CN1132809C - Process for preparing diethyl carbonate - Google Patents
Process for preparing diethyl carbonate Download PDFInfo
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- CN1132809C CN1132809C CN 01105860 CN01105860A CN1132809C CN 1132809 C CN1132809 C CN 1132809C CN 01105860 CN01105860 CN 01105860 CN 01105860 A CN01105860 A CN 01105860A CN 1132809 C CN1132809 C CN 1132809C
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- carbonate
- diethyl carbonate
- ethanol
- methylcarbonate
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Abstract
The present invention relates to a method for preparing diethyl carbonate, which uses dimethyl carbonate and ethanol as raw materials. A complex of potassium carbonate and polyethylene glycol is used as a catalyst of reactions, has high solubility in the diethyl carbonate, can avoid generating alkali metal carbonate through reactions with a large amount of carbonate to cause the deactivation of the catalyst, and is difficult to precipitate in a reboiler to plug pipelines. The catalyst has the advantages of high activity, difficult deactivation in continuous use, high solubility in the carbonate, difficult precipitation, etc. and can be circularly used, and production cost for producing the diethyl carbonate by ester exchange methods is reduced.
Description
The present invention relates to be undertaken the method for transesterify synthesizing diethyl carbonate, relate in particular to the catalyzer that adopts in the building-up process by methylcarbonate and ethanol.
Diethyl carbonate is a kind of purposes organic compound very widely, contain alkoxyl group and carbonyl in its molecule, chemical property is active, can with reactions such as multiple alcohol, phenol, amine and ester, be a kind of solvent of excellent property and important organic synthesis intermediate, be widely used in industries such as electrolyte for Lithium Battery solvent, synthon, synthetic resins, pharmacy, also be a kind of good gasoline dope, thereby have very high industrial application value.
The traditional synthetic method of diethyl carbonate is a phosgenation, generates methyl-chloroformate by phosgene and ebullient ethanol synthesis earlier, continues to make diethyl carbonate with the dehydrated alcohol reaction again.To the back single step reaction, JP6-41019 (1994) has designed a flow process, and speed of reaction and yield all are significantly improved.The shortcoming of phosgenation is fairly obvious, its technical process complexity, and the operational cycle is long, and the toxicity of phosgene and intermediate methyl-chloroformate is big, and environmental pollution is serious, and by-product hydrochloric acid is serious to equipment corrosion.
In order to reduce the influence that phosgenation synthesizing diethyl carbonate operational path brings to environment, the Nie Zhaoguang (seeing East China University of Science's academic dissertation, 1995) of China proposes to carry out transesterification reaction with propylene carbonate and ethanol and makes diethyl carbonate.But because the equilibrium conversion (110 ℃ time be 25%) and the speed of response of reaction are all lower.Therefore, this method is also undesirable.
The catalyzer that adopts in above-mentioned transesterify process mostly is alkaline matter, can be homogeneous phase and heterogeneous.As patent US 4691041 strong alkali resin that proposes and the SiO that floods rare metal
2Deng, organic basess such as triethylamine that US 4062884 proposes and trolamine, the organophosphorus that US 4734518 proposes etc., NaOH, KOH, NaOCH that US 3803201 proposes
3, KOCH
3Derivative in basic metal, alkaline-earth metal.In these catalyzer, there is not the later separation problem in heterogeneous catalyst, but its activity is minimum; Though organic alkali catalyst has certain activity, than still low 10～100 times of mineral alkali activity.Therefore, in many cases, mineral alkali still becomes first-selected catalyzer with its high reactivity and low cost.
In Chinese patent 01105822.6, the contriver has proposed a kind of novel process of carrying out the transesterification reaction synthesizing diethyl carbonate with methylcarbonate and ethanol, in this patented technology, adopt highly basic such as alkali metal hydroxide, basic metal methylate or ethylate to make catalyzer, speed of response is very high, in actual application, find, alkali metal derivant catalyzer solubleness in diethyl carbonate is low, easily with a large amount of carbonic ethers that exist generation alkaline carbonate that reacts, cause catalyst deactivation, and in reboiler, separate out blocking pipe easily.Therefore Chinese patent 01105822.6 being further improved, is very necessary.
