WO2010058983A2 - Procédé d'extraction d'ester d'acide (méth)acrylique - Google Patents

Procédé d'extraction d'ester d'acide (méth)acrylique Download PDF

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WO2010058983A2
WO2010058983A2 PCT/KR2009/006835 KR2009006835W WO2010058983A2 WO 2010058983 A2 WO2010058983 A2 WO 2010058983A2 KR 2009006835 W KR2009006835 W KR 2009006835W WO 2010058983 A2 WO2010058983 A2 WO 2010058983A2
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meth
acrylic acid
water
reactor
reaction
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PCT/KR2009/006835
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Korean (ko)
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WO2010058983A3 (fr
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백세원
김현규
고준석
하경수
박성규
우동현
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주식회사 엘지화학
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Priority to CN2009801293524A priority Critical patent/CN102105432B/zh
Priority to BRPI0915932-0A priority patent/BRPI0915932B1/pt
Priority to US13/055,425 priority patent/US8772534B2/en
Publication of WO2010058983A2 publication Critical patent/WO2010058983A2/fr
Publication of WO2010058983A3 publication Critical patent/WO2010058983A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • 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
    • 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
    • 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
    • C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
    • 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

Definitions

  • the present invention relates to a method for recovering (meth) acrylic acid esters, which recovers (meth) acrylic acid, alcohols and (meth) acrylic acid esters from reaction by-products produced in the process of obtaining (meth) acrylic acid esters.
  • Acrylic acid esters are prepared by esterification of acrylic acid with alcohols.
  • the catalyst for the ester reaction inorganic acids, organic acids, solid acids and the like are used.
  • an inorganic acid that is difficult to separate such as sulfuric acid
  • a method of converting the acid catalyst component in the product stream after the reaction to a salt by separation by adding a corresponding base such as sodium hydroxide is used.
  • Solid acids require catalyst deactivation (mechanical, thermal and chemical) tendency during the reaction, requiring replacement or replenishment of the catalyst and a relatively difficult solid separation process.
  • Organic acids have the advantage that the recycling of the catalyst is relatively easy when the separation is easy in the product stream.
  • Butyl acrylate (Butyl acrylate) process for example, butyl-b-butoxy propionate (BPB), b-Butoxypropionic acid (BPA) and n-butyl diacrylate (BDA) are such representative by-products. These by-products are hereinafter referred to as Michael adducts. Optimization of the ester reaction conditions can minimize these side reactions, but the production of these by-products is inevitable in almost all processes. The prior art thus suggests effective methods of decomposition and recovery of these by-products.
  • BPB butyl-b-butoxy propionate
  • BPA b-Butoxypropionic acid
  • BDA n-butyl diacrylate
  • Japanese Patent JP 1993-025086 proposed a method for decomposing Michael adducts by adding excess water with sulfuric acid as a catalyst. However, since the conversion rate shows a low recovery rate of about 30% and an excessive amount of water is used, energy consumption is high for the same reaction.
  • This technique shows a conversion rate of 80% in the temperature range of 150 ° C to 250 ° C when using an organic acid catalyst, but also requires a high temperature and severe fouling in the residual flow after the cracking reaction.
  • the problem and process application problems due to leaching of the catalyst components have not been solved.
  • the present invention provides a step of obtaining a (meth) acrylic acid ester through an ester reaction of (meth) acrylic acid with an alcohol under a catalyst, wherein a by-product is produced together with the (meth) acrylic acid ester; And b) reacting the by-products produced in step a) with the catalyst and water in the reactor, wherein the water content is greater than zero based on the total weight of the reactants comprising the by-products, the catalyst and the water in the reactor during the reaction.
