CN100554231C - The method for preparing butyl glycol ether - Google Patents
The method for preparing butyl glycol ether Download PDFInfo
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- CN100554231C CN100554231C CNB2007100357428A CN200710035742A CN100554231C CN 100554231 C CN100554231 C CN 100554231C CN B2007100357428 A CNB2007100357428 A CN B2007100357428A CN 200710035742 A CN200710035742 A CN 200710035742A CN 100554231 C CN100554231 C CN 100554231C
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- hydrogen peroxide
- propyl carbinol
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Abstract
The invention discloses a kind of ethene, hydrogen peroxide, propyl carbinol of utilizing and be raw material, single step reaction prepares the method for butyl glycol ether, be make ethene, hydrogen peroxide, propyl carbinol in the presence of HTS or the modifying titanium-silicon molecular sieve, propyl carbinol and hydrogen peroxide according to 1～20 mol ratio, 5～280 ℃ with 0.1～5.0MPa under contact 0.2～10 hour, the consumption of HTS or modifying titanium-silicon molecular sieve should make in every gram reaction solution 0.001～0.5g molecular sieve.This method has not only overcome traditional method technical process length, big, the high problem of energy consumption material consumption of facility investment, and purpose selectivity of product height; Hydrogen peroxide utilization ratio height; Catalyst activity, stability height, renewable recycling; Hydrogen peroxide carries out becoming water, environmentally safe after the oxidizing reaction.
Description
Technical field
The invention relates to the preparation method of butyl glycol ether, be specifically related to utilize HTS or modifying titanium-silicon molecular sieve to make catalyzer, is raw material with ethene, hydrogen peroxide, propyl carbinol, and single step reaction prepares the method for butyl glycol ether.
Background technology
Butyl glycol ether (Ethylene glycol monobutyl ether), chemical name ethylene glycol monobutyl ether (or butyl glycol ether), the another name ethylene glycol butyl ether is a kind of colourless inflammable liquid, it is smelly to have moderate ether, low toxicity, 171 ℃ of boiling points, relative density (d
4 20) 0.9015, specific refractory power (nD20) 1.4198, vapour pressure (20 ℃) 0.101kPa, 61.1 ℃ of flash-points, 472 ℃ of spontaneous ignition temperatures.Butyl glycol ether is dissolved in most of organic solvents and mineral oil.Can be miscible with benzene, acetone, tetracol phenixin, ether, normal heptane, have the characteristics of low velocity of evaporation and highly diluted ratio.Has high thinning ratio with petroleum hydrocarbon.
The chemical molecular formula of butyl glycol ether is C
6H
14O
2, molecular weight 118.17, CAS NO.:111-76-2, its molecular structural formula are CH
3CH
2CH
2CH
2OCH
2CH
2OH.
Butyl glycol ether mainly is used as topcoating solvent, metal cleaner, unicircuit, electronic component clean-out system, petroleum drilling acidizing fluid additive, household liquids washing composition, fiber wetting agent, pesticide dispersing agent, resin plasticizer, organic synthesis intermediate etc.Be excellent solvent, also be used as extraction agent, water-resisting agent and organic intermediate etc.
Existing butyl glycol ether production technique is mainly carried out in two steps: one, adopt silver to be catalyzer, oxidation of ethylene epoxy ethane; Two, be raw material preparing ethylene glycol butyl ether by oxyethane and propyl carbinol again.In ethene epoxy ethane process, a large amount of CO of by-product
2Deng impurity, how to recycle these CO
2By product is a research topic.For oxyethane and propyl carbinol is raw material preparing ethylene glycol butyl ether, can adopt BF on the industrial production
3, AlCl
3, sodium alkoxide etc. makes catalyzer, temperature of reaction is 100～250 ℃, pressure 0.2～5MPa.Also can synthesize when catalyst-free, temperature of reaction 180-200 ℃, pressure is 3.8～4MPa.The oxyethane transformation efficiency is higher, but all can a certain amount of butyl carbitol of by-product.So the operational path of this method of employing is longer, facility investment is big, the energy consumption material consumption is higher.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of technology is simple, and facility investment is little, and energy consumption, material consumption are low, products obtained therefrom selectivity height, and the preparation method of the butyl glycol ether that the feature of environmental protection is good is to overcome the deficiency that exists in the existing commercial run.
