• 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 invention relates to a process for producing an alkyl (meth) acrylate having a linear or branched alkyl chain having from 4 to 10 carbon atoms, by direct esterification of (meth) acrylic acid with an alcohol linear or branched chain comprising from 4 to 10 carbon atoms in the presence of a catalyst, resulting in the formation of a reaction mixture comprising the desired ester, unreacted acid and alcohol, light by-products and heavy byproducts, which is subjected to a purification treatment by means of separation, in order to obtain the purified alkyl (meth) acrylate, said purification treatment being characterized in that it comprises a dehydration step by membrane separation applied to at least one of the following streams: the stream subjected to the final distillation leading to the recovery of the purified (meth) acrylic ester, the aqueous stream originating from the decantation of the reaction mixture , or the stream from the distillation of light byproducts present in the reaction mixture.
    公开号:FR3014870A1
    申请号:FR1362560
    申请日:2013-12-13
    公开日:2015-06-19
    发明作者:Serge Tretjak；Anne Moreliere
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the production of (meth) acrylic esters, and more particularly to an improvement in the production of C 4 alkyl (meth) acrylates. - C10, consisting in the implementation of a dehydration step by membrane separation of at least one stream generated during the purification of said alkyl (meth) acrylate. TECHNICAL BACKGROUND It is known to produce (meth) acrylic esters from an esterification reaction between an alcohol and a (meth) acrylic acid. This reaction is a balanced catalyzed reaction with water generation. It is also accompanied by side reactions producing impurities. It is necessary to remove the water produced to shift the equilibrium, to recycle the unreacted reagents (the alcohol and the acid), as well as to eliminate the impurities, in particular the lighter compounds than the ester and compounds heavier than the ester, so as to obtain a product meeting commercial specifications. For this purpose, a set of treatment of the reaction mixture is generally carried out by means of distillations and / or extractions and settlements, which assembly is at the same time relatively complex to implement, in particular because of the presence of azeotropic mixtures, and energy-intensive. The reaction mixture contains the desired ester, water, acid and unreacted alcohol, so-called "light" by-products having a boiling point lower than that of the ester and sub-products. -Products called "heavy", that is to say having a boiling temperature greater than that of the ester. The purification train applied to the reaction mixture generates different streams whose composition varies according to the apolar nature of the alcohol and the ester, that is to say according to the length of the alkyl chain of the alcohol used. These streams have in common to contain water resulting from the reaction and / or extraction steps. In the process for producing (meth) acrylic ester described in the patent application FR 2 980 475 in the name of the Applicant, membrane separation dehydration modules are used to dehydrate streams comprising (meth) acrylic ester and unreacted alcohol to effectively remove water and lead to good (meth) acrylic ester selectivity. These modules are especially applied at the level of the reaction stage, or at the level of the recycling of the unreacted alcohol for a concentration range of the various well-defined compounds, and mainly in the case of the production of (meth) C1 to C4 alkyl acrylates, such as methyl acrylate, ethyl acrylate or butyl acrylate.
