• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The subject of the invention is 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 purification system. comprising a partition column and a decanter, leading to a simplification of the process and a high productivity of the ester product meeting the standards for purity. The invention also relates to a method for producing (C 1 -C 4) (meth) acrylic ester comprising this recovery / purification process
    公开号:FR3047004A1
    申请号:FR1650469
    申请日:2016-01-21
    公开日:2017-07-28
    发明作者:Serge Tretjak；Nathalie Hess；Rose Aguiar；Pierre-Emmanuel Conoir；Christophe Oses
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    PROCESS FOR PURIFYING (METH) ACRYLIC ESTERS
    TECHNICAL AREA
    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.
    BACKGROUND AND TECHNICAL PROBLEM
    It is known to produce (meth) acrylic esters, in particular the C 1 -C 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.
    In such processes, a high purity finished product is sought, while optimizing the balance of the raw materials. For these purposes, light compounds with a lower boiling point than the ester - mainly unreacted reagents - are isolated for recycling to the reaction, and the heavy products generated during the process are separated before they are separated. recovered by treatment for example on a film evaporator and / or thermal cracking.
    Consequently, 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.
    Schematically, the purification of the crude reaction mixture generally comprises at least the following steps: the crude reaction mixture is subjected to distillation in a first column, called a topping column, which makes it possible to obtain: at the top, a stream consisting essentially of light compounds; at the bottom, a stream comprising the desired ester, and heavy by-products; the bottom stream of the stripping column is subjected to a second column called a stripping column which makes it possible to separate: at the top, the desired purified ester; o at the bottom of a stream containing essentially the heavy by-products; at least part of the light compounds of the head stream of the first column are recycled to the reaction, after optional separation; the foot flow of the second column is subjected to different treatments in order to valorize 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, before the final obtaining of the ester by distillation using the second column and removal 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.
    Moreover, 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. For this purpose, a first polymerization inhibitor, usually hydroquinone (HQ), is injected onto the first column, and a second polymerization inhibitor, generally methylhydroquinone ether (QHQH) is injected onto the second column, resulting in a purified (meth) acrylic ester stabilized with hydroquinone methyl ether which can be stored and transported before use.
    A recent development in the field of distillation has come to light under the name DWC (Divided wall column) or in 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. By way of example, 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. Although 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 a transesterification reaction between methacrylate of methyl and butanol.
    In the documents of the prior art, the additional problem of separating water in a partition column for a process for producing light acrylates by direct esterification is not raised. Moreover, the presence of water in the medium to be treated requires a more complex stabilization to limit the polymerization reactions. It is necessary firstly to use a stabilizer for the organic medium and the aqueous medium present at the top of the column, and secondly to stabilize the purified ester to obtain a so-called commercial quality. To the inventors' knowledge, a purification technology combining a partition column and a decanter has never used to purify light (meth) acrylic esters, in particular ethyl acrylate, and the question of the stabilization necessary for its purification. good operation has not been treated in the prior art. 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.
    SUMMARY OF THE INVENTION 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 implemented using a purification system comprising a partition column equipped with an internal partial partition creating separation zones in the column, and a decanter.
    More particularly, the purification system comprises: a partition column equipped with an internal partial partition creating separation zones in the column, and associated in foot with a single boiler and at the head with a single condenser, said partition column comprising a common rectification section above the partition, 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 section reboiling below the partition; and a decanter placed at the outlet of the overhead condenser.
    According to one embodiment, the stabilization of the purification system is carried out using a single polymerization inhibitor, the purified (meth) acrylic ester being withdrawn laterally from the partition column in the form of a liquid stream or gas already stabilized.
    According to one embodiment, the stabilization of the purification system is carried out using a first polymerization inhibitor, the purified (meth) acrylic ester being withdrawn laterally from the partition column in the form of a gaseous stream which after condensation, is then stabilized with a polymerization inhibitor different from that introduced into the condenser.
    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. Examples of alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanol.
    Preferably, the alcohol is ethanol.
