CN1150158C - Process for continuously preparing diethyl carbonate - Google Patents
Process for continuously preparing diethyl carbonate Download PDFInfo
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- CN1150158C CN1150158C CNB011058226A CN01105822A CN1150158C CN 1150158 C CN1150158 C CN 1150158C CN B011058226 A CNB011058226 A CN B011058226A CN 01105822 A CN01105822 A CN 01105822A CN 1150158 C CN1150158 C CN 1150158C
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Abstract
The present invention relates to a method for continuously preparing diethyl carbonate, which uses dimethyl carbonate and ethanol as raw materials. The diethyl carbonate is prepared through reactive distillation under the existence of catalysts, and the separated ethanol and catalysts can be circularly used after the ethanol, the diethyl carbonate and the catalysts are separated in a tower kettle. The concentration of the obtained diethyl carbonate can achieve more than 99.5%(wt), and the ethanol can be circularly used back to a reactive distillation tower after methanol and ethanol at the top of the tower are separated. The diethyl carbonate can be continuously and efficiently prepared according to the method of the present invention, which undoubtedly brings good development prospects and great economic benefit for diethyl carbonate industry.
Description
The present invention relates to the production method of diethyl carbonate, more particularly, relate to a kind of method of continuous manufacturing diethyl carbonate.
Diethyl carbonate is a kind of solvent of excellent property and important organic synthesis intermediate, is widely used in industries such as electrolyte for Lithium Battery solvent, synthon, synthetic resins, pharmacy, also is a kind of good gasoline dope.
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, Japanese Patent 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.
For this reason, U.S. Pat 5534649 (1996) discloses the method that a kind of non-phosgene prepares diethyl carbonate, adopts urea, Urethylane or urethanum and ethanol to react the manufacturing diethyl carbonate under catalyst action.But have ammonia to discharge in this method product, the yield of long reaction time, diethyl carbonate is low simultaneously, so less economical.
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, the catalyzer of Cai Yonging solubleness in diethyl carbonate is low simultaneously, separates out blocking pipe in reboiler easily.Therefore, this method is also undesirable.
In sum, up to the present, both safe, environmentally friendly, economical and practical again when also not having a kind of technology to produce diethyl carbonate.
The objective of the invention is to propose a kind of production process safety, environmentally friendly, can obtain high yield again simultaneously, can carry out the method that quantity-produced prepares diethyl carbonate with stable manner.
Realize the technical scheme of the object of the invention:
The present invention is a raw material with methylcarbonate and ethanol, in the presence of catalyzer, prepares diethyl carbonate by transesterification reaction, and methylcarbonate and alcoholic acid reaction can be represented by the formula:
This reaction is carried out in fact in two steps:
Promptly under catalyst action, ethanol at first generates intermediate Methyl ethyl carbonate and methyl alcohol with dimethyl carbonate, and Methyl ethyl carbonate and ethanol continue reaction generation diethyl carbonate and methyl alcohol then.Reaction (II) is a fast response, and reaction (III) is a long response time, and the speed of entire reaction is determined by (III).
Owing to be reversible reaction, for breaking molecular balance, reaction is carried out to the direction that helps generating product, the methylcarbonate total overall reaction is fallen, the present invention imports a reaction fractionating tower continuously with ethanol and methylcarbonate and catalyzer, reaction is carried out in conversion zone with separating all, the reaction product generation promptly is removed the time, thereby can realize the continuous production of diethyl carbonate.
Ethanol, diethyl carbonate and mixture of catalysts in the reactive distillation Tata still then can adopt conventional method to separate, and isolated ethanol and catalyzer can recycle, and the concentration of the diethyl carbonate that is obtained can reach more than 99.5% (wt).
Can preferentially adopt following method that the ethanol in the tower still, diethyl carbonate and mixture of catalysts are separated: earlier said mixture to be evaporated in vaporizer, with most ethanol, diethyl carbonate vaporization, in rectifying tower ethanol, diethyl carbonate are separated then, residual catalyzer and a spot of ethanol and small amount of carbon diethyl phthalate then can be sent reaction fractionating tower back to and recycled in the vaporizer.