    [0002] Surprisingly, the Applicant has now found that in the case of the production of C4-C10 alkyl (meth) acrylates, it is possible to apply a dehydration step by membrane separation to aqueous streams outside ranges. described in FR 2,980,475. This leads to the efficient removal of the water present in flows intended to be purified and / or recycled, distinct from the aqueous fluxes treated in the process of the aforementioned document, and thus avoids the formation of a water loop harmful to the productivity and energy consumption of the process. In particular, the dehydration step is advantageously applied upstream of the finishing column of the desired ester, or at the top of the separation column of the light compounds, or on the aqueous phase after decantation of the crude reaction mixture. SUMMARY OF THE INVENTION The subject of the invention is therefore a process for the production of an alkyl (meth) acrylate comprising a linear or branched alkyl chain containing from 4 to 10 carbon atoms, by direct esterification of the acid ( meth) acrylic with a linear or branched alcohol having 4 to 10 carbon atoms in the presence of a catalyst, resulting in the formation of a reaction mixture comprising the desired ester, unreacted acid and alcohol, by-products and heavy by-products, which is subjected to a purification treatment by means of separation, in order to obtain the purified alkyl (meth) acrylate, said purification treatment being characterized in that comprises a membrane separation dehydration step applied to at least one of the following streams: the stream subjected to the final distillation leading to the recovery of the purified (meth) acrylic ester, the aqueous stream coming from the decanted reaction mixture, or the stream from the distillation of the light byproducts present in the reaction mixture. According to one embodiment, the membrane separation dehydration is dehydration by pervaporation or by vapor permeation. According to one embodiment, the membrane separation is a separation on an inorganic membrane, preferably zeolite, and more preferably T-type zeolite; or on a polymeric membrane, preferably a hydrophilic membrane based on polyvinyl alcohol. According to one embodiment, the membrane separation is a separation on a hydrophobic polymeric membrane such as the 4060 membrane marketed by Sulzer.
    [0003] According to one embodiment, the method is chosen from continuous, semi-continuous or discontinuous type processes. The present invention more particularly provides a process for producing (meth) acrylic esters having a good selectivity, allowing an effective removal of water and to reduce the energy cost while minimizing the installation cost which is directly proportional to a membrane process at the permeate hourly flux per square meter of installed membrane. Moreover, in the particular case of the use of hydrophobic membrane, it is possible to treat an aqueous stream containing less than 7% of organic compounds and thus to reduce the size of the purification column which will be placed downstream and therefore its energy consumption, or even totally eliminate it. Moreover, surprisingly with respect to the process described in document FR 2 980 475, the membrane separation treatment steps have very good performances outside the concentration ranges described, mainly because of the choice of alcohol and therefore the ester used, in particular because of their apolar nature which makes easy the passage of water through the hydrophilic membrane.
    [0004] BRIEF DESCRIPTION OF THE FIGURES FIG. 1 schematically represents an installation for implementing a semicontinuous process for producing (meth) acrylic ester. FIG. 2 schematically represents an installation for implementing a continuous process for producing (meth) acrylic ester with homogeneous catalysis. Figure 3 schematically shows an installation for implementing a continuous process for producing (meth) acrylic ester with heterogeneous catalysis.
    [0005] DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows.
    [0006] The terms "(meth) acrylic" and "(meth) acrylate" conventionally mean "acrylic or methacrylic" and "acrylate or methacrylate" respectively. Unless otherwise stated, the compositions given in percentages are expressed in mass values.
    [0007] The alcohol compound used in the context of the invention may be linear or branched. It may be a primary alcohol or a secondary alcohol. It can have 4 or 5 or 6 or 7 or 8 or 9 or 10 carbon atoms. It may be substituted or unsubstituted, and preferably it is unsubstituted. The alcohol compound may especially be butanol, 2-ethylhexanol or 2-octanol.
