CN102844292A - Process for preparing carboxylic esters by reactive distillation - Google Patents
Process for preparing carboxylic esters by reactive distillation Download PDFInfo
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- CN102844292A CN102844292A CN2011800196488A CN201180019648A CN102844292A CN 102844292 A CN102844292 A CN 102844292A CN 2011800196488 A CN2011800196488 A CN 2011800196488A CN 201180019648 A CN201180019648 A CN 201180019648A CN 102844292 A CN102844292 A CN 102844292A
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- alcohol
- carboxylicesters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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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
- Y02P20/10—Process efficiency
Abstract
In a process for preparing carboxylic esters by transesterification, a first feed stream comprising a first carboxylic ester, e.g. methyl formate, is introduced at the side into a reaction column at a first inlet located between the top and the bottom of the reaction column and a second feed stream comprising a first alcohol, e.g. ethanol, is introduced at the side into the reaction column at a second inlet located above the first inlet and the feed streams are reacted in a reaction zone of the reaction column to form a second carboxylic ester and a second alcohol. The first alcohol has a higher molecular weight than the second alcohol. A product fraction comprising the second carboxylic ester and unreacted first carboxylic ester is taken off at an offtake located above the second inlet.; A bottom fraction comprising the second alcohol and unreacted first alcohol is taken off at the bottom of the reaction column. The product fraction is separated by distillation at a pressure which is different from the pressure in the reaction column into second carboxylic ester and a fraction containing unreacted first carboxylic ester and the fraction containing unreacted first carboxylic ester is at least partly recirculated to the reaction zone.
Description
The present invention relates to a kind ofly prepare carboxylicesters, especially the method for ethyl formate through transesterify.
Low-molecular-weight ester such as manthanoate for example are used as spices, sterilant, mycocide or are used for organic synthesis.The method for preparing low-molecular-weight ester extensively is described in the document.A kind of possibility of cheapness is to make carboxylic acid and pure esterification, distills said ester subsequently.In many cases, be the compound of minimum boiling point owing to be the product of ester-formin, this method can be carried out in industry very simply.
US-A 5,302, and 747 have described a kind of method, wherein make rare gas element through comprising the esterification mixture of alcohol and carboxylic acid, and remain at least under the boiling temperature of said alcohol to discharge said ester.
Purity is higher than 99.5 weight %, and the high purity ester, the especially manthanoate that especially are higher than 99.8 weight % are difficult to preparation, and this is with setting forth among formic acid and the alcoholic acid esterification embodiment hereinafter.Formic acid and alcoholic acid esterification form water and ethyl formate.In the still-process of said reaction product, both can not be from said ester separating alcohol fully, also can not from said ester, divide dried uply fully, this is because these two kinds of materials form azeotrope with said ester in wide pressure range.Therefore, can't obtain the high purity ethyl formate through this method.
JP 10175916 has described the preparation of high purity manthanoate.Formic acid carries out through reactive distillation with the esterification of alcohol, wherein by diacetyl oxide the gained distillate is dewatered.Although can dewater through using siccative in the method, can't remove unreacted alcohol in a similar manner.
WO 2007/099071 has described through reactive distillation and has prepared ester.Carboxylic acid, pure and mild entrainment agent are introduced in the reaction tower.The tower bottoms stream comprises formed ester and unreacted carboxylic acid.Top stream comprises unreacted alcohol, water and entrainment agent.
Have following shortcoming by carboxylic acid and alcohol preparation ester: said acid is generally corrosive, must use acid resisting material that it is handled.
The purpose of this invention is to provide a kind of method for preparing the high purity ester, it is implemented economical and has lower equipment initial cost, especially can overcome this requirement of acid resisting material.
According to the present invention; This purpose is through a kind of method realization for preparing carboxylicesters through transesterify; Wherein will comprise first incoming flow of first carboxylicesters and comprise the first second pure incoming flow and introduce in the reaction tower; And reaction is to form second carboxylicesters and second alcohol in the reaction zone of said reaction tower, and wherein said first alcohol has the molecular weight higher than second alcohol, and from said reaction zone, takes out said second carboxylicesters and second alcohol continuously.