The method for preparing butyl glycol ether provided by the invention is to be raw material with ethene, hydrogen peroxide, propyl carbinol, is catalyzer with the HTS, makes by single step reaction.Concrete technology is: be 1～20 in molar ratio, be preferably 2～15 ratio, propyl carbinol and hydrogen peroxide are added in the reactor, simultaneously, drop into HTS or modifying titanium-silicon molecular sieve by the consumption that 0.001～0.5g molecular sieve is arranged in every gram reaction solution, stir airtight back, the while heat temperature raising, temperature reaches 5～280 ℃, is preferably 20～150 ℃, stops heating.Continue to feed in reactor ethene, control pressure is 0.1～5.0Mpa, be preferably 0.5～3.0Mpa, and temperature is 5～280 ℃, is preferably 20～150 ℃, reacts to get final product in 0.2～10 hour.
Method provided by the invention is not particularly limited the raw material propyl carbinol, and analytical pure, chemical pure, technical pure all can.
Method provided by the invention is not particularly limited the raw material hydrogen peroxide, any purity all can, but consider that from economical and practical angle its mass concentration is being good more than 25%.
Method provided by the invention also is not particularly limited raw material ethene, any purity all can, but consider that from economical and practical angle its mass concentration is being good more than 60%.
The HTS that method provided by the invention is suitable for can be synthesized according to any prior art, but preferably according to the disclosed method synthetic of CN1301599A.
The HTS that method provided by the invention is suitable for can also be the modification of HTS that any prior art is synthesized, but preferably according to the modification of the disclosed method synthetic of CN1301599A HTS.
The method of new synthesizing butyl cellosolve provided by the invention has overcome not only that the traditional method technical process is long, facility investment is big, the high problem of energy consumption material consumption, and purpose selectivity of product height; Hydrogen peroxide utilization ratio height; Catalyst activity, stability height, renewable recycling; Hydrogen peroxide carries out becoming water, environmentally safe after the oxidizing reaction.
Embodiment
The invention will be further described by following example, but not thereby limiting the invention.
Employed HTS among the embodiment is according to the disclosed method synthetic of CN1301599A.
The preparation method of the modifying titanium-silicon molecular sieve among the embodiment is: 10g is added in the 100g distilled water according to the disclosed method synthetic of CN1301599A HTS, stirring is warmed up to 65 ℃, adding the 1.1g tween 80 stirred 10 minutes, add 1.45g aluminum isopropylate and 1.3g department benzene 80, elevated temperature to 90 ℃ stirring 4 hours, be pressurized to 5Kg/cm2, elevated temperature to 120 ℃, constant temperature and pressure reaction 24 hours, take out washing and filtering, dried 5 hours, and, promptly obtained modifying titanium-silicon molecular sieve for 110 ℃ 600 ℃ of roastings 6 hours.
Among the embodiment, hydrogen peroxide is that concentration is 30% H
2O
2, analytical pure; Ethene, analytical pure; Propyl carbinol, analytical pure.The three is commercially available.
Among the embodiment, reactor is the COF2/10 type stainless steel cauldron that the Beijing Chemical Research Institute produces, and its volume is 2L.Mechanical stirring is adopted in reaction, adopts the heating rate and the mixing speed of the GK-I autoclave controller conditioned reaction still of Beijing Chemical Research Institute's production.Reactor is furnished with heat production coil pipe, by the water yield in the control feeding heat production coil pipe, can in time take the heat in the reactor away, thereby reach the purpose of control reaction temperature.For eliminating the influence of impurity in the reaction system, reduce H as far as possible
2O
2Invalid decomposition, before experimentizing, reactor is carried out alkali passivation, sour passivation and about 10%H
2O
2Soak.
The concentration of each material of reaction back is carried out quantitative analysis with gas chromatograph among the embodiment.Adopt HP5890 II type gas chromatograph, split stream injector; Are furnished with the temperature programming parts; Flame ionization ditector.Capillary chromatograph is elastic quartz capillary tube PONA dedicated columns (HP) 50m * 0.2mm * 0.5 μ m, column length 50m, column internal diameter 0.2mm, stationary liquid film thickness 0.5 μ m.
Butyl glycol ether selectivity, hydrogen peroxide utilization ratio, propyl carbinol transformation efficiency calculate respectively according to the following equation among the embodiment:
Propyl carbinol transformation efficiency=(propyl carbinol molar content in the 1-product) * 100%
Hydrogen peroxide utilization ratio=propyl carbinol transformation efficiency * (propyl carbinol and H
2O
2Molar ratio)
Embodiment 1
With 100g HTS, 887g propyl carbinol, 113g concentration 30% H
2O
2Add successively in the reactor that volume is 2L, this moment, the mol ratio of propyl carbinol and hydrogen peroxide was 12.After airtight, start and stir, heat up simultaneously,, stop heating when temperature reaches 100 ℃.
