99.0%) 63.3g and MTBE (mass content 99.0%) 177.8g be added in the 1L reaction kettle of band band stirring, will react warm
Degree control is at 60 DEG C, and reaction pressure control is in 0.2MPa, and after stirring 1h, cool down filtration catalytic agent；Reaction product is analyzed,
The selectivity 92.6% of ethylene glycol mono-tert-butyl ether, the conversion ratio of MTBE are 48.5%.
Embodiment 10
By the heteropolyacid catalyst of 50g, ethylene glycol (mass content 99.0%) 63.3g and MTBE (mass content 99.0%)
533.4g is added in the 1L reaction kettle with stirring, and by reaction temperature control at 90 DEG C, reaction pressure control stirs 1h in 0.3MPa
Afterwards, cool down filtration catalytic agent；Reaction product is analyzed, reaction product is analyzed, the choosing of ethylene glycol mono-tert-butyl ether
Selecting property 92.9%, the conversion ratio of MTBE are 14.3%.
Embodiment 11
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of partial size of 50g, ethylene glycol (mass content
99.0%) 63.3g and MTBE (mass content 99.0%) 177.8g is added in the 1L reaction kettle with stirring, and reaction temperature is controlled
At 60 DEG C, reaction pressure control is in 0.2MPa, and after stirring 3h, cool down filtration catalytic agent；Reaction product is analyzed, ethylene glycol
The selectivity 93.6% of single tertbutyl ether, the conversion ratio of MTBE are 48.2%.
Embodiment 12
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of partial size of 50g, ethylene glycol (mass content
99.0%) 63.3g and MTBE (mass content 99.0%) 177.8g is added in the 1L reaction kettle with stirring, and reaction temperature is controlled
At 60 DEG C, reaction pressure control is in 0.2MPa, and after stirring 0.5h, cool down filtration catalytic agent；Reaction product is analyzed, second two
The selectivity 90.7% of alcohol list tertbutyl ether, the conversion ratio of MTBE are 47.9%.
Embodiment 13
By the macropore sulfonic acid cation resin catalyst of 0.1~1.3mm of 50g partial size, ethylene glycol (mass content
99.0%) 126.6g and MTBE (mass content 99.0%) 88.9g is added in the 1L reaction kettle with stirring, and reaction temperature is controlled
At 40 DEG C, reaction pressure control is in 0.1MPa, and after stirring 3h, cool down filtration catalytic agent；Reaction product is analyzed, ethylene glycol
The selectivity 88.9% of single tertbutyl ether, the conversion ratio of MTBE are 92.1%.
Embodiment 14
By the heteropolyacid catalyst of 50g, ethylene glycol (mass content 99.0%) 126.6g and MTBE (mass content
99.0%) 88.9g is added in the 1L reaction kettle with stirring, and by reaction temperature control at 100 DEG C, reaction pressure control exists
0.6MPa, after stirring 0.5h, cool down filtration catalytic agent；Reaction product is analyzed, the selectivity of ethylene glycol mono-tert-butyl ether
The conversion ratio of 88.2%, MTBE are 91.7%.
Claims (10)
1. a kind of method for producing ethylene glycol mono-tert-butyl ether, it is characterised in that: by solid catalyst, ethylene glycol and methyl- tert fourth
Base ether, which is added in reaction kettle, to react, and end of reaction is filtered to remove solid catalyst, obtains ethylene glycol mono-tert-butyl ether product.
2. the method for production ethylene glycol mono-tert-butyl ether according to claim 1, it is characterised in that: the solid catalysis
The dosage of agent is the 5~30% of ethylene glycol and methyl tertiary butyl ether(MTBE) gross mass.
3. the method for production ethylene glycol mono-tert-butyl ether according to claim 1 or 2, it is characterised in that: the solid
Catalyst is one of resin catalyst or heteropolyacid catalyst.
4. the method for production ethylene glycol mono-tert-butyl ether according to claim 3, it is characterised in that: the solid catalysis
Agent is macropore sulfonic acid cation resin catalyst.
5. the method for production ethylene glycol mono-tert-butyl ether according to claim 4, it is characterised in that: the macropore sulfonic acid
The partial size of type cation resin catalyzing agent is 0.1~1.3mm.
6. the method for production ethylene glycol mono-tert-butyl ether according to claim 1, it is characterised in that: the reaction temperature
It is 40~100 DEG C, reaction pressure is 0.1~0.6MPa, and the reaction time is 0.5~3h.
7. the method for production ethylene glycol mono-tert-butyl ether according to claim 6, it is characterised in that: the reaction temperature
It is 55~70 DEG C, reaction pressure is 0.1~0.3MPa, and the reaction time is 1~1.5h.
8. the method for production ethylene glycol mono-tert-butyl ether according to claim 1, it is characterised in that: the ethylene glycol with
The molar ratio of methyl tertiary butyl ether(MTBE) is 6:1~1:6.
9. the method for production ethylene glycol mono-tert-butyl ether according to claim 8, it is characterised in that: the ethylene glycol with
The molar ratio of methyl tertiary butyl ether(MTBE) is 3:1~1:1.
10. the method for production ethylene glycol mono-tert-butyl ether according to claim 1, it is characterised in that: described is filtered into
It is filtered under room temperature and micro-positive pressure.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240950A (en) * | 2019-07-10 | 2019-09-17 | 深圳市前海博扬研究院有限公司 | Methanol gasoline additive, preparation method and the methanol gasoline containing the additive |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397137A (en) * | 2015-07-27 | 2017-02-15 | 万华化学集团股份有限公司 | Method for preparing diol mono-tert-butyl ether |
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- 2017-08-02 CN CN201710652493.0A patent/CN109384654B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397137A (en) * | 2015-07-27 | 2017-02-15 | 万华化学集团股份有限公司 | Method for preparing diol mono-tert-butyl ether |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240950A (en) * | 2019-07-10 | 2019-09-17 | 深圳市前海博扬研究院有限公司 | Methanol gasoline additive, preparation method and the methanol gasoline containing the additive |
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