KR20170001088A - Method for Producing Acrylic Acid - Google Patents

Method for Producing Acrylic Acid Download PDF

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KR20170001088A
KR20170001088A KR1020150090550A KR20150090550A KR20170001088A KR 20170001088 A KR20170001088 A KR 20170001088A KR 1020150090550 A KR1020150090550 A KR 1020150090550A KR 20150090550 A KR20150090550 A KR 20150090550A KR 20170001088 A KR20170001088 A KR 20170001088A
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acrylic acid
acid
catalyst
hydroxypropionic
sio
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KR1020150090550A
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Korean (ko)
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김대성
이원재
하현배
정소이
최용진
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주식회사 엘지화학
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid

Abstract

The present invention relates to a process for producing acrylic acid, and more particularly, to an aqueous solution containing acrylic acid, 3-hydroxypropionic acid (3-HPA) and other impurities generated as a result of oxidation reaction of allyl alcohol, To yield acrylic acid.

Description

Method for Producing Acrylic Acid "

The present invention relates to a process for producing acrylic acid, and more particularly, to an aqueous solution containing acrylic acid, 3-hydroxypropionic acid (3-HPA) and other impurities generated as a result of oxidation reaction of allyl alcohol, To yield acrylic acid.

Acrylic acid is the most simple unsaturated carboxylic acid containing a carboxylic acid and a vinyl group. It is a super absorbent polymer (SAP (Super Absorbent Polymer) having a function of absorbing moisture of about 500 to 1,000 times its own weight ). In addition to hygiene products such as diapers for children, hygiene products such as soil remediation agents for gardening, index materials for civil engineering and construction, seedling-use sheets, freshness preservatives in the field of food distribution, and fomentation materials And is widely used as a material of the substrate. Therefore, Super Absorbent Polymer (SAP), which is known to have superior absorption capacity when compared with conventional absorbers, has a wider range of applications, and thus has a high market value. The acrylic acid used as the raw material Have significant market value. In addition, acrylic acid is used as a key raw material for various applications such as acrylic fiber, paints, dots, adhesives and coatings. As a result of high oil prices and eco-friendly issues, new manufacturing methods for replacing conventional petrochemicals (propylene) -based acrylic acid (AA) production methods have been extensively studied. As a method for producing acrylic acid at present, A process for producing acrylic acid from propylene through acrolein is common.

On the other hand, when producing biodiesel from vegetable oil, glycerol is produced as a by-product. In the case of producing acrylic acid from allyl alcohol derived from glycerol, acrylic acid can be produced from environmentally friendly biomass without using fossil fuel. In this case, there is a problem that 3-hydroxypropionic acid (3-HPA) is simultaneously produced and the yield of acrylic acid is low.

Therefore, 3-hydroxypropionic acid (3-HPA) is efficiently separated from the oxidation reaction product of allyl alcohol and converted into acrylic acid through a dehydration reaction, so that a high yield of acrylic acid can be obtained as a whole. However, until now, there has been no known purification process for purifying the reaction product of allyl alcohol to obtain acrylic acid in a high yield. Therefore, there is a need to study a method for purifying acrylic acid at a high yield using a specific synthesis condition.

US 7,279,598

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the problems of the prior art described above, and it is an object of the present invention to further purify an aqueous solution containing acrylic acid, 3-hydroxypropionic acid (3-HPA) and other impurities generated as a result of oxidation reaction of allyl alcohol And a method for producing acrylic acid having a high yield.

In order to accomplish the above object, the present invention provides a method for producing an acrylic acid-containing organic phase, which comprises the steps of (a) using an organic extractant in an aqueous solution containing acrylic acid and 3-hydroxypropionic acid (hereinafter referred to as 3-HPA) And 3-hydroxypropionic acid (3-HPA); (b) converting the aqueous phase containing 3-hydroxypropionic acid (3-HPA) obtained in the step (a) into an aqueous phase containing acrylic acid through dehydration; And (c) obtaining a high purity acrylic acid from a mixed solution of the aqueous phase containing acrylic acid obtained in the step (a) and the aqueous phase containing acrylic acid obtained in step (b), and do.