Continue to feed in reactor ethene, control reactor pressure is 2.5MPa, and the water yield controlled temperature that feeds in the reactor heat production coil pipe by adjusting is 100 ℃.Behind the reaction 0.5h, the butyl glycol ether selectivity is 100%, and the propyl carbinol transformation efficiency is 7.2%, and the hydrogen peroxide utilization ratio is 86.4%.
Embodiment 2
With 5g HTS, 907.4g propyl carbinol, 92.6g concentration 30% H
2O
2Add successively in the reactor that volume is 2L, this moment, the mol ratio of propyl carbinol and hydrogen peroxide was 15.After airtight, start and stir, heat up simultaneously,, stop heating when temperature reaches 40 ℃.
Continue to feed in reactor ethene, control reactor pressure is 3.0MPa, and the water yield controlled temperature that feeds in the reactor heat production coil pipe by adjusting is 40 ℃.Behind the reaction 10h, the butyl glycol ether selectivity is 100%, and the propyl carbinol transformation efficiency is 4.8%, and the hydrogen peroxide utilization ratio is 72%.
Embodiment 3
With 60g HTS, 566g propyl carbinol, 434g concentration 30% H
2O
2Add successively in the reactor that volume is 2L, this moment, the mol ratio of propyl carbinol and hydrogen peroxide was 2.After airtight, start and stir, heat up simultaneously,, stop heating when temperature reaches 60 ℃.
Continue to feed in reactor ethene, control reactor pressure is 2.5MPa, and the water yield controlled temperature that feeds in the reactor heat production coil pipe by adjusting is 60 ℃.Behind the reaction 3h, the butyl glycol ether selectivity is 100%, and the propyl carbinol transformation efficiency is 38.1%, and the hydrogen peroxide utilization ratio is 76.2%.
Embodiment 4
With 40g HTS, 662g propyl carbinol, 338g concentration 30% H
2O
2Add successively in the reactor that volume is 2L, this moment, the mol ratio of propyl carbinol and hydrogen peroxide was 3.After airtight, start and stir, heat up simultaneously,, stop heating when temperature reaches 50 ℃.
Continue to feed in reactor ethene, control reactor pressure is 0.8MPa, and the water yield controlled temperature that feeds in the reactor heat production coil pipe by adjusting is 50 ℃.Behind the reaction 3h, the butyl glycol ether selectivity is 100%, and the propyl carbinol transformation efficiency is 26.8%, and the hydrogen peroxide utilization ratio is 80.4%.
Embodiment 5
With 40g HTS, 723g propyl carbinol, 277g concentration 30% H
2O
2Add successively in the reactor that volume is 2L, this moment, the mol ratio of propyl carbinol and hydrogen peroxide was 4.After airtight, start and stir, heat up simultaneously,, stop heating when temperature reaches 80 ℃.
Continue to feed in reactor ethene, control reactor pressure is 2.0MPa, and the water yield controlled temperature that feeds in the reactor heat production coil pipe by adjusting is 80 ℃.Behind the reaction 2.5h, the butyl glycol ether selectivity is 100%, and the propyl carbinol transformation efficiency is 21.1%, and the hydrogen peroxide utilization ratio is 84.4%.
Embodiment 6
With 20g HTS, 887g propyl carbinol, 113g concentration 30% H
2O
2Add successively in the reactor that volume is 2L, this moment, the mol ratio of propyl carbinol and hydrogen peroxide was 12.After airtight, start and stir, heat up simultaneously,, stop heating when temperature reaches 150 ℃.
Continue to feed in reactor ethene, control reactor pressure is 2.5MPa, and the water yield controlled temperature that feeds in the reactor heat production coil pipe by adjusting is 150 ℃.Behind the reaction 20min, the butyl glycol ether selectivity is 100%, and the propyl carbinol transformation efficiency is 6.5%, and the hydrogen peroxide utilization ratio is 78.0%.
Embodiment 7
With 30g modifying titanium-silicon molecular sieve, 887g propyl carbinol, 113g concentration 30% H
2O
2Add successively in the reactor that volume is 2L, this moment, the mol ratio of propyl carbinol and hydrogen peroxide was 12.After airtight, start and stir, heat up simultaneously,, stop heating when temperature reaches 120 ℃.
