EP2560943A2 - Procédé de production d'esters d'acides carboxyliques par distillation réactive - Google Patents

Procédé de production d'esters d'acides carboxyliques par distillation réactive

Info

Publication number
EP2560943A2
EP2560943A2 EP11714782A EP11714782A EP2560943A2 EP 2560943 A2 EP2560943 A2 EP 2560943A2 EP 11714782 A EP11714782 A EP 11714782A EP 11714782 A EP11714782 A EP 11714782A EP 2560943 A2 EP2560943 A2 EP 2560943A2
Authority
EP
European Patent Office
Prior art keywords
alcohol
carboxylic acid
acid ester
reaction
reaction column
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11714782A
Other languages
German (de)
English (en)
Inventor
Helmut Kronemayer
Ellen Dahlhoff
Andreas Lanver
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11714782A priority Critical patent/EP2560943A2/fr
Publication of EP2560943A2 publication Critical patent/EP2560943A2/fr
Withdrawn legal-status Critical Current

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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

Definitions

  • the invention relates to a process for the preparation of carboxylic acid esters, in particular of ethyl formate, by transesterification.
  • Low molecular weight esters such as formic acid esters find z. B. as fragrances, insecticides, fungicides or in organic synthesis application. Methods for the preparation of low molecular weight esters are described in various ways in the literature. An inexpensive option is the esterification of carboxylic acid and alcohol followed by distillation of the ester. This process is in many cases technically very easy to carry out because the product in the form of the ester is the lowest-boiling compound.
  • the esterification of formic acid and alcohol is carried out by reactive distillation, wherein the resulting distillate is dehydrated by means of acetic anhydride.
  • acetic anhydride a distillate of acetic anhydride
  • water can be removed by the use of drying agents. Unreacted alcohol can not be removed in a comparable manner.
  • WO 2007/099071 describes the preparation of esters by a reactive distillation.
  • a carboxylic acid, an alcohol and an entraining agent are introduced.
  • the bottom stream comprises the ester formed and not um- put carboxylic acid.
  • the top stream comprises unreacted alcohol, water and entrainers.
  • the invention has for its object to provide a process for the production of high purity ester, which is economical to carry out and provides a lower equipment investment requirements and in particular bypasses the requirement of acid-resistant materials.
  • the object is achieved by a process for the preparation of carboxylic acid esters by transesterification, in which one introduces a first feed comprising a first carboxylic acid ester, and a second feed comprising a first alcohol in a reaction column and in a reaction zone of the reaction column below Forming a second carboxylic acid ester and a second alcohol, wherein the first alcohol has a higher molecular weight than the second alcohol and wherein the second carboxylic acid ester and the second alcohol is continuously removed from the reaction zone.
  • the process is suitable for the preparation of low molecular weight carboxylic acid esters which can be evaporated without decomposition.
  • the starting material is a first carboxylic acid ester which is the ester of a carboxylic acid with the second alcohol.
  • the first carboxylic acid ester is preferably an ester of a C 1 -C 8 -carboxylic acid, eg. As an ester of formic acid, acetic acid, propionic acid, chloroacetic acid, bromoacetic acid, lactic acid, glycolic acid.
  • the first carboxylic acid ester is a formic acid ester.
  • the first alcohol has a higher molecular weight than the second alcohol.
  • the first alcohol is a C 2 -C 8 alcohol, preferably ethanol, and the second alcohol is methanol.
  • a particularly preferred embodiment relates to a process for the preparation of ethyl formate in which the first carboxylic acid ester is methyl formate and the first alcohol is ethanol.
  • reaction zone is meant a region of the reaction column in which suitable conditions, in particular with respect to temperature, pressure and presence a catalyst, so that the reaction between the first carboxylic ester and the first alcohol proceeds at an appropriate rate. Parallel to the chemical reaction in the reaction zone, a mass transfer takes place. The removal of the second carboxylic acid ester and the second alcohol from the reaction zone on the one hand causes a shift in the reaction equilibrium and on the other hand prevents subsequent reactions, whereby the selectivity of the reaction is greatly increased.
  • the reaction column contains separating internals, such as separating trays, z.
  • separating internals such as separating trays, z.
  • ordered packings eg. B. sheet or tissue packings such as Sulzer Mellapak 250 Y, Sulzer BX, Montz B1 or Montz A3 or Kühni Rhombopak, or random beds of packing, such.
  • Orderly packages, preferably sheet metal or fabric packages have a specific surface area of 100 to 750 m 2 / m 3 , in particular 250 to 500 m 2 / m 3 . They allow high separation performance at low pressure drops.