  • the production efficiency of the (meth) acrylic acid ester is increased, thereby reducing the environmental burden of the process and enabling the smooth operation of the actual process.
  • FIG. 1 is a view showing a recovery process of butyl acrylate according to the first embodiment of the present invention.
  • FIG. 2 is a view showing a recovery process of butyl acrylate according to a second embodiment of the present invention.
  • the method for recovering the (meth) acrylic acid ester according to the present invention is a step of obtaining a (meth) acrylic acid ester through an ester reaction of (meth) acrylic acid and an alcohol under a catalyst, by-products together with the (meth) acrylic acid ester Is generated; And b) reacting the by-products produced in step a) together with catalyst and water in the reactor, wherein the water content is greater than zero based on the total weight of the reactants comprising the by-products, the catalyst and the water in the reactor during the reaction.
  • the catalyst of step a) at least one inorganic acid selected from sulfuric acid, phosphoric acid and nitric acid; At least one organic acid selected from methanesulfonic acid and paratoluenesulfonic acid (pTSA); And at least one solid acid selected from zeolite and polymer resin catalysts.
  • inorganic acid selected from sulfuric acid, phosphoric acid and nitric acid
  • organic acid selected from methanesulfonic acid and paratoluenesulfonic acid (pTSA)
  • pTSA paratoluenesulfonic acid
  • solid acid selected from zeolite and polymer resin catalysts.
  • Step a) is a1) proceeding the ester reaction; And a2) a distillation step of separating the resulting product into the (meth) acrylic acid ester and the byproduct after the ester reaction.
  • the ester reaction is carried out in an ester reactor
  • the distillation step is carried out in a distillation column.
  • step b) may be specifically supplied through two routes, but embodiments are not limited thereto.
  • reaction by-products discharged to the bottom of the distillation column ie, by-products separated in the distillation step, It may be fed to the cracking reactor without passing through a recovery column.
  • the catalyst of step b) is at least one inorganic acid selected from sulfuric acid, phosphoric acid and nitric acid; At least one organic acid selected from methanesulfonic acid and paratoluenesulfonic acid (pTSA); And at least one solid acid selected from zeolite and polymer resin catalysts.
  • the amount of catalyst introduced into the reactor in step b) may be 1 to 20% by weight based on the total weight of the reactants in the reactor.
  • the amount of catalyst introduced into the reactor is preferably 5 to 15% by weight, more preferably 8 to 12% by weight based on the total weight of the reactants in the reactor.
  • the catalyst of step a) included in the by-product acts as a catalyst in step b). It may not be supplied a separate catalyst for the step).
  • a separate catalyst supply line is provided, a separate catalyst to be used in the reaction of step b) the b) It can be fed to the reactor of the stage.
  • the water supplied to the reactor in step b) may be supplied into the reactor so as to be greater than 0 and 10% by weight or less based on the total weight of the reactants (byproduct + catalyst + water) in the reactor. It is desirable to maintain water in the reactor at greater than 0 and up to 10% by weight while feeding water into the reactor. This also makes it possible to easily control the reaction temperature and reaction pressure in the reactor. It is also possible to provide high conversion and recovery rates for Michael adducts.
  • the water supplied to the reactor in step b) is preferably more than 0 to 8% by weight, more preferably 3.5 to 5% by weight, based on the total weight of the reactants in the reactor.
  • the water participates in the decomposition reaction, and can also increase the role of the azeotropic agent to lower the boiling point by azeotropic with the recovery of the step b) recovered by the decomposition reaction of step b). That is, after the reaction, the azeotrope and the azeotrope may serve to promote the reaction with the effect of removing it out of the reaction system.
  • the azeotrope and the azeotrope may serve to promote the reaction with the effect of removing it out of the reaction system.
