CN101468941A - Preparation of dialkyl ether - Google Patents
Preparation of dialkyl ether Download PDFInfo
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- CN101468941A CN101468941A CN 200710308599 CN200710308599A CN101468941A CN 101468941 A CN101468941 A CN 101468941A CN 200710308599 CN200710308599 CN 200710308599 CN 200710308599 A CN200710308599 A CN 200710308599A CN 101468941 A CN101468941 A CN 101468941A
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- butyl ether
- tertiary butyl
- ionic liquid
- methyl tertiary
- methyl
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Abstract
The invention discloses a method for preparing dialkyl ether. The method comprises the steps of taking acid-functionalized ionic liquid as a catalyst, taking tert butyl alcohol and methanol as reactants and performing dehydration reaction at a temperature between 20 and 200 DEG C in order to prepare the dialkyl ether. The method has the main advantages of high reaction activity, convenient operation and easiness of separating products and recovering the catalyst, and the ionic liquid catalyst is simple in composition and good in reusability.
Description
Technical field
The present invention relates to a kind of preparation method of dialkyl ether.
Background technology
Oil, coal, Sweet natural gas are the world's three big pillar energy.Along with developing rapidly of world car industry, the consumption of gasoline/diesel oil constantly increases, and the problem of environmental pollution that the oil product burning causes is also serious day by day.Conventional gasoline additive lead alkylide toxicity is big, the ejecta serious environment pollution.Along with the continuous enhancing of people's environmental consciousness and the increasingly stringent of environmental requirement, the raising of quality of gasoline is all attached great importance in countries in the world.Western developed country just comes into effect the unleaded gasoline scheme from the eighties in 20th century, most countries all bans use of leaded up gasoline at present, China is implementing also to have carried out unremitting effort aspect the unleaded gasoline, issued in September, 1998 " stopping the notice of the automobile-used doped fuel of production and sales about time limit ", require from July 1st, 2000 the start-stop shotpin sell and use doped fuel.In order to guarantee the smooth implementation of these policies, domestic vast researcher has been developed a series of stop bracket gasoline additives through secular effort, the clean gasoline of China is enhanced and develops.
Methyl tertiary butyl ether (MTBE), tert amyl methyl ether(TAME) (TAME), Di Iso Propyl Ether (DIPE), Ethyl Tertisry Butyl Ether ether compounds such as (ETBE) have the octane value height, and be good with the gasoline mutual solubility, low toxin and enjoy favor.Especially methyl tertiary butyl ether, having that boiling point is low, oxygen level is high, be in harmonious proportion the high performance that obviously is better than other ethers of octane value, be called third generation petroleum chemicals abroad, is recent two decades sales volume maximum, chemical with fastest developing speed is used for gasoline dope in a large number.The gasoline that contains 10% methyl tertiary butyl ether can make fuel descend 6.8%, and production cost saves about 21%, and can reduce the quantity discharged of automobile exhaust pollution thing.Since first 10 tons of/year MTBE device of Italy in 1973 were constructed and put into operation, countries in the world MTBE development rapidly.2005, the ultimate production of world's methyl tertiary butyl ether was 2,500 ten thousand tons, and the U.S. is the main consumption area in the whole world, accounts for 56% of the whole world, and Europe accounts for 18%, and South America accounts for 7%, and the Middle East accounts for 6%, and other area, Asia accounts for 13%.China from nineteen eighty-three Qilu Petrochemical build up 5500 tons of/year methyl tertbutyl ether production equipments of first cover and play the present whole nation nearly 40 cover production equipments are arranged, and annual production only is about 1,600,000 tons.3,800 ten thousand tons/year of China's year petrol consumptions calculate with mediation amount 10%, need 3,800,000 tons of methyl tertiary butyl ethers every year, the space of developing on a large scale very much in addition therebetween.Particularly along with the fast development of automotive industry in recent years, do not searching out more under the ideal gasoline dope situation, the demand of methyl tertiary butyl ether will improve constantly.
The production technique of synthesize methyl tert-butyl ether mainly is an etherification technology at present, is raw material with iso-butylene in methyl alcohol and the hybrid C 4 promptly, in the presence of strong-acid ion exchange resin, and the catalytic synthesis of methyl tertbutyl ether, this reaction is a reversible thermopositive reaction.According to the concrete grammar difference of building-up reactions, mainly contain fixed bed reaction technology, expanded bed reaction technology, catalytic distillation reaction technology, expanded bed-catalytic distillation reaction technology, mixed phase reaction technology etc.In all etherificate technology, owing to employed catalyzer poor heat stability, short, easy inactivation of life-span in the reaction, this has seriously limited the large-scale production of methyl tertiary butyl ether.
