Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/02—Inorganic material
  • B01D71/024—Oxides
  • B01D71/027—Silicium oxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2475—Membrane reactors
• • 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
• • 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
  • C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
• • 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
  • C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • 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
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• the present invention relates to the production of (meth) acrylic esters, and more particularly to a process for the synthesis of (C 1 -C 10) alkyl (meth) acrylates, by direct esterification of (meth) acrylic acid with corresponding alcohol, the reaction being carried out in a membrane reactor under conditions where the water generated by the reaction is removed from the reaction mixture as it is formed.
• 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 flows 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.
• dehydration modules may be implemented at different locations of the plant, for example at the outlet of the reaction stage or at the level of flow recycling comprising the unreacted alcohol for a concentration range of the various well-defined compounds.
• a dehydration step may be performed on an intermediate reaction stream from a first stage of the reaction and feeding a second reactor in which a second stage of the reaction is carried out.
• Dehydration by membrane separation can also be carried out directly in the reactor, using a dipping module, equipped with tubes filled with ceramic membranes, with extraction of water inside the tubes.
• the process described in document WO 2015/063388 makes it possible to significantly reduce the formation of heavy by-products and thus to improve the productivity of a process for the synthesis of methyl (meth) acrylate or ethyl, in minimizing the amount of water introduced into the reactor.
• the introduced water may come from the supply of alcohol or the recycling of aqueous flows comprising unreacted acid and / or unreacted alcohol.
• a dehydration step by membrane separation, distillation or pressure swing adsorption is applied to at least one of the streams feeding the reactor.
• Patent Application CN 105170033 discloses a circulating bed annular reactor technology and its use for performing esterification reactions while continuously removing water generated by the reaction. This technology makes it possible to obtain conversions higher than those of a traditional fixed bed reactor, but has the disadvantage of being complex to implement.
• the ceramic membrane used operates in a pressure gradient nanofiltration process, and has a high porosity which limits the selectivity of the separation.
• (meth) acrylates are highly reactive molecules due to the presence of a double bond, which can form polymers and thus foul membranes. It is therefore necessary to adapt the operating conditions so that these monomers do not polymerize on the surface of the membrane or in the porous structure during the separation.
• the inventors have now discovered that by implementing a membrane reactor comprising a separation membrane and an esterification catalyst in an acid medium, it is possible to carry out the esterification reaction while eliminating the water generated by the reaction. as and when it is formed, without any fouling of the membrane.
• the invention thus provides a process for the synthesis of (meth) acrylic esters having improved productivity and selectivity, and able to function under conditions for which the reagents are not in excess, thereby minimizing the size and energy of the separation / recycling equipment of the streams generated during the purification of the reaction medium.
• the subject of the present invention is a process for the production of an alkyl (meth) acrylate by direct esterification of (meth) acrylic acid with a linear or branched alcohol containing from 1 to 10 carbon atoms, in the presence of an esterification catalyst, characterized in that it implements a fixed-bed membrane reactor in which the esterification reaction is carried out while removing the water generated by the reaction as it is formed.
• membrane reactor By “membrane reactor” is meant according to the invention a dehydration membrane module coupled to a heterogeneous esterification catalyst.
• the esterification catalyst is deposited on the surface of a dehydration membrane module.
• the esterification catalyst is deposited inside a dehydration membrane module, for example in the form of a tube.
• the esterification catalyst is an acidic heterogeneous catalyst.
• the membrane dehydration is dehydration by pervaporation or by vapor permeation.
• the membrane module comprises a membrane of hydrophilic type, either polymeric, or hybrid (polymeric membrane deposited on an inorganic support), or of inorganic type for example based on ceramic or modified silica.
• the method is chosen from continuous, semi-continuous or discontinuous type processes.
• the process is continuous.
• FIG. 1 shows schematically two examples of dehydration membrane module coupled to a heterogeneous esterification catalyst.