  • butanol and butyl acrylate recovered by the decomposition reaction can be azeotrope with the effect of removing to the outside of the reaction system to serve to promote the reaction.
  • the flow rate of the water in step b) can be adjusted according to the size of the reactor used. For example, while adding water at a flow rate of 0.3 to 3 g / min may be reacted for 0.5 to 10 hours, but is not limited thereto. If the water supply rate is too fast, recovery objects such as BPB contained in the by-products may fall out of the system, and the slower the water supply rate, for example, less BPB outflow may be desirable.
  • the reactor in step b) may be operated at a residence time of 0.5 to 10 hours at a reaction pressure of atmospheric pressure (1,013 mmbar) or reduced pressure (1 to 1,013 mmbar) and a reaction temperature of 80 to 180 ° C. .
  • the residence time means the average residence time in the reactor while reacting by-products, water, and catalyst as reactants in the reactor.
  • the reactor of step b) is most preferably operated under reduced pressure conditions of 1 ⁇ 1,013mmbar and reaction temperature conditions of 100 ⁇ 150 °C.
  • the recovered product may be recovered in the vapor phase, and the recovered product of step b) may be discharged to the upper side of the reactor and fed back to the distillation stage, that is, to the distillation column.
  • the recovered product of step b) may be discharged to the upper side of the reactor and fed back to the a2) distillation stage, that is, the distillation column through a recovery column, and the recovered product of step b) may be discharged to the upper side of the reactor and recovered.
  • the column may be fed back to the a1) ester reaction step.
  • the recovered vapor phase which is discharged to the upper side of the reactor and passed through the recovery column of step b) is condensed from the vapor phase recovered liquid.
  • the water removal step of removing the water contained in the recovery after the liquid phase conversion step it is returned to the a2) distillation step or the a1) ester reaction step. Can be supplied. And, the water removed in the water removal step, may be supplied back to the reactor of step b).
  • the liquid phase conversion step may be performed in a condenser, and the water removal step may be performed in a bed separator.
  • the water separated in the layer separator in which the water removal step is performed is discharged to the lower side of the layer separator and re-supplied to the reactor of step b), and the water is removed from the layer separator in which the water removal step is performed.
  • the recovered product can be discharged to the upper side of the layer separator and fed back to the a1) ester reaction step or a2) distillation step.
  • the recovered product is separated into an organic layer and a water layer in the layer separator.
  • the organic layer is a recovery from which water is removed, and the water layer is water included in the recovery.
  • the water layer is discharged to the lower side of the bed separator, and reused as water in the reactor of step b), and the recovered water removed from the bed separator can be fed back to the a2) distillation step or the ester reactor. have.
  • the water layer of the layer separator can be replenished through the process water line in an amount that is reduced by the reaction.
  • step b) The recovery of step b) is recovered in the vapor phase as described above and discharged to the upper side of the decomposition reactor, the waste generated in addition to the recovery in step b) may be discharged to the lower side of the reactor.
  • the waste generated in addition to the recovery in step b) may be discharged to the lower side of the reactor.
  • Acrylic esters are obtained by reaction of an acid catalyst phase of acrylic acid and alcohol. Most acrylic acid and alcohol are obtained as acrylic esters, but are converted to Michael adducts by some side reactions. Michael adducts obtained as reaction byproducts generally have higher boiling points than acrylic esters and are obtained as a bottoms stream in the final distillation step.
  • the lower stream is reacted once more in the presence of an acid catalyst to cause a reverse conversion from Michael adducts to alcohols, acrylic acid and acrylic acid esters, i.e., recovering it as a raw material such as acrylic acid or alcohol and a product of acrylic acid esters.