    [0008] The corresponding obtained esters are butyl acrylate or butyl methacrylate, 2-ethylhexyl acrylate or 2-ethylhexyl methacrylate, 2-octyl acrylate or 2-octyl methacrylate. Preferably, the (meth) acrylic acid is acrylic acid. The esterification reaction of the (meth) acrylic acid with the alcohol is carried out in the presence of a catalyst which may be, for example, an acidic cation exchange resin in the case of heterogeneous catalysis, or in the case of homogeneous catalysis, which may be an inorganic acid of sulfuric acid type or an organic sulfonic acid such as methanesulfonic acid, para-toluenesulphonic acid, benzenesulphonic acid, dodecylsulphonic acid, or their mixtures. In general, the esterification reaction is carried out in the presence of a stoichiometric excess of alcohol. The reaction mixture (hereinafter also referred to as the reaction stream) contains the ester product as well as the unreacted reagents mainly alcohol - which represent the light compounds to be separated and if possible to be recycled, and heavy by-products from secondary reactions. According to the invention, the streams subjected to dehydration by membrane separation are aqueous streams that are free from or almost free of heavy by-products, that is to say downstream streams of treatment for the separation of by-products having a temperature. boiling point higher than that of the (meth) acrylic ester. According to one embodiment, the flux treated by membrane separation is a flux subjected to the final distillation, leading to the recovery of the purified (meth) acrylic ester. According to this embodiment, the aqueous stream therefore contains a large content of (meth) acrylic ester, generally greater than 50%. According to one embodiment, the flux treated by membrane separation is an aqueous stream generated by decantation of the reaction mixture, the organic phase separated by decantation being almost free of water. According to this embodiment, the aqueous stream contains more than 80% water and a low content of organic compounds, generally less than 10%. According to one embodiment, the flux treated by membrane separation is a stream resulting from the distillation of the light by-products present in the reaction mixture. According to this embodiment, the aqueous stream therefore contains a high alcohol content, generally greater than 20%. According to the invention, the membrane-treated treated streams may contain water in a wide range, from 0.5 to 99%, of alcohol in a concentration range of from about 1 to 60%, the ester in a concentration range of about 0.5 to 70%, and to a lesser extent the acid in a concentration range of up to 15%. According to one embodiment, the membrane-treated flux comprises 50 to 70% (meth) acrylic ester, 20 to 30% alcohol, 0 to 12% (meth) acrylic acid, and from 3 to 12% of water.
    [0009] According to one embodiment, the membrane-treated flux comprises from 80 to 99% of water, less than 2% of (meth) acrylic ester and 1 to 20% of alcohol. According to one embodiment, the flux treated by membrane separation comprises from 0.5 to 15% of (meth) acrylic acid, from 25 to 65% of (meth) acrylic ester, from 20 to 60% of alcohol and from 0.5 to 15% water. According to the invention, the dehydration step by membrane separation is carried out by pervaporation (charge in the liquid phase and vaporization of the permeate at the crossing of the membrane), or by vapor permeation (vapor phase charge), preferably at a temperature of temperature ranging from 50 ° C to 100 ° C, more preferably 55 ° C to 85 ° C. Figure 1 illustrates the embodiment in which the membrane separation step is applied to a stream subjected to the final distillation leading to the recovery of the purified (meth) acrylic ester. FIG. 1 corresponds to a semi-continuous process (with a "batch" reaction), the installation comprising a single reactor 35. This reactor 35 is fed by a feed line of alcohol compound 32 (from a feed tank). alcohol compound 31), a (meth) acrylic acid feed line 33 and an additive (s) feed line 34, for example an acid catalyst feed line such as sulfuric acid and / or polymerization inhibitor. The reactor 35 is provided with a water removal system 36 comprising a column, a decanter, a recycle line, a water purge line.