The objective of the invention is to disclose a kind of homogeneous complex that forms with alkaline carbonate and polyoxyethylene glycol (PEG) is the method for Preparation of catalysts diethyl carbonate, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention is such:
The present invention is a raw material with methylcarbonate and ethanol, in the presence of catalyzer, carry out transesterification reaction and obtain diethyl carbonate, the present invention with the complex compound of alkaline carbonate and polyoxyethylene glycol (PEG) as catalyst for reaction, because alkaline carbonate is a kind of weak base, polyoxyethylene glycol can form homogeneous complex with alkaline carbonate simultaneously, this complex compound solubleness in diethyl carbonate is higher, therefore, can avoid reacting with a large amount of carbonic ethers that exist, cause catalyst deactivation, and be difficult in reboiler, separating out blocking pipe.
Realize the technical scheme of the object of the invention:
The present invention is a raw material with methylcarbonate and ethanol, carries out transesterification reaction and obtain diethyl carbonate in the presence of catalyzer, and temperature of reaction is generally 25～130 ℃, and the reaction times is generally 10～120min; Be reflected under the normal pressure and carry out.
Said catalyzer is the complex compound of alkaline carbonate and polyoxyethylene glycol, and in the raw material total amount, the catalyzer add-on is 0.1%～10%, and is preferred 0.5%～5%, and wherein the mol ratio of alkaline carbonate and polyoxyethylene glycol is 0.2～5, preferred 0.5～3;
Said alkaline carbonate is one or more in yellow soda ash, salt of wormwood or the Quilonum Retard etc., preferably salt of wormwood.
After reaction finishes, adopt conventional method to separate, the alkaline carbonate and the polyoxyethylene glycol that are added are reusable, and be generally reusable more than 50 times and non-inactivation.
The homogeneous phase complex catalyst that alkaline carbonate provided by the invention and polyoxyethylene glycol (PEG) form, have advantages of high catalytic activity and speed of reaction faster, mol ratio as alkaline carbonate and polyoxyethylene glycol is 3, catalyst concn is 1% o'clock, under 60 ℃, the transformation efficiency of methylcarbonate is 91%, and the Option stage of diethyl carbonate is 50%.
By above-mentioned disclosed technical scheme as seen, compare with existing transesterification catalyst, the homogeneous phase complex catalyst that the present invention proposes has active high, the continuous use and is difficult for advantages such as inactivation can be recycled, the solubleness in carbonic ether is difficult for greatly separating out, further reduced the production cost of carbonate production by transesterification diethyl ester, improved and the perfect synthesis technique of ester-interchange method diethyl carbonate.Below will the present invention is further illustrated by embodiment.
Embodiment 1
In the 500ml jacket reactor, carry out heating in water bath with super constant temperature trough, stir with electronic stirring arm, rotating speed is enough to eliminate mass transfer and heat transmission resistance greater than 500 commentaries on classics/min.In reactor, add 130 gram ethanol, 42.3 gram methylcarbonates, 1.76 gram salt of wormwood and 4.98 gram PEG, 60 ℃ of reactions down.React after 45 minutes, solution composition is methyl alcohol 11.40% (wt%), (following not being specifically noted all refers to mass content), ethanol 59.33%, methylcarbonate 2.26%, Methyl ethyl carbonate 14.03%, diethyl carbonate 12.98%.
Embodiment 2
0.863 gram salt of wormwood, 2.49 gram PEG, other is with embodiment 1.React after 60 minutes, solution composition is methyl alcohol 8.7%, ethanol 65.01%, methylcarbonate 4.85%, Methyl ethyl carbonate 15.60%, diethyl carbonate 5.83%.