  • an acid catalyst to cause a reverse conversion from Michael adducts to alcohols, acrylic acid and acrylic acid esters, i.e., recovering it as a raw material such as acrylic acid or alcohol and a product of acrylic acid esters.
  • water as a reaction medium during the acid catalytic decomposition process, it is possible to provide flexibility in the process by lowering the decomposition reaction temperature, aiding in-system removal of the product to increase the conversion rate, and securing fluidity of the final waste oil.
  • butyl acrylate (Butylacrylate) is taken as an example, but is not limited thereto.
  • Michael adducts generated in the production of butyl acrylate include buty-b-butoxy propionate (BPB), b-butoxypropionic acid (BPA) and n-butyl diacrylate (BDA), and the emissions obtained during the final distillation step.
  • the composition of the flow may vary from process to process, but it is approximately butanol (0 to 5%), acrylic acid (0 to 10%), butyl acrylate (0 to 15%), BPB (0 to 40%), BDA (0 To 20%) and BPA (0 to 5%).
  • FIG 1 and 2 are views showing a recovery process of butyl acrylate according to the present invention.
  • reaction by-product discharged to the bottom of the distillation column is passed through the reaction by-product supply line (1) and the recovery column (B) (A) Is supplied.
  • the reaction byproduct discharged to the bottom of the distillation column may be directly supplied to the decomposition reactor A through another reaction byproduct supply line 1.
  • a small amount of water supplied to the decomposition reactor (A) is discharged to the lower side of the bed separator (D), and the water layer of the bed separator (D) is replenished through the process water line (3) by an amount reduced by the reaction. .
  • the decomposition reactor A may be operated at a temperature of 80 to 180 ° C, and preferably at a temperature of 100 to 150 ° C.
  • the reaction pressure may be depressurized to facilitate the removal of the product, and may be 1 to 1,013 mmbar in consideration of the amount of water introduced into the decomposition reactor (A).
  • the type of reaction can be both batch reaction and continuous reaction.
  • the catalyst introduced into the decomposition reactor (A) may be introduced in a separate line, but is preferably the same as the catalyst used in the process for obtaining butyl acrylate and included in the reaction by-product supplied to the reaction by-product supply line (1).
  • Inorganic acids such as a sulfuric acid, phosphoric acid, nitric acid
  • Organic acids such as methanesulfonic acid and paratoluenesulfonic acid (pTSA); Zeolites
  • solid acids such as polymer resin catalysts, but are not limited thereto.
  • Butanol, butyl acrylate, and acrylic acid produced by the decomposition in the reaction in the decomposition reactor (A) are discharged together with water to the vapor phase through the recovery column (B), converted to a liquid phase in the condenser (C) and the bed separator ( Is introduced into D).
  • a recovery column (B) is required, but in some cases, vaporous recovered products (butanol, butyl acrylate, and acrylic acid) discharged from the decomposition reactor (A) do not go through a recovery column, thereby obtaining butyl acrylate. It can be introduced into the distillation column in which the distillation process of the ester reactor or butyl acrylate proceeds the ester reaction for.
  • the water layer and the organic layer (recovery) are separated, and the organic layer (recovery) is fed back to the ester reactor (not shown) or the distillation column through the recovery discharge line 2. The water layer is then fed back to the decomposition reactor (A).
  • the waste after the reaction for a certain time in the decomposition reactor (A) is finally disposed of through the waste discharge line (4).
  • the flowability of this stream is very important for the practical application of the process and is determined by the degree of decomposition reaction and the physical properties of the residue.
  • a catalyst such as an organic acid, which is widely used in the ester process
  • a large amount of catalyst flows in the waste discharge line 4 so that precipitation problems are likely to occur, and as the degree of reaction increases, tar and tar
  • the discharge of high viscosity materials of the same shape is increased.