According to a preferred embodiment of the present invention, the step (c) may be carried out using a distillation or crystallization method to obtain acrylic acid. In the step (c), the organic extractant may be separated from the mixed solution.

According to the method for producing acrylic acid of the present invention, an aqueous solution containing acrylic acid, 3-hydroxypropionic acid (3-HPA) and other impurities generated as a result of the oxidation reaction of allyl alcohol is further purified to synthesize acrylic acid in a high yield Therefore, it is possible to produce acrylic acid on a commercial scale, and the productivity of acrylic acid production can be significantly improved as compared with the conventional method.

1 is a schematic process diagram showing a method for producing acrylic acid according to an embodiment of the present invention.
FIG. 2 shows the ASPEN process chart of Example 1 and the simulation results thereof, showing the composition of each STREAM component.
FIG. 3 shows the composition of each STREAM as ASPEN process chart and simulation result of Example 2.

Hereinafter, the method for producing acrylic acid of the present invention will be described in detail.

The present invention relates to a method for purifying acrylic acid as the main product, using a particular synthesis condition, to greatly increase the yield of acrylic acid. Therefore, acrylic acid can be produced at a remarkably high yield compared to the conventional art.

The present invention relates to a process for the preparation of (a) an organic phase comprising acrylic acid and an organic phase comprising 3-hydroxypropionic acid (3-hydroxypropionic acid: 3-HPA) 3-HPA); (b) converting the aqueous phase containing 3-hydroxypropionic acid (3-HPA) obtained in the step (a) into an aqueous phase containing acrylic acid through dehydration; And (c) purifying a mixed solution of the aqueous phase containing the acrylic acid obtained in the step (a) and the aqueous phase containing acrylic acid obtained in the step (b) to obtain acrylic acid, to provide.

An aqueous solution containing acrylic acid and 3-hydroxypropionic acid (hereinafter referred to as 3-HPA) can be defined as FEED in the specification.

An aqueous solution containing acrylic acid and 3-hydroxypropionic acid (3-HPA) used in the present invention, an organic phase containing acrylic acid, and an acrylic acid, may be prepared by reacting acrylic acid and other Means a solution containing impurities.

Further, it means a water-containing extractor comprising 3-hydroxypropionic acid (3-HPA) or a solution containing 3-hydroxypropionic acid and other impurities generated from the reactor and not yet purified.

More specifically, the step (a) comprises using an organic extractant from an aqueous solution containing acrylic acid and 3-hydroxypropionic acid (3-HPA) to extract an organic phase containing acrylic acid and a 3-hydroxypropionic acid Acid (3-HPA).

The organic extractant used in step (a) may include at least one selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters, tertiary amines, and aromatic compounds. But it is not limited thereto.

More specifically, the organic extractant used in step (a) may be ethyl acetate (EA), methyl isobutyl ketone (MIBK), methyl tert-butyl ether, MTBE), trioctylamine (TOA), 2-ethylhexanol (2EH), n-butanol (BuOH) and 1-octanol And the like. The weight ratio of the aqueous solution (FEED) and the organic extracting agent in step (a) may be from 1:20 to 20: 1, and preferably from 1: 5 to 5: 1. If the mass ratio of the aqueous solution is too large, the flow rate of the organic extractant required for the extraction is insufficient, which complicates the extraction process and increases the cost. On the other hand, there is a disadvantage that the unnecessary waste of organic extractant is worsened. The extraction temperature may be 0 to 100 占 폚 in case of atmospheric pressure, and preferably 15 to 30 占 폚. This may change when pressurized or decompressed. The extraction method of adding the organic extractant to the aqueous solution can be any known method, for example, any method such as cross current, counter current, co-current, etc. can be used have. The aqueous phase containing 3-hydroxypropionic acid (3-HPA) contains 3-hydroxypropionic acid (3-HPA) and water . The organic phase containing acrylic acid contains little water. Conversely, the aqueous phase containing 3-hydroxypropionic acid (3-HPA) preferably contains no organic extraction agent. However, the organic phase containing acrylic acid may contain a small amount of water, and the aqueous phase containing 3-hydroxypropionic acid (3-HPA) may contain a small amount of organic extractant.