    [0010] At the outlet of the reactor 35 is recovered the reaction stream by a reaction flow withdrawal line 37. This feeds a storage tank 38 at the output of which the reaction flow is recovered by a first transfer line 40. A line Neutralizing compound supplying 39 is connected to the first transfer line 40 and allows the neutralization of the reaction flow. As a neutralizing compound, a basic compound such as sodium hydroxide is used. The first transfer line 40 feeds a decanter 41 for purging a portion of the water contained in the reaction stream 40. At the outlet of the decanter 41 is connected a second transfer line 42 which feeds a washing column 43 provided with a water supply 44. A third transfer line 45 is connected at the outlet of the washing column 43, which feeds a distillation column 46, after a removal of water carried out by means of a membrane separation dewatering unit 50 disposed at the transfer line 45. At the bottom of the distillation column 46 is connected a flow-rich withdrawal line (meth) acrylic ester compound 47, from which the essentially purified (meth) acrylic ester compound is recovered. At the top of the distillation column 46 is connected a flow recycle line 48 rich in unreacted reagents, in particular rich in unreacted alcohol compound, by which is recovered a mixture of alcohol compound, acid, ester compound (meth) acrylic and water. This mixture is returned to the reaction, the flow recycling line rich in unreacted alcohol compound 48 being connected to the inlet of the reactor 35, after possible additional removal of the water contained in the mixture. This further removal may be effected by means of a membrane separation dewatering unit (not shown) disposed on the unreacted alcohol rich stream recycle line 48. The membrane separation dewatering unit 50 may be a unit. of pervaporation (charge in liquid phase and vaporization of the permeate at the crossing of the membrane), or a unit of vapor permeation (charge in vapor phase). The dehydration is preferably carried out at a temperature ranging from 50 ° C to 100 ° C, more preferably 55 ° C to 85 ° C. The membranes used are preferably hydrophilic membranes based on polyvinyl alcohol or a ceramic inorganic membrane such as a zeolite. The mixture which is dehydrated in the membrane separation dehydration unit 50 comprises from 50 to 70% (meth) acrylic ester, from 20 to 30% alcohol, from 0 to 12% (meth) acid. acrylic, and 3 to 12% water.
    [0011] The installation shown in FIG. 1 can in particular be used for the semi-continuous production of butyl acrylate from butanol, of 2-ethylhexyl acrylate from 2-ethyl hexanol, or of acrylate of 2 octyl from 2-octanol.
    [0012] Figure 2 illustrates an embodiment in which the membrane separation step is applied to the aqueous stream generated by decantation of the reaction mixture.
    [0013] According to FIG. 2, illustrating a continuous process, the installation comprises a single reactor R1. This reactor R1 is fed by an alcohol compound feed line 1, a (meth) acrylic acid feed line 2 and an additive feed line 3, for example a feed line of catalyst such as sulfuric acid, methanesulfonic acid or para toluene sulfonic acid. The reactor R1 is connected to a column (not shown), a decanter D1, a recycling line. On leaving the reactor and its column, the top products are sent via line 12 to a decanter D1. The organic phase is withdrawn line 13 to be returned either to the reactor line 22 or to a distillation column C1 via line 21. The final product after distillation in the column C1 being sent to S1 via a lateral withdrawal line 26.
    [0014] The Cl column product essentially comprising the formed ester and heavy products is recycled to the reaction via line 20 while the light products are sent to a purge treatment system via line 25. The aqueous phase of the clarifier D1 is sent via line 14, either at reflux of the reactor column via 15, or to a C2 distillation column via 16. Column C2 makes it possible to recover the organic compounds contained in this aqueous phase and to return them via the line 17 to the reactor. According to the invention, a membrane separation dewatering unit 51 is placed at the outlet of the decanter D1 on the line 14 of the aqueous phase. It is then possible to send the organic phase contained in this water-rich phase separated by said dehydration unit to the reactor via line 18, and the aqueous phase free of organic compounds, either to column C2 via line 16, or directly to the water treatment station as a function of the number of separation stages of the membrane process via the line 27. The calorie supply of the reactor R1 is provided by the circulation loop 4 which is heated at the level of the boiler H1 and then returned to the reactor via line 7, or sent to a heat treatment system via line 8 such as a film evaporator or thermal cracker so as to regenerate a portion of the flow to