  • the present invention unlike the conventional method through the introduction of a small amount of water continuously in the decomposition reactor (A) to solve this, it can be confirmed a satisfactory decomposition reactivity of the reaction by-products even at a relatively low temperature.
  • the conversion rate of the by-product defined by the following formula after step b) may be 60 to 99%, preferably 70 to 99%, and 70 to 95% More preferably.
  • the selectivity of the recovered product defined by the following formula may be 45 to 85%, preferably 50 to 80%, more preferably 55 to 75%.
  • the recovery rate of the recovered product defined by the following formula may be 35 to 80%, preferably 45 to 75%, more preferably 50 to 70%.
  • Examples and comparative examples were made in the reaction system. And butanol (1%), acrylic acid (4%), butyl acrylate (2%), BPB (50%), BDA (30%), BPA (3%), other (polymerization inhibitors and heavy components) ( 30 g of the pTSA catalyst was added to 300 g of the final distillate discharge having a composition of 10%), and the reaction was performed at a reaction temperature of 120 to 150 ° C, reduced pressure, and atmospheric pressure. During the reaction, water was circulated at a constant flow rate (0.3 to 3 g / min) through a metering pump. After analyzing the composition of the organic phase and the water layer of the gas phase condensate obtained after the reaction for 3 to 10 hours, the conversion, selectivity, and recovery of the Michael by-product of the reaction by-products defined as follows were compared.
  • Organic layer selectivity (total amount of butanol, acrylic acid and butyl acrylate recovered to organic layer / total amount of Michael adducts consumed by reaction) ⁇ 100
  • Organic layer recovery rate (total amount of butanol, acrylic acid, and butyl acrylate recovered to the organic layer / total amount of Michael adduct added) ⁇ 100
  • the reaction was carried out for 3 hours at a reaction temperature of 120 ° C. and a reaction pressure of 400 mmbar at a rate of 1.5 g / min of water input to the reactor.
  • 45% of the feed amount 300g was recovered as the organic phase and the BPB composition of the organic phase was obtained as 7.6%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the flow flowing out of the reactor bottom was a single phase flow without precipitation of solid phase pTSA, and the amount of water was measured to be maintained at 5 wt%.
  • the reaction was performed at 130 ° C. and a reaction pressure of 1,013 mmbar for 3 hours at 1.5 g / min. As a result, 52% of the feed amount 300g was recovered as the organic phase, and the BPB composition of the organic phase was obtained as 6.4%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the flow flowing out of the reactor bottom was a single phase flow without precipitation of solid phase pTSA, and the amount of water was measured to be maintained at 4 wt%.
  • the reaction was carried out for 3 hours at a reaction temperature of 130 ° C. and a reaction pressure of 1,013 mmbar at a rate of 0.35 g / min of water input to the reactor.
  • a reaction temperature of 130 ° C. and a reaction pressure of 1,013 mmbar at a rate of 0.35 g / min of water input to the reactor.
  • 24% of the feed amount 300g was recovered as the organic phase, and the BPB composition of the organic phase was obtained as 0.3%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the flow flowing out of the reactor bottom was a single phase flow without precipitation of solid phase pTSA, and the amount of water was measured to be maintained at 4 wt%.
  • the reaction was carried out at a reaction temperature of 150 ° C. and a reaction pressure of 1,013 mmbar for 4 hours at a rate of 0.35 g / min water input to the reactor.
  • 44% of the feed amount 300g was recovered as the organic phase and the BPB composition of the organic phase was obtained as 0.1%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the flow out of the reactor bottom was a single phase flow without precipitation of solid phase pTSA, and the amount of water was measured to be maintained at 3.5 wt%.
  • the reaction was carried out at a reaction temperature of 120 ° C. and a reaction pressure of 400 mmbar for 10 hours at a rate of 0.35 g / min of water input to the reactor.
  • 54% of the feed amount 300g was recovered as the organic phase and the BPB composition of the organic phase was obtained as 1%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the reaction was carried out for 3 hours at a reaction temperature of 100 ° C. and a reaction pressure of 200 mmbar at a rate of 1.5 g / min of water input to the reactor.
