KR101362353B1 - Process for producing (meth)acrylate - Google Patents
Process for producing (meth)acrylate Download PDFInfo
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- KR101362353B1 KR101362353B1 KR1020100066180A KR20100066180A KR101362353B1 KR 101362353 B1 KR101362353 B1 KR 101362353B1 KR 1020100066180 A KR1020100066180 A KR 1020100066180A KR 20100066180 A KR20100066180 A KR 20100066180A KR 101362353 B1 KR101362353 B1 KR 101362353B1
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- 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
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Abstract
The present invention provides a method for producing (meth) acrylate by esterifying a reactant comprising (meth) acrylic acid and an alcohol in the presence of a catalyst, wherein a) conversion of the (meth) acrylic acid to (meth) acrylate 95% or more to obtain a reaction product containing (meth) acrylate, unreacted (meth) acrylic acid, unreacted alcohol, reaction byproduct and water; And b) separating the (meth) acrylate by azeotropically separating and purifying the reaction product by adding only water with reflux at the time of separation and purification by introducing the reaction product into an acid separation tower. It provides a manufacturing method.
Description
The present invention relates to a method for producing (meth) acrylate.
More specifically, it relates to a process by which the composition of the reaction product can be optimized to allow for smooth acid separation in the separation process to continuously produce (meth) acrylates in high yield.
When (meth) acrylic acid and alcohol are esterified in the presence of a catalyst, (meth) acrylate and water are produced, and some of (meth) acrylic acid and alcohol remain as unreacted starting materials, and by-products are generated.
The esterification reaction analyzes the composition of the inlet and outlet liquids of the reactor to confirm the conversion rate of acrylic acid, and based on the time when the conversion rate reaches a steady state, the conversion rate of acrylic acid and the selectivity of acrylate, etc. Determine.
In the manufacturing method of (meth) acrylate, ion exchange resin, an inorganic acid, an organic acid, etc. are generally used as a catalyst of esterification reaction.
Although esterification which uses (meth) acrylic acid as a raw material changes with the target ester product, Preferably it is 50 degreeC-150 degreeC, More preferably, it is performed within 70 degreeC-120 degreeC. At this time, the esterification reaction is carried out in a liquid phase, and the reaction type may be either a fluidized bed or a fixed bed.
The esterification reaction is usually carried out using a polymerization inhibitor. Examples of the polymerization inhibitor used in this case include hydroquinone, methoxy hydroquinone, phenothiazine, hydroxyl amine, phenylene diamine, and the like. In addition, when the esterification reaction is carried out in the presence of molecular oxygen, the effect of the polymerization inhibitor can be further enhanced.
The esterification reaction product obtained in this way is used to remove (meth) acrylate as a target product, acrylic acid and alcohol as unreacted raw materials, various by-products generated in the reaction process, and a small amount of water that cannot be removed in the reaction process. It contains. The reaction product is separated and purified to undergo a purification process using a distillation column in order to obtain the desired object.
The esterification product is fed to a distillation column, and distillation finally yields the desired product material.
When unreacted acrylic acid, water, alcohol and (meth) acrylate in the reaction product are separated by azeotropic distillation, problems such as acrylic acid may follow to the top of the separation tower due to strong affinity between water and unreacted acrylic acid. Can be.
In order to solve the above problems, in order to reduce the affinity between water and acrylic acid, a method of adding an organic solvent having a greater affinity with water has been proposed, but a separate process for recovering and separating the organic solvent after the reaction is added. Therefore, there is an unfavorable problem economically.
In the separation step, impurities often go up to the tower during purification of the reaction product in the distillation column and mix with the target product, which not only lowers the purity of the product but also causes secondary problems due to impurities during processing of the final product. Since this is likely to occur, studies are continued on how to operate such that impurities which may affect the purity of the final product at the time of distillation of the reaction product do not rise to the column.