    Preferably, acrylic acid is used.
    The recovery process according to the invention leads to 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 the thermal degradation of the thermosensitive compounds, and in more economical energy conditions.
    In addition, 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. Indeed, 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. Alternatively, 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 the production of 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.
    Thus, the invention makes it possible to achieve the desired specifications in terms of purity of light (meth) acrylic esters under economic conditions.
    BRIEF DESCRIPTION OF THE FIGURES
    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.
    DETAILED DESCRIPTION OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows.
    Referring to FIG. 1, 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 either side of the column; other of the partition, and a lower zone. According to one embodiment, 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. In this section, 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.
    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 controllably distributing the liquid from the bottom of the rectification section to the pre-fractionation and withdrawal sections.
    The foot of the partition column constitutes a common stripping section S6 ("stripping") for distributing the steam from the boiler B placed at the bottom of the column in the pre-fractionation and withdrawal sections. At the bottom of the column is drawn a stream consisting essentially of heavy compounds H.
    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. previously, 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.
    These different parameters can be determined from methods known to those skilled in the art so that the (meth) acrylic ester is produced with a purity meeting the desired specifications.
    The 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.
    According to one embodiment, 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.
    According to one embodiment, 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 S3 is between 5 and 15.
    According to one embodiment, 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. Advantageously, the column operates under a vacuum ranging from 100 to 500 mmHg (or 130 mbar to 755 mbar).
    Advantageously, 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.
    For the sake of simplicity, the process of the invention is described with reference to a process for the production of C1-C4 acrylic ester, and in particular to the production of ethyl acrylate from acrylic acid and ethanol.
    As secondary reactions leading to the formation of heavy by-products during the manufacture of ethyl acrylate, it is essentially the formation of oligomers of unreacted acrylic acid, under dimer acrylic acid form (3-acryloxypropionic acid, n = 1) and to a lesser extent trimer acrylic acid (3-acryloxy, 3-propioxypropionic acid, n = 2), but also Michael (Michael adducts), especially between the already formed ethyl acrylate and the unreacted ethanol leading to ethyl ethoxy propionate, or the formation of 2-ethoxy ethanol.
    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.
    Apart from suitable operating conditions for the esterification reaction minimizing the formation of heavy compounds and optimizing the reaction yield, it is necessary to introduce polymerization inhibitors (also known as stabilizers) not only during the reaction, but also during the purification of the crude reaction mixture leaving the esterification reactor.
    As polymerization inhibitors that may be used, mention may be made, for example, of phenothiazine, hydroquinone (HQ), hydroquinone monoethyl ether (EMHQ), diterbutyl para-cresol (BHT), paraphenylene diamine, TEMPO (2 , 2,6,6-tetramethyl-1-piperidinyloxy), di-tert-butylcatechol, or TEMPO derivatives, such as OH-TEMPO, alone or mixtures thereof in all proportions.
    Advantageously, from 500 to 5000 ppm of polymerization inhibitor is introduced during the purification of the reaction mixture in the purification system according to the method of the invention.
    According to a first embodiment, 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. According to this embodiment, it is preferred to use mono methyl hydroquinone ether as a stabilizer.
    According to a second embodiment, 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 withdrawn in the form of a gas stream which, after condensation, is stabilized with a polymerization inhibitor different from the previous one. According to this embodiment, it is possible to use a first substantially cheaper inhibitor and overcome its presence in the purified product by performing a gas phase withdrawal, the first polymerization inhibitor remaining in the flow of by-products. heavy separated at the foot of the column. Hydroquinone is suitable as the first polymerization inhibitor because it also makes it possible to stabilize the aqueous phase resulting 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.
    By 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 process for the production of 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 C1-C4 (meth) acrylic ester in a compact plant whose investment and operating cost is reduced, and providing a product of high purity with optimized yield.
    The following examples illustrate the present invention without limiting its scope.