• FIG. 2 schematically represents membrane reactors that can be used in the process according to the invention.
• FIG. 3 schematically shows an installation for carrying out the process according to the invention, applied in particular to the synthesis of ethyl acrylate.
• (meth) acrylic and “(meth) acrylate” conventionally mean “acrylic or methacrylic” and “acrylate or methacrylate” respectively.
• the alcohol used in the context of the invention may be linear or branched. It may be a primary alcohol or a secondary alcohol. It can comprise from 1 to 10 carbon atoms. It may be substituted or unsubstituted, and preferably it is unsubstituted.
• the alcohol may especially be methanol, ethanol, butanol, 2-ethylhexanol or 2-octanol. Preferably, the alcohol is ethanol.
• esters are methyl acrylate or methyl methacrylate, ethyl acrylate or ethyl methacrylate, butyl acrylate or butyl methacrylate, 2-ethylhexyl acrylate or methacrylate. 2-ethylhexyl, 2-octyl acrylate or 2-octyl methacrylate.
• the (meth) acrylic acid is acrylic acid.
• the ester is ethyl acrylate.
• esterification reaction of the (meth) acrylic acid with the alcohol requires the presence of an esterification catalyst which according to the invention is a catalyst heterogeneous, of solid type, such as for example an acidic cation exchange resin.
• acidic cation exchange resins there may be mentioned the range of the gel or macroporous Amberlyst ® resins from Dow, for example Amberlyst ® 15 or 131, the range Lewatit ® from Lanxess, e.g. Lewatit ® K1461 or range Diaion ® of MCC or Dowex ® A.
• the catalyst is generally in the form of size grains ranging from 300 to 800 microns.
• the esterification reaction is carried out in a fixed-bed membrane reactor comprising a dehydration membrane module coupled to the heterogeneous esterification catalyst.
• the water generated by the esterification reaction can be separated from the reaction medium as it is formed using the membrane dehydration module.
• the dehydration membrane module may be a pervaporation unit (charge in the liquid phase and vaporization of the aqueous permeate through the membrane) or a vapor permeation unit (vapor phase charge).
• the dehydration membrane module is a pervaporation separation unit, that is to say with selective evaporation of water through a membrane.
• the flow of the water to be evaporated is characterized by a chemical potential difference on both sides of the membrane module. This concentration gradient is maximized by raising the temperature and imposing a low pressure on the permeate (or evaporated) side. It is possible to obtain according to this method a high purity permeate, greater than 95%, favoring its treatment or its elimination, and minimizing the loss of organic compounds recovered by recycling in the process.
• the membranes may be hydrophilic, either of polymeric type or hybrid (polymeric membrane deposited on an inorganic support). Can be used for example resins Pervap ® 1005, Pervap ® 1201 or Pervap ® 4101 sold by Sulzer.
• the membranes may be inorganic to promote resistance in an acid medium.
• a ceramic membrane or a Modified silica-based membrane for example HybSi ® type marketed by the company Technical and Industrial Ceramics (CTI).
• the membranes are selected because of their performance in terms of separation selectivity (permeate water purity) and permeate flow through the membrane. It has been observed that the inorganic membranes based on modified silica not only have good resistance in an acrylic acid / acrylic ester medium, but lead to a permeate very rich in water (water content greater than 88%) and containing less 1% ester, with flow rates much higher than those generally achieved with polymer type membranes.
• the membrane reactor comprises a modified silica-based pervaporation dehydration membrane module, leading to a high productivity for the process according to the invention.
• the membrane reactor comprises a dehydration membrane module on the surface of which the esterification catalyst is deposited.
• the module can be flat or tubular.
• the membrane reactor comprises a tubular membrane dehydration module inside which there is an esterification catalyst.
• the membrane reactor is of the multitubular type.
• the membrane reactor is coupled to a vacuum pump in order to extract the water from the reaction medium.
• a vacuum compatible with industrial voids is used, generally less than 100 mbar, for example between 20 and 50 mbar.