Embodiment 3
3.74 gram salt of wormwood, 10.78 gram PEG, other is with embodiment 1.React after 30 minutes, solution composition is methyl alcohol 12.82%, ethanol 58.94%, methylcarbonate 1.66%, Methyl ethyl carbonate 11.14%, diethyl carbonate 15.44%.React after 60 minutes, solution composition is methyl alcohol 13.0%, ethanol 58.65%, methylcarbonate 1.51%, Methyl ethyl carbonate 10.88%, diethyl carbonate 15.95%.
Embodiment 4
5.886 gram salt of wormwood, 17.05 gram PEG, other is with embodiment 1.React after 60 minutes, solution composition is methyl alcohol 13.24%, ethanol 57.99%, methylcarbonate 1.62%, Methyl ethyl carbonate 10.76%, diethyl carbonate 16.39%.
Embodiment 5
0.892 gram salt of wormwood, 5.164 gram PEG, other is with embodiment 1.React after 60 minutes, solution composition is methyl alcohol 8.30%, ethanol 64.06%, methylcarbonate 5.66%, Methyl ethyl carbonate 16.52%, diethyl carbonate 5.46%.
Embodiment 6
1.851 gram salt of wormwood, 10.704 gram PEG, other is with embodiment 1.React after 60 minutes, solution is methyl alcohol 11.92%, ethanol 59.37%, methylcarbonate 1.97%, Methyl ethyl carbonate 13.24%, diethyl carbonate 13.50%.
Embodiment 7
4 gram salt of wormwood, 23.12 gram PEG, other is with embodiment 1.React after 60 minutes, solution is that methyl alcohol 13.54%, ethanol are 58.70%, methylcarbonate 1.49%, Methyl ethyl carbonate 10.32%, diethyl carbonate 15.96%.
Embodiment 8
6.495 gram salt of wormwood, 37.576 gram PEG, other is with embodiment 1.React after 60 minutes, solution is 13.26%, ethanol 59.82%, methylcarbonate 132%, Methyl ethyl carbonate 9.81%, diethyl carbonate 15.77%.
Embodiment 9
13.04 gram salt of wormwood, 75.52 gram PEG, other is with embodiment 1.React after 60 minutes, solution is 13.39%, 61.51%, methylcarbonate 1.28%, Methyl ethyl carbonate 9.16%, diethyl carbonate 14.66%.
Embodiment 10
1.357 gram yellow soda ash, 2.561 gram PEG, other is with embodiment 1.React after 60 minutes, solution is methyl alcohol 10.38%, ethanol 60.49%, methylcarbonate 2.64 grams, Methyl ethyl carbonate 15.16%, diethyl carbonate 11.33%.
Embodiment 11
4.263 gram salt of wormwood, 37.095 gram PEG, other is with embodiment 1.React after 60 minutes, solution is 12.53%, ethanol 59.89%, methylcarbonate 1.45%, Methyl ethyl carbonate 10.11%, diethyl carbonate 16.0%.
Embodiment 12
Catalytic amount is with embodiment 3,75 ℃ of temperature of reaction, and other is with embodiment 1.React after 30 minutes, solution composition is methyl alcohol 11.88%, ethanol 59.88%, methylcarbonate 2.03%, Methyl ethyl carbonate 13.32%, diethyl carbonate 12.89%; React after 60 minutes methyl alcohol 12.51%, ethanol 59.15%, methylcarbonate 1.73%, Methyl ethyl carbonate 11.97%, diethyl carbonate 14.64%
Embodiment 13
28 ℃ of temperature of reaction, other is with embodiment 12.React after 30 minutes, solution composition is methyl alcohol 11.65%, ethanol 60.30%, methylcarbonate 2.18%, Methyl ethyl carbonate 13.91%, diethyl carbonate 11.95%.React after 60 minutes, solution composition is methyl alcohol 12.69%, ethanol 58.90%, methylcarbonate 1.72%, Methyl ethyl carbonate 11.58%, diethyl carbonate 15.10%.
