EP3405450A1 - Verfahren zur reinigung von (meth)-acrylsäureestern - Google Patents

Verfahren zur reinigung von (meth)-acrylsäureestern

Info

Publication number
EP3405450A1
EP3405450A1 EP17702671.3A EP17702671A EP3405450A1 EP 3405450 A1 EP3405450 A1 EP 3405450A1 EP 17702671 A EP17702671 A EP 17702671A EP 3405450 A1 EP3405450 A1 EP 3405450A1
Authority
EP
European Patent Office
Prior art keywords
column
meth
partition
section
ester
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.)
Pending
Application number
EP17702671.3A
Other languages
English (en)
French (fr)
Inventor
Serge Tretjak
Nathalie Hess
Rose AGUIAR
Pierre-Emmanuel CONOIR
Christophe OSES
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.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of EP3405450A1 publication Critical patent/EP3405450A1/de
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/48Separation; Purification; Stabilisation; Use of additives
    • C07C67/52Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D3/00Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14Fractional distillation or use of a fractionation or rectification column
    • B01D3/141Fractional distillation or use of a fractionation or rectification column where at least one distillation column contains at least one dividing wall
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D5/00Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B01D5/006Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/08Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/48Separation; Purification; Stabilisation; Use of additives
    • C07C67/62Use of additives, e.g. for stabilisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54Acrylic acid esters; Methacrylic acid esters

