CN102844292B - Process for preparing carboxylic esters by reactive distillation - Google Patents
Process for preparing carboxylic esters by reactive distillation Download PDFInfo
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- CN102844292B CN102844292B CN201180019648.8A CN201180019648A CN102844292B CN 102844292 B CN102844292 B CN 102844292B CN 201180019648 A CN201180019648 A CN 201180019648A CN 102844292 B CN102844292 B CN 102844292B
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- alcohol
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- carboxylicesters
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- 150000001733 carboxylic acid esters Chemical class 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000000066 reactive distillation Methods 0.000 title description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 238000004821 distillation Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 14
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- 238000005194 fractionation Methods 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 238000000895 extractive distillation Methods 0.000 claims description 2
- -1 methyl formate Chemical class 0.000 abstract 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 abstract 2
- 238000005809 transesterification reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000002638 heterogeneous catalyst Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940031815 mycocide Drugs 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical group CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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 one and prepare carboxylicesters by transesterify, the especially method of ethyl formate.
Low-molecular-weight ester is if manthanoate is for example as spices, sterilant, mycocide or for organic synthesis.The method of preparing low-molecular-weight ester is extensively described in document.The possibility of cheapness is to make carboxylic acid and an alcohol esterification, distills subsequently described ester.In many cases, owing to being the compound that the product of ester-formin is minimum boiling point, the method can be carried out very simply industrial.
US-A 5,302,747 has described a kind of method, wherein makes rare gas element by comprising the esterification mixture of alcohol and carboxylic acid, and at least remains under the boiling temperature of described alcohol to discharge described ester.
Purity is higher than 99.5 % by weight, is especially difficult to preparation higher than high purity ester, the especially manthanoate of 99.8 % by weight, and this will be set forth in the esterification embodiment of below formic acid and ethanol.The esterification of formic acid and ethanol forms water and ethyl formate.In the still-process of described reaction product, both can not be from described ester separating alcohol completely, also can not be from described ester Separation of Water completely, this is because these two kinds of materials form azeotrope with described ester in wide pressure range.Therefore, cannot obtain high purity ethyl formate by the method.
JP 10175916 has described the preparation of high purity manthanoate.The esterification of formic acid and alcohol is undertaken by reactive distillation, wherein by diacetyl oxide, gained distillate is dewatered.Although can, by using siccative to dewater, cannot remove in a similar manner unreacted alcohol in the method.
WO 2007/099071 has described by reactive distillation and has prepared ester.Carboxylic acid, alcohol and entrainment agent are introduced in reaction tower.Tower bottoms stream comprises formed ester and unreacted carboxylic acid.Top stream comprises unreacted alcohol, water and entrainment agent.
Prepare ester by Carboxylic acid and alcohol and there is following shortcoming: described acid is generally corrosive, must use acid resisting material to process it.
The object of this invention is to provide a kind of method of preparing 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 object is by a kind of method realization of preparing carboxylicesters by transesterify, wherein the first incoming flow that comprises the first carboxylicesters and the second incoming flow of comprising the first alcohol are introduced in reaction tower, and react to form the second carboxylicesters and the second alcohol in the reaction zone of described reaction tower, wherein said the first alcohol has the molecular weight higher than the second alcohol, and takes out continuously described the second carboxylicesters and the second alcohol from described reaction zone.
Described method is suitable for preparation can be the low-molecular-weight carboxylic acid ester regardless of taking off evaporation.Using as the first carboxylicesters of the ester of carboxylic acid and described the first alcohol as raw material.Described the first carboxylicesters is preferably C
1-C
5the ester of carboxylic acid, for example ester of formic acid, acetic acid, propionic acid, Mono Chloro Acetic Acid, bromoacetic acid, lactic acid, oxyacetic acid.Described the first carboxylicesters is especially manthanoate.
Described the first alcohol has the molecular weight higher than the second alcohol.In suitable embodiment, described the first alcohol is C
2-C
5alcohol, is preferably ethanol, and described the second alcohol is methyl alcohol.
Particularly preferred embodiment provides a kind of method of preparing ethyl formate, and wherein said the first carboxylicesters is that methyl-formiate and described the first alcohol are ethanol.