Further, reactive distillation column overhead methyl alcohol also can adopt conventional method to separate with the alcoholic acid mixture, separate the concentration that is obtained and can be used as by product greater than the above methyl alcohol of 99.5% (wt), the above ethanol of concentration＞99.5% (wt) then can be got back to reaction fractionating tower and recycle.Below will give a detailed account to the present invention by accompanying drawing.
Fig. 1 is a schema of the present invention.
As seen from Figure 1, the present invention adopts methylcarbonate and ethanol to carry out transesterification reaction and makes diethyl carbonate, comprises that reactive distillation, methyl alcohol separation, catalyst recovery separate four technological processs with diethyl carbonate:
(1). enter reaction fractionating tower 1 from the top of the conversion zone 102 of reaction fractionating tower 1 from storage tank after metering with the catalyzer of the catalyzer of ethanol preparation and recycling use, enter the reaction fractionating tower 1 from the mixture of the ethanol of the ethanol of storage tank and reuse and methylcarbonate middle part from conversion zone 102.Ethanol carries out transesterification reaction and separates under the effect of catalyzer with methylcarbonate, reaction product methyl alcohol and alcoholic acid mixing steam are up, after removing the diethyl carbonate of wherein carrying secretly through rectifying section 103, discharge by outlet 104, after condenser 105 condensations, according to the required reflux ratio of tower operation, a part is returned reaction fractionating tower 1, another part then enters in the methyl alcohol knockout tower 2: reaction product diethyl carbonate, ethanol and catalyzer etc. then are advanced in the tower still down, and, enter follow-up workshop section by outside the pump 5 discharge towers;
Said reaction fractionating tower 1 is conventional tray column or packing tower, comprises sieve-tray tower, valve tray column, bubble-plate column, New VST etc.
Said catalyzer is a kind of in alkaline carbonate, KOH, NaOH or the sodium methylate;
Preferred catalyzer is a salt of wormwood.
The theoretical plate number of reaction fractionating tower 1 is 20～60, and working pressure is 90～110Kpa, should operate under normal pressure, and the raw materials components mole ratio of ethanol/methylcarbonate can be selected in 2～8 scopes, and reflux ratio can be selected in 0.5～10 scope;
(2). the material from reaction fractionating tower 1 tower still enters in the vaporizer 3, the ethanol and the diethyl carbonate of the overwhelming majority are vaporized, be sent to follow-up workshop section, a spot of ethanol, diethyl carbonate and catalyzer enter the bottom of vaporizer 3, are returned in the reaction fractionating tower 1 by catalyst recirculation pump 6 to recycle;
(3). come the ethanol of flash-pot 3 and the middle part that diethyl carbonate steam enters diethyl carbonate knockout tower 4, through separating, can obtain purity greater than 99.5% ethanol at cat head, return in the reaction fractionating tower 1 and recycle, the tower still can obtain purity greater than 99.5% diethyl carbonate product;
20～50 of stage number, trim the top of column should be operated under normal pressure than 0.5～5.
(4). methyl alcohol and alcohol mixture from reaction fractionating tower 1 cat head enter methyl alcohol knockout tower 2, in methyl alcohol knockout tower 2, cat head can obtain purity can be greater than the methyl alcohol of 99.5% (wt), the tower still can obtain purity can be greater than the ethanol of 99.5% (wt), and can return in the reaction fractionating tower 1 by ethanol pump 7 and recycle.
30～80 of stage number, trim the top of column are than 2～8, and working pressure 101kPa～120kPa should operate under normal pressure.
By above-mentioned disclosed technical scheme as seen, can produce diethyl carbonate according to method of the present invention, this brings bright development prospect and huge economic benefit for the industry of diethyl carbonate undoubtedly continuous high-efficient.