The step (b) is a step of converting an aqueous phase containing 3-hydroxypropionic acid (3-HPA) obtained in the step (a) into an aqueous phase containing acrylic acid through a dehydration reaction, .

[Reaction Scheme 1]

Figure pat00001

The dehydration reaction may be performed by adjusting one or more conditions from the group consisting of the phase change of the catalyst, the liquid phase or the gas phase, the reaction temperature and the reaction time.

The step (b) is preferably dehydrated by a catalyst, and the catalyst may be an acidic catalyst or a basic catalyst. According to a preferred embodiment of the present invention, the acid catalyst comprises a catalyst comprising at least one selected from a natural quartz material, a synthetic quartz material, an acidic zeolite, a heteropoly acid and an acidic ion exchange resin; A metal phosphate catalyst comprising at least one material selected from chromium, manganese, iron, cobalt, nickel, boron, lanthanum, calcium, strontium, barium, molybdenum and ruthenium metal; And TiO 2, Al 2 O 3, SiO 2 And SiO 2 -Al 2 O 3 ; and a metal phosphate catalyst supported on at least one selected from the group consisting of SiO 2 -Al 2 O 3 ; TiO 2, Al 2 O 3, SiO 2, ZrO 2, SnO 2, Ta 2 O 3, Nb 2 O 5 And SiO 2 -Al 2 O 3 or more of the selected one metal oxide; ZrO 2 -SO 4 , ZrO 2 -PO 4 , ZrO 2 -WO 3 , ZrO 2 -SiO 2 , TiO 2 -SO 4 , TnO 2 -SO 4 , H 3 PO 4 -Al 2 O 3 , H 3 PO 4 -SiO 2 and H 3 PO 4 -ZrO 2 ; Inorganic acids including at least one selected from hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; ≪ / RTI > may be used.

The basic catalyst includes an oxide of an alkali metal; Hydroxides of alkali metals; Oxides of alkaline earth metals; Hydroxides of alkaline earth metals; Amines containing at least one member selected from the group consisting of trimethylamine, triethylamine, trihexylamine, trioctylamine and tridodecylamine; And a basic ion-exchange resin, can be used.

The reaction temperature in step (b) is 70 to 300 ° C, preferably 100 to 280 ° C. The pressure can be any of the conditions of reduced pressure, atmospheric pressure, and pressurized, and the production yield of acrylic acid from 3-hydroxypropionic acid is 80% or more, preferably 90% or more, more preferably 95% or more.

According to a preferred embodiment of the present invention, the step of purifying the aqueous phase containing 3-hydroxypropionic acid (3-HPA) during the step (a) and the step (b) before the dehydration reaction is further carried out . That is, since the aqueous phase containing 3-hydroxypropionic acid (3-HPA) obtained in the step (a) is low in concentration and contains impurities, it is preferable to undergo further purification steps before the dehydration reaction. As a preferable purification method, a distillation method can be used and can be carried out under atmospheric pressure or reduced pressure. The distillation is preferably carried out at 220 ° C or lower, which is lower than the boiling point of 3-hydroxypropionic acid (3-HPA) in case of normal pressure, and the distillation is carried out at a temperature of not higher than the boiling point of 3-hydroxypropionic acid The concentration of the water phase is preferably 20 to 90%. If the concentration of the aqueous phase containing 3-hydroxypropionic acid (3-HPA) introduced into the dehydration reactor is lower than 20%, an additional amount of heat for removing water in the reaction and subsequent separation step becomes excessively required, It is economical. If the concentration is higher than 90%, the viscosity of the solution becomes too high, which is disadvantageous to transportation.

According to a preferred embodiment of the present invention, the step (c) is a step of distillation (distillation) of a mixed solution of the acrylic acid-containing organic phase obtained in the step (a) and the acrylic acid- ) Or crystallization can be used to obtain high purity acrylic acid.

The distillation can be operated under reduced pressure, atmospheric pressure and pressure by a method of separating using the difference in boiling point of the mixed solution. In this case, a solvent may be added to improve separation efficiency. Reactive distillation can be used to simultaneously perform the reaction and the separation. In this case, a dehydration catalyst may be installed in the distillation column to separate 3-hydroxypropionic acid into acrylic acid while separating the mixture. The distillation conditions of step (c) may be determined according to the type of the organic extractant and / or the boiling point and / or the formation of the azeotrope.