• the water leaving the membrane reactor is condensed and can be sent to one of the purification columns, in order to recycle any traces of organic compounds that may have passed through the membrane.
• the condensed water is sent to the biological station for treatment of the residual organic compounds.
• the membrane reactor operates at a temperature of from 50 ° C to 100 ° C, preferably from 55 ° C to 90 ° C.
• the membrane reactor is fed with (meth) acrylic acid and alcohol.
• the acid / alcohol or alcohol / acid molar ratio refers to the acid and alcohol contents of all the feeds to the membrane reactor.
• the process according to the invention can be carried out in the presence of a stoichiometric excess of alcohol, in the presence of a stoichiometric excess of acid, or under stoichiometric conditions of the reactants.
• the process according to the invention is carried out under stoichiometric conditions of the reactants.
• the conversion is substantially equivalent to that obtained with a reaction carried out in excess of acid or in excess of alcohol.
• the purification of the reaction medium is simplified with a lower recycling rate for the streams generated by the purification treatment.
• the energy consumption to recycle alcohol its reacted is much lower.
• polymerization inhibitor such as, for example, hydroquinone, hydroquinone methyl ether, diterbutyl paracresol (BHT), phenothiazine, para-phenylene diamine, Tempo (2,2,6,6-tetramethyl-1-piperidinyloxy) or its derivatives or di-tert-butylcatechol, activated by continuous injection of depleted air (7). % O2).
• BHT diterbutyl paracresol
• FIG. 1 Examples of membrane reactors that can be used in the process according to the invention are illustrated in FIG. 1 and FIG.
• FIG. 1 a there is shown a tube consisting of a membrane, around which there is an esterification catalyst.
• the assembly is carried out so that the permeate (separated water) exits axially with respect to the tube, the retentate comprising the reaction medium freed from most of the water, leaving the module radially.
• a membrane tube contains an esterification catalyst.
• the assembly comprises a radial outlet for the permeate, and the retentate exits axially opposite the reagent supply.
• FIG. 2 a illustrates a membrane reactor of the multitubular exchanger type comprising tubes according to the configuration of FIG. 1 a).
• Figure 2 b corresponds to a multitubular exchanger in radial configuration of the permeate.
• Water is removed through the tubes to the shell which serves as the body for this reactor.
• This calender is equipped with a tubing that allows to put it under vacuum.
• the condensation of the water vapor thus extracted from the reaction medium is carried out outside the shell via an external exchanger. Heating of the reaction medium is done by an exchanger which preheats the feed.
• FIG. 3 shows an installation for producing alkyl (meth) acrylate according to the invention comprising a membrane reactor RM.
• This reactor RM is fed by an acid feed line 1, an alcohol feed line 2.
• the reactor preferably contains an acid cation exchange resin type catalyst contained in a tubular pervaporation module.
• the reaction mixture 3 is sent to a distillation column C which separates, at the bottom, a stream comprising essentially the unreacted acid, traces of light products (boiling point lower than acid), and the products having a higher boiling point than the acid and, at the top, a stream 6 comprising the formed ester and products lighter than the acid (unreacted alcohol, by-products such as as ethyl acetate, acetic acid in the case of the synthesis of ethyl acrylate, for example).
• a distillation column C which separates, at the bottom, a stream comprising essentially the unreacted acid, traces of light products (boiling point lower than acid), and the products having a higher boiling point than the acid and, at the top, a stream 6 comprising the formed ester and products lighter than the acid (unreacted alcohol, by-products such as as ethyl acetate, acetic acid in the case of the synthesis of ethyl acrylate, for example).
• the water removed through the membrane wall of the flow membrane reactor 15 is condensed and sent (not shown in the diagram) into one of the purification columns to recycle any traces of organic compounds present, in particular the water that may be present. used for the liquid / liquid extraction phase.