Said method is suitable for preparing and can be regardless of the low-molecular-weight carboxylic acid ester who takes off evaporation.Will be as first carboxylicesters of the ester of carboxylic acid and said first alcohol as raw material.Said first carboxylicesters is preferably C
1-C
5The ester of carboxylic acid, the for example ester of formic acid, acetate, propionic acid, Mono Chloro Acetic Acid, bromoacetic acid, lactic acid, oxyacetic acid.Said first carboxylicesters especially is a manthanoate.
Said first alcohol has the molecular weight higher than second alcohol.In suitable embodiment, said first alcohol is C
2-C
5Alcohol is preferably ethanol, and said second alcohol is methyl alcohol.
Particularly preferred embodiment provides a kind of method for preparing ethyl formate, and wherein said first carboxylicesters is that methyl-formiate and said first alcohol are ethanol.
With regard to the present invention, " reaction zone " is meant that wherein appropriate condition (especially with regard to the existence of temperature, pressure and catalyzer) is occupied an leading position, so that the reaction tower zone that the reaction of said first carboxylicesters and first alcohol is carried out with suitable rate.In said reaction zone, parallel generation mass transfer with said chemical reaction.Second carboxylicesters and second alcohol removing from said reaction zone at first makes the molecular balance skew, and next has prevented subsequent reaction, thereby the selectivity of said reaction is improved greatly.
Said reaction tower comprises isolating active internals such as separation tray; For example porous plate, valve tray or column plate, structured packing such as sheet metal or knitmesh filler such as Sulzer Mellapak 250Y, Sulzer BX, Montz B1 or Montz A3 or K ü hni Rhombopak with long residence time characteristic, or the diffusing heap bed of packing elements as Dixon ring, Raschig ring, High-Flow encircle or super Raschig ring.Found that specific surface area is 100-750m
2/ m
3Structured packing, preferred sheet metal or knitmesh filler are useful especially.They have high score from performance and low pressure drop.As reaction tower, advantageously use to have the 5-100 piece rectifying tower of preferred 20-50 piece reality or theoretical tray.
The bottom of reaction tower is by at least one inside and/or external heater heating.Said external heater can be worked with the mode of pump circulation or natural convection.
The operating pressure of said reaction tower advantageously is the 0.5-7 crust, is preferably the 1-5 crust, is preferably 1-3 crust (definitely) especially.Bottom temp depends on the character of said first carboxylicesters and/or first alcohol, and in methyl-formiate and alcoholic acid reaction, is generally 50-150 ° of C, is preferably 60-100 ° of C.
Said reaction can be carried out in the presence of suitable catalyst, and said catalyzer for example is acidity or basic catalyst, is preferably basic catalyst.Said catalyzer can be heterogeneous catalyst or homogeneous phase soluble catalyst.With regard to the present invention, " homogeneous phase is solvable " means catalyst system therefor and can be dissolved at least in used first alcohol with the degree that under 22 ° of C, surpasses 1g/100ml.
Heterogeneous basic catalyst is advantageously located at the appropriate position of said reaction zone.Heterogeneous catalyst for example is selected from basic oxide, mixed oxide or oxyhydroxide and is amine or the ionite of OH-form.
Said material can be in mixture, titanium oxide, ZIRCONIUM DIOXIDE 99.5 or the clay former state or that be embedded in oxide adhesive matrix such as aluminum oxide, silicon-dioxide, silicon-dioxide in small, broken bits and aluminum oxide to obtain formed body such as extrudate or pill.Said heterogeneous basic catalyst is 1-10mm with granularity (overall dimension) preferably, and the particle form that is preferably 1-4mm exists.
Be the anionite of OH-form, as to have the vinylbenzene or the acrylic resin that are bonded to the quaternary ammonium group on insoluble vinylbenzene or the acrylic acid polymer matrix be suitable equally.