Embodiment 1
Mainly contain in the process unit that reaction fractionating tower, methyl alcohol knockout tower, vaporizer and diethyl carbonate knockout tower formed one, material carbon dimethyl phthalate and ethanol are produced diethyl carbonate under the effect of catalyzer sodium methylate.
Reaction fractionating tower is a diameter 500mm, the tray column of high 16000mm, in establish 30 of column plates; The methyl alcohol knockout tower is a diameter 400mm, the packing tower of high 12000mm, and interior dress structured packing, number of theoretical plate is 70; The diethyl carbonate knockout tower is the packing tower of a diameter 400mm, high 8000mm, interior dress structured packing, and number of theoretical plate is 50.
Reaction fractionating tower operation operating mode:
Feed ethanol enters the bottom of reaction fractionating tower with the speed of 48.8kg/h with 149.7kg/h, methylcarbonate, catalyzer sodium methylate (being dissolved in the ethanol in advance) enters with the speed of the 1.98kg/h top from tower, provides reactive distillation processes required whole energy by tower still reheater by outer heat.The trim the top of column ratio is 5,100～105 ℃ of tower still temperature, 72～75 ℃ of tower top temperatures.The cat head load is 134.6kg/h, consists of methyl alcohol 17.5% (wt), ethanol 82.5% (wt), enters the methyl alcohol knockout tower.Tower still load is 68.66kg/h, and ethanol content is that 6.79% (wt), diethyl carbonate are 93.13%, and all the other are for Methyl ethyl carbonate is 0.055%, methyl alcohol 0.025%.In reaction fractionating tower, the transformation efficiency of material carbon dimethyl phthalate is 100%, and the selectivity of diethyl carbonate is 99.96%, yield is 99.96%.Tower still feed liquid is after vaporizer reclaims catalyzer, and steam enters in the diethyl carbonate knockout tower.
Methyl alcohol knockout tower operation operating mode:
Enter the bottom of methyl alcohol knockout tower with the speed of 134.6kg/h from the feed liquid of reactive distillation column overhead, provide sepn process required energy by tower still reheater, the trim the top of column ratio is 6,64～66 ℃ of tower top temperatures, 78～85 ℃ of tower still temperature, working pressure are normal pressure.Cat head can obtain the above methyl alcohol 23.6kg/h of purity 99.7% (wt), can be used as the commercially available prod; The tower still can obtain the above ethanol of purity 99.8% (wt), returns reaction fractionating tower and uses.
Diethyl carbonate knockout tower operation operating mode:
Come the mixing steam of the ethanol of flash-pot and diethyl carbonate to enter the middle part of diethyl carbonate knockout tower, provide sepn process required energy by tower still reheater, the trim the top of column ratio is 2,78～80 ℃ of tower top temperatures, 126～130 ℃ of tower still temperature, working pressure are normal pressure.Cat head can obtain the ethanol 4.7kg/h of purity more than 99.6%, returns reaction fractionating tower; The tower still can obtain the above diethyl carbonate 63.9kg/h of purity 99.7% (wt).
Embodiment 2
Mainly contain in the process unit that reaction fractionating tower, methyl alcohol knockout tower, vaporizer and diethyl carbonate knockout tower formed one, material carbon dimethyl phthalate and ethanol are produced diethyl carbonate under the effect of catalyzer KOH.
Reaction fractionating tower is a diameter 500mm, the tray column of high 12000mm, in establish 20 of column plates; Methyl alcohol knockout tower, vaporizer and diethyl carbonate knockout tower are with embodiment 1.