  • the reaction column used is advantageously a rectification column which has 5 to 100, preferably 20 to 50, actual or theoretical plates.
  • the bottom of the reaction column is heated with at least one built-in and / or external heater.
  • the external heater can work with forced or natural circulation.
  • the operating pressure of the reaction column is 0.5 to 7 bar, preferably 1 to 5 bar and more preferably 1 to 3 bar (absolute).
  • the temperature in the sump depends on the nature of the first carboxylic ester and / or first alcohol and in the reaction of methyl formate with ethanol is usually 50 to 150 ° C, preferably 60 to 100 ° C.
  • the reaction can be carried out in the presence of a suitable catalyst, for.
  • a suitable catalyst for.
  • an acidic or basic catalyst preferably a basic catalyst.
  • the catalyst can be both heterogeneous catalysts and homogeneously soluble catalysts.
  • homogeneously soluble is intended to mean that the catalyst used is soluble to more than 1 g / 100 ml at 22 ° C., at least in the first alcohol used.
  • heterogeneous basic catalysts are arranged in a stationary manner in the reaction zone.
  • Heterogeneous catalysts are selected, for example, below basic oxides, mixed oxides or hydroxides and ion exchangers in amine or hydroxyl form.
  • the materials may be used as such or embedded in an oxidic binder matrix, e.g., from alumina, silica, mixtures of fumed silica and alumina, titania, zirconia or clay into moldings such as strands or tablets are formed.
  • an oxidic binder matrix e.g.
  • the heterogeneous basic catalyst is in particulate form having a particle size (maximum elongation) of 1 to 10 mm, preferably 1 to 4 mm.
  • the heterogeneous catalyst is introduced into the reaction zone in such a way that sufficient gaps remain so that a rectificative mass transfer can take place.
  • the catalyst is preferably used in a concentration of 10 to 60% by volume, based on the void volume of the column.
  • the heterogeneous catalyst can be placed on trays or installed as a catalyst bed in the reaction zone.
  • catalyst-containing packages e.g. Montz MULTIPAK or Sulzer KATAPAK, or to introduce the catalyst in the form of packing in the column.
  • the heterogeneous catalysts between an inert fabric or knitted fabric, for. B. fiberglass bring in and roll up into bales (so-called Bales).
  • the bales can be arranged next to and above each other so that the bales of one layer cover the interstices of the underlying layer.
  • the heterogeneous catalyst has a suitable particle size and shape such that it can be introduced into the reaction zone as a packing, optionally mixed with inert fillers.
  • Homogeneously soluble basic catalysts are metered into the reaction column at any suitable point in the lower to middle column range, expediently together with the first alcohol.
  • the homogeneously soluble catalysts used are, for. B. selected from alkali metal hydroxides and / or alcoholates, such as potassium, sodium methylate.
  • the catalysts are expediently metered in the form of a solution in a suitable solvent.
  • a preferred solvent is the first or second alcohol used in the process of the invention.
  • the homogeneously soluble catalyst if used, is usually used in an amount of 0.00001 to 0.2, preferably 0.0001 to 0.1, and more preferably 0.0005 to 0.05, equivalents based on the first carboxylic acid ester.
  • the first feed is preferably introduced laterally into the reaction column at at least one first feed point located between the top and bottom of the reaction column, and introduces the second feed laterally into the reaction column at a second feed point located above the first feed point.
  • the reaction zone extends at least partially to the column section between the first and second feed points.
  • the ongoing removal of the reaction products from the reaction zone is achieved by the mass transfer processes taking place in the reaction column.
  • vapors of a low-boiling fraction which comprises the second carboxylic acid ester formed and the unconverted first carboxylic acid ester and the unreacted first alcohol and the second alcohol are removed.
  • the low-boiling fraction passes into a rectifying section of the reaction column, in which the entrained unreacted first alcohol and the second alcohol are separated and run back into the reaction zone.
  • a product fraction comprising the second carboxylic acid ester and unconverted first carboxylic acid ester, preferably as a side draw.
  • the second carboxylic acid ester and the first carboxylic acid ester form azeotropes with the alcohols, so that the composition of the product fraction substantially corresponds to the azeotrope composition.
  • the product fraction may contain minor amounts of first alcohol and second alcohol.
  • top fraction At the top of the reaction column mainly unreacted first carboxylic acid ester is condensed and partly recycled as a head reflux in the reaction column and partially withdrawn as a top fraction.
  • the top fraction is at least partially returned to the reaction zone, for example by admixing with the first feed. Another part of the top fraction can be removed to prevent accumulation of low boilers.