With said heterogeneous catalyst so that the mode that residual gap is enough to make the rectifying mass transfer be able to carry out introduce in the reaction zone.Said catalyzer preferably is the concentration use of 10-60 volume % with the void volume based on said reaction tower.
Said heterogeneous catalyst can be positioned on the column plate, perhaps is installed in the reaction zone as catalyst bed.Yet, also can use the filler such as Montz MULTIPAK or the Sulzer KATAPAK that comprise catalyzer, perhaps said catalyzer is introduced in the tower with the form of random packing element.Also can heterogeneous catalyst be introduced between inertia weaving or braided fabric such as the spun glass, and it is rolled into bundle.Said bundle can be provided with adjacent one another are and each other with piling up, cover the gap that lower floor ties so that one deck is tied.In addition, can use the knitmesh bag (being called Texas Tea Bags) that is filled with catalyzer.
Perhaps, said heterogeneous catalyst has and can make it introduce the granularity and the shape of (optional with the form of mixtures of inertia packing elements) said reaction zone as filler.
If you are using, with any appropriate point of heterogeneous solvable basic catalyst in tower zone, bottom to middle part, advantageously introduce said reaction tower with said first alcohol.
Used homogeneous phase soluble catalyst for example is selected from alkali metal hydroxide and/or alkoxide, for example potassium methylate, sodium methylate.Said catalyzer is advantageously introduced with the solution form that is in the suitable solvent.Preferred solvent is first or second used in the inventive method alcohol.
If you are using, said homogeneous phase soluble catalyst to be the 0.00001-0.2 equivalent based on said first carboxylicesters, is preferably the 0.0001-0.1 equivalent usually, especially is that the normal amount of 0.0005-0.05 is used.
Said first incoming flow is preferably being introduced in the said reaction tower at the top of said reaction tower and at least one the first feed points place side direction between the bottom, and said second incoming flow is introduced in the said reaction tower in the second feed points place side direction that is higher than said first feed points.Said reaction zone part at least extends in the tower section between first and second feed points.
The middle part tower zone of reaction tower is preferably introduced in said second incoming flow, that is, preferably be in the stage number on it and its stage number down are divided into 3:1-1:3, preferably the level of 2:1-1:2 ratio.
Usually will be the 0.5-2 equivalent based on said first carboxylicesters, and be preferably the 0.7-1.2 equivalent, especially be that normal first alcohol of 0.9-1.1 is introduced in this system.
From reaction zone, taking out reaction product continuously realizes through the mass transfer process that in reaction tower, takes place.The low boiler cut steam of unreacted first pure and mild second alcohol that comprises formed second carboxylicesters and unreacted first carboxylicesters and carry secretly leaves reaction zone.Said low boiler cut gets into the enrichment section of reaction tower, wherein isolates unreacted first pure and mild second alcohol of carrying secretly and is back in the reaction zone.
The product cut that comprises second carboxylicesters and unreacted first carboxylicesters can take out at the conveying end place that is positioned at above second feed points, preferably as side-draw stream.
In many cases, said second carboxylicesters and first carboxylicesters and said alcohol form azeotrope, and therefore the composition of said product cut and azeotrope are formed basic identical.Said product cut can comprise a small amount of first pure and mild second alcohol.
Most of unreacted first carboxylicesters of condensation and it partly is back in the reaction tower as trim the top of column at the top of reaction tower, and part is taken out as overhead fraction.In preferred embodiments, said overhead fraction at least partly is back in the reaction zone, for example through sneaking in first incoming flow.Another part of said overhead fraction can be discharged to prevent the accumulation of low-boiler.
In addition, the condensation product of high boiling fraction that comprises unreacted first pure and mild second alcohol flows down from reaction zone with second carboxylicesters of carrying secretly and unreacted first carboxylicesters.Said high boiling fraction gets into exhausting section of column, and second carboxylicesters of wherein carrying secretly and unreacted first carboxylicesters are gone out by stripping and be recycled in the reaction zone.