It is an object of the present invention to prepare a (meth) acrylate by esterifying a reactant comprising (meth) acrylic acid with an alcohol in the presence of a catalyst, wherein the (meth) acrylic acid is separated in the separation step of the reaction product in an acid separation column. It is possible to maximize the separation efficiency of the rate and unreacted acrylic acid, and to provide a method for producing a (meth) acrylate capable of effective operation of the distillation apparatus.
In order to achieve the above object, the present invention is a method for producing a (meth) acrylate by esterifying a reactant containing (meth) acrylic acid and alcohol in the presence of a catalyst,
a) the conversion of (meth) acrylic acid to (meth) acrylate is 95% or more to obtain a reaction product containing (meth) acrylate, unreacted (meth) acrylic acid, unreacted alcohol, reaction byproduct and water Making; And
b) When the reaction product is introduced into the acid separation tower and separated and purified, the reaction product is subjected to azeotropic separation purification by only adding water to the flux from the acid separation tower to separate (meth) acrylate. Provided are methods for preparing acrylates.
According to the present invention, in the method for preparing (meth) acrylate by esterification, it is possible to maximize the separation efficiency of (meth) acrylate in the separation step of the reaction product in the acid separation column and to effectively Driving is possible.
1 is a schematic diagram of a (meth) acrylate manufacturing process according to the present invention.
Hereinafter, the present invention will be described in more detail.
The present invention provides a method for producing (meth) acrylate by esterifying a reactant containing (meth) acrylic acid and an alcohol in the presence of a catalyst,
a) the conversion of (meth) acrylic acid to (meth) acrylate is 95% or more to obtain a reaction product containing (meth) acrylate, unreacted (meth) acrylic acid, unreacted alcohol, reaction byproduct and water Making; And
b) injecting the reaction product into an acid separation column, and adding water only as an azeotropic substance without adding an organic solvent to reflux, and separating (meth) acrylate from unreacted acrylic acid in the reaction product. It is related with the manufacturing method of the (meth) acrylate characterized by the above-mentioned.
As used herein, (meth) acrylic acid is a meaning including acrylic acid or methacrylic acid unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms,
(Meth) acrylate means a acrylate or methacrylate unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms.
In addition, the alcohol may be an alkyl alcohol having 1 to 6 carbon atoms, for example, butanol, but is not limited thereto.
Reaction byproducts in the present invention are meant to include various heavy byproducts produced by side reactions such as Michael addition during the reaction.
In order to make the conversion rate of (meth) acrylic acid into (meth) acrylate at 95% or more in step a), the amount of catalyst used, reaction temperature, molar ratio of (meth) acrylic acid and alcohol, etc. must be maintained under constant conditions.
In general, in the case of using a liquid catalyst, the amount of the catalyst is preferably used in 0.01 to 5% by weight of the reaction product. The amount of catalyst used is an important factor in determining the conversion rate of the reactants and the reaction selectivity to the product.
In addition, it is important to ensure that the reaction temperature and residence time are optimal in order for the reactants to have adequate conversion and product selectivity.
In general, higher reaction temperatures result in faster reaction rates, but tend to accelerate the production of by-products. In the esterification reaction of this invention, 50-150 degreeC is preferable and 70-120 degreeC is more preferable.
In addition, sufficient retention time of the reactants is required to maintain the conversion above a certain level. The residence time for maintaining at least 95% acrylic acid conversion in the esterification reaction of the present invention is at least 3 hours. However, this depends on the amount of catalyst, the reaction temperature, the molar ratio of the reactants, the rate of removal of the water produced, and the like.
The molar ratio of alcohol to (meth) acrylic acid introduced into the reactor is preferably 0.7 to 3, more preferably 1 to 2.
The composition of the optimum reaction product for efficiently performing the separation process in the acid separation column under the above reaction conditions is 0 to 4% by weight of water, 5 to 25% by weight of alcohol, 0 to 5% by weight of (meth) acrylic acid and (meth ) Acrylate 70% by weight or more. The presence of more than 10% by weight of (meth) acrylic acid in the reaction product composition reduces the separation efficiency of the unreacted (meth) acrylic acid and the reaction product in the acid separation column, thereby increasing the possibility of unreacted acid discharged from the top of the column. .
