CN103087035B - Preparation methods of 2,2-dimethyl-1,3-dioxolane and ethylene glycol - Google Patents

Preparation methods of 2,2-dimethyl-1,3-dioxolane and ethylene glycol Download PDF

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CN103087035B
CN103087035B CN201110341569.0A CN201110341569A CN103087035B CN 103087035 B CN103087035 B CN 103087035B CN 201110341569 A CN201110341569 A CN 201110341569A CN 103087035 B CN103087035 B CN 103087035B
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dimethyl
zinc chloride
ionic liquid
ion
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CN103087035A (en
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谢伦嘉
郭顺
亢宇
田宇
冯再兴
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • 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
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Abstract

The invention provides a preparation method of 2,2-dimethyl-1,3-dioxolane. The method comprises the steps that: under a cyclization reaction condition, ethylene oxide and acetone contact a catalyst, such that a mixture is obtained; and the 2,2-dimethyl-1,3-dioxolane is separated from the mixture, wherein the catalyst comprises ionic liquid 1-alkyl-3-methylimidazolium salt and anhydrous zinc chloride. The invention also provides a preparation method of ethylene glycol. According to the 2,2-dimethyl-1,3-dioxolane preparation method provided by the invention, the catalyst composed of the ionic liquid 1-alkyl-3-methylimidazolium salt and anhydrous zinc chloride is adopted, such that defects such as high catalyst cost and severe environment pollution of prior arts in which zinc trifluoromethanesulfonate is adopted as a catalyst for catalyzing the reaction of ethylene oxide and acetone are solved. Also, catalytic efficiency is improved compared with a method for using single anhydrous zinc chloride as a catalyst to replace zinc trifluoromethanesulfonate, and catalyst recycling and reutilization can be facilitated.

Description

A kind of 2, the preparation method of 2-dimethyl-DOX and ethylene glycol
Technical field
The present invention relates to a kind of a kind of method and method of preparing ethylene glycol of preparing 2,2-dimethyl-DOX.
Background technology
The production technique of existing ethylene glycol, is mainly under High Temperature High Pressure, and oxyethane is reacted with large water gaging, and the two mass ratio is about 1: 10, and this technique glycol selectivity is low, long flow path, and energy consumption is large, and facility investment is also larger.Also have first oxyethane to be reacted with acetone and generate 1,3-dioxolane compound, then the technique of ethylene glycol is prepared in hydrolysis, the energy consumption that this technique has solved traditional oxyethane hydrolysis technique existence is large, the problem that facility investment is large, when reducing water consumption, can reduce by product glycol ether.Yet the key of this technique is the preparation of DOX compounds.
At present, the method for preparing DOX compounds has a lot, press reactant classification, generally have two kinds: the first, take adjacent glycols compound and be reactant containing the compound (aldehydes or ketones) of carbonyl, reaction generates DOX compounds and water; The second, epoxy compounds reacts with aldehydes or ketones and generates DOX compounds.In organic synthesis field, first method is usually used in o-dihydroxy or carbonyl functional group's protection and the gas chromatographic analysis of adjacent glycols compound; Second method bibliographical information less, the example wherein with potential industrial application value is under catalyst action, oxyethane and acetone reaction preparation 2,2-dimethyl-DOX, is then hydrolyzed 2,2-dimethyl-DOX is prepared ethylene glycol.The second method of bibliographical information typically has following several:
American Chemical Society's periodical literature (J.Org.Chem.1978,43,438-440) to have reported under anhydrous cupric sulfate catalyst action, epoxy compounds (I) reacts preparation 2,2-dimethyl-DOX derivative with acetone.But the method is the epoxy compounds of (I) formula for general structure, works as R 1to R 4in group, have that 1 or 2 groups are alkyl, all the other are during for hydrogen atom, the transformation efficiency lower (5-50%) that described epoxy compounds react with acetone, and a large amount of acetone (acetone and epoxy compounds mol ratio are greater than 16) of reaction need use.
CN101519397A discloses a kind of preparation method of DOX compounds, and the method comprises, under the effect of catalyzer trifluoromethane sulfonic acid zinc, epoxy compounds and general formula that general formula is (I) formula are R 5cOR 6aldehydes or ketones reaction, generate DOX compounds.Meanwhile, disclose with oxyethane and prepared ketal and hydrolysis preparing ethylene glycol process flow diagram thereof.When the molar ratio of oxyethane and acetone is 1: 3.7, the transformation efficiency 99% of oxyethane, the selectivity 99% of generation 2,2-dimethyl-DOX.