  • a condensate of a high-boiling fraction comprising in addition to unreacted first alcohol and second alcohol entrained second carboxylic acid ester and unreacted first carboxylic acid ester.
  • the high-boiling fraction passes into a stripping section of the column in which the entrained second carboxylic acid ester and unreacted first carboxylic acid ester are stripped off and returned to the reaction zone.
  • a bottoms fraction comprising the second alcohol and unreacted first alcohol can be withdrawn. In order to remove forming high-boiling components, part of the bottoms fraction can be discarded.
  • the bottom fraction is separated by distillation into the second alcohol and unconverted first alcohol, preferably in a further distillation column.
  • the unreacted first alcohol is advantageously at least partially recycled to the reaction zone by admixing it, for example, the second feed.
  • the product fraction contains in addition to the second carboxylic acid ester usually unreacted first carboxylic acid ester and small amounts of second alcohol and unreacted first alcohol.
  • the product fraction is therefore preferably separated by distillation into pure second carboxylic acid ester and a fraction containing unreacted first carboxylic acid ester.
  • the distillative separation is preferably carried out continuously in a second column.
  • the fraction containing the unreacted first carboxylic acid ester is preferably at least partly returned to the reaction zone, for example by admixing with the first feed.
  • the product fraction comprises azeotropes of the second carboxylic acid ester with second alcohol and unreacted first alcohol and unreacted first Carbonklareester. Since the azeotrope composition is generally pressure-dependent, the separation of the azeotrope succeeds by distillation at a pressure which is different from the pressure in the reaction column. The person skilled in this phenomenon is known as a two-pressure process or pressure swing rectification or pressure swing distillation. At a different pressure from the pressure in the reaction column, the composition of the product fraction corresponds to another azeotrope composition.
  • the second carboxylic acid ester in the second column, can be withdrawn purely at the bottom or in the lower part of the column, for example near the bottom region of the column, while an azeotropic mixture is formed in the top, albeit in a significantly different composition than in the product fraction.
  • This azeotropic mixture can be fed back into the reaction zone.
  • the stream obtained at the bottom of the second column contains 99.0 to 100% by weight (in particular 99.8 to 100% by weight) Ethyl formate, 0 to 1 wt .-% (in particular 0 to 0.2 wt .-%) of ethanol and 0 to 1 wt .-% (in particular 0 to 0.2 wt .-%) of other compounds.
  • Fig. 1 shows schematically a suitable for carrying out the method according to the invention plant.
  • reaction column T1 is introduced via a lateral inlet 2, which is located at the upper end of the reaction zone 1, a first alcohol.
  • a heterogeneous catalyst (not shown) is introduced in a stationary manner.
  • the reaction takes place to the second carboxylic acid ester and second alcohol.
  • the second carboxylic acid ester and unconverted first carboxylic acid ester enter the enrichment section 4 of the reaction column T1, where they are largely freed from entrained second alcohol and unreacted first alcohol.
  • Second alcohol and unreacted first alcohol from the reaction zone 1 enter the stripping section 5 of the Christshkolonne T1, where they are stripped off entrained second carboxylic acid ester and unreacted first carboxylic acid ester.
  • the bottoms fraction withdrawn via line 7 consists mainly of second alcohol and unreacted first alcohol.
  • the vapor 8 obtained at the top of the reaction column is condensed and partly returned to the reaction column via line 9 as a head reflux and partially fed via line 10 as feed into the reaction zone.
  • the withdrawn at the side offtake 6 product fraction from the reaction column T1 is fed to a distillation column T2 at its upper portion.
  • the column T2 is operated at a different pressure, usually a higher pressure, than the reaction column T1.
  • At the bottom of the distillation column T2 falls to pure second carboxylic acid ester, which is removed via line 1 1.
  • the top hatch of the distillation column T2 is returned via the line 12 in the reaction column T1.
  • the bottoms fraction from the reaction column T1 is withdrawn via line 7 and fed to a distillation column T3.
  • reaction column operated at 1 bar with 30 theoretical stages were fed at stage 10 about 60 g / h of ethanol. At level 5, 81 g / h of methyl formate was added. It is assumed that on the intervening soils the reaction to ethyl formate and methanol takes place up to chemical equilibrium.
  • the reflux ratio of the reaction column was about 11.
  • the overhead condensate consisting essentially of methyl formate was partially returned as reflux and partially recycled to the lower part of the reaction column.