Reaction fractionating tower operation operating mode:
Catalyzer is KOH (being dissolved in the ethanol in advance), and raw material and catalyst charge amount are with embodiment 1, from the tower underfeed.The trim the top of column ratio is 5,101～104 ℃ of tower still temperature, 72～75 ℃ of tower top temperatures.The cat head load is 134.6kg/h, consists of methyl alcohol 17.38% (wt), ethanol 82.62% (wt), enters the methyl alcohol knockout tower.Tower still load is 68.66kg/h, and wherein ethanol content is that 6.88% (wt), diethyl carbonate are 91.61%, and all the other are for Methyl ethyl carbonate is 1.19%, methyl alcohol 0.32%.In reaction fractionating tower, the transformation efficiency of material carbon dimethyl phthalate is 100%, and the selectivity of diethyl carbonate is 98.55%, yield is 98.55%.Tower still feed liquid is after vaporizer reclaims catalyzer, and steam enters in the diethyl carbonate knockout tower.
Methyl alcohol knockout tower operation operating mode:
Enter the bottom of methyl alcohol knockout tower with the speed of 134.6kg/h from the feed liquid of reactive distillation column overhead, provide sepn process required energy by tower still reheater, the trim the top of column ratio is 6,64～66 ℃ of tower top temperatures, 78～85 ℃ of tower still temperature, working pressure are normal pressure.Cat head can obtain the above methyl alcohol 23.6kg/h of purity 99.6% (wt), can be used as the commercially available prod; The tower still can obtain the above ethanol 111kg/h of purity 99.8% (wt), returns reaction fractionating tower and uses.
Diethyl carbonate knockout tower operation operating mode:
Come the mixing steam of the ethanol of flash-pot and diethyl carbonate to enter the middle part of diethyl carbonate knockout tower, provide sepn process required energy by tower still reheater, the trim the top of column ratio is 2,78～80 ℃ of tower top temperatures, 126～130 ℃ of tower still temperature, working pressure are normal pressure.Cat head can obtain the ethanol 4.72kg/h of purity more than 99.5%, returns reaction fractionating tower; The tower still can obtain the above diethyl carbonate 63.94kg/h of purity 99.5% (wt).
Embodiment 3
Mainly contain in the process unit that reaction fractionating tower, methyl alcohol knockout tower, vaporizer and diethyl carbonate knockout tower formed one, material carbon dimethyl phthalate and ethanol are produced diethyl carbonate under the effect of catalyzer carbonic acid potassium.
Said reaction fractionating tower is a diameter 500mm, the packing tower of high 10000mm, interior dress structured packing 7m, 50 of number of theoretical plates; Methyl alcohol knockout tower, vaporizer and diethyl carbonate knockout tower are with embodiment 1.
Reaction fractionating tower operation operating mode
Catalyzer is salt of wormwood (being dissolved in the ethanol in advance), and raw material and catalyst charge amount are with embodiment 1, from the tower underfeed.The trim the top of column ratio is 3,102～107 ℃ of tower still temperature, 72～75 ℃ of tower top temperatures.The cat head load is 134.6kg/h, consists of methyl alcohol 17.56% (wt), ethanol 82.44% (wt), enters the methyl alcohol knockout tower.Tower still load is 68.66kg/h, and wherein ethanol content is that 6.85% (wt), diethyl carbonate are 93.15%.In reaction fractionating tower, the transformation efficiency of material carbon dimethyl phthalate is 100%, and the selectivity of diethyl carbonate is 100%, yield is 100%.Tower still feed liquid is after vaporizer reclaims catalyzer, and steam enters in the diethyl carbonate knockout tower.
Methyl alcohol knockout tower operation operating mode:
Enter the bottom of methyl alcohol knockout tower with the speed of 134.6kg/h from the feed liquid of reactive distillation column overhead, provide sepn process required energy by tower still reheater, the trim the top of column ratio is 5,64～66 ℃ of tower top temperatures, 78～85 ℃ of tower still temperature, working pressure are normal pressure.Cat head can obtain the above methyl alcohol 23.6kg/h of purity 99.7% (wt), can be used as the commercially available prod; The tower still can obtain the above ethanol 111kg/h of purity 99.8% (wt), returns reaction fractionating tower and uses.
