CN103172495A - Method for preparing ethylene glycol by directly oxidizing ethylene - Google Patents
Method for preparing ethylene glycol by directly oxidizing ethylene Download PDFInfo
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- CN103172495A CN103172495A CN2011104364164A CN201110436416A CN103172495A CN 103172495 A CN103172495 A CN 103172495A CN 2011104364164 A CN2011104364164 A CN 2011104364164A CN 201110436416 A CN201110436416 A CN 201110436416A CN 103172495 A CN103172495 A CN 103172495A
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- ethylene glycol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention relates to a method for directly preparing ethylene glycol by oxidizing ethylene with hydrogen peroxide. According to the method, with phosphotungstic acid quaternary ammonium salt with the characteristic of reaction controlled phase transfer as a catalyst and phosphoric acid, tungstic acid or the mixture of phosphoric acid and tungstic acid as an additive, ethylene is oxidized with hydrogen peroxide to generate ethylene glycol under the conditions that the reaction temperature is 20-100 DEG C and the pressure is 0.3-4.0Mpa. The method has the advantages of mild reaction conditions, high selectivity and catalyst recoverability.
Description
Technical field
The present invention relates to a kind of method for preparing ethylene glycol.
Background technology
Ethylene glycol (Ethylene Glycol), be called for short EG or MEG, mainly for the production of polyester, account for more than 80% of overall consumption, can be used in addition the production of deicing fluid, lubricant, softening agent, tensio-active agent, explosive, paint, tackiness agent, printing ink, soup, hydraulic brake liquid etc., is a kind of important petrochemical complex basic material.At present domestic due to pulling that polyester industry grows at top speed, the consumption rapid growth of ethylene glycol.China ethylene glycol apparent consumption amount broke through 3,000,000 tons of high pointes in 2002, and surpassing the U.S. becomes the large ethylene glycol of the first in the world country of consumption.
The production technology of ethylene glycol mainly comprises petrochemical complex route and the large class of the synthetic gas route take Sweet natural gas (or coal) as raw material two.Can be divided into again specifically that ethene direct hydration method, epoxyethane water are legal, NSC 11801 (EthyleneCarbonate, abbreviation EC) method, synthetic gas synthesis method, methyl alcohol formaldehyde synthesis method, barkite synthesis method etc., prevailing in current industrial production is the oxyethane direct hydration method.
The oxyethane direct hydration method is the main method of at present domestic and international suitability for industrialized production ethylene glycol.But in production process the selectivity of ethylene glycol still relatively poor, water is more excessive than also, cause the concentration of product lower, therefore the investment of the concentrated equipment for purifying of product is large, the purification process energy consumption is higher, and the by-product glycol ether of the new purposes of nothing has become the major obstacle that hinders ethylene glycol production Sustainable development.
Therefore, people extensively carry out the catalytic hydration reaction of oxyethane, the selectivity that wish effectively to reduce the water ratio, improves ethylene glycol, the generation of reduction glycol ether.But in existing minority Catalytic Hydration technique, remain in problems such as catalyst recovery are difficult, equipment corrosion is serious; And the catalytic performance of heterogeneous catalyst is still not ideal enough at present, and heat resistance is poor, and work-ing life is short.
Oxyethane is in the silver-colored oxygen catalytic oxidation ethene preparation of industrial employing, although this process is an ideal oxidising process, even people constantly improve silver-colored catalyst system for many years, the oxyethane selectivity is still in 80% left and right.Also there is no so far the research about other oxygen source ethylene oxide epoxy ethane.
About take hydrogen peroxide as oxygen source, the research of direct oxidation ethene preparing ethylene glycol yet there are no patent and pertinent literature report.
We adopt document: Xi Z W, Zhou N, Sun Y, Li K L.Reaction-Controlled Phase-Transfer Catalysis for Propylene Epoxidation to Propylene Oxide[J] .Science, 2001, the catalyzer of 292:1139 preparation, take hydrogen peroxide as oxygen source direct oxidation ethene one-step synthesis ethylene glycol.
Summary of the invention
The invention provides a kind of method that hydrogen peroxide oxidation ethene directly prepares ethylene glycol.