In order to easily obtain the target product in the reaction product, water is introduced into the reflux at the top of the distillation apparatus so that the target (meth) acrylate and the alcohol, which is a raw material for the esterification reaction, can be obtained by azeotropic distillation with water to obtain a column. Can be used.
In general, when water is introduced into the reflux, acid is discharged to the top of the acid separation tower due to the strong affinity between unreacted (meth) acrylic acid and water in the reaction product, but in the present invention, the (meth) Since the conversion rate of acrylic acid is more than 95%, the acid content of the reaction product introduced into the acid separation column is small, so it is suitable to use water as the reflux, and additional addition of the organic solvent to the reflux and purification column It is unnecessary.
As a result, a separate process for the recovery and separation of the solvent after the reaction is minimized, and thus the operating cost is reduced, which is preferable from an economical point of view compared to the method of adding the organic solvent to the reflux. The amount of water introduced into the reflux in step b) is determined according to the amount of (meth) acrylic acid to be recovered. In other words, as long as there is no contamination of (meth) acrylic acid on the column, the amount of (meth) acrylate to be recovered in the reaction product provided to the purification tower is determined, and then the three-phase azeotropy of water, (meth) acrylate and butanol is determined. The amount of water to be supplied is determined.
When the product discharged from the reactor is fed to the bottom of the acid separation column and heated, (meth) acrylate, water, unreacted alcohol is (meth) acrylate, water, Unreacted alcohol is obtained at the top of the acid separation column, at the bottom of the acid separation column (meth) acrylate which is not obtained as the top of the acid separation column, alcohol as the reaction starting material, another reaction starting material and purification (Meth) acrylic acid and high boiling point reaction byproducts which are to be separated in the tower are obtained.
For example, in the case of the manufacturing process of butyl acrylate, the heavy by-products remaining at the bottom of the acid separation column are butyl b-butoxy propionate (BPB), b-butoxypropionic acid (BPA), n-butyl diacrylate (BDA). ) And some unreacted (meth) acrylic acid and butanol remain.
If the acid separation tower is ideally operated, only (meth) acrylic acid, free substances above the three-phase azeotropy ratio and high boiling point substances are detected at the bottom of the acid separation tower, and purified by three-phase azeotropy at the top of the acid separation tower. Only water, butanol, and (meth) acrylates are detected, but since the product cannot be recovered 100% of (meth) acrylates in reality, products that should be obtained from the top of the acid separation tower, such as alcohol, are also acid separation towers. At the bottom of the part will remain together. This is because the materials are mixed in accordance with the solubility and volatilities of the target materials (meth) acrylate, alcohol, and (meth) acrylic acid, and the optimum process conditions for the purification tower. This is because it is impossible to obtain.
When these impurities rise to the top when the reaction product is purified in the acid separation column and are mixed with the product of the target product, not only the purity of the product is reduced but also secondary problems due to impurities are easily generated during processing of the final product. It is preferable to operate so that impurities of a higher boiling point than a target product are not contained together in the column top at the time of distillation of a product.
When additional heat is additionally supplied to completely obtain the desired material at the top of the acid separation column, (meth) acrylic acid or a high boiling by-product can be obtained at the top of the distillation apparatus. As a result, not only it is difficult to secure the purpose of operating the distillation apparatus to obtain a pure target substance, but also unnecessary energy is excessively consumed, which makes it difficult to secure economic feasibility when comparing the additional yield and energy consumption of the target substance. In addition, the operation of the acid separation tower may also become unstable, such as an increased risk of generating a polymer by polymerization of a target material and (meth) acrylic acid.
The inventors have found that numerous test results show that the separation efficiency of the acid separation column is highly dependent on the composition of the reaction product flowing into the acid separation column, and that the stability and distillation efficiency of the operation of the distillation apparatus are affected by the composition of the reaction product. .