Definitions

  • the present invention relates to the production of (C 1 -C 4) (meth) acrylic esters by direct esterification of (meth) acrylic acid with the corresponding alcohol.
  • the subject of the invention is more particularly a process for the recovery / purification of a (C 1 -C 4) (meth) acrylic ester from a crude reaction mixture comprising the said ester, the process being carried out using a system method of purification comprising a partition column and a decanter, leading to process simplification and high productivity of the product ester meeting purity standards.
  • the invention also relates to a process for producing (C1-C4) (meth) acrylic ester comprising this recovery / purification process.
  • (meth) acrylic esters in particular the C.sub.1 -C.sub.4 esters generally known under the name light (meth) acrylic esters or light (meth) acrylates, such as methyl acrylate or methacrylate, and acrylate. or ethyl methacrylate, by direct esterification of the (meth) acrylic acid with the corresponding alcohol, catalyzed for example by sulfuric acid or an ion exchange resin.
  • the esterification reaction generates water and is generally accompanied by secondary reactions producing impurities, in particular heavy compounds, that is to say having a high boiling point, greater than that of the ester. research.
  • a treatment set of the crude reaction mixture resulting from the esterification reaction is generally carried out by means of distillations and / or extractions and settlements, which assembly is at the same time relatively complex to implement. , and expensive in terms of energy.
  • the purification of the crude reaction mixture generally comprises at least the following stages:
  • the crude reaction mixture is subjected to distillation in a first column, called a topping column, which makes it possible to obtain:
  • a rectification column which separates:
  • the foot flow of the second column is subjected to different treatments in order to efficiently conserve the heavy by-products.
  • the use of these two columns in series has the disadvantage that the streams are subjected to high temperatures and high residence times, especially in the reboiler associated with the first column, or at the bottom of the first column.
  • the purified ester is obtained by distillation using the second column with elimination of heavy by-products. This thermal exposure results in the additional formation of heavy by-products by thermal degradation, for example in the form of Michael adducts, thus reducing the recovery yield of the purified ester and increasing the final amount of heavy impurities to be removed.
  • the purification treatment needs to be controlled using stabilizers to limit the polymerization reactions that can occur under the operating conditions of the two columns.
  • a first inhibitor of polymerization usually hydroquinone (HQ)
  • HQ hydroquinone
  • QHQH methylhydroquinone methyl ether
  • DWC Divided wall column
  • French French "column à partition”.
  • This technology uses a single column, comprising an internal partition wall which allows to combine the operation of two columns traditionally in series in a single apparatus, by implementing a reboiler and a single condenser.
  • patent application EP 2 659 943 describes a configuration of a partition column and its operation in a process for producing high purity 2-ethylhexyl acrylate.
  • this column is complex to manufacture and operate, it has the advantage of reducing the equipment cost and energy consumption of the purification process, compared to a conventional installation comprising two distillation columns. The question of the stabilization necessary for its proper functioning is however not addressed.
  • the purification method described in this document does not apply to the production of light acrylates by direct esterification. Indeed, in the case for example of the synthesis of ethyl acrylate, the crude reaction medium comprises, in addition to the desired ethyl acrylate, but also the water produced by the reaction, ethyl acrylate. and since water has very similar boiling temperatures, the separation of water in a single column remains problematic.
  • Patent Application JP 2005-239564 also describes the use of a partition column in a process for the synthesis of (meth) acrylic esters, exemplified in the case of the synthesis of butyl methacrylate by transesterification reaction between methacrylate of methyl and butanol.
  • a separator is associated with the partition column to prevent entrainment of stabilizer droplets in the side draw and control the amount of stabilizers in the purified product.
  • the partition column makes it possible to separate the targeted ester with the heavy products and the lighter products.
  • the document WO 2012/071158 describes a process for the synthesis of (meth) acrylates of C1-C4 alkyl, in particular of butyl acrylate, in which the problem of water arises during the reaction stage of 'esterification. In fact, it is necessary to eliminate the water to shift the equilibrium of the reaction, but also it is necessary to maintain water in the reactor to favor certain azeotropes and to avoid the loss of ester or alcohol at the head of the column. This is done by placing a decanter at the top of the reactor-distillation column assembly to separate an aqueous phase which is refluxed at the top of the column.
  • the column surmounting the reactor may be a conventional column or a partition column, but it is not intended to purify the reaction mixture.
  • the purified ester is obtained in a conventional purification section from the separated organic phase using the clarifier placed at the top of the distillation column surmounting the reactor.
  • the objective of the present invention is therefore to provide a process for recovering a purified C1-C4 (meth) acrylic ester using a purification system comprising a partition column and a decanter.
  • the present invention thus provides a techno-economic solution to the problem of purifying a crude reaction mixture resulting from the esterification reaction of (meth) acrylic acid with a C1-C4 alcohol.
  • the subject of the invention is a process for recovering a purified C1-C4 (meth) acrylic ester from a crude reaction mixture obtained by direct esterification of (meth) acrylic acid with the corresponding alcohol, characterized in that it is carried out using a purification system comprising:
  • partition column equipped with an internal partial partition creating separation zones in the column, and associated in foot with a single boiler and leading at a single condenser, said partition column comprising a common rectification section above the septum, a pre-fractionation section comprising the supply of the column, a withdrawal section separated from the prefractionation section by the partition comprising the withdrawal of the purified ester, and a common reboiling section below the partition;
  • the stabilization of the purification system is carried out using a single polymerization inhibitor, preferably injected at the top condenser, the purified (meth) acrylic ester being withdrawn laterally from the column. partition in the form of a liquid or gaseous flow already stabilized.
  • the stabilization of the purification system is carried out using a first polymerization inhibitor, preferably injected at the top condenser, the purified (meth) acrylic ester being withdrawn laterally from the column. partitioning in the form of a gas stream which, after condensation, is then stabilized with a polymerization inhibitor different from the first inhibitor.
  • the process according to the invention is applicable to the synthesis of light alkyl (meth) acrylates, the esterifying alcohol being a primary or secondary aliphatic alcohol comprising a linear or branched alkyl chain containing from 1 to 4 carbon atoms.
  • the esterifying alcohol being a primary or secondary aliphatic alcohol comprising a linear or branched alkyl chain containing from 1 to 4 carbon atoms.
  • examples of alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanol.
  • the alcohol is ethanol.
  • acrylic acid is used.
  • the recovery process according to the invention results in a C 1 -C 4 (meth) acrylate of purity at least equivalent to that obtained in a conventional plant comprising two distillation columns, and this under operating conditions which minimize thermal degradation. thermosensitive compounds, and in more economical energy conditions.
  • the inventors have discovered that the stabilization of the purification system combining a partition column and a clarifier is more advantageous than the stabilization of a conventional installation comprising two columns in series.
  • the polymerization inhibitor used to stabilize the desired ester can be introduced into the purification system as a single polymerization inhibitor, it follows a simplification and stability stabilization.
  • a less expensive polymerization inhibitor can be used to stabilize the partition column, and the purified ester is then stabilized with another compound more suitable for stabilizing the finished product for storage and subsequent use. In this case, the cost related to the polymerization inhibitors can be greatly reduced.
  • Another subject of the invention is a process for producing a purified (C 1 -C 4) (meth) acrylic ester by direct esterification of (meth) acrylic acid with the corresponding alcohol, characterized in that the crude reaction mixture is subjected to the recovery process using the purification system as defined above.
  • the invention makes it possible to achieve the desired specifications in terms of purity of light (meth) acrylic esters under economic conditions.
  • FIG. 1 represents an exemplary configuration of a purification system comprising a partition column and a decanter that can be used in the process according to the invention.
  • the partition column comprises a partial vertical partition (or wall) P, placed inside the column thus defining four distinct zones: an upper zone, a central zone comprising two zones on the other hand; other of the partition, and a lower zone.
  • the partition may be partly diagonal.
  • the partition can be flat or cylindrical so that the spaces separated by the partition can be arranged in concentric form.
  • the partition as set up does not necessarily separate the central zone into two equal zones, it may indeed be advantageous in some embodiments to have unequal zones in order to minimize the pressure drop or the tendency to clogging. depending on the nature or intensity of the flows flowing in the column.
  • the central zone consists of two zones on either side of the partition, one of which represents a so-called pre-fractionation section and the other a withdrawal section of the pure product.
  • the pre-fractionation section includes the supply F of the column, thus separating a section S1 above the feed and a section S2 below the feed.
  • the pre-fractionation section has the effect of concentrating the most volatile products called light compounds, as well as water, at the top of the column, and concentrating the less volatile products called heavy compounds at the bottom of the column.
  • the withdrawal section has a lateral outlet for withdrawing the purified ester S, the lateral outlet dividing the withdrawal section into two sections S4 and S5.
  • the withdrawal of the purified ester can be carried out in the form of a liquid stream or a gaseous stream, preferably a gas stream is withdrawn.
  • light compounds as well as water are sent to the top of the column and heavy compounds are sent to the bottom of the column.
  • the rectification section S3 Above the bulkhead at the top of the partition column is a common zone, called the rectification section S3, which makes it possible to separate the light compounds which are condensed in the condenser C associated with the column.
  • the settler D placed at the outlet of the condenser C, is used to continuously or discontinuously separate an aqueous phase A and to ensure a reflux of a part of the organic phase L comprising the light compounds at the level of the rectification section S3. other part of the organic phase L being withdrawn.
  • the aqueous phase A can be sent continuously or discontinuously to a biological station.
  • the liquid reflux on the pre-fractionation and withdrawal sections (not shown) is provided by a collection means for distributing in a controlled manner the liquid from the bottom of the section. rectification to the pre-fractionation and withdrawal sections.
  • the foot of the partition column is an S6 reboiling section