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  • 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

L'invention concerne un procédé de production d'esters d'acides carboxyliques par transestérification, selon lequel une première alimentation qui contient un premier ester d'acide carboxylique, par exemple du formiate de méthyle est introduit latéralement dans la colonne de réaction par au moins un premier point d'alimentation situé entre la tête et le fond d'une colonne de réaction et une deuxième alimentation contenant un premier alcool, par exemple de l'éthanol, est introduite latéralement dans la colonne de réaction au niveau d'un deuxième point d'alimentation situé au-dessus du premier point d'alimentation, et entre en réaction dans une zone de réaction de la colonne de réaction en formant un deuxième ester d'acide carboxylique et un deuxième alcool. Le premier alcool présente un poids moléculaire supérieur à celui du deuxième alcool. A un point de soutirage situé au-dessus du deuxième point d'alimentation, on récupère une fraction de produit contenant le deuxième ester d'acide carboxylique et le premier ester d'acide carboxylique non transformé. Dans le fond de la colonne de réaction, on soutire une fraction de fond contenant le deuxième alcool et le premier alcool non transformé. On sépare la fraction de produit à une pression, différente de la pression régnant dans la colonne de réaction, par distillation en un deuxième ester d'acide carboxylique et en une fraction contenant le premier ester d'acide carboxylique non transformé puis on renvoie la fraction contenant l'ester d'acide carboxylique non transformé au moins partiellement dans le zone de réaction.
EP11714782A 2010-04-19 2011-04-19 Procédé de production d'esters d'acides carboxyliques par distillation réactive Withdrawn EP2560943A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11714782A EP2560943A2 (fr) 2010-04-19 2011-04-19 Procédé de production d'esters d'acides carboxyliques par distillation réactive

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10160353 2010-04-19
PCT/EP2011/056189 WO2011131643A2 (fr) 2010-04-19 2011-04-19 Procédé de production d'esters d'acides carboxyliques par distillation réactive
EP11714782A EP2560943A2 (fr) 2010-04-19 2011-04-19 Procédé de production d'esters d'acides carboxyliques par distillation réactive

Publications (1)

Publication Number Publication Date
EP2560943A2 true EP2560943A2 (fr) 2013-02-27

Family

ID=44625874

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11714782A Withdrawn EP2560943A2 (fr) 2010-04-19 2011-04-19 Procédé de production d'esters d'acides carboxyliques par distillation réactive

Country Status (5)

Country Link
EP (1) EP2560943A2 (fr)
JP (1) JP2013525325A (fr)
KR (1) KR20130051452A (fr)
CN (1) CN102844292B (fr)
WO (1) WO2011131643A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014050788A1 (fr) * 2012-09-28 2014-04-03 Ｊｘ日鉱日石エネルギー株式会社 Procédé de production d'un anhydride d'acide carboxylique
CN106083586B (zh) * 2016-08-10 2021-09-14 烟台国邦化工机械科技有限公司 一种利用甲酸和乙醇合成甲酸乙酯并提纯产品的工艺方法
KR102019037B1 (ko) * 2017-05-26 2019-09-06 지에스칼텍스 주식회사 알킬 카르복실산 에스테르의 제조 방법
US20230295071A1 (en) * 2020-09-24 2023-09-21 Lg Chem, Ltd. Method for preparing ester-based composition
CN116162025A (zh) * 2021-11-24 2023-05-26 中国石油化工股份有限公司 一种分离甲酸甲酯的方法

Family Cites Families (5)

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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 (ja) 1996-12-13 1998-06-30 Daicel Chem Ind Ltd ギ酸エステルの製造方法
JP2000016966A (ja) * 1998-07-01 2000-01-18 Mitsubishi Gas Chem Co Inc アクリル酸エステルまたはメタクリル酸エステルの製造方法
BRPI0707394A2 (pt) 2006-02-28 2011-05-03 Shell Internationale Res Maartschappij B V processo para destilação reativa
DE102007006917A1 (de) * 2007-02-13 2008-08-14 Technocon Gmbh Verfahren und Vorrichtung zur kontinuierlichen katalytischen Umesterung

Non-Patent Citations (1)

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Title
See references of WO2011131643A2 *

Also Published As

Publication number Publication date
CN102844292A (zh) 2012-12-26
CN102844292B (zh) 2014-07-16
WO2011131643A3 (fr) 2011-12-29
JP2013525325A (ja) 2013-06-20
WO2011131643A2 (fr) 2011-10-27
KR20130051452A (ko) 2013-05-20

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