return it to the reactor via line 9. The treated stream 10 (heavy products) is purged via line 11 or partially recycled via line 5. The membrane separation dewatering unit 51 may be as described above in connection with Figure 1, but with preferably a hydrophobic membrane, such as the 4060 membrane marketed by Sulzer. In this embodiment, the stream which is subjected to membrane separation dehydration 51 is a water-rich stream comprising from 80 to 99% water, less than 2% (meth) acrylic ester, and 1 to 5% by weight. at 20% alcohol. The plant shown in FIG. 2 can in particular be used for the continuous production of butyl acrylate from butanol and acrylic acid by homogeneous acid catalysis. FIG. 3 illustrates an embodiment according to which the membrane separation step is applied to a stream resulting from the distillation of the light by-products present in the reaction mixture. Referring to FIG. 3, according to another embodiment of a continuous process, the plant comprises a single RS reactor. This RS reactor contains an acidic resin as a heterogeneous catalyst. It is surmounted by a distillation column C3 which makes it possible to eliminate the water of reaction towards the sewage treatment station. Column C3 is fed at the top by a flow of fresh alcohol 28. The bottom of column C3 is sent to the RS reactor. The acrylic or methacrylic acid used in the reaction is injected via line 27. The product at the top of the RS reactor returns to the bottom of the column via line 38 and partly to a distillation column C4. The recycled alcohol from the column head C4 via line 54 is fed into the reactor via line 27. According to the invention, the C4 column top stream is subjected to a dehydration step in a membrane separation unit 52 which allows to eliminate a large part of the water contained in the stream before recycling to the reaction. Column foot flow C4 is sent via line 35 to the final tailing column C5 which makes it possible to separate the heavy by-products at the bottom, and at the top the desired ester. The purified ester is sent to the storage tank PF via the line 58. The column foot stream C5 is either partially recycled to the feed of the column C4 or sent to an effluent treatment station. The membrane separation dewatering unit 52 may be as described above in connection with Figure 1.
    [0015] According to this embodiment, the stream which is subjected to the membrane separation dehydration unit 52 comprises from 0.5 to 15% of (meth) acrylic acid, from 25 to 65% of (meth) acrylic ester, 20 to 60% alcohol and 0.5 to 15% water.
    [0016] The installation shown in FIG. 3 can in particular be used for the continuous production of 2-ethylhexyl acrylate from 2-ethylhexanol and acrylic acid by heterogeneous acid catalysis. The following examples illustrate the present invention and are not intended to limit the scope of the invention as defined by the appended claims. EXAMPLES Example 1 Tests were carried out on a Sulzer membrane separation pilot having a membrane area of 170 cm 2. The membrane tested is a hydrophilic membrane based on Pervape 1201 reference polyvinyl alcohol. Different streams from a real butyl acrylate production plant have been applied to the membrane. These flows correspond to the flow 45 shown in FIG. 1. The flows mainly comprise butyl acrylate, butanol, water, and possibly acrylic acid. The permeate obtained contains between 95% and 99% water. In other words, the selectivity of the membrane is excellent, and this is not substantially affected by the presence of remaining. Depending on the temperatures and the test conditions, the flux passing through the membrane varies from 0.8 kg / m2.h to 2.7 kg / m2.h, which represents high values compared to the values generally attained in the methods of the prior art. No degradation of the membrane was observed despite the presence of acrylic acid and acrylic ester. The results obtained with the Pervap® 1201 membrane are summarized in Table 1.
    [0017] Table 1 Percentage mass P down Weight percent Permeate Selectivity Flux Permeate TC> C) BuOH ABU 1120 AA Mbar BuOH ..._ ... ABU ........ AA kerni 2.ha f120 / 1% 13 H20f / F1201 1120 A 65.0 26.9 56.4 5.5 11.1 60.0 0.7 0.2 98.4 0.6 0.8 1081 18.0 75.0 26.9 56, 4 5.5 11.1 60.0 0.6 0.1 98.1 1.1 1.3 901 18.0 80.0 26.9 56.4 5.5 11.1 60.0 OA 02 98 , 5 0.7 1.7 1115 18.0 90.0 26.9 56.4 5.5 11.1 60.0 0.3 0.1 99.2 0.4 1.8 2235 18.2 B 62.8 30.0 66.7 3.3 0.0 60.0 4.1 0.1 95.6 0.0 09 638 29.3 69.0 30.0 66.7 3.3 0.0 60.0 29 02 96.8 0.0 1.3 909 29.7 80.0 30.0 66.7 3.3 0.0 60.0 1.9 0.2 979 00 2.0 1401 30, 0 87.2 30.0 66.7 3.3 0.0 60.0 1.4 0.1 98.5 0.0 2.7 1922 30.2 The separation factor a is calculated by: 3120 / 37R Cei12.0 = x R IxR with y0 and XH2O are the mass fractions of water in the permeate and in the feed, respectively. In the case of pervaporation of multicomponent mixtures, yR and xR are (1- y1120) and (1- xH20), respectively.