Continue to feed in reactor ethene, control reactor pressure is 3.0MPa, and the water yield controlled temperature that feeds in the reactor heat production coil pipe by adjusting is 120 ℃.Behind the reaction 20min, the butyl glycol ether selectivity is 100%, and the propyl carbinol transformation efficiency is 7.5%, and the hydrogen peroxide utilization ratio is 90.0%.
Embodiment 8
With 30g modifying titanium-silicon molecular sieve, 662g propyl carbinol, 338g concentration 30% H
2O
2Add successively in the reactor that volume is 2L, this moment, the mol ratio of propyl carbinol and hydrogen peroxide was 3.After airtight, start and stir, heat up simultaneously,, stop heating when temperature reaches 20 ℃.
Continue to feed in reactor ethene, control reactor pressure is 2.0MPa, and the water yield controlled temperature that feeds in the reactor heat production coil pipe by adjusting is 20 ℃.Behind the reaction 4h, the butyl glycol ether selectivity is 100%, and the propyl carbinol transformation efficiency is 28.8%, and the hydrogen peroxide utilization ratio is 86.4%.
Embodiment 9
With 200g modifying titanium-silicon molecular sieve, 907.4g propyl carbinol, 92.6g concentration 30% H
2O
2Add successively in the reactor that volume is 2L, this moment, the mol ratio of propyl carbinol and hydrogen peroxide was 15.After airtight, start and stir, heat up simultaneously,, stop heating when temperature reaches 40 ℃.
Continue to feed in reactor ethene, control reactor pressure is 2.0MPa, and the water yield controlled temperature that feeds in the reactor heat production coil pipe by adjusting is 40 ℃.Behind the reaction 0.5h, the butyl glycol ether selectivity is 100%, and the propyl carbinol transformation efficiency is 27.4%, and the hydrogen peroxide utilization ratio is 82.2%.
Claims (4)
1, a kind of method for preparing butyl glycol ether is characterized in that: be 1～20 ratio in molar ratio, propyl carbinol and hydrogen peroxide are added in the reactor, simultaneously, drop into HTS by the consumption that 0.001～0.5g molecular sieve is arranged in every gram reaction solution, stir airtight back, simultaneously heat temperature raising, temperature reaches 5～280 ℃, stop heating, continue to feed ethene in reactor, control pressure is 0.1～5.0Mpa, temperature is 5～280 ℃, reacts to get final product in 0.2～10 hour.
2, method according to claim 1, it is characterized in that the HTS after described HTS is for the process modification, its method of modifying is: the HTS of 10 parts of quality is joined in the distilled water of 100 parts of quality, stirring is warmed up to 65 ℃, the tween 80 that adds 1.1 parts of quality stirred 10 minutes, add the aluminum isopropylate of 1.45 parts of quality and department's benzene 80 of 1.3 parts of quality, elevated temperature to 90 ℃ stirring 4 hours is pressurized to 5Kg/cm
2, elevated temperature to 120 ℃, washing and filtering is taken out in constant temperature and pressure reaction 24 hours, 110 ℃ of oven dry 5 hours, 600 ℃ of roastings 6 hours, modification finished.
3, method according to claim 1 is characterized in that: the mol ratio of propyl carbinol and hydrogen peroxide is 2～15.
4, according to each described method in the claim 1～3, it is characterized in that: temperature of reaction is 20～150 ℃, and reaction pressure is 0.5～3.0Mpa.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921180B (en) * | 2010-08-12 | 2013-08-28 | 江苏怡达化学股份有限公司 | Method for synthesizing butyl cellosolve |
| CN102452908B (en) * | 2010-10-15 | 2014-04-02 | 中国石油化工股份有限公司 | Method for preparing glycol monoether from ethylene |
| CN103193636B (en) * | 2013-04-15 | 2016-01-13 | 湖南长岭石化科技开发有限公司 | A kind of method of synthesizing 2,3-butanediol ester |
| CN105883845B (en) * | 2016-04-14 | 2017-11-24 | 沈阳理工大学 | A kind of method prepared using Ti Al oxides as the molecular sieve of skeleton |
| CN106006659B (en) * | 2016-05-20 | 2017-10-27 | 沈阳理工大学 | A kind of method for preparing titanium aluminum molecular screen photochemical catalyst |
| CN112920911A (en) * | 2021-01-29 | 2021-06-08 | 广东丽臣奥威实业有限公司 | Method for producing surfactant composition containing nonylphenol polyoxyethylene ether |
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2007
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| 乙二醇单丁醚合成方法的改进. 王晓春.化学试剂，第15卷第1期. 1993 |
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