In the bottom of reaction tower, can take out the bottom fraction that comprises second pure and mild unreacted first alcohol.In order to discharge formed high boiling compound, the disposable portion bottom fraction.
Said bottom fraction preferably becomes second pure and mild unreacted first alcohol through fractionation by distillation, preferably in another distillation tower, carries out.Advantageously unreacted first alcohol of part is recycled in the reaction zone at least, for example through it is sneaked in second incoming flow.
The product cut not only comprises second carboxylicesters usually, and comprises unreacted first carboxylicesters and a small amount of second pure and mild unreacted first alcohol.Therefore, the product cut preferably becomes pure second carboxylicesters and the cut that comprises unreacted first carboxylicesters through fractionation by distillation.Preferably in second tower, carry out continuously through fractionation by distillation.The cut that preferably at least a portion is comprised unreacted first carboxylicesters is recycled in the reaction zone, for example through sneaking in first incoming flow.
Said product cut comprises the azeotrope of second carboxylicesters and second alcohol, unreacted first alcohol and unreacted first carboxylicesters usually.Usually depend on pressure because azeotrope is formed, therefore separate through distillation under the pressure of said azeotrope pressure in being different from reaction tower.This phenomenon is called two pressure methods or variable-pressure rectification or transformation distillation by those skilled in the art.Under the pressure of pressure, the composition of product cut is formed corresponding to different azeotropes in being different from reaction tower.In second tower, second carboxylicesters can take out from the bottom of tower or bottom the part bottom section of tower (for example near) with pure form, and azeotropic mixture obtains at the top, although it has and the remarkable different composition of said product cut.Can this azeotropic mixture be supplied to be back in the reaction zone.
The pressure that is different from pressure in the reaction tower for example can be the 1-40 crust, is preferably 5-15 crust (definitely).
Said therein first carboxylicesters is that methyl-formiate and said first alcohol are in the preferred embodiment of alcoholic acid method; The materials flow that obtains in the bottom of second tower comprises the ethyl formate of 99.0-100 weight % (especially 99.8-100 weight %), other compounds of the ethanol of 0-1 weight % (especially 0-0.2 weight %) and 0-1 weight % (especially 0-0.2 weight %).
Perhaps, can carry out with the extractive distillation mode through fractionation by distillation product cut.
Set forth the present invention through accompanying drawing and hereinafter embodiment.
Fig. 1 has schematically shown the device that is suitable for the embodiment of the present invention method.
First alcohol is introduced reaction tower T1 via the side opening for feed that is arranged in reaction zone 1 upper end 2.The heterogeneous catalyst (not shown) is fixed on the correct position of reaction zone.First carboxylicesters is introduced reaction tower T1 via the side opening for feed that is arranged in reaction zone 1 lower end 3.Obtain being reflected in the reaction zone 1 and carrying out of second carboxylicesters and second alcohol.Second carboxylicesters and unreacted first carboxylicesters get in the enrichment section 4 of reaction tower T1, in enrichment section 4, make it remove second pure and mild unreacted first alcohol of carrying secretly basically.Take out the product cut that comprises second carboxylicesters and unreacted first carboxylicesters via lateral tap 6.The second pure and mild unreacted first pure autoreaction district 1 gets in the stripping stage 5 of reaction tower T1 second carboxylicesters that stripping is carried secretly in stripping stage 5 and unreacted first carboxylicesters.The bottom fraction of taking out via pipe 7 mainly comprises second pure and mild unreacted first alcohol.
To infeed in the upper area of distillation tower T2 at the product cut that lateral tap 6 takes out from reaction tower T1.Tower T2 moves under the pressure higher than reaction tower T1 at different pressures usually.Pure second carboxylicesters obtains in the bottom of distillation tower T2 and discharges via pipe 11.The materials flow that to take out at distillation tower T2 top is recycled among the reaction tower T1 via pipe 12.
The bottom fraction of autoreaction tower T1 is taken out and is infeeded among the distillation tower T3 via pipe 7 in the future.In distillation tower T3, it is separated into second alcohol (taking out at the top of tower T3 via pipe 13) and first alcohol (its bottom at tower T3 obtains and is recycled among the reaction tower T1 via pipe 14).