In step b), a reheater is connected to the lower portion of the acid separation tower so that the product is heated.
In addition, the bottom temperature in the reheating furnace of the purification column is preferably maintained in the range of 60 to 110 ℃. When the heating temperature range of the reheating furnace is in the above range, the process can be smoothly performed while the water content in the heated product is maintained at a desired level.
The reaction product collected at the bottom of the acid separation column is heated while passing through the reheating furnace and fed back to the bottom of the acid separation column, and then distilled according to the boiling point.
In the step b), the acid separation column is generally operated at a reduced pressure (50 to 700 torr), and the internal temperature may vary depending on the ratio of the reduced pressure condition and the three phase azeotropy.
In the present invention, the reaction by-products may be discharged to the bottom of the acid separation column. By-products discharged to the bottom of the acid separation column may be re-supplied to step b) and distilled again, or may be re-supplied to step a) and reused as a reaction starting material. do.
In the present invention, the catalyst is an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid; Organic acids such as methanesulfonic acid (MSA), paratoluenesulfonic acid (pTSA) and alkyl sulfuric acid containing sulfonic groups; Natural / synthetic zeolites, cation and anion exchange resins; Metal salts such as lithium fluoride, potassium chloride, cesium chloride, calcium chloride, iron chloride and aluminum phosphate; Metal oxides such as heteropolyacids; Organic metals such as tetra alkyl titanate and polymers thereof; At least 1 sort (s) chosen from each group mentioned above is preferable.
Among these, methanesulfonic acid (MSA) or paratoluenesulfonic acid (pTSA) is more preferable.
The amount of the catalyst is preferably 0.1 to 5% by weight based on 100% by weight of the reactants.
In addition, the acid separation tower is provided with a downcomer tray (tray). In general, downcomer trays are superior in terms of purification efficiency. However, downcomer trays were difficult to use as trays of acid separation towers because they could polymerize as the bottom surface of the tray where vaporized materials contacted dried. However, in the present invention, the amount of (meth) acrylic acid in the reaction product introduced into the acid separation column is very small as compared with the conventional one, and (meth) acrylic acid is present only at the bottom of the column during operation. Therefore, since the possibility of polymerization in a purification tower is low, it is possible to use a downcomer tray which is advantageous in terms of purification efficiency than a conventional dual folw tray. More stably, a dual flow tray may be used only in a region where (meth) acrylic acid is present at the bottom of the purification column. As a result, a stable and efficient operation of the distillation apparatus is possible.
The method of preparing the (meth) acrylate may be batch or continuous, but is preferably a continuous manufacturing method.
Referring to Figure 1 through the process of the present invention.
1 is a simplified schematic diagram of a butyl acrylate manufacturing process according to the present invention. Acrylic acid, butanol and a catalyst are introduced into the pipes 1, 2 and 3, respectively. The primary reactor (A) is a pre-reactor to maintain the conversion of acrylic acid above a certain level with a residence time of 1.0 to 2 hr. Secondary reactor (A ') converts acrylic acid to at least 95% with a residence time of 1.0 to 5.0 hr. In the reactors A and A ', a conventional MSA catalyst is uniformly dissolved in the reactant, and the catalyst, acrylic acid and butanol used as the reactant flows into the reactors A and A' through the pipes 1, 2 and 3. do. The reactants introduced into the reactor cause an esterification reaction and produce the corresponding butyl acrylate and water. Water generated in the reactor is efficiently removed from the water separation tower (B) during the reaction process, and only a small amount of water remaining without removal is transferred to the acid separation tower (C) through a pipe together with alcohol and butyl acrylate. The water and the organic gas produced during the reaction are liquefied through the first condenser, and then separated into an organic layer and a water layer in a decanter. Of these, the organic layer is refluxed with the alcohol supplied to the upper portion of the water separation tower B through a pipe and refluxed to the upper portion of the water separation tower, and is transferred to the reactor through the pipe to prevent the discharge of acid and organic matter from the reactor to the water separation tower to the maximum. do. The reaction liquid of the primary reactor (A) is