CN101993430A discloses a kind of preparation method of DOX compounds, and the method has been reported employing mesoporous material after load trifluoromethane sulfonic acid zinc, as heterogeneous catalyst, carry out reacting of catalytic epoxyethane and acetone, obtained higher yield (when the molar ratio of oxyethane and acetone is 1: 3.7, oxyethane generates 2, the selectivity of 2-dimethyl-DOX is greater than 99.9%).
As can be seen here, current yield, the preparation 1 that selectivity is higher, the method of 3-dioxolane compound all needs to use trifluoromethane sulfonic acid zinc as catalyzer, yet, trifluoromethanesulfonic acid zincon corrodibility is strong, is unfavorable for environmental protection, and expensive, therefore develop a kind of cheap, catalyzer that environmental pollution is little is suitable for preparing DOX compounds and will be the emphasis of research in for some time or even very long a section from now on.
Summary of the invention
The object of the invention is to overcome the preparation 2 of prior art, 2-dimethyl-1, the defect that catalyzer trifluoromethane sulfonic acid zinc is expensive, environmental pollution is comparatively serious of the use existing in the method for 3-dioxolane, provide a kind of for reusable cheap catalyst, and the catalytic epoxyethane that target product yield is high reacts preparation 2 with acetone, the method of 2-dimethyl-DOX and prepare the method for ethylene glycol.
From background technology, prior art prepares 2, 2-dimethyl-1, catalyzer trifluoromethane sulfonic acid zinc that the method for 3-dioxolane adopts is expensive and environmental pollution is serious, therefore, preparation 2 at present, 2-dimethyl-1, the key of the method for 3-dioxolane is just the exploitation of catalyzer, the present inventor finds in test of long duration process, adopt Zinc Chloride Anhydrous to replace trifluoromethane sulfonic acid zinc can overcome trifluoromethane sulfonic acid zinc as catalyzer expensive, the defect that environmental pollution is serious, but than trifluoromethane sulfonic acid zinc during as catalyzer, target product yield decreases, therefore, how under the condition that adopts Zinc Chloride Anhydrous as catalyzer, the yield that further improves target product becomes the difficult point of research, by further research, the present inventor finds finally, in system at Zinc Chloride Anhydrous as catalyzer, add ionic liquid can realize the target of the yield that improves target product, and on this basis, while adopting Zinc Chloride Anhydrous and ionic liquid as catalyzer co-catalysis, catalyzer can more effectively reuse.Based on this, find, completed the present invention.
The invention provides and a kind ofly prepare 2,2-dimethyl-1, the method of 3-dioxolane, the method comprises: under cyclization condition, oxyethane is contacted and obtains mixture with catalyzer with acetone, from described mixture, separation obtains 2,2-dimethyl-1,3-dioxolane, wherein, described catalyzer contains ionic liquid 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous.
The invention provides a kind of method of preparing ethylene glycol, the method comprises the following steps:
(1) prepare 2,2-dimethyl-DOX;
(2) under acidic solid catalyst exists, under hydrolysising condition, by described prepare 2,2-dimethyl-DOX contacts with water;
Wherein, prepare describedly 2, the method for 2-dimethyl-DOX is method of the present invention.
Preparation 2 of the present invention, 2-dimethyl-1, the method of 3-dioxolane is by the catalyzer that uses ionic liquid 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous to form, having overcome prior art uses trifluoromethane sulfonic acid zinc as catalyst oxyethane, to react the shortcoming that catalyzer is expensive, environmental pollution is serious existing with acetone, improved separately simultaneously and substituted trifluoromethane sulfonic acid zinc as the catalytic efficiency of catalyzer with Zinc Chloride Anhydrous, and be conducive to the use that is cycled to repeat of catalyzer.
The preparation method of ethylene glycol of the present invention, compares energy consumption and cost with the production technique of existing oxyethane direct hydrolysis preparing ethylene glycol.
Embodiment
The invention provides and a kind ofly prepare 2,2-dimethyl-1, the method of 3-dioxolane, the method comprises: under cyclization condition, oxyethane is contacted and obtains mixture with catalyzer with acetone, from described mixture, separation obtains 2,2-dimethyl-1,3-dioxolane, wherein, described catalyzer contains ionic liquid 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous.