    EXPERIMENTAL PART
    In the examples, the percentages are by weight unless otherwise indicated and the following abbreviations have been used: AE: Ethyl acrylate EOH: Ethanol ACE: Ethyl acetate EPRO: Ethyl propionate EPE: Ethyl ethoxy propionate ECROTONA : ethyl crotonate
    Furfural: Furfural HQ: hydroquinone EMHQ: methyl ether of hydroquinone Example 1 (comparative)
    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 ΓΑΕ, as well as heavy byproducts such as furfural, 1ΈΡΕ 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. The feed of the first column has the mass composition and the following characteristics: AE: 93.88% - EOH: 0.26% - ACE: 0.38% - EPRO: 0.4% - EPE: 2.02% - Furfural: 0. 05% - ECROTONA: 0,34% - water: 3,02%
    Total flow: 12983 kg / h - temperature: 72,2 ° C - pressure: 0,394 bar
    An ASPEN simulation using the NRTL thermodynamic model was performed and provides the following mass composition for the purified product distilled at the top of the second column. AE: 99.91% - EOH: none - ACE: 0.0232% - EPRO: 0.04% - EPE: 0.002% - Furfural: none - ECROTONA: 0.0168% - EMHQ: 0.002%
    Total flow: 12069 kg / h
    Temperature: 35 ° C
    Pressure: 0.394 bar
    In this configuration, ΓΑΕ is recovered with a yield of the order of 98.9% relative to the feed stream, and ΓΑΕ has a purity greater than 99.9%.
    Example 2 (according to the invention)
    An ASPEN simulation using the NRTL thermodynamic model was carried out on the same crude reaction mixture of ethyl acrylate as that described in Example 1, but subjected to purification using the purification system such as shown in Figure 1.
    In this example, the partition column is stabilized at the top condenser with THQ and the ethyl acrylate withdrawn at the side in the gas phase is stabilized by EMHQ.
    In this configuration, the number of trays of the different sections is as follows: NI: 2 - N2: 5 - N3: 9 - N4: 6 - N5: 2 - N6: 6 The energy supplied by the boiler is 3.3 Gcal / h.
    The purified product withdrawn laterally has the following mass composition: AE: 99.92% - EOH: nil - ACE: 0.0223% - EPRO: 0.04% - EPE: 0.001% - Furfural: none - ECROTONA: 0.0149 % - EMHQ: 0.002%
    Total flow: 12065,8 kg / h
    Temperature: 76.8 ° C
    Pressure: 0.393 bars
    In this configuration, the AE is recovered with a yield of the order of 98.9% with respect to the feed stream, and the AE has a purity greater than 99.9%.
    Compared to the conventional process, the heat required for the boiler to ensure purification is reduced by around 28% (3.3 Gcal / h vs 4.61 Gcal / h), which makes the energy cost of operation more economical. .
    权利要求:
    Claims (12)
    [1" id="c-fr-0001]
    A process for recovering a purified C1-C4 (meth) acrylic ester from a crude reaction mixture obtained by direct esterification of the (meth) acrylic acid with the corresponding alcohol, characterized in that it is implemented using a purification system comprising a partition column equipped with an internal partial partition creating separation zones in the column, and a decanter.
    [2" id="c-fr-0002]
    2. Method according to claim 1 characterized in that the purification system comprises: - a partition column equipped with an internal partial partition creating separation zones in the column, and associated foot in a single boiler and head to a single condenser, said partition column comprising a common rectification section above the partition, 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 section of reboiling below the septum; and - a settling tank placed at the outlet of the overhead condenser.
    [3" id="c-fr-0003]
    3. Method according to claim 2 characterized in that the number of theoretical stages of the rectification section is between 5 and 15.
    [4" id="c-fr-0004]
    4. Method according to claim 2 or 3 characterized in that the number of theoretical stages of the prefractionation section is between 1 and 10.
    [5" id="c-fr-0005]
    5. Method according to any one of claims 2 to 4 characterized in that the number of theoretical stages of the withdrawal section is between 2 and 15.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 2 to 5 characterized in that the number of theoretical stages of the reboiling section is between 2 and 10.