supplied to the upper portion of the secondary reactor (A ') via a pipe. The reaction liquid of the secondary reactor is introduced into the bottom of the acid separation tower (C) through the pipe (4) via a pump. The acid separation tower uses a downcomer tray of more than 50 theoretical stages. The material entering the acid separation column consists of water, butanol, butyl acrylic acid, butyl acrylate and other byproducts. Among them, water, butyl acrylate and alcohol are moved to the top of the acid separation column by the respective azeotropic composition. In the introduced reaction product, an undivided material including acrylic acid remains at the bottom of the acid separation column, and in this way, separation of the reaction product and unreacted acrylic acid is performed. The gas that has traveled to the top of the acid separation column is liquefied through a condenser and then sent to the receiver through a pipe, where it is separated into an organic layer and a water layer. Water is supplied through the
The organic layer obtained in the acid separation column is again transferred to the purification tower (D) through a pipe. The solution containing unreacted acrylic acid under the acid separation column is circulated through the pipe to the reactor for reuse. In the reactor and the acid separation tower, a small amount of phenothiazine, a polymerization inhibitor, is introduced together with air in order to prevent polymerization during the production reaction of butyl acrylate and the separation of acrylic acid.
Hereinafter, the present invention will be described in more detail with reference to Examples. In Examples and Comparative Examples, the target of the esterification reaction was limited to butyl acrylate, but those skilled in the art can easily apply the experimental results of the following Examples and Comparative Examples to other types of (meth) acrylates. The following examples are intended to illustrate the invention and are not intended to limit the scope thereof.
< Example >
Total acid (TA) was measured to determine whether (meth) acrylic acid used as a reaction starting material in Examples and Comparative Examples was obtained on the column of an acid separation tower during operation of the purification apparatus. The measurement of TA was carried out by taking a certain amount of the organic material and the water layer obtained on the column, using Gas Chromatography.
After the reaction product is first introduced into the acid separation column to remove (meth) acrylic acid and the high boiling point of reaction impurities, it is common to proceed with a further purification process. Therefore, since the purification process can be smoothly operated only after the removal of the high boiling point material from the acid separation column is perfect, the amount of TA on the tower of the acid separation column is a criterion for determining whether the operation of the acid separation column is successful.
Example One
5.9 g / min acrylic acid and 8,7 g / min butanol were reacted as a starting material at a temperature of 95 to 105 ° C., a residence time of 5 hours, and an acrylic acid conversion rate of 95% in the presence of a catalyst, followed by acid separation. Transfer to the tower was used as input liquid. The input flow rate in the acid separation column was 18 g / min, the yield at the top of the column was 21.7 g / min, and the effluent at the bottom of the acid separation column was 5.7 g / min. At this time, the amount of water refluxed to the top of the acid separation column was 8.2g / min. The operation of the acid separation tower was performed such that the bottom temperature was 65 ° C. to 85 ° C., the tower top temperature 54 ° C., and the tower top pressure was about 150 torr. TA (total acid) contained in the organic layer obtained from the top of the acid separation tower was 5ppm or less, TA (total acid) contained in the water layer obtained from the top of the acid separation tower was confirmed to be less than 10ppm.
Comparative Example One
The input liquid of the acid separation column is the same as the operating conditions of Example 1 except that the conversion rate of (meth) acrylic acid in the reaction step is 70% level. The input flow rate of the acid separation column was 18 g / min, the yield at the top of the column was 21.7 g / min, and the effluent at the bottom of the acid separation column was obtained at 5.8 g / min. At this time, the amount of water refluxed to the top of the acid separation column was 8.2g / min. The operation of the acid separation tower was performed such that the bottom temperature was 70 ° C. to 90 ° C., the tower top temperature 54 ° C., and the tower top pressure about 150 torr. TA (total acid) contained in the organic layer obtained from the top of the acid separation tower was 680ppm, TA (total acid) contained in the water layer obtained from the top of the acid separation tower was found to be 2560ppm.