The method according to this invention, as long as contain ionic liquid 1-alkyl-3-methylimidazole salt in described catalyzer and Zinc Chloride Anhydrous can be realized object of the present invention, optional a wider range of the mol ratio of described ionic liquid 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous, and in order further to improve 2, the selectivity of 2-dimethyl-DOX, under preferable case, the mol ratio of described ionic liquid 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous is 0.1-10: 1, be preferably 1-4: 1.
In the present invention, described cyclization condition can be for conventional cyclization condition, and for the present invention, under preferable case, described cyclization condition comprises: the temperature of contact is subzero 20 ℃ to 150 ℃ above freezing, is preferably 30 ℃-80 ℃; Pressure be normal pressure to 5MPa, be preferably normal pressure to 2MPa; The mol ratio of oxyethane, acetone and Zinc Chloride Anhydrous is 1: 0.1-10: 0.1-1, is preferably 1: 1-4: 0.1-0.4.
According to the present invention, optional a wider range of described ionic liquid 1-alkyl-3-methylimidazole salt, for the present invention, under preferable case, a kind of in the straight or branched alkyl that the alkyl in described ionic liquid 1-alkyl-3-methylimidazole salt is C1-C10; Negatively charged ion is halogen ion, PF 6 -, a kind of in borate ion, tetrafluoroborate ion, sulfate ion, hydrogen sulfate ion, alkyl sulfonate ion, trifluoromethane sulfonic acid radical ion and tosic acid radical ion.More preferably in situation, a kind of in the straight chained alkyl that described alkyl is C1-C10, more preferably a kind of in the straight chained alkyl of C1-C5.
According to of the present invention preferred embodiment a kind of, the positively charged ion of described ionic liquid 1-alkyl-3-methylimidazole salt is 1-butyl-3-Methylimidazole, and negatively charged ion is a kind of in bromide anion, chlorion, trifluoromethane sulfonic acid radical ion, methanesulfonate ions, tosic acid radical ion.
Concrete, described ionic liquid 1-alkyl-3-methylimidazole salt can be 1-butyl-3-methylimidazolium bromide, chlorination 1-butyl-3-Methylimidazole, 1-butyl-3-Methylimidazole hydrosulfate, 1-butyl-3-Methylimidazole mesylate, 1-butyl-3-Methylimidazole fluoroform sulphonate, 1-butyl-3-Methylimidazole tosilate etc., and more preferably described ionic liquid is 1-butyl-3-methylimidazolium bromide.Above-described ionic liquid can prepare by means commonly known in the art (referring to Koichi Mikami chief editor's < < Green Reaction Media in Organic Synthesis > >, the documents such as 2005, Blackwell Publishing Ltd.).
According to of the present invention preferred embodiment a kind of, described ionic liquid 1-alkyl-3-methylimidazole salt is 1-butyl-3-methylimidazolium bromide, and the mol ratio of 1-butyl-3-methylimidazolium bromide and Zinc Chloride Anhydrous is 1-4: 1, be preferably 2: 1.
According to a kind of preferred embodiment of the present invention, described ionic liquid 1-alkyl-3-methylimidazole salt is 1-butyl-3-methylimidazolium bromide, and the mol ratio of 1-butyl-3-methylimidazolium bromide and Zinc Chloride Anhydrous is 1-4: 1, be preferably 2: 1; The mol ratio of described oxyethane and acetone is 1: 1-4, is preferably 1-3.5-4.
According to a kind of particularly preferred embodiment of the present invention, described oxyethane, acetone, 1-butyl-3-methylimidazolium bromide and Zinc Chloride Anhydrous are 5: 20: 2: 1.
The present invention to the time of described contact without particular requirement, can adjust according to the temperature and pressure of contact, in general, under fixation reaction volume conditions (being confined reaction condition), temperature of reaction is higher, and the required reaction times is fewer, for example, under preferred temperature of reaction is the condition of 30-80 ℃, the time of contact is generally 3-20 hour, is preferably 5-12 hour.
In the present invention, the temperature of described contact can provide by the various known methods in this area, and for example 11-100 ℃ of scope can heat to provide by water-bath or oil bath, and the temperature range of 100-150 ℃ can provide by pressured steam.The pressure of described contact can be adjusted by the temperature of contact, and generally speaking, under the condition of fixation reaction volume (being confined reaction condition), the temperature of contact is higher, and pressure is also higher, and these are common practise, and this is no longer going to repeat them.