  • a number of parameters characterize the design and operation of the partition column. This is mainly the number of theoretical stages in each section of the partition column, in particular the numbers N1, N2, N3, N4, N5 and N6 respectively corresponding to the number of stages of each of the sections S1 to S6 described.
  • the reflux ratio of the column the ratio of liquid flow from the rectification section on each side of the partition, the gas flow ratio from the reboiling section on each side of the partition, the positioning of the point, feed F or lateral draw-off point S of the pure product.
  • partition column and the internals present are chosen to obtain the number of theoretical stages required in each section. Trays, ordered packing such as structured packing or bulk packing may be used as trays.
  • the number of theoretical stages of the prefractionation section S1 + S2 is between 1 and 10, and the supply of the column is preferably placed in the first third of this section.
  • the number of theoretical stages of the withdrawal section S4 + S5 is between 2 and 15, and the withdrawal point of the purified ester is preferably placed approximately 3/4 of this section. According to one embodiment, the number of theoretical stages of the rectification section S 3 is between 5 and 15.
  • the number of theoretical stages of the reboiling section S6 is between 2 and 10.
  • the column can operate under vacuum, in order to minimize the thermal exposure of the heat-sensitive compounds within the column.
  • the column operates under a vacuum ranging from 100 to 500 mmHg (or 130 mbar to 755 mbar).
  • the operating temperature is between 50 ° C. and 120 ° C.
  • the internals used for the column can be either valve trays or perforated trays with spillways, or ordered packing as structured packing such as the Sulzer Mellapack 250X.
  • the settler placed at the outlet of the condenser may be a horizontal settler with an interface setting that allows a constant withdrawal of the aqueous phase and the organic phase which is partially returned to the column.
  • This decanter can also be in the case of discontinuous operation, a tank equipped with an overflow to redistribute the organic phase and a bottom tank emptying system that will eliminate water intermittently.
  • the light compounds present in the reaction medium are generally the residual reagents - acrylic acid and ethanol - ethyl acetate and the water generated by the reaction.
  • HQ hydroquinone
  • EMHQ hydroquinone monoethyl ether
  • BHT diterbutyl para-cresol
  • paraphenylene diamine paraphenylene diamine
  • TEMPO 2,6,6-tetramethyl-1-piperidinyloxy
  • di-tert-butylcatechol di-tert-butylcatechol
  • TEMPO derivatives such as OH-TEMPO, alone or mixtures thereof in all proportions.
  • a single stabilizer is used, injected at the top condenser, the purified ethyl acrylate being withdrawn laterally from the withdrawal section in the form of a liquid flow or a gaseous flow.
  • the purified ethyl acrylate is then directly stabilized and able to be stored for later use.
  • a first polymerization inhibitor injected at the top condenser, is used to limit the secondary reactions of polymerization in the partition column, and the purified ethyl acrylate is laterally withdrawn in the form of a gaseous flow which, after condensation, is stabilized with a polymerization inhibitor different from the previous injected into the overhead condenser.
  • Hydroquinone is suitable as the first polymerization inhibitor because it also helps to stabilize the phase aqueous solution from the presence of water at the top of the column.
  • the ethyl acrylate withdrawn is then stabilized according to conventional practice, for example with the aid of methyl ether of hydroquinone.
  • purified (meth) acrylic ester is meant a product having a content of (meth) acrylic ester> 99.9% by weight, and generally the following impurity contents: alkyl acetate ⁇ 230 ppm, alkyl crotonate ⁇ 170 ppm.
  • the invention also relates to a method for producing a purified (C1-C4) (meth) acrylic ester by direct esterification of (meth) acrylic acid with the corresponding alcohol, characterized in that the crude reaction mixture is subjected to the recovery process using a purification system as defined above.
  • the conditions of the esterification reaction are those known to those skilled in the art, and may be implemented according to a continuous, semi-continuous or discontinuous type process.
  • the invention thus provides a process for producing a (meth) acrylic ester in
  • ECROTONA ethyl crotonate
  • Furfural Furfural HQ: hydroquinone
  • a crude reaction mixture of ethyl acrylate from the synthesis by direct esterification of acrylic acid with ethanol was subjected to a purification treatment using two columns of distillation in series.
  • the first column has an equivalent in theoretical stages of 15 and is associated at the bottom with a boiler, and at the top with a condenser / decanter in which an organic phase is separated and recycled partially in the column to ensure a reflux of it.
  • the column is stabilized by injection of HQ at the top condenser.
  • the energy supplied by the boiler is 2.94 Gcal / h.
  • the second column has an equivalent in theoretical stages of 10 and is associated in foot with a boiler and head at a condenser. It is fed by the foot flow of the first column that includes ⁇ , as well as heavy byproducts such as furfural, ⁇ and HQ stabilizer. The second column is stabilized by injection of EMHQ at the top condenser. The energy supplied by the boiler is 1.67 Gcal / h.
  • is recovered with a yield of the order of 98.9% relative to the feed stream, and ⁇ has a purity greater than 99.9%.
  • the partition column is stabilized at the top condenser with HQ and the ethyl acrylate withdrawn at the side in the gas phase is stabilized by EMHQ.
  • the energy supplied by the boiler is 3.3 Gcal / h.
  • the purified product withdrawn laterally has the following mass composition:
  • is recovered with a yield of the order of 98.9%> with respect to the feed stream, and ⁇ has a purity greater than 99.9%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP17702671.3A 2016-01-21 2017-01-03 Verfahren zur reinigung von (meth)-acrylsäureestern Pending EP3405450A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1650469A FR3047004B1 (fr) 2016-01-21 2016-01-21 Procede de purification d'esters (meth)acryliques
PCT/FR2017/050005 WO2017125657A1 (fr) 2016-01-21 2017-01-03 Procede de purification d'esters (meth)acryliques