Embodiment 14
45 ℃ of temperature of reaction, other is with embodiment 12.React after 30 minutes, solution composition is methyl alcohol 11.68%, ethanol 60.12%, methylcarbonate 2.23%, Methyl ethyl carbonate 13.93%, diethyl carbonate 12.03%.React after 60 minutes, solution composition is methyl alcohol 12.85%, ethanol 58.57%, methylcarbonate 1.63%, Methyl ethyl carbonate 11.11%, diethyl carbonate 15.82%.
Embodiment 15
From reaction product 179 grams of embodiment 1, isolate 1.74 gram salt of wormwood and 4.95 gram PEG, repeat the operating process of embodiment 1, final solution composition is methyl alcohol 11.52%, ethanol 59.20%, methylcarbonate 2.24%, Methyl ethyl carbonate 14.10%, diethyl carbonate 12.94%.
Claims (9)
1. method for preparing diethyl carbonate, comprise that with methylcarbonate and ethanol be raw material, the transesterification reaction of in the presence of catalyzer, carrying out, it is characterized in that: said catalyzer is the complex compound of alkaline carbonate and polyoxyethylene glycol, and the mol ratio of alkaline carbonate and polyoxyethylene glycol is 0.2～5.
2. the method for claim 1, it is characterized in that: the mol ratio of alkaline carbonate and polyoxyethylene glycol is 0.5～3.
3. method as claimed in claim 1 or 2 is characterized in that: in the raw material total amount, the catalyzer add-on is 0.1%～10%.
4. method as claimed in claim 3 is characterized in that: in the raw material total amount, the catalyzer add-on is 0.5%～5%.
5. method as claimed in claim 1 or 2 is characterized in that: alkaline carbonate is a salt of wormwood.
6. method as claimed in claim 4 is characterized in that: alkaline carbonate is a salt of wormwood.
7. method as claimed in claim 3 is characterized in that: alkaline carbonate is a salt of wormwood.
8. the method for claim 1, it is characterized in that: temperature of reaction is 25～130 ℃, and the reaction times is 10～120min, is reflected under the normal pressure and carries out.
9. method as claimed in claim 3 is characterized in that: temperature of reaction is 25～130 ℃, and the reaction times is 10～120min, is reflected under the normal pressure and carries out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01105860 CN1132809C (en) | 2001-04-05 | 2001-04-05 | Process for preparing diethyl carbonate |
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|---|---|---|---|
| CN 01105860 CN1132809C (en) | 2001-04-05 | 2001-04-05 | Process for preparing diethyl carbonate |
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| CN1314338A CN1314338A (en) | 2001-09-26 |
| CN1132809C true CN1132809C (en) | 2003-12-31 |
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| CN 01105860 Expired - Fee Related CN1132809C (en) | 2001-04-05 | 2001-04-05 | Process for preparing diethyl carbonate |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387338C (en) * | 2002-10-11 | 2008-05-14 | 中国科学院成都有机化学研究所 | Ester exchange catalyst and its use |
| CN100435951C (en) * | 2003-09-17 | 2008-11-26 | 中国科学院成都有机化学有限公司 | Preparing methyl ethyl carbonate catalyst by ester exchange |
| CN102850223B (en) * | 2012-09-18 | 2014-10-29 | 常州大学 | Method for synthesizing methylethyl carbonate |
| CN105817266A (en) * | 2016-04-27 | 2016-08-03 | 屈强好 | Catalyst for producing ethyl methyl carbonate and coproducing diethyl carbonate with transesterification method |
| CN113457735A (en) * | 2021-07-22 | 2021-10-01 | 沈阳化工大学 | Preparation of strong alkaline homogeneous phase dihydric alcohol metal salt catalyst and method for synthesizing carbonic ester by using same |
| CN113354540A (en) * | 2021-07-26 | 2021-09-07 | 华东理工大学 | Method for efficiently and continuously preparing methyl ethyl carbonate |
| CN114292182A (en) * | 2021-12-14 | 2022-04-08 | 沈阳化工大学 | Method for synthesizing efficient catalyst from alkyl oxalate |
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