For the present invention, " reaction zone " refers to that wherein suitable condition (especially with regard to the existence of temperature, pressure and catalyzer) occupies an leading position, with the reaction tower region that described the first carboxylicesters is carried out with suitable rate with reacting of the first alcohol.In described reaction zone, generation mass transfer parallel with described chemical reaction.First the second carboxylicesters and the second alcohol removing from described reaction zone make molecular balance skew, and next has prevented reaction subsequently, thereby the selectivity of described reaction is improved greatly.
Described reaction tower comprises that isolating active internals are as separation tray; for example porous plate, valve tray or the column plate, structured packing with long residence time feature be if sheet metal or knitmesh filler are as Sulzer Mellapak 250Y, Sulzer BX, Montz B1 or Montz A3 or K ü hni Rhombopak, or the loose heap bed of packing elements as Dixon ring, Raschig ring, High-Flow encircle or super Raschig ring.Find that specific surface area is 100-750m
2/ m
3structured packing, preferably sheet metal or knitmesh filler are useful especially.They have high separation performance and low pressure drop.As reaction tower, advantageously use and there is 5-100 piece, preferably the rectifying tower of 20-50 piece reality or theoretical tray.
The bottom of reaction tower is heated by least one inside and/or external heater.Described external heater can be worked in the mode of pump circulation or natural convection.
The operating pressure of described reaction tower is advantageously 0.5-7 bar, is preferably 1-5 bar, is particularly preferably 1-3 bar (definitely).Bottom temp depends on the character of described the first carboxylicesters and/or the first alcohol, and is generally 50-150 ° of C in the reacting of methyl-formiate and ethanol, and is preferably 60-100 ° of C.
Described reaction can be carried out under suitable catalyst exists, and described catalyzer is for example acidity or basic catalyst, is preferably basic catalyst.Described catalyzer can be heterogeneous catalyst or homogeneous phase soluble catalyst.For the present invention, " homogeneous phase is solvable " means used catalyst and can at least be dissolved in the first alcohol used with the degree that exceedes 1g/100ml under 22 ° of C.
Heterogeneous basic catalyst is advantageously located at the appropriate position of described reaction zone.Heterogeneous catalyst is for example selected from basic oxide, mixed oxide or oxyhydroxide and is amine or the ion-exchanger of OH-form.
That described material can be former state or be embedded in oxide adhesive matrix as in mixture, titanium dioxide, zirconium dioxide or the clay of aluminum oxide, silicon-dioxide, silicon-dioxide in small, broken bits and aluminum oxide to obtain formed body as extrudate or pill.Described heterogeneous basic catalyst is preferably taking granularity (overall dimension) as 1-10mm, and the particle form that is preferably 1-4mm exists.
Be the anionite of OH-form, the vinylbenzene or the acrylic resin that are bonded to the quaternary ammonium group on insoluble vinylbenzene or acrylic acid polymer matrix as having are suitable equally.
Described heterogeneous catalyst is introduced in reaction zone in the mode that residual gap is enough to rectifying mass transfer is carried out.The described catalyzer preferably concentration taking the void volume based on described reaction tower as 10-60 volume % uses.
Described heterogeneous catalyst can be positioned on column plate, or is arranged in reaction zone as catalyst bed.But, also can use the filler that comprises catalyzer as Montz MULTIPAK or Sulzer KATAPAK, or described catalyzer is introduced in tower with the form of random packing element.Also heterogeneous catalyst can be introduced to inertia weaving or braided fabric as between glass fibre, and be rolled into bundle.Described bundle can arrange adjacent one another are and each other stackingly, to make one deck bundle cover the gap of lower floor's bundle.In addition, can use the knitmesh bag (being called Texas Tea Bags) that is filled with catalyzer.
Or described heterogeneous catalyst has can make it introduce granularity and the shape of (optionally with the form of mixtures of inertia packing elements) described reaction zone as filler.
If you are using, any appropriate point by heterogeneous solvable basic catalyst in tower region, bottom to middle part is advantageously introduced described reaction tower together with described the first alcohol.