• Column foot flow C is sent to a distillation column C1 which separates a stream 4 comprising the residual acrylic acid and the lighter products, this stream 4 being recycled in the reactor RM.
• a stream 7 consisting essentially of heavy products (adducts) is separated from the column C1 and subjected to thermal cracking in the thermal cracker CT.
• Thermal cracking makes it possible to recycle the noble products (starting compounds or finished product) potentially recoverable from the heavy product fraction.
• the stream 9 of acid is recycled at the level of the column C1, the stream 8 being incinerated.
• the flow 6 of the top of the distillation column C is sent to a liquid / liquid extraction section (decanter or contactor) to generate, on the one hand, an aqueous phase containing alcohol which is recycled to the reaction. (stream 13) after distillation in a column C2 (the aqueous stream 14 depleted in alcohol that can be recycled for the liquid / liquid extraction phase), and secondly, an organic phase 1 1.
• the organic phase 11 may be subjected to one or more additional distillation steps to yield purified ester 12.
• the method according to the invention significantly saves the energy consumption of the installation.
• the invention is illustrated with the synthesis reaction of ethyl acrylate by esterification of acrylic acid with ethanol.
• the reaction is carried out in a conventional reactor R at a temperature between 70 and 90 ° C.
• the reaction is carried out in a RM membrane reactor at a temperature of between 70 and 90 ° C., and 80% of the water formed is removed from the RM reactor as it is formed.
• the membrane reactor operating under stoichiometric conditions leads to a conversion substantially identical to that obtained with a conventional reactor operating with an excess of alcohol or that obtained with a conventional reactor operating with an excess of acid.
• the membrane reactor according to the invention has the specific advantage of operating under conditions close to stoichiometry, leading to conversions comparable to those existing with conventional processes which require either an excess of alcohol or an excess of acid. .
• the residual amounts of alcohol and acid are lower, which minimizes the energetic loop of recycling of the alcohol and reduces the risks of fouling related to the residence time of the acrylic acid in the process.
• the volume of esterification catalyst (or reaction volume) is determined as the product of the flow rate of reactants entering with the residence time in this reactor.
• a volume of 170 I of heterogeneous catalyst e.g., Amberlyst ® type resin, allows to produce 100 kg / h of ethyl acrylate corresponding to the simultaneous formation of about 18 kg / h of water.
• a membrane reactor adapted to remove about 80% of the water generated, ie 14.4 kg / h of water may for example be a membrane module comprising, in a tubular exchanger configuration, 360 tubular membrane tubes of HybSi ® type. 25 mm diameter and 1 m in height, filled with the catalyst, which corresponds to an area of approximately 8.5 m 2 for a membrane having a specific capacity of 0.5 kg aqueous permeate. m 2 . h.
• Aspen simulation was performed for an ethyl acrylate AE synthesis unit comprising a membrane reactor removing 80% of the water formed during the reaction, and a purification set based on the use of a first distillation column C separating the residual acid, and a second column C2 separating the residual alcohol which is recycled to the reaction.
• the following table 3 summarizes the energy data obtained in comparison with the energy data of an industrial unit of ethyl acrylate.

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• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2016
  • 2016-03-10 FR FR1652001A patent/FR3048697B1/fr active Active
• 2017
  • 2017-02-14 BR BR112018015652-3A patent/BR112018015652B1/pt active IP Right Grant
  • 2017-02-14 CN CN201780015909.6A patent/CN108713011A/zh active Pending
  • 2017-02-14 US US16/081,060 patent/US10676421B2/en active Active
  • 2017-02-14 WO PCT/FR2017/050331 patent/WO2017153653A1/fr active Application Filing
  • 2017-02-14 EP EP17709153.5A patent/EP3426628A1/fr not_active Ceased
  • 2017-02-14 JP JP2018547483A patent/JP6909800B2/ja active Active
  • 2017-02-14 KR KR1020187025849A patent/KR102644405B1/ko active IP Right Grant
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