The present invention controls the quaternary ammonium salt phosphor-tungstic heteropoly acid of phase transition characteristics as catalyzer to have reaction, take phosphoric acid, wolframic acid or mixture both as additive, under the temperature of reaction of 20 ℃-100 ℃, under the condition of 0.3-4.0MPa, use hydrogen peroxide oxidation ethene generating glycol.
Described reaction medium is a kind of of toluene, ethyl acetate, acetonitrile.
Catalyzer used is controlled phase transition characteristics quaternary ammonium salt phosphor-tungstic heteropoly acid for having reaction, and phosphorus heteropoly tungstic acid quaternary amine catalyzer is selected from least a in dodecyl Trimethylamine phospho heteropoly tungstate, cetyl trimethyl amine phospho heteropoly tungstate, Octadecyl trimethylamine phospho heteropoly tungstate or two octadecyl dimethyl amine phospho heteropoly tungstate.Catalyst molecule forms Q
mH
nPW
xO
y, Q is the alkyl cationic moiety, 1≤m≤7,1≤x≤12,0≤n≤1,7≤y≤40.
The part by weight of additive and catalyzer is between 1: 1000 to 1: 50, and additive is a kind of or its mixture in phosphoric acid, wolframic acid.
Hydrogen peroxide concentration is 10%-50%.
Hydrogen peroxide and catalyst molar ratio are between 500: 1 to 50: 1.
Ethene and hydrogen peroxide mol ratio are 50: 1-1: 5.
After reaction finished, the catalyzer filtered and recycled was used for reaction again.
The inventive method has the reaction conditions gentleness, and selectivity is high, the callable advantage of catalyzer.
Embodiment
Give further instruction below by embodiment to the present invention:
Embodiment 1
Kaolinite Preparation of Catalyst: reference Journal of Molecular Catalysis A, 2001,166:219..
It is in 30% hydrogen peroxide, to be heated to while stirring 60 ℃ that weighing 2.50g wolframic acid joins the 10ml mass concentration, obtains colourless transparent solution after 60 minutes.Adding the 0.29g mass concentration in this solution is 85% phosphoric acid, adds 20ml distilled water and continues to stir 30min.Weighing 2.5g palmityl trimethyl ammonium chloride is dissolved in the ethylene dichloride of 40ml, and this solution is added drop-wise in above-mentioned hydrogen peroxide solution fast, continues to stir 60min, is precipitated.The PH that is precipitated to filtrate with distilled water wash approximates 4.Filtrate obtains phosphorus heteropoly tungstic acid quaternary amine catalyzer 50-60 ℃ of lower vacuum-drying.
Oxidation of ethylene hydration reaction: in the 250ml stainless steel cauldron of glass lining is arranged, add toluene 50ml, mass concentration 30% hydrogen peroxide 11g, catalyzer 0.6g, phosphoric acid 0.012g, be filled with 5.6g ethene, under 0.7Mpa pressure, stir 4h under 40 ℃ of temperature of reaction, cooling.Add ethanol to make water oil two-phase become a phase in reaction system, then the quantitative ethanolic soln, add the interior mark trimethyl carbinol by chromatogram ration analysis ethylene glycol, and ethylene glycol is 60% to the productive rate of hydrogen peroxide, and the rate of recovery of catalyzer is 90%.
Embodiment 2
With reference to embodiment 1 process operation, difference from Example 1 is, changes the solvent of embodiment 1 into acetonitrile, and 40 ℃ of temperature of reaction are changed to 70 ℃.By gas chromatographic analysis, ethylene glycol is 80% to the productive rate of hydrogen peroxide, and the rate of recovery of catalyzer is 80%.
Embodiment 3
With reference to embodiment 1 process operation, difference from Example 1 is, changes the solvent of embodiment 1 into ethyl acetate, additive changes wolframic acid into, is filled with 8.4g ethene, by gas chromatographic analysis, propylene oxide is 65% to the productive rate of hydrogen peroxide, and the rate of recovery of catalyzer is 79%.
Claims (8)
1. a direct oxidation ethene prepares the method for ethylene glycol, it is characterized in that:
Toluene, ethyl acetate or acetonitrile are reaction medium, use the quaternary ammonium salt phosphor-tungstic heteropoly acid with reaction control phase transition characteristics to be catalyzer, take phosphoric acid, wolframic acid or mixture both as additive, use hydrogen peroxide oxidation ethene generating glycol, described temperature of reaction is between 20 ℃-100 ℃, and pressure is under the condition of 0.3-4.0Mpa.