Homogeneous phase soluble catalyst used is for example selected from alkali metal hydroxide and/or alkoxide, for example potassium methylate, sodium methylate.Described catalyzer is advantageously introduced with the solution form in suitable solvent.Preferred solvent is the first or second alcohol used in the inventive method.
If you are using, described homogeneous phase soluble catalyst conventionally taking based on described the first carboxylicesters as 0.00001-0.2 equivalent, be preferably 0.0001-0.1 equivalent, be especially 0.0005-0.05 equivalent amount use.
Described the first incoming flow preferably at least one the first feed points place side direction between top and bottom at described reaction tower is introduced in described reaction tower, and described the second incoming flow is introduced in described reaction tower in the second feed points place side direction higher than described the first feed points.Described reaction zone extends in the tower section between the first and second feed points at least partly.
The tower region, middle part of reaction tower is preferably introduced in described the second incoming flow, that is, preferably in the stage number on it and the stage number under it are divided into 3:1-1:3, the preferably level of 2:1-1:2 ratio.
Conventionally will be 0.5-2 equivalent based on described the first carboxylicesters, be preferably 0.7-1.2 equivalent, especially for the first alcohol of 0.9-1.1 equivalent is introduced in this system.
From reaction zone, taking out continuously reaction product realizes by the mass transfer process occurring in reaction tower.Comprise the second formed carboxylicesters and unreacted the first carboxylicesters and unreacted the first alcohol of carrying secretly and the low boiler cut steam of the second alcohol and leave reaction zone.Described low boiler cut enters the enrichment section of reaction tower, wherein isolates unreacted the first alcohol and the second alcohol of carrying secretly and is back in reaction zone.
The product cut that comprises the second carboxylicesters and unreacted the first carboxylicesters can take out at the conveying end place being positioned at above the second feed points, preferably as side-draw stream.
In many cases, described the second carboxylicesters and the first carboxylicesters and described alcohol form azeotrope, and therefore the composition of described product cut and azeotrope composition are basic identical.Described product cut can comprise a small amount of the first alcohol and the second alcohol.
At most of unreacted the first carboxylicesters of the top of reaction tower condensation and set it as trim the top of column part and be back in reaction tower, and part is taken out as overhead fraction.In preferred embodiments, described overhead fraction is back in reaction zone at least partly, for example, by sneaking in the first incoming flow.Another part of described overhead fraction can discharge to prevent the accumulation of low-boiler.
In addition the condensation product that, comprises unreacted the first alcohol and the high boiling fraction of the second alcohol flows down from reaction zone together with unreacted the first carboxylicesters with the second carboxylicesters of carrying secretly.Described high boiling fraction enters exhausting section of column, and the second carboxylicesters of wherein carrying secretly and unreacted the first carboxylicesters are gone out by stripping and be recycled in reaction zone.
In the bottom of reaction tower, can take out the bottom fraction that comprises the second alcohol and unreacted the first alcohol.In order to discharge formed high boiling compound, disposable portion bottom fraction.
Described bottom fraction is preferably separated by distillation into the second alcohol and unreacted the first alcohol, preferably in another distillation tower, carries out.Advantageously unreacted the first alcohol is recycled in reaction zone at least partly, for example, by being sneaked in the second incoming flow.
Product cut not only comprises the second carboxylicesters conventionally, and comprises unreacted the first carboxylicesters and a small amount of the second alcohol and unreacted the first alcohol.Therefore the cut that, product cut is preferably separated by distillation into pure the second carboxylicesters and comprises unreacted the first carboxylicesters.Preferably in the second tower, carry out continuously by fractionation by distillation.The cut that preferably at least a portion is comprised to unreacted the first carboxylicesters is recycled in reaction zone, for example, by sneaking in the first incoming flow.
Described product cut comprises the azeotrope of the second carboxylicesters and the second alcohol, unreacted the first alcohol and unreacted the first carboxylicesters conventionally.Because azeotrope composition depends on pressure conventionally, therefore described azeotrope separates by distilling under the pressure that is different from pressure in reaction tower.This phenomenon is called two pressure methods or variable-pressure rectification or transformation by those skilled in the art and distills.Being different under the pressure of pressure in reaction tower, the composition of product cut is corresponding to different azeotrope compositions.In the second tower, the second carboxylicesters can for example, take out with pure form from the bottom of tower or bottom the part bottom section of tower (near), and azeotropic mixture obtains at top, although it has and the remarkable different composition of described product cut.Can be by this azeotropic mixture for being back in reaction zone.