In the present invention, ionic liquid, 2,2-dimethyl-1, the boiling-point difference of 3-dioxolane, acetone, oxyethane large (2, the boiling point of 2-dimethyl-DOX is more than 100 ℃, and the boiling point of acetone is 56.05 ℃, the boiling point of oxyethane is 10.7 ℃), therefore can they be carried out to separation by rectifying.
In order to utilize more fully various reaction raw materials, according to of the present invention preferred embodiment a kind of, the mol ratio of described oxyethane and acetone is 1: 1-10, described mixture is obtained to the mixture and 2 of mixture, ionic liquid and the zinc chloride of acetone and oxyethane by rectifying separation, 2-dimethyl-1,3-dioxolane, the mixture of the acetone that separation is obtained and the mixture of oxyethane, ionic liquid and zinc chloride (mixture of ionic liquid and zinc chloride is generally stayed tower bottom of rectifying tower) reuse.
The invention provides a kind of method of preparing ethylene glycol, the method comprises the following steps:
(1) prepare 2,2-dimethyl-DOX;
(2) under acidic solid catalyst exists, under hydrolysising condition, by described prepare 2,2-dimethyl-DOX contacts with water;
Wherein, prepare describedly 2, the method for 2-dimethyl-DOX is method of the present invention.
According to the present invention, described acidic solid catalyst can be the conventional acidic solid catalyst using in this area, and for the present invention, under preferable case, described acidic solid catalyst is storng-acid cation exchange resin.
Method of the present invention, the preparation method who reports with CN101993430A with CN101519397A compares, the catalyzer forming by introduce ionic liquid 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous in reaction, guaranteeing that reaction possesses under the prerequisite of high conversion and highly selective, has successfully substituted strong, the expensive trifluoromethane sulfonic acid zinc of corrodibility with more cheap Zinc Chloride Anhydrous.In the preparation 2 that reacts of catalytic epoxyethane and acetone, 2-dimethyl-1, under the optimization reaction conditions of 3-dioxolane, under the katalysis of the catalyzer forming at bromination 1-butyl-3-Methylimidazole and Zinc Chloride Anhydrous, the transformation efficiency of oxyethane reaches 99%, far above take separately the transformation efficiency (77%) that Zinc Chloride Anhydrous is catalyzer, they are 2 years old, 2-dimethyl-1, the selectivity of 3-dioxolane reaches 100%, higher than take trifluoromethane sulfonic acid zinc as selectivity of catalyst (99%).
Further, of the present invention 2, the preparation method of 2-dimethyl-DOX, every mole of needed amounts of acetone of described epoxy reaction is greater than 16 by document (J.Org.Chem.1978,43,438～440) report, is reduced to below 4.And the catalyzer being comprised of 1-butyl-3-methylimidazolium bromide ionic liquid and Zinc Chloride Anhydrous can be reused.
In the present invention, the mass spectrum providing according to gas chromatograph-mass spectrometer (GC-MS) and computer Plays spectrum library compare and determine various materials, and those skilled in the art all can know this, not repeat them here.
Adopt gas-chromatography to carry out each analysis forming in system, by proofreading and correct normalization method, undertaken quantitatively, all can carrying out with reference to prior art, calculate on this basis the evaluation indexes such as the transformation efficiency of reactant, the yield of product and selectivity.
Below in conjunction with embodiment, the present invention is described in detail.
In comparative example and embodiment:
Embodiment 1
Magnetic stir bar is put into 25mL teflon-lined reactor, add 0.1mol (5.8g) acetone, 0.025mol (1.1g) oxyethane, add again by 0.01mol 1-butyl-3-methylimidazolium bromide ionic liquid and 0.005mol (0.68g) Zinc Chloride Anhydrous and evenly mix the catalyzer forming, capping still, under 65 ℃ of oil baths, stirring reaction 8 hours.React complete, be cooled to after room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is that 99%, 2,2-dimethyl-DOX selectivity is 100%.
Comparative example 1
According to the method for embodiment 1, prepare 2,2-dimethyl-DOX, different: catalyzer is 0.02mol (2.7g) Zinc Chloride Anhydrous.The transformation efficiency of oxyethane is that the selectivity of 77%, 2,2-dimethyl-DOX is 100%.
Comparative example 2
According to the method for embodiment 1, prepare 2,2-dimethyl-DOX, different: catalyzer is the anhydrous trifluoromethane sulfonic acid zinc of 1.8g.The transformation efficiency of oxyethane is that the selectivity of 99%, 2,2-dimethyl-DOX is 99%.
Data by above embodiment 1 and comparative example 1-2 can be found out: in the preparation 2 that reacts of catalytic epoxyethane and acetone, 2-dimethyl-1, in the method for 3-dioxolane, the transformation efficiency of oxyethane reaches 99%, higher than take the transformation efficiency (77%) that Zinc Chloride Anhydrous is catalyzer, the selectivity of 2,2-dimethyl-DOX reaches 100% higher than take trifluoromethane sulfonic acid zinc as selectivity of catalyst (99%).
Embodiment 2
The reaction mixture that embodiment 1 is obtained distills under nitrogen protection, after the complete fractionation by distillation of product and raw material, and the remaining ionic liquid that contains zinc chloride that is.By embodiment 1 method, prepare 2,2-dimethyl-DOX, with the catalyzer of the ionic liquid alternate embodiment 1 that contains zinc chloride of this recovery, preparation 2,2-dimethyl-DOX.Oxyethane transformation efficiency is that 99%, 2,2-dimethyl-DOX selectivity is 98%.
Comparative example 3
The reaction mixture that comparative example 1 is obtained distills under nitrogen protection, and after the complete fractionation by distillation of product and raw material, residuum contains zinc chloride.By comparative example 1 method, with the distillation residuum that contains zinc chloride of this recovery, substitute the catalyzer of comparative example 1, preparation 2,2-dimethyl-DOX.Be cooled to after room temperature, get fluid sample analysis, oxyethane transformation efficiency is 11%.
Comparative example 2 and comparative example 3 are known: the catalyzer that 1-butyl-3-methylimidazolium bromide ionic liquid and Zinc Chloride Anhydrous form, through the preparation 2 that reacts of catalytic epoxyethane and acetone for the first time, 2-dimethyl-1, after 3-dioxolane, after can reclaiming, catalytic epoxyethane and acetone react catalyzer again, and still keep high oxyethane transformation efficiency and high by 2, the selectivity of 2-dimethyl-DOX; And take Zinc Chloride Anhydrous as catalyzer, after catalytic epoxyethane and acetone react for the first time, the catalyzer of recovery for the second time catalytic effect obviously reduces.This explanation 1-butyl-3-methylimidazolium bromide ionic liquid has not only strengthened the katalysis of Zinc Chloride Anhydrous, and is conducive to the use that is cycled to repeat of catalyzer.
Embodiment 3
Magnetic stir bar is put into 100mL teflon-lined reactor, add 0.2mol (11.6g) acetone, 0.05mol (2.2g) oxyethane, add again by 0.02mol 1-butyl-3-methylimidazolium bromide ionic liquid and 0.01mol (1.36g) Zinc Chloride Anhydrous and evenly mix the catalyzer forming, capping still, under 65 ℃ of oil baths, stirring reaction 8 hours.React complete, be cooled to after room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is that the selectivity of 99%, 2,2-dimethyl-DOX is 98%.
Embodiment 4
According to the method for embodiment 3, prepare 2,2-dimethyl-DOX, different: the consumption of Zinc Chloride Anhydrous is 0.02mol (2.72g).React complete, be cooled to after room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is that the selectivity of 95%, 2,2-dimethyl-DOX is 90%.
Embodiment 5
According to the method for embodiment 3, prepare 2,2-dimethyl-DOX, different: the consumption of Zinc Chloride Anhydrous is 0.005mol (0.68g).React complete, be cooled to after room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is that the selectivity of 56%, 2,2-dimethyl-DOX is 94%.
Embodiment 6
According to the method for embodiment 3, prepare 2,2-dimethyl-DOX, different: the consumption of oxyethane is 0.1mol (4.4g).React complete, be cooled to after room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is that the selectivity of 87%, 2,2-dimethyl-DOX is 90%.
From embodiment 3-6, by 1-butyl-3-methylimidazolium bromide ionic liquid and Zinc Chloride Anhydrous, evenly mix the catalyzer forming, its catalytic effect is relevant with the molar ratio of ionic liquid and Zinc Chloride Anhydrous.Particularly preferred molar feed ratio is: oxyethane: acetone: 1-butyl-3-methylimidazolium bromide: Zinc Chloride Anhydrous=5: 20: 2: 1.
Embodiment 7
According to the method for embodiment 6, prepare 2,2-dimethyl-DOX, different: ionic liquid is 1-butyl-3-Methylimidazole tosilate.React complete, be cooled to after room temperature, get fluid sample analysis, oxyethane transformation efficiency 85%, 2,2-dimethyl-DOX selectivity is 100%.
Comparative example 6 and embodiment 7 are known, and in catalyst component of the present invention, available other ionic liquid (as 1-butyl-3-Methylimidazole tosilate) substitutes 1-butyl-3-methylimidazolium bromide, and effect is without marked difference.
Comparative example 4
According to the method for embodiment 6, prepare 2,2-dimethyl-DOX, different: the Zinc Chloride Anhydrous that substitutes 0.01mol (1.36g) with the trifluoromethanesulfonic acid zinc of 0.01mol.React complete, be cooled to after room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is that the selectivity of 83%, 2,2-dimethyl-DOX is 86%.
Comparative example 6 is known with comparative example 4, substitutes after Zinc Chloride Anhydrous 2,2-dimethyl-DOX elective reduction in catalyst component with trifluoromethanesulfonic acid zinc.The catalyzer that this explanation 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous form is superior to the catalyzer of 1-alkyl-3-methylimidazole salt and trifluoromethanesulfonic acid zinc composition.

Claims (12)

1. prepare 2 for one kind, 2-dimethyl-1, the method of 3-dioxolane, the method comprises: under cyclization condition, oxyethane is contacted and obtains mixture with catalyzer with acetone, from described mixture, separation obtains 2,2-dimethyl-1,3-dioxolane, is characterized in that, described catalyzer contains ionic liquid 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous.
2. method according to claim 1, wherein, the mol ratio of described ionic liquid 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous is 0.1-10:1.
3. method according to claim 2, wherein, the mol ratio of described ionic liquid 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous is 1-4:1.
4. method according to claim 1, wherein, described cyclization condition comprises: the temperature of contact is subzero 20 ℃ to 150 ℃ above freezing; Pressure is that normal pressure is to 5MPa; The mol ratio of oxyethane, acetone and Zinc Chloride Anhydrous is 1:0.1-10:0.1-1.
5. method according to claim 4, wherein, described cyclization condition comprises: the temperature of contact is 30 ℃-80 ℃; Pressure is that normal pressure is to 2MPa; The mol ratio of oxyethane, acetone and Zinc Chloride Anhydrous is 1:1-4:0.1-0.4.
6. according to the method described in any one in claim 1-5, wherein, a kind of in the straight or branched alkyl that the alkyl in described ionic liquid 1-alkyl-3-methylimidazole salt is C1-C10; Negatively charged ion is halogen ion, PF 6 -, a kind of in borate ion, tetrafluoroborate ion, sulfate ion, hydrogen sulfate ion, alkyl sulfonate ion, trifluoromethane sulfonic acid radical ion and tosic acid radical ion.
7. method according to claim 6, wherein, a kind of in the straight chained alkyl that described alkyl is C1-C10.
8. method according to claim 7, wherein, a kind of in the straight chained alkyl that described alkyl is C1-C5.
9. method according to claim 8, wherein, the positively charged ion of described ionic liquid 1-alkyl-3-methylimidazole salt is 1-butyl-3-Methylimidazole, and negatively charged ion is a kind of in bromide anion, chlorion, trifluoromethane sulfonic acid radical ion, methanesulfonate ions, tosic acid radical ion.
10. according to the method described in any one in claim 1-5, wherein, described mixture is carried out to the mixture and 2 that rectifying separation obtains mixture, ionic liquid 1-alkyl-3-methylimidazole salt and the zinc chloride of acetone and oxyethane, 2-dimethyl-1,3-dioxolane, the mixture cyclically utilizing of the acetone that separation is obtained and the mixture of oxyethane and ionic liquid 1-alkyl-3-methylimidazole salt and zinc chloride.
11. 1 kinds of methods of preparing ethylene glycol, the method comprises the following steps:
(1) prepare 2,2-dimethyl-DOX;
(2) under acidic solid catalyst exists, under hydrolysising condition, by described prepare 2,2-dimethyl-DOX contacts with water;
It is characterized in that, prepare describedly 2, the method for 2-dimethyl-DOX is the method described in any one in claim 1-10.
12. methods according to claim 11, wherein, described acidic solid catalyst is storng-acid cation exchange resin.
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