Embodiment (simulation)
About 60g/h ethanol is infeeded in the reaction tower with 30 blocks of theoretical trays and operation under 1 crust at the 10th column plate place.At the 5th column plate place, infeed the 81g/h methyl-formiate.Suppose that the therebetween column plate place that is reflected at that forms ethyl formate and methyl alcohol reaches chemical equilibrium.
The reflux ratio of said reaction tower is about 11.Basically the overhead condensate that is made up of methyl-formiate is returned as the part that refluxes, and part is recycled in the bottom of reaction tower.
At the lateral tap place that is positioned at the 25th column plate place, take out the 305g/h mixture, it comprises about 60.0 weight % ethyl formates, 27 weight % methyl-formiates, 6 weight % methyl alcohol and 2 weight % ethanol.
This mixture infeeded have the distillation tower top that 30 blocks of theoretical trays and pressure are 7 crust.Bottom at this distillation tower obtains the 100g/h mixture, and it comprises about 99.9 weight % ethyl formates and 0.1 weight % ethanol.Overhead distillate is returned (reflux ratio is about 3) as the part that refluxes and part is recycled in the reaction tower.
About 242g/h mixture is taken out in bottom at reaction tower, and it comprises about 19 weight % methyl alcohol and 81 weight % ethanol.With the fractionation in having another distillation tower that 30 blocks of theoretical trays and pressure are 1 crust of this mixture.Take out methyl alcohol at the top; The ethanol of about 99 weight % concentration that will obtain in the bottom is recycled in the reaction tower.
Claims (14)
1. method for preparing carboxylicesters through transesterify; Wherein will comprise first incoming flow of first carboxylicesters and comprise the first second pure incoming flow and introduce in the reaction tower; And in the reaction zone of said reaction tower, react to form second carboxylicesters and second alcohol; Wherein said first alcohol has the molecular weight higher than second alcohol, and second carboxylicesters and second alcohol are taken out from reaction zone continuously.
2. according to the method for claim 1; Wherein said first incoming flow is being introduced in the said reaction tower at the top of said reaction tower and at least one the first feed points place side direction between the bottom, and said second incoming flow is being introduced in the said reaction tower in the second feed points place side direction that is higher than said first feed points.
3. according to the method for claim 1 or 2; Wherein take out the product cut that comprises said second carboxylicesters and unreacted first carboxylicesters, take out the bottom fraction that comprises said second pure and mild unreacted first alcohol in the bottom of said reaction tower at the point of draw place that is positioned at above said second feed points.
4. according to the method for claim 3, the overhead fraction that wherein extra taking-up is made up of unreacted first carboxylicesters basically at the top of said reaction tower.
5. according to the method for claim 4, wherein said overhead fraction at least partly is recycled in the reaction zone.
6. according to each method among the claim 3-5; Wherein said product cut is become second carboxylicesters and comprises the cut of unreacted first carboxylicesters through fractionation by distillation, and the cut that will comprise unreacted first carboxylicesters at least part be recycled in the reaction zone.
7. according to the method for claim 6, carry out under the wherein said pressure through fractionation by distillation product cut pressure in being different from reaction tower.
8. according to the method for claim 6, wherein saidly carry out with the extractive distillation mode through fractionation by distillation product cut.
9. according to each method among the claim 3-8, wherein said bottom fraction is become second pure and mild unreacted first alcohol through fractionation by distillation, and with unreacted first alcohol at least part be recycled in the reaction zone.
10. according to each method in the aforementioned claim, wherein solvable basic catalyst is introduced in the said reaction tower.
11., have heterogeneous basic catalyst in the wherein said reaction zone according to each method among the claim 1-9.
12. according to each method in the aforementioned claim, wherein said first carboxylicesters is a manthanoate.
13. according to each method in the aforementioned claim, wherein said first alcohol is ethanol, said second alcohol is methyl alcohol.