The pressure that is different from pressure in reaction tower for example can be 1-40 bar, is preferably 5-15 bar (definitely).
Described the first carboxylicesters is in the preferred embodiment of methyl-formiate and described the first alcohol method that is ethanol therein, the ethyl formate that the material stream obtaining in the bottom of the second tower comprises 99.0-100 % by weight (especially 99.8-100 % by weight), other compounds of the ethanol of 0-1 % by weight (especially 0-0.2 % by weight) and 0-1 % by weight (especially 0-0.2 % by weight).
Or, can carry out in extractive distillation mode by fractionation by distillation product cut.
By accompanying drawing and below embodiment set forth the present invention.
Fig. 1 has schematically shown the device that is suitable for implementing the inventive method.
The first alcohol is introduced to reaction tower T1 via the side opening for feed 2 that is arranged in 1 upper end, reaction zone.Heterogeneous catalyst (not shown) is fixed on the correct position of reaction zone.The first carboxylicesters is introduced to reaction tower T1 via the side opening for feed 3 that is arranged in 1 lower end, reaction zone.The reaction that obtains the second carboxylicesters and the second alcohol is carried out in reaction zone 1.The second carboxylicesters and unreacted the first carboxylicesters enter in the enrichment section 4 of reaction tower T1, make it substantially remove the second alcohol and unreacted the first alcohol of carrying secretly in enrichment section 4.Take out via lateral tap 6 the product cut that comprises the second carboxylicesters and unreacted the first carboxylicesters.The second alcohol and unreacted the first alcohol autoreaction district 1 enter in the stripping stage 5 of reaction tower T1, the second carboxylicesters that stripping is carried secretly in stripping stage 5 and unreacted the first carboxylicesters.The bottom fraction of taking out via pipe 7 mainly comprises the second alcohol and unreacted the first alcohol.
Reflux and be back in reaction tower as top via pipe 9 by steam 8 condensations that obtain at reaction tower top and using a part, and transfer in reaction zone via pipe 10 part as charging.
The product cut taking out from reaction tower T1 at lateral tap 6 is fed in the upper area of distillation tower T2.Tower T2, at different pressures, moves conventionally under the pressure higher than reaction tower T1.Pure the second carboxylicesters obtains in the bottom of distillation tower T2 and discharges via pipe 11.The material taking out at distillation tower T2 top is flowed through and is recycled in reaction tower T1 by pipe 12.
The bottom fraction of autoreaction tower T1 is taken out and is fed in distillation tower T3 via pipe 7 in the future.In distillation tower T3, be isolated into the second alcohol (taking out via pipe 13 tops at tower T3) and the first alcohol (its bottom at tower T3 obtains and is recycled in reaction tower T1 via pipe 14).
Embodiment (simulation)
About 60g/h ethanol is fed in the reaction tower that has 30 blocks of theoretical trays and move under 1 bar at the 10th column plate place.At the 5th column plate place, feed 81g/h methyl-formiate.Suppose that the reaction that forms ethyl formate and methyl alcohol reaches chemical equilibrium at therebetween column plate place.
The reflux ratio of described reaction tower is approximately 11.Substantially the overhead condensate being 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 305g/h mixture, it comprises approximately 60.0 % by weight ethyl formates, 27 % by weight methyl-formiates, 6 % by weight methyl alcohol and 2 % by weight ethanol.
This mixture is fed and has 30 blocks of theoretical trays and pressure is the distillation tower top of 7 bar.Bottom at this distillation tower obtains 100g/h mixture, and it comprises approximately 99.9 % by weight ethyl formates and 0.1 % by weight ethanol.Return to using overhead distillate as the part that refluxes to (reflux ratio is about 3) and be partly recycled in reaction tower.