    [7" id="c-fr-0007]
    7. Method according to any one of the preceding claims, characterized in that the stabilization of the purification system is carried out using a single polymerization inhibitor, the purified (meth) acrylic ester being withdrawn laterally from the column to partition in the form of a liquid or gaseous flow already stabilized.
    [8" id="c-fr-0008]
    8. Process according to claim 7, characterized in that methylhydroquinone ether is used as polymerization inhibitor.
    [9" id="c-fr-0009]
    9. A method according to any one of claims 1 to 6 characterized in that the stabilization of the purification system is carried out using a first polymerization inhibitor, the purified (meth) acrylic ester being withdrawn laterally from the partition column in the form of a gas stream which, after condensation, is then stabilized with a polymerization inhibitor different from that introduced into the condenser.
    [10" id="c-fr-0010]
    10. The method of claim 9 characterized in that the first inhibitor is hydroquinone, and the purified (meth) acrylic ester is stabilized with methyl ether hydroquinone.
    [11" id="c-fr-0011]
    11. Method according to any one of the preceding claims, characterized in that the (meth) acrylic ester C1-C4 is ethyl acrylate.
    [12" id="c-fr-0012]
    A process 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 the purification system as defined in any one of the preceding claims.
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    同族专利:
    公开号 | 公开日
    BR112018013060A2|2018-12-11|
    US10508074B2|2019-12-17|
    TW201738199A|2017-11-01|
    US20190016665A1|2019-01-17|
    FR3047004B1|2019-08-09|
    WO2017125657A1|2017-07-27|
    KR20180108644A|2018-10-04|
    EP3405450A1|2018-11-28|
    JP2019504078A|2019-02-14|
    CN108473412A|2018-08-31|
    引用文献:
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    EP3558923B1|2016-12-21|2020-12-02|Basf Se|Method for the recovery of pure 2-ethylhexylacrylate or pure 2-propylheptylacrylate from the corresponding raw alkyl acrylate|
    EP3558921B1|2016-12-21|2020-10-14|Basf Se|Method for the recovery of pure butyl acrylate from raw butyl acrylate by means of distillation, wherein butyl stands for n-butyl or isobutyl|
    FR3083233B1|2018-06-27|2020-05-29|Arkema France|PROCESS FOR THE PURIFICATION OF LIGHT ACRYLATES.|
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    法律状态:
    2016-12-15| PLFP| Fee payment|Year of fee payment: 2 |
    2017-07-28| PLSC| Publication of the preliminary search report|Effective date: 20170728 |
    2017-12-11| PLFP| Fee payment|Year of fee payment: 3 |
    2018-12-13| PLFP| Fee payment|Year of fee payment: 4 |
    2019-12-16| PLFP| Fee payment|Year of fee payment: 5 |
    2020-12-10| PLFP| Fee payment|Year of fee payment: 6 |
    2021-12-17| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1650469A|FR3047004B1|2016-01-21|2016-01-21|PROCESS FOR PURIFYINGACRYLIC ESTERS|
    FR1650469|2016-01-21|FR1650469A| FR3047004B1|2016-01-21|2016-01-21|PROCESS FOR PURIFYINGACRYLIC ESTERS|
    JP2018538078A| JP2019504078A|2016-01-21|2017-01-03| acrylic acid ester purification method|
    EP17702671.3A| EP3405450A1|2016-01-21|2017-01-03|Method for purifying acrylic esters|
    PCT/FR2017/050005| WO2017125657A1|2016-01-21|2017-01-03|Method for purifying acrylic esters|
    KR1020187022465A| KR20180108644A|2016-01-21|2017-01-03| acrylic ester|
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    US16/068,974| US10508074B2|2016-01-20|2017-01-03|Method for purifying acrylic esters|
    TW106101041A| TW201738199A|2016-01-21|2017-01-12|Process for purifying acrylic esters|
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