Diethyl carbonate knockout tower operation operating mode:
Come the mixing steam of the ethanol of flash-pot and diethyl carbonate to enter the middle part of diethyl carbonate knockout tower, provide sepn process required energy by tower still reheater, the trim the top of column ratio is 2,78～80 ℃ of tower top temperatures, 126～130 ℃ of tower still temperature, working pressure are normal pressure.Cat head can obtain the ethanol 4.71kg/h of purity more than 99.8%, returns reaction fractionating tower; The tower still can obtain the above diethyl carbonate 63.95kg/h of purity 99.8% (wt).
Embodiment 4
Mainly contain in the process unit that reaction fractionating tower, methyl alcohol knockout tower, vaporizer and diethyl carbonate knockout tower formed one, material carbon dimethyl phthalate and ethanol are produced diethyl carbonate under the effect of catalyst n aOH.
Said reaction fractionating tower is a diameter 500mm, the tray column of high 25mm, in establish 50 of column plates; Methyl alcohol knockout tower, vaporizer and diethyl carbonate knockout tower are with embodiment 1.
Reaction fractionating tower operation operating mode:
Feed ethanol enters the bottom of reaction fractionating tower with the speed of 68.34kg/h with 139.7kg/h, methylcarbonate, catalyst n aOH (being dissolved in the ethanol in advance) enters with the speed of the 4.16kg/h top from tower, provides reactive distillation processes required whole energy by tower still reheater by outer heat.The trim the top of column ratio is 5,125～135 ℃ of tower still temperature, 71～75 ℃ of tower top temperatures.The cat head load is 138.72kg/h, consists of methyl alcohol 21.92% (wt), ethanol 68.56% (wt), and all the other are Methyl ethyl carbonate 4.67%, diethyl carbonate 1.12%, and methylcarbonate 3.73% enters the methyl alcohol knockout tower.Tower still load is 73.48kg/h, and wherein diethyl carbonate content is 99.99%.In reaction fractionating tower, the transformation efficiency of material carbon dimethyl phthalate is 92.46%, and the selectivity of diethyl carbonate is 92.86%, yield is 85.86%.Tower still feed liquid is after vaporizer reclaims catalyzer, and steam enters in the diethyl carbonate knockout tower.
Methyl alcohol knockout tower operation operating mode:
Enter the bottom of methyl alcohol knockout tower with the speed of 138.72kg/h from the feed liquid of reactive distillation column overhead, provide sepn process required energy by tower still reheater, the trim the top of column ratio is 5,64～68 ℃ of tower top temperatures, 78～85 ℃ of tower still temperature, working pressure are normal pressure.Cat head can obtain the methyl alcohol 35.58kg/h of purity 85.4% (wt), and all the other are methylcarbonate 14.6%; Tower still discharging 103.14kg/h, wherein ethanol content is 92.2% (wt), and the methyl ethyl carbonate ester content is 6.3%, and diethyl carbonate content is 1.5%, returns reaction fractionating tower and uses.
Diethyl carbonate knockout tower operation operating mode:
Come the diethyl carbonate steam of flash-pot to enter the middle part of diethyl carbonate knockout tower, provide sepn process required energy by tower still reheater, the trim the top of column ratio is 0.2,125～128 ℃ of tower top temperatures, and 126～135 ℃ of tower still temperature, working pressure is a normal pressure.Cat head can obtain the diethyl carbonate product 69.32kg/h of purity more than 99.99%.
Claims (7)
1. the method for a continuous production diethyl carbonate is characterized in that, comprises the steps:
(1) catalyzer, methylcarbonate and ethanol import reaction fractionating tower (1) continuously and carry out reactive distillation;
(2) adopt conventional method from reaction product, to collect diethyl carbonate;
Catalyzer is a kind of in alkaline carbonate, KOH, NaOH or the sodium methylate; The raw materials components mole ratio of ethanol/methylcarbonate is 2～8, and the reflux ratio of reaction fractionating tower (1) is 0.5～10.