Therefore, on existing etherificate synthesis technique basis, the dewatering agent of catalyst for etherification that preparation high reactivity, catalytic performance is stable or exploitation highly selective is two Basic Ways that solve current methyl tertiary butyl ether composition problem by the synthetic dialkyl ether of dehydration of alcohols method.And the trimethyl carbinol and methyl alcohol are through the method for intermolecular dehydration synthesize methyl tert-butyl ether; it is 120 ℃ generally in temperature; pressure is under the 2.29MPa; under many metals remodeling zeolite catalysts catalysis of IB, IIB, IVB, VIIB, VIII bunch, carry out; corresponding trimethyl carbinol transformation efficiency has only 68%; MTBE selectivity 74%, this can not be used for extensive chemical industry production far away, and the synthetic of highly selective dewatering agent is the industrialized key of this technology success.
Task-specific ionic liquid (RTILs) be a kind of process to constitute ion liquid positively charged ion carry out functional modification or introduce the functionalization negatively charged ion, in room temperature or be bordering on the molten salt system that is in a liquid state under the room temperature, have the incomparable special performance of a lot of molecular solvent.Along with the widespread use of ionic liquid in every field such as Green Chemistry and chemical industry, compartment analysis, life science, Materials science, design synthetic " demand is specific " (task-specific) or " cutting the garment according to the figure " task-specific ionic liquid (tailor-making) can be satisfied differential responses condition and special reaction environment requirement.
The sulfonate functional ionic liquid at room temperature is a kind of ionic liquid with dehydration, is widely used in esterification, olefin oligomerization, carboxylamine ester synthesis reaction of acid catalyzed reaction, lipid acid etc.And because ionic liquid has non-volatility and selective dissolution power, after reaction finished, product and ionic liquid lock out operation were simple, are easy to suitability for industrialized production.
Summary of the invention
The objective of the invention is to overcome problems such as catalyzer poor heat stability in the present etherification technology synthesize methyl tert-butyl ether method, short, easy inactivation of life-span, adopt the trimethyl carbinol and methyl alcohol to prepare the method for corresponding dialkyl ether through the ionic liquid-catalyzed dehydration reaction of acid functionalization.
A kind of preparation method of dialkyl ether is characterized in that with the acid functionalization ionic liquid be catalyzer, is reactant with the trimethyl carbinol and methyl alcohol, carries out dehydration reaction and prepare dialkyl ether under 20-200 ℃ of condition; The ion liquid positively charged ion of described acid functionalization is:
In a kind of, wherein m is the integer between 0 to 8, comprises 0 and 8, n is 0 to 10 integer, comprises 0 and 10; The ion liquid anion structure formula of described acid functionalization is: BF
4 -, PF
6 -, CF
3SO
3 -, SO
3 -, Cl
-And Br
-In a kind of.
The used ionic liquid of the present invention plays double-deck effect, and it is a catalyzer, also is reaction medium.
The ionic-liquid catalyst that the present invention is used, its preparation method and character can be referring to Deng Youquan. ionic liquid-character, preparation and application [M]. and Sinopec press, 2006,7.
Used ionic liquid among the present invention, its concrete synthetic method is according to reference (a.Y L Gu, Pechmannreaction in nonchloroaluminate Acidic Ionic Liquids under Solvent-free Conditions.Advanced Synthesis ﹠amp; Catalysis., 2005.b.C C Amanda, Novel
Acidicionic liquids and their use as dual solvents-catalysts.J.Am.Chem.Soc., 2002. and c.DC Forbes,
Acidic ionic liquids:the dependence on water of the Fischeresterification of acetic acid and ethanol.J.Mol.Catal.A:Chem., 2004 etc.) method is synthetic in.
Reaction times of the present invention can be controlled at 0.5-24 hour.
Reaction pressure of the present invention can normal pressure also can add to depress and carry out.
The mol ratio of the trimethyl carbinol of the present invention and methyl alcohol is 1:1-1:10.
The mol ratio of the catalyzer of the present invention and the trimethyl carbinol is 1:1000-1:1.