    [0018] The factor f3 or enrichment factor is the ratio between the concentration of water in the permeate and the water concentration of the feed. Example 2 Tests were carried out on a Sulzer membrane separation pilot, having a membrane surface of 170 cm2. The membrane tested is a Pervap® 4060 hydrophobic reference membrane. A flow from a real butyl acrylate production plant was applied to the membrane. This flow corresponds to the flow 14 shown in FIG. 2. This flow mainly comprises water (95.2%) with a little butanol (4.7%) and traces of butyl acrylate (0.1% ). The results obtained at different temperatures with the membrane Pervap ' 4060 are summarized in Table 2.
    [0019] Table 2 Percentage Weight P Down Weight Percent Permeate Flow Selectivity Selectivity Feed Permeate T ("C) BuOH ABU H2O mbar BuOH ABU H20 J (kg / m2.h) Q. 1-120 / R 13 H20f / 1-120i 59 , 75 4.7 0.1 95.2 60 76.3 8.0 15.2 1.86 111 17.6 67.15 4.7 0.1 95.2 60 76.2 8.0 15.2 3.26 111 17.6 78.4 4.7 0.1 95.2 60 77.3 5.4 16.0 6.06 105 17.3 90.65 4.7 0.1 95.2 60 78 The alcohol-enriched permeate can be advantageously recycled to the reaction Example 3 Tests were carried out on a Sulzer membrane separation pilot, having a membrane surface of 170.degree. The tested membrane is a Pervap® 1201 reference polyvinyl alcohol hydrophilic membrane. Two streams from a real plant producing 2-ethylhexyl acrylate (AE2H) from 2-ethyl hexanol ( 2EHeOH) were applied to the membrane at different temperatures, corresponding to stream 54 shown in FIG. 3. Flows include alcohol, ester, acid and some water. The results obtained with the Pervap® 1201 membrane are summarized in Table 3.
    [0020] Table 3 Percentage Weight P Down Weight Percent Permeate Flow Selectivity Selectivity Feed Permeate T (* C) 2EHeOH AE2H H20 AA mbar 2EHeOH AE2H H2O AA J {kg / m2.h) a H20 / R 13.1-120f / H20i 43.5 61.6 31.9 55.5 2.2 10.1 60 0.0 0.0 96.3 3.4 1.01 1134 69.75 31.9 55.5 2.2 10.1 60 0, 0 0.0 95.1 4.6 1.46 848 42.9 78.8 31.9 55.5 2.2 10.1 60 0.0 0.0 95.0 4.7 2.17 832 42 , 9 85.5 31.9 55.5 2.2 10.1 60 0.0 0.0 95.0 4.8 2.55 830 42.9 60.8 52.8 32.5 2.1 12 , 3 60 0.1 0.0 96.3 3.3 0.79 1213 45.4 69.05 52.8 32.5 2.1 12.3 60 0.1 0.0 95.7 4.0 1.24 1027 45.1 79.95 52.8 32.5 2.1 12.3 60 0.0 0.0 95.7 4.3 1.75 1015 45.0 87.75 52.8 32 5 2.1 12.3 60 0.1 0.0 96.4 3.3 2.12 1224 45.4 The dehydration unit makes it possible to eliminate most of the water present in the stream containing the 2- residual hexanol before recycling to the reaction.