2. the method for claim 1 is characterized in that, said catalyzer is a salt of wormwood.
3. method as claimed in claim 1 or 2 is characterized in that:
(1) enters reaction fractionating tower (1) with the catalyzer of ethanol preparation from the top of the conversion zone (102) of reaction fractionating tower (1), the mixture of ethanol and methylcarbonate enters the reaction fractionating tower (1) from the middle part of conversion zone (102), and reaction product methyl alcohol and alcoholic acid mixing steam are discharged by outlet (104); Reaction product diethyl carbonate, ethanol and catalyzer enter in the tower still, and discharge outside the tower by pump (5), enter follow-up workshop section;
(2). the material from reaction fractionating tower (1) tower still enters in the vaporizer (3), ethanol and diethyl carbonate are vaporized, be sent to follow-up workshop section, a spot of ethanol, diethyl carbonate and catalyzer enter the bottom of vaporizer (3), are returned in the reaction fractionating tower (1) by catalyst recirculation pump (6) to recycle;
(3). come the ethanol of flash-pot (3) and diethyl carbonate steam to enter diethyl carbonate knockout tower (4), isolate ethanol, return in the reaction fractionating tower (1) and recycle, the tower still is the diethyl carbonate product.
4. method as claimed in claim 3 is characterized in that, said reaction fractionating tower (1) is tray column or packing tower, and working pressure is 90～110Kpa.
5. method as claimed in claim 4 is characterized in that, operates under normal pressure.
6. method as claimed in claim 3 is characterized in that, enters methyl alcohol knockout tower (2) from the methyl alcohol and the alcohol mixture of reaction fractionating tower (1) cat head, and the ethanol that the tower still obtains returns in the reaction fractionating tower (1) by ethanol pump (7) and recycles.
7. as claim 4 or 5 described methods, it is characterized in that enter methyl alcohol knockout tower (2) from the methyl alcohol and the alcohol mixture of reaction fractionating tower (1) cat head, the ethanol that the tower still obtains returns in the reaction fractionating tower (1) by ethanol pump (7) and recycles.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011058226A CN1150158C (en) | 2001-04-03 | 2001-04-03 | Process for continuously preparing diethyl carbonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011058226A CN1150158C (en) | 2001-04-03 | 2001-04-03 | Process for continuously preparing diethyl carbonate |
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| CN1320594A CN1320594A (en) | 2001-11-07 |
| CN1150158C true CN1150158C (en) | 2004-05-19 |
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Cited By (1)
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| CN116116025A (en) * | 2023-01-31 | 2023-05-16 | 安徽东科新材料有限公司 | Device and process for preparing diethyl carbonate based on dimethyl carbonate exchange method |
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| 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 |
| CN101367733B (en) * | 2008-10-08 | 2011-12-07 | 西安交通大学 | Heat pump distillation apparatus and process for diethyl carbonate |
| CN102304048B (en) * | 2011-04-27 | 2012-07-04 | 铜陵金泰化工实业有限责任公司 | Method and equipment for refining high-purity diethyl carbonate |
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| KR20230080590A (en) * | 2021-11-30 | 2023-06-07 | 롯데케미칼 주식회사 | Manufacturing method of carbonates |
| CN114634415B (en) * | 2022-04-22 | 2024-03-22 | 天津凯美特化工科技有限公司 | Method for separating azeotrope of dimethyl carbonate and methanol by diethyl carbonate reaction and producing methyl ethyl carbonate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116116025A (en) * | 2023-01-31 | 2023-05-16 | 安徽东科新材料有限公司 | Device and process for preparing diethyl carbonate based on dimethyl carbonate exchange method |
| CN116116025B (en) * | 2023-01-31 | 2023-09-01 | 安徽东科新材料有限公司 | Device and process for preparing diethyl carbonate based on dimethyl carbonate exchange method |
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