2. prepare according to claim 1 the method for ethylene glycol, it is characterized in that: catalyzer used is controlled phase transition characteristics quaternary ammonium salt phosphor-tungstic heteropoly acid for having reaction, and phosphorus heteropoly tungstic acid quaternary amine catalyzer is selected from least a in dodecyl Trimethylamine phospho heteropoly tungstate, cetyl trimethyl amine phospho heteropoly tungstate, Octadecyl trimethylamine phospho heteropoly tungstate or two octadecyl dimethyl amine phospho heteropoly tungstate; Catalyst molecule forms Q
mH
nPW
xO
y, Q is the alkyl cationic moiety, 1≤m≤7,1≤x≤12,0≤n≤1,7≤y≤40.
3. prepare according to claim 1 the method for ethylene glycol, it is characterized in that: the part by weight of additive and catalyzer is between 1: 1000 to 1: 50.
4. prepare according to claim 1 the method for ethylene glycol, it is characterized in that: hydrogen peroxide and catalyst molar ratio are between 500: 1 to 50: 1.
5. according to claim 1 or 4 described methods that prepare ethylene glycol, it is characterized in that: adding the hydrogen peroxide mass concentration is 10%-50%.
6. prepare according to claim 1 the method for ethylene glycol, it is characterized in that: ethene and hydrogen peroxide mol ratio are 50: 1-1: 5.
7. prepare according to claim 5 the method for ethylene glycol, it is characterized in that: take toluene, ethyl acetate or acetonitrile as reaction medium, the volume ratio of hydrogen peroxide and reaction medium is 1: 100-10: 1.
8. prepare according to claim 1 the method for ethylene glycol, it is characterized in that: after reaction finished, the catalyzer filtered and recycled was used for the reaction that direct oxidation ethene prepares ethylene glycol again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2011104364164A CN103172495A (en) | 2011-12-22 | 2011-12-22 | Method for preparing ethylene glycol by directly oxidizing ethylene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011104364164A CN103172495A (en) | 2011-12-22 | 2011-12-22 | Method for preparing ethylene glycol by directly oxidizing ethylene |
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| CN103172495A true CN103172495A (en) | 2013-06-26 |
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| CN2011104364164A Pending CN103172495A (en) | 2011-12-22 | 2011-12-22 | Method for preparing ethylene glycol by directly oxidizing ethylene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418376A (en) * | 2014-09-15 | 2016-03-23 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol through catalytic oxidation hydration of ethylene by using phase-transfer catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004000868A (en) * | 2002-04-25 | 2004-01-08 | Nissan Chem Ind Ltd | Production method for oxirane compound and diol compound |
| CN1923777B (en) * | 2005-08-31 | 2011-07-20 | 中国科学院大连化学物理研究所 | Preparation method of 1,2-aliphatic glycol |
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2011
- 2011-12-22 CN CN2011104364164A patent/CN103172495A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004000868A (en) * | 2002-04-25 | 2004-01-08 | Nissan Chem Ind Ltd | Production method for oxirane compound and diol compound |
| CN1923777B (en) * | 2005-08-31 | 2011-07-20 | 中国科学院大连化学物理研究所 | Preparation method of 1,2-aliphatic glycol |
Non-Patent Citations (2)
| Title |
|---|
| XI ZUWEI ET AL.: "Reaction-Controlled Phase-Transfer Catalysis for Propylene Epoxidation to Propylene Oxide", 《SCIENCE》, vol. 292, 11 May 2001 (2001-05-11), pages 1139 - 1141 * |
| YU SUN ET AL.: "Epoxidation of olefins catalyzed by [p-C5H5NC16H33]3[PW4O16] with molecular oxygen and a recyclable reductant 2-ethylanthrahydroquinone", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 166, 31 December 2001 (2001-12-31), pages 219 - 224 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418376A (en) * | 2014-09-15 | 2016-03-23 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol through catalytic oxidation hydration of ethylene by using phase-transfer catalyst |
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Application publication date: 20130626 |