Take out about 242g/h mixture in the bottom of reaction tower, it comprises approximately 19 % by weight methyl alcohol and 81 % by weight ethanol.By this mixture thering is fractionation in another distillation tower that 30 blocks of theoretical trays and pressure are 1 bar.Take out methyl alcohol at top; The ethanol of the approximately 99 % by weight concentration that obtain in bottom is recycled in reaction tower.
Claims (9)
1. prepare the method for ethyl formate by transesterify for one kind, wherein by the first incoming flow that comprises the first carboxylicesters that is methyl-formiate form, at least one the first feed points place side direction between top and bottom at reaction tower is introduced in described reaction tower, and the second incoming flow that comprises the first alcohol that is alcohol form is introduced in described reaction tower in the second feed points place side direction higher than described the first feed points, and reaction is the second carboxylicesters and second alcohol of ethyl formate form to form in the reaction zone of described reaction tower, wherein from described reaction zone, take out continuously described the second carboxylicesters and the second alcohol, wherein take out at the point of draw place being positioned at above described the second feed points the product cut that comprises described the second carboxylicesters and unreacted the first carboxylicesters, the bottom fraction that comprises described the second alcohol and unreacted the first alcohol is taken out in bottom at described reaction tower, the cut that described product cut is separated by distillation into the second carboxylicesters and comprises unreacted the first carboxylicesters, and the described cut that comprises unreacted the first carboxylicesters is recycled in described reaction zone at least partly, wherein saidly under the pressure that is different from pressure in reaction tower, carry out or describedly carry out in extractive distillation mode by fractionation by distillation product cut by fractionation by distillation product cut.
2. according to the process of claim 1 wherein at the extra overhead fraction substantially being formed by unreacted the first carboxylicesters that takes out in the top of described reaction tower.
3. according to the method for claim 2, wherein described overhead fraction is recycled in reaction zone at least partly.
4. according to the process of claim 1 wherein, described bottom fraction is separated by distillation into the second alcohol and unreacted the first alcohol, and unreacted the first alcohol is recycled in described reaction zone at least partly.
5. according to the method for claim 2, wherein described bottom fraction is separated by distillation into the second alcohol and unreacted the first alcohol, and unreacted the first alcohol is recycled in described reaction zone at least partly.
6. according to the method for claim 3, wherein described bottom fraction is separated by distillation into the second alcohol and unreacted the first alcohol, and unreacted the first alcohol is recycled in described reaction zone at least partly.
7. according to the method for any one in claim 1-6, wherein solvable basic catalyst is introduced in described reaction tower.
8. according to the method for any one in claim 1-6, in wherein said reaction zone, there is heterogeneous basic catalyst.
9. according to the method for claim 7, in wherein said reaction zone, there is heterogeneous basic catalyst.
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 CN102844292A (en) | 2012-12-26 |
| CN102844292B true CN102844292B (en) | 2014-07-16 |
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| 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 |
| WO2022065853A1 (en) * | 2020-09-24 | 2022-03-31 | 주식회사 엘지화학 | Method for producing ester-based composition |
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 |
| WO2007099071A1 (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 KR KR1020127030034A patent/KR20130051452A/en not_active Application Discontinuation
- 2011-04-19 EP EP11714782A patent/EP2560943A2/en not_active Withdrawn
- 2011-04-19 CN CN201180019648.8A patent/CN102844292B/en not_active Expired - Fee Related
- 2011-04-19 JP JP2013505444A patent/JP2013525325A/en not_active Withdrawn
- 2011-04-19 WO PCT/EP2011/056189 patent/WO2011131643A2/en active Application Filing
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 (2)
| 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》.1998,第7卷(第4期),第313-318页. |
| TRANSESTERIFICATION OF METHANOL WITH ETHYL ACETATE AND ETHANOL WITH METHYL FORMATE CATALYZED BY DBN;LIU Xing Quan et al.;《Journal of Natural Gas Chemistry》;19981231;第7卷(第4期);第313-318页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130051452A (en) | 2013-05-20 |
| EP2560943A2 (en) | 2013-02-27 |
| WO2011131643A3 (en) | 2011-12-29 |
| JP2013525325A (en) | 2013-06-20 |
| WO2011131643A2 (en) | 2011-10-27 |
| CN102844292A (en) | 2012-12-26 |
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