  • 30% of the feed amount 300g was recovered as the organic phase, and the BPB composition of the organic phase was obtained as 6.7%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the decomposition reaction was carried out in the same apparatus as Examples 1 to 5 except that water was not added. After 5 hours of reaction at a reaction temperature of 150 ° C. and a reaction pressure of 1,013 mmbar, 3.5% of the feed amount was found to be recovered as an organic phase. The BPB composition of the organic phase was obtained at 1.3%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the decomposition reaction was carried out in the same apparatus as Examples 1 to 5 except that water was not added. After 3 hours of reaction at a reaction temperature of 150 ° C. and a reaction pressure of 50 mmbar, 49.6% of the feed amount was recovered as an organic phase, and the BPB composition of the organic phase was obtained as 10%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the decomposition reaction was carried out in the same apparatus as Examples 1 to 5 except that water was not added. After 3 hours of reaction at a reaction temperature of 180 ° C. and a reaction pressure of 1,013 mmbar, 82.7% of the feed amount was recovered as an organic phase and a BPB composition of the organic phase was obtained as 8%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the reaction was carried out for 4 hours at a reaction temperature of 105 ° C. and a reaction pressure of 1,013 mmbar at a rate of 0.35 g / min.
  • 8% of the feed amount 300g was recovered as the organic phase, and the BPB composition of the organic phase was obtained as 0.1%.
  • the conversion rate and selectivity recovery rate according to the definition are as follows.
  • the flow flowing out of the reactor bottom was a single phase flow without precipitation of solid phase pTSA, and the amount of water was measured to be maintained at 12.4 wt%.
  • the problem of the conventional process of recovering the reaction by-products can be solved by continuously adding and recycling a small amount of water to the decomposition reactor.
  • a small amount of water to the recovery reaction of the reaction by-products proceeding in the decomposition reactor, it was possible to lower the temperature of the reaction by causing a hydrolysis reaction, and also in the step b) recovered by the decomposition reaction of step b) It also acts as an azeotropic agent to lower the boiling point by azeotroping with the recovered product, so that the immediate off-system removal of the produced (meth) acrylic acid, alcohol and (meth) acrylic acid ester can be easily provided, thereby providing a high conversion rate.
  • the reactor when the water is to be maintained at more than 0 to 10% by weight or less, the reactor can be operated stably under the conditions other than high temperature and high pressure.
  • waste oil which is a waste generated after the recovery reaction
  • single phase outflow is possible due to an increase in the solubility of organic acids, thereby solving the problem of process application of waste oil outflow.
  • the amount of water consumed by the reaction and additionally supplied may be small.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé d'extraction d'ester d'acide (méth)acrylique comprenant les étapes consistant à : (a) obtenir un ester d'acide (méth)acrylique par une réaction entre l'ester d'un alcool et un acide (méth)acrylique en présence d'un catalyseur, les sous-produits étant produits conjointement à l'ester d'acide (méth)acrylique; et (b) obtenir de l'acide (méth)acrylique, de l'alcool et de l'ester d'acide (méth)acrylique en tant que matières extraites par réaction des sous-produits produits à l'étape (a) avec un catalyseur et à de l'eau dans un contenant de réaction, l'eau étant fournie au contenant de réaction de sorte que la teneur de l'eau fournie dans le contenant de réaction est supérieure à 0 et inférieure à 10 % en poids du poids total des réactifs constitués par les sous-produits, le catalyseur et l'eau, dans le contenant de réaction, puis à extraire l'acide (méth)acrylique, l'alcool et l'ester d'acide (méth)acrylique contenus dans les sous-produits en les isolant des sous-produits.
PCT/KR2009/006835 2008-11-19 2009-11-19 Procédé d'extraction d'ester d'acide (méth)acrylique WO2010058983A2 (fr)