Comparative Example 2
The input liquid of the acid separation column is the same as the operating conditions of Example 1. However, an organic solvent was added together with water at the top of the acid separation column. The input flow rate of the acid separation column was 18 g / min, the yield at the top of the column was 21.7 g / min, and the effluent at the bottom of the acid separation column was obtained at 7.0 g / min. At this time, the amount of water refluxed to the top of the acid separation column was 7.0g / min, the amount of butanol was 1.2g / min. The operation of the acid separation column was performed so that the bottom temperature was 63 ° C. to 82 ° C., the tower temperature was 54 ° C., and the tower upper pressure was about 150 torr. TA (total acid) contained in the organic layer obtained from the top of the acid separation tower was 0ppm, TA (total acid) contained in the water layer obtained from the top of the acid separation tower was confirmed to be 3ppm.
The results of the Examples and Comparative Examples are summarized in Table 1 below.
As a result of the above experiment, when the conversion rate of acrylic acid in the reaction product is high in the operation of the acid separation tower for the purification of the reaction product, it was confirmed that the operation can be stably while ensuring the desired level of BA recovery. In addition, when the organic solvent is used without using water as an azeotrope, it can be seen that the amount of the product recovered in the purification tower is reduced by that amount. In conclusion, it can be seen that the additional amount of the organic solvent added to the purification tower to reduce the amount of recovery of the product to be purified.
As a result, in the purification of the esterification reaction product of (meth) acrylic acid and alcohol as shown in the present example and the comparative example, when the (meth) acrylic acid conversion rate of the reaction product is constant, Contamination of the product by (meth) acrylic acid can be minimized, and organic materials introduced in order to reduce contamination by existing (meth) acrylic acid are not required. ) Maximization of acrylate separation was possible.
A, A ': Reactor B: Water Separation Tower
C: acid separation tower D: purification tower
Claims (13)
a) Conversion rate of the (meth) acrylic acid to (meth) acrylate is at least 95%, 0 to 4% by weight of water, 5 to 25% by weight of unreacted alcohol, 0 to 5% by weight of unreacted (meth) acrylic acid Obtaining a reaction product containing 70 to 95 wt% of (meth) acrylate; And
b) When the reaction product is introduced into the acid separation tower and separated and purified, the reaction product is subjected to azeotropic separation purification by only adding water to the flux from the acid separation tower to separate (meth) acrylate. Process for the preparation of acrylates.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0130555B1 (en) * | 1991-07-02 | 1998-04-07 | 티모시 엔. 비숍 | Esterification process |
| KR20000057213A (en) * | 1996-11-25 | 2000-09-15 | 스타르크, 카르크 | Method for producing (meth)acrylic acid esters |
| JP2003226668A (en) * | 2001-11-28 | 2003-08-12 | Mitsubishi Chemicals Corp | Method for decomposing by-product of process for producing (meth)acrylic acid ester |
| KR20100056415A (en) * | 2008-11-19 | 2010-05-27 | 주식회사 엘지화학 | Method for collecting (meth)acrylic acid ester |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0130555B1 (en) * | 1991-07-02 | 1998-04-07 | 티모시 엔. 비숍 | Esterification process |
| KR20000057213A (en) * | 1996-11-25 | 2000-09-15 | 스타르크, 카르크 | Method for producing (meth)acrylic acid esters |
| JP2003226668A (en) * | 2001-11-28 | 2003-08-12 | Mitsubishi Chemicals Corp | Method for decomposing by-product of process for producing (meth)acrylic acid ester |
| KR20100056415A (en) * | 2008-11-19 | 2010-05-27 | 주식회사 엘지화학 | Method for collecting (meth)acrylic acid ester |
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