14. according to each method in the aforementioned claim, be used to prepare ethyl formate, wherein said first carboxylicesters is a methyl-formiate, said first alcohol is ethanol.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10160353.8 | 2010-04-19 | ||
| EP10160353 | 2010-04-19 | ||
| PCT/EP2011/056189 WO2011131643A2 (en) | 2010-04-19 | 2011-04-19 | Process for preparing carboxylic esters by reactive distillation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102844292A true CN102844292A (en) | 2012-12-26 |
| CN102844292B CN102844292B (en) | 2014-07-16 |
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ID=44625874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180019648.8A Expired - Fee Related CN102844292B (en) | 2010-04-19 | 2011-04-19 | Process for preparing carboxylic esters by reactive distillation |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2560943A2 (en) |
| JP (1) | JP2013525325A (en) |
| KR (1) | KR20130051452A (en) |
| CN (1) | CN102844292B (en) |
| WO (1) | WO2011131643A2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014050788A1 (en) * | 2012-09-28 | 2014-04-03 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing carboxylic acid anhydride |
| CN106083586B (en) * | 2016-08-10 | 2021-09-14 | 烟台国邦化工机械科技有限公司 | Technological method for synthesizing ethyl formate by using formic acid and ethanol and purifying product |
| KR102019037B1 (en) * | 2017-05-26 | 2019-09-06 | 지에스칼텍스 주식회사 | Method of preparing alkyl carboxylic acid ester |
| CN116209653A (en) * | 2020-09-24 | 2023-06-02 | 株式会社Lg化学 | Process for the preparation of ester compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0968995A1 (en) * | 1998-07-01 | 2000-01-05 | Mitsubishi Gas Chemical Company, Inc. | Process for continuously producing ester of acrylic or methacrylic acid |
| DE102007006917A1 (en) * | 2007-02-13 | 2008-08-14 | Technocon Gmbh | Continuous catalytic transesterification process, for preparing esters, is carried out in single reactive distillation column with integrated stripper section for alcohol removal |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302747A (en) | 1992-08-24 | 1994-04-12 | Purdue Research Foundation | Process for the manufacture of esters |
| JPH10175916A (en) | 1996-12-13 | 1998-06-30 | Daicel Chem Ind Ltd | Production of formic acid ester |
| AU2007220541A1 (en) | 2006-02-28 | 2007-09-07 | Shell Internationale Research Maatschappij B.V. | A process for reactive distillation of a carboxylic acid |
-
2011
- 2011-04-19 CN CN201180019648.8A patent/CN102844292B/en not_active Expired - Fee Related
- 2011-04-19 KR KR1020127030034A patent/KR20130051452A/en not_active Application Discontinuation
- 2011-04-19 EP EP11714782A patent/EP2560943A2/en not_active Withdrawn
- 2011-04-19 WO PCT/EP2011/056189 patent/WO2011131643A2/en active Application Filing
- 2011-04-19 JP JP2013505444A patent/JP2013525325A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0968995A1 (en) * | 1998-07-01 | 2000-01-05 | Mitsubishi Gas Chemical Company, Inc. | Process for continuously producing ester of acrylic or methacrylic acid |
| DE102007006917A1 (en) * | 2007-02-13 | 2008-08-14 | Technocon Gmbh | Continuous catalytic transesterification process, for preparing esters, is carried out in single reactive distillation column with integrated stripper section for alcohol removal |
Non-Patent Citations (1)
| Title |
|---|
| LIU XING QUAN ET AL.: "TRANSESTERIFICATION OF METHANOL WITH ETHYL ACETATE AND ETHANOL WITH METHYL FORMATE CATALYZED BY DBN", 《JOURNAL OF NATURAL GAS CHEMISTRY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2560943A2 (en) | 2013-02-27 |
| JP2013525325A (en) | 2013-06-20 |
| WO2011131643A2 (en) | 2011-10-27 |
| KR20130051452A (en) | 2013-05-20 |
| WO2011131643A3 (en) | 2011-12-29 |
| CN102844292B (en) | 2014-07-16 |
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