Publications (1)

Publication Number Publication Date
EP3405450A1 true EP3405450A1 (de) 2018-11-28

Family

ID=55542938

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17702671.3A Pending EP3405450A1 (de) 2016-01-21 2017-01-03 Verfahren zur reinigung von (meth)-acrylsäureestern

Country Status (9)

Country Link
US (1) US10508074B2 (de)
EP (1) EP3405450A1 (de)
JP (1) JP2019504078A (de)
KR (1) KR102647454B1 (de)
CN (1) CN108473412A (de)
BR (1) BR112018013060B1 (de)
FR (1) FR3047004B1 (de)
TW (1) TW201738199A (de)
WO (1) WO2017125657A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10894223B2 (en) 2016-12-21 2021-01-19 Basf Se Process for isolating pure 2-ethylhexyl acrylate or pure 2-propylheptyl acrylate from the corresponding crude alkyl acrylate by distillation
US10906862B2 (en) 2016-12-21 2021-02-02 Basf Se Process for isolating pure butyl acrylate from crude butyl acrylate by distillation, where butyl is n-butyl or isobutyl
KR102519200B1 (ko) 2016-12-21 2023-04-06 바스프 에스이 조질 t-부틸 (메트)아크릴레이트로부터 증류에 의해 순수 t-부틸 (메트)아크릴레이트를 단리하는 방법
FR3083233B1 (fr) * 2018-06-27 2020-05-29 Arkema France Procede de purification d'acrylates legers.
FR3091871B1 (fr) * 2019-01-22 2020-12-18 Arkema France Procede de purification d’esters (meth)acryliques a l’aide d’une colonne a partition
CN113574047A (zh) * 2019-04-16 2021-10-29 罗门哈斯公司 由丙烯酸和甲醇进行的酸催化的丙烯酸甲酯合成
CN112552174B (zh) * 2020-12-23 2023-04-11 江门谦信化工发展有限公司 一种精馏乙酸酯的装置及方法
CN114011341A (zh) * 2021-11-15 2022-02-08 丹东明珠特种树脂有限公司 催化精馏塔和深脱除异丁烯之高纯度mtbe制备系统

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JPS6299345A (ja) * 1985-10-24 1987-05-08 Nippon Kayaku Co Ltd アクリル酸エステル又はメタクリル酸エステルの回収法
JP3999926B2 (ja) * 2000-05-12 2007-10-31 三菱レイヨン株式会社 メタクリル酸エステルの精製方法
JP3672818B2 (ja) * 2000-12-26 2005-07-20 三菱レイヨン株式会社 (メタ)アクリル酸エステルの精製方法
JP4733275B2 (ja) * 2001-01-10 2011-07-27 三菱レイヨン株式会社 (メタ)アクリル酸エステルの精製方法
JP2005239564A (ja) * 2004-02-24 2005-09-08 Mitsubishi Rayon Co Ltd (メタ)アクリル酸エステルの製造方法
JP2007045803A (ja) * 2005-08-12 2007-02-22 Asahi Kasei Chemicals Corp 精製されたメタクリル酸メチルを得る方法
CN101367720A (zh) * 2008-09-18 2009-02-18 中国石油大学(华东) 一种隔壁共沸精馏塔提纯丙烯酸的工艺方法及装置
JP6030564B2 (ja) * 2010-11-22 2016-11-24 ローム アンド ハース カンパニーRohm And Haas Company ブチルアクリレートの製造方法
KR101496488B1 (ko) * 2010-12-29 2015-02-26 주식회사 엘지화학 고순도 2-에틸헥실-아크릴레이트 생산을 위한 분리벽형 증류탑 및 이를 이용한 제조방법

Also Published As

Publication number Publication date
WO2017125657A1 (fr) 2017-07-27
KR102647454B1 (ko) 2024-03-13
FR3047004A1 (fr) 2017-07-28
FR3047004B1 (fr) 2019-08-09
BR112018013060A2 (pt) 2018-12-11
US20190016665A1 (en) 2019-01-17
US10508074B2 (en) 2019-12-17
CN108473412A (zh) 2018-08-31
BR112018013060B1 (pt) 2022-02-15
TW201738199A (zh) 2017-11-01
KR20180108644A (ko) 2018-10-04
JP2019504078A (ja) 2019-02-14

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