The crystallization may be performed by suspension crystallization or a layer crystallization method using a difference in solubility of the mixed solution.

According to a preferred embodiment of the present invention, it is possible to further include a step of isolating and obtaining an organic extractant in the mixed solution of the step (c). In this case, it is possible to separate easily by phase separation due to the polarity difference between the organic extractant and water, and if necessary, the organic extractant of high purity can be recovered through an additional distillation process. That is, in the step (c), the organic extractant may be separated from the mixed solution in addition to acrylic acid.

Specifically, in the case of using a distillation column, the order of separation of acrylic acid and organic extractant may vary depending on the boiling point of the organic extractant and acrylic acid. Accordingly, a substance having a high boiling point in the organic extractant and acrylic acid can be firstly taken from the bottom through the first distillation step, and the remaining light can be separated in the second distillation stage (Example 1 And Example 2).

For example, when the organic extractant is methyl tert-butyl ether (MTBE), the distillation is performed at a column temperature of 30 to 150 ° C. and a pressure of 0.4 to 1.2 atm. The highest acrylic acid can be separated. The mixture of water and the organic extractant obtained from the top phase can be separated through an additional distillation process or phase separation using the polarity difference between the materials, thereby recovering the high purity organic extractant.

As another example, when the organic extractant is trioctylamine (TOA), the organic extractant having the highest boiling point may be separated from the column bottom of the distillation column and recovered. The mixture of water and acrylic acid obtained from the top phase can be separated through an additional distillation or crystallization process to finally obtain high purity acrylic acid.

1 is an apparatus for producing acrylic acid according to a preferred embodiment of the present invention. That is, it comprises an extraction device 100, a 3-hydroxypropionic acid purification device 200, a dehydration reaction device 300, an acrylic acid purification device 400 and an organic extractive recovery device 500, (1 to 13).

Specifically, the reactants comprising acrylic acid and 3-hydroxypropionic acid (3-HPA) are transferred to the reactant transferring line 2, the water and the organic extracting agent are transferred to the transferring line 1 and the transferring line 3 And then flows into the extraction device 100 through the pipe. The organic phase containing the separated acrylic acid is introduced into the acrylic acid purification apparatus 400 through the transfer line 4. The aqueous phase containing 3-hydroxypropionic acid (3-HPA) separated from the extraction apparatus 100 is introduced into the 3-hydroxypropionic acid purification apparatus 200 through the transfer line 5 and purified And then flows into the dehydration reactor 300 through the transfer line 7. In the dehydration reaction apparatus 300, the aqueous phase containing 3-hydroxypropionic acid (3-HPA) is dehydrated and converted into an aqueous phase containing acrylic acid. The water phase containing the converted acrylic acid is transferred to the acrylic acid purification apparatus 400 through the transfer line 8. The transfer line 4 and the transfer line 8 are brought into contact with each other before being transferred to the acrylic acid purification apparatus 400. The aqueous phase containing acrylic acid and acrylic acid are mixed with each other to be mixed with the acrylic acid purification apparatus 400 ≪ / RTI > The mixture is purified in an acrylic acid purification apparatus (400) to obtain acrylic acid through the transfer line (11). The solution containing the organic extractant and water separated in the acrylic acid purification apparatus is purified in the organic extractant recovery apparatus 500 and separated into the organic extractant and the remaining waste water. The purified organic extractant is recycled through the transfer line 12.

The extraction device 100 includes a pack column (not shown) including a filling material such as a rashing ring, a pall ring, a saddle, a gauze, and a structured packing packed column) or in the form of a typical multi-column column. And the purification apparatus may be a distillation column.

The production yield of acrylic acid obtained in the step (c) of the acrylic acid produced by the production method of acrylic acid of the present invention is 80 moles per mole of the sum of moles of acrylic acid and 3-HPA contained in the aqueous solution (FEED) %. That is, the acrylic acid yield is a value calculated by the following equation (7), and