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CN2009801293524A CN102105432B (zh) 2008-11-19 2009-11-19 回收(甲基)丙烯酸酯的方法
BRPI0915932-0A BRPI0915932B1 (pt) 2008-11-19 2009-11-19 método para recuperação de um éster de ácido (met)acrílico
US13/055,425 US8772534B2 (en) 2008-11-19 2009-11-19 Method of recovering (meth) acrylic acid ester

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KR10-2008-0115393 2008-11-19

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WO2012026661A1 (fr) * 2010-08-26 2012-03-01 Lg Chem, Ltd. Procédé de préparation d'un (méth)acrylate d'alkyle
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KR101362353B1 (ko) * 2010-07-09 2014-02-12 주식회사 엘지화학 (메트)아크릴레이트의 제조방법
CN111362786B (zh) * 2018-12-25 2023-01-13 万华化学集团股份有限公司 一种丙烯酸甲酯重组分回收利用的方法
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FR3141174A1 (fr) 2022-10-19 2024-04-26 Arkema France Procede perfectionne de fabrication d’acrylate de butyle de purete elevee

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910603A (en) * 1995-09-28 1999-06-08 Basf Aktiengesellschaft Esterification of (meth)acrylic acid with an alkanol
JP2003226671A (ja) * 2002-01-31 2003-08-12 Toagosei Co Ltd （メタ）アクリル酸エステルの製造方法
US6617470B1 (en) * 1998-11-11 2003-09-09 Basf Aktiengesellschaft Method for esterifying (meth)acrylic acid with an alkanol
US20040225149A1 (en) * 2001-12-26 2004-11-11 Mitsubishi Chemical Corporation Method of decomposing by-product during the production of (meth)acrylic ester
US20040267045A1 (en) * 2001-11-28 2004-12-30 Mitsubishi Chemical Corporation Processes for producing (meth)acrylic acid compound
US20060287550A1 (en) * 2003-05-28 2006-12-21 Mitsubishi Rayon Co., Ltd. Process for the production of n-alkylaminoalkyl (meth)acrylates

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0768168B2 (ja) * 1991-07-12 1995-07-26 東亞合成株式会社 アクリル酸エステルのミカエル付加物の分解方法
JP2861983B2 (ja) * 1997-04-07 1999-02-24 東亞合成株式会社 アクリル酸エステルのミカエル付加物の分解方法
US6655469B1 (en) * 2002-05-23 2003-12-02 Greensgroomer Worldwide, Inc. Turf comber

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910603A (en) * 1995-09-28 1999-06-08 Basf Aktiengesellschaft Esterification of (meth)acrylic acid with an alkanol
US6617470B1 (en) * 1998-11-11 2003-09-09 Basf Aktiengesellschaft Method for esterifying (meth)acrylic acid with an alkanol
US20040267045A1 (en) * 2001-11-28 2004-12-30 Mitsubishi Chemical Corporation Processes for producing (meth)acrylic acid compound
US20040225149A1 (en) * 2001-12-26 2004-11-11 Mitsubishi Chemical Corporation Method of decomposing by-product during the production of (meth)acrylic ester
JP2003226671A (ja) * 2002-01-31 2003-08-12 Toagosei Co Ltd （メタ）アクリル酸エステルの製造方法
US20060287550A1 (en) * 2003-05-28 2006-12-21 Mitsubishi Rayon Co., Ltd. Process for the production of n-alkylaminoalkyl (meth)acrylates

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012026661A1 (fr) * 2010-08-26 2012-03-01 Lg Chem, Ltd. Procédé de préparation d'un (méth)acrylate d'alkyle
CN103080065A (zh) * 2010-08-26 2013-05-01 Lg化学株式会社 制备（甲基）丙烯酸烷基酯的方法
US8703995B2 (en) 2010-08-26 2014-04-22 Lg Chem, Ltd. Method of preparing alkyl (meth)acrylate
CN103080065B (zh) * 2010-08-26 2015-10-14 Lg化学株式会社 制备(甲基)丙烯酸烷基酯的方法
CN113511973A (zh) * 2021-03-16 2021-10-19 南京福昌环保有限公司 利用串联催化酯化反应装置回收丙烯酸及酯类废油的方法

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US20110230675A1 (en) 2011-09-22
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BRPI0915932A2 (pt) 2019-11-26
US8772534B2 (en) 2014-07-08
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CN102105432A (zh) 2011-06-22
CN102105432B (zh) 2013-10-16

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