    权利要求:
    Claims (9)
    [0001]
    REVENDICATIONS1. Process for the production of an alkyl (meth) acrylate having a linear or branched alkyl chain having from 4 to 10 carbon atoms, by direct esterification of (meth) acrylic acid with a linear or branched alcohol containing from 4 to 10 carbon atoms in the presence of a catalyst, resulting in formation of a reaction mixture comprising the desired ester, unreacted acid and alcohol, light byproducts and heavy by-products, which is subjected to a purification treatment by means of separation, in order to obtain the purified alkyl (meth) acrylate, said purification treatment being characterized in that it comprises a membrane separation dehydration step applied to one at least one of the following streams: the stream subjected to the final distillation leading to the recovery of the purified (meth) acrylic ester, the aqueous stream coming from the decantation of the reaction mixture, or the stream coming from the stillation of the light byproducts present in the reaction mixture.
    [0002]
    2. Method according to claim 1 characterized in that the alcohol is butanol, 2-ethylhexanol or 2-octanol.
    [0003]
    3. Method according to claim 1 or 2 characterized in that the acid is acrylic acid.
    [0004]
    4. Method according to any one of the preceding claims, characterized in that the dehydration by membrane separation is dehydration by pervaporation or by vapor permeation.
    [0005]
    5. Method according to any one of the preceding claims, characterized in that the membrane separation is a separation on an inorganic membrane, preferably zeolite, and more preferably T-type zeolite; or on a polymeric membrane, preferably a hydrophilic membrane based on polyvinyl alcohol; or a separation on a hydrophobic polymeric membrane.
    [0006]
    6. Method according to any one of the preceding claims, characterized in that it is of continuous, serai-continuous or discontinuous type.
    [0007]
    7. Process according to any one of the preceding claims, characterized in that the flux treated by membrane separation comprises from 50 to 70% by weight of (meth) acrylic ester, from 20 to 30% by weight of alcohol, from 0 to 12. % by weight of (meth) acrylic acid, and from 3 to 12% by weight of water.
    [0008]
    8. Process according to any one of Claims 1 to 6, characterized in that the flux treated by membrane separation comprises from 80 to 99% by weight of water, less than 2% by mass of (meth) acrylic ester and from 1 to 20% by weight of alcohol.
    [0009]
    9. Process according to any one of Claims 1 to 6, characterized in that the flux treated by membrane separation comprises from 0.5 to 15% by weight of (meth) acrylic acid, from 25 to 65% by weight of ester ( meth) acrylic, from 20 to 60% by weight of alcohol and from 0.5 to 15% by weight of water.
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    同族专利:
    公开号 | 公开日
    EP3079797A1|2016-10-19|
    US10647657B2|2020-05-12|
    JP6606496B2|2019-11-13|
    JP2017502942A|2017-01-26|
    US20160376217A1|2016-12-29|
    EP3079797B1|2018-08-15|
    WO2015086978A9|2018-05-03|
    FR3014870B1|2015-12-11|
    WO2015086978A1|2015-06-18|
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    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 3 |
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    申请号 | 申请日 | 专利标题
    FR1362560A|FR3014870B1|2013-12-13|2013-12-13|PROCESS FOR PRODUCINGACRYLIC ESTERS|FR1362560A| FR3014870B1|2013-12-13|2013-12-13|PROCESS FOR PRODUCINGACRYLIC ESTERS|
    US15/102,921| US10647657B2|2013-12-13|2014-12-09|Purification of acrylic esters by membrane separation dehydration|
    EP14827479.8A| EP3079797B1|2013-12-13|2014-12-09|Purification of acrylic esters by membrane separation dehydration|
    PCT/FR2014/053223| WO2015086978A1|2013-12-13|2014-12-09|Purification of acrylic esters by membrane separation dehydration|
    JP2016538618A| JP6606496B2|2013-12-13|2014-12-09|Purification ofacrylic acid ester by membrane separation dehydration|
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