The present invention and traditional catalyst and reaction process relatively have the following advantages:
1. catalyst system is simple, and deionization liquid does not add other solvent and catalyzer outward;
2. product separation is simple, purity is high;
3. ionic liquid can recycle, and belongs to eco-friendly production process;
4. it is simple to react required condition, is easy to suitability for industrialized production;
5. the reaction times weak point is reflected under the normal pressure and carries out operational safety.
Embodiment
Embodiment 1-6.
In 500 milliliters high-pressure reactor, add trimethyl carbinol 80ml, methyl alcohol 320ml, 1-fourth sulfonic group-3-Methylimidazole fluoroform sulphonate ionic liquid 8ml, sealing.Under agitation be warming up to 110 ℃.React 10 hours postcooling to room temperature, fractionation by distillation goes out upper strata methyl tertiary butyl ether and excessive methanol.The methyl tertiary butyl ether and the carbinol mixture that obtain are gone out methyl tertiary butyl ether through rectifying separation, and the methyl tertiary butyl ether purity that obtains is 99.5%, yield 93%.Reaction finishes isolated ionic liquid 1-fourth sulfonic group-3-Methylimidazole fluoroform sulphonate and reuse (embodiment 2-6) behind the suction filtration 1h under 110 ℃, 8mmHg vacuum tightness.
Table 1.1-fourth sulfonic group-ionic liquid-catalyzed trimethyl carbinol of 3-Methylimidazole fluoroform sulphonate and methyl alcohol reaction system methyl tertiary butyl ether
Embodiment 7-12.
In 500 milliliters high-pressure reactor, add trimethyl carbinol 80ml, methyl alcohol 320ml, 1-fourth sulfonic group-3-methyl imidazolium tetrafluoroborate ionic liquid 8ml, sealing.Under agitation be warming up to 110 ℃.React 10 hours postcooling to room temperature, fractionation by distillation goes out upper strata methyl tertiary butyl ether and excessive methanol.The methyl tertiary butyl ether and the carbinol mixture that obtain are gone out methyl tertiary butyl ether through rectifying separation, and obtaining methyl tertiary butyl ether purity is 99.6%, yield 88%.Reaction finishes isolated ionic liquid 1-fourth sulfonic group-3-methyl imidazolium tetrafluoroborate and reuse (embodiment 8-12) behind the suction filtration 1h under 110 ℃, 8mmHg vacuum tightness.
Table 2.1-fourth sulfonic group-ionic liquid-catalyzed trimethyl carbinol of 3-methyl imidazolium tetrafluoroborate and methyl alcohol reaction system methyl tertiary butyl ether
Embodiment 13
In 500 milliliters high-pressure reactor, add trimethyl carbinol 80ml, methyl alcohol 320ml, 1-decyl-3-methyl imidazolium tetrafluoroborate ionic liquid 8ml, sealing.Under agitation be warming up to 110 ℃.React 10 hours postcooling to room temperature, fractionation by distillation goes out upper strata methyl tertiary butyl ether and excessive methanol.The methyl tertiary butyl ether and the carbinol mixture that obtain are gone out methyl tertiary butyl ether through rectifying separation, and obtaining methyl tertiary butyl ether purity is 99.8%, yield 55%.
Embodiment 14
In 500 milliliters high-pressure reactor, add trimethyl carbinol 80ml, methyl alcohol 320ml, chlorination-1-butyl-3-methylimidazole salt ionic liquid 8g, sealing.Under agitation be warming up to 110 ℃.React 10 hours postcooling to room temperature, fractionation by distillation goes out upper strata methyl tertiary butyl ether and excessive methanol.The methyl tertiary butyl ether and the carbinol mixture that obtain are gone out methyl tertiary butyl ether through rectifying separation, and obtaining methyl tertiary butyl ether purity is 99.8%, yield 26%.
Embodiment 15
In 500 milliliters high-pressure reactor, add trimethyl carbinol 80ml, methyl alcohol 320ml, hexanolactam tetrafluoroborate ion liquid 8ml, sealing.Under agitation be warming up to 110 ℃.React 10 hours postcooling to room temperature, fractionation by distillation goes out upper strata methyl tertiary butyl ether and excessive methanol.The methyl tertiary butyl ether and the carbinol mixture that obtain are gone out methyl tertiary butyl ether through rectifying separation, and obtaining methyl tertiary butyl ether purity is 99%, yield 56%.
Embodiment 16
In 500 milliliters high-pressure reactor, add trimethyl carbinol 80ml, methyl alcohol 320ml, chlorination-1-acetoxyl-3-methylimidazole salt ionic liquid 8ml, sealing.Under agitation be warming up to 110 ℃.React 10 hours postcooling to room temperature, fractionation by distillation goes out upper strata methyl tertiary butyl ether and excessive methanol.The methyl tertiary butyl ether and the carbinol mixture that obtain are gone out methyl tertiary butyl ether through rectifying separation, and obtaining methyl tertiary butyl ether purity is 99%, yield 58%.
Embodiment 17
In 500 milliliters high-pressure reactor, add trimethyl carbinol 80ml, ethanol 320ml, 1-fourth sulfonic group-3-Methylimidazole fluoroform sulphonate ionic liquid 8ml, sealing.Under agitation be warming up to 110 ℃.React 10 hours postcooling to room temperature, fractionation by distillation goes out upper strata Ethyl Tertisry Butyl Ether and excess ethyl alcohol.The Ethyl Tertisry Butyl Ether and the alcohol mixture that obtain are gone out Ethyl Tertisry Butyl Ether through rectifying separation, and obtaining Ethyl Tertisry Butyl Ether purity is 99.1%, yield 82%.
Embodiment 18
In 500 milliliters high-pressure reactor, add trimethyl carbinol 80ml, methyl alcohol 320ml, 1-fourth sulfonic group-3-Methylimidazole fluoroform sulphonate ionic liquid 8ml, sealing charges into N in reactor
2, make P
N2=10atm.Under agitation be warming up to 110 ℃.React 10 hours postcooling to room temperature, fractionation by distillation goes out upper strata methyl tertiary butyl ether and excessive methanol.The methyl tertiary butyl ether and the carbinol mixture that obtain are gone out methyl tertiary butyl ether through rectifying separation, and obtaining methyl tertiary butyl ether purity is 99.6%, yield 95.7%.
Claims (3)
1, a kind of preparation method of dialkyl ether is characterized in that with the acid functionalization ionic liquid be catalyzer, is reactant with the trimethyl carbinol and methyl alcohol, carries out dehydration reaction and prepare dialkyl ether under 20-200 ℃ of condition; The ion liquid positively charged ion of described acid functionalization is:
In a kind of, wherein m is the integer between 0 to 8, comprises 0 and 8, n is 0 to 10 integer, comprises 0 and 10; The ion liquid anion structure formula of described acid functionalization is: BF
4 -, PF
6 -, CF
3SO
3 -, SOX
-, Cl
-And Br
-In a kind of.
2, the method for claim 1, the mol ratio that it is characterized in that the trimethyl carbinol and methyl alcohol is 1:1-1:10.
3, the method for claim 1, the mol ratio that it is characterized in that the catalyzer and the trimethyl carbinol is 1:1000-1:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408316A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Method for preparing tertiary amyl methyl ether |
| CN109721584A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A method of preparing 1,4- dioxane |
| CN114437000A (en) * | 2020-11-05 | 2022-05-06 | 中国科学院化学研究所 | Method for preparing cyclic ether by dehydrating and cyclizing diol |
| CN114436786A (en) * | 2020-11-05 | 2022-05-06 | 中国科学院化学研究所 | Method for preparing ether compound by dehydration of monohydric alcohol |
-
2007
- 2007-12-28 CN CN 200710308599 patent/CN101468941A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408316A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Method for preparing tertiary amyl methyl ether |
| CN102408316B (en) * | 2010-09-21 | 2014-08-06 | 中国石油天然气股份有限公司 | Method for preparing tertiary amyl methyl ether |
| CN109721584A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A method of preparing 1,4- dioxane |
| CN109721584B (en) * | 2017-10-30 | 2020-07-28 | 中国石油化工股份有限公司 | Method for preparing 1, 4-dioxane |
| CN114437000A (en) * | 2020-11-05 | 2022-05-06 | 中国科学院化学研究所 | Method for preparing cyclic ether by dehydrating and cyclizing diol |
| CN114436786A (en) * | 2020-11-05 | 2022-05-06 | 中国科学院化学研究所 | Method for preparing ether compound by dehydration of monohydric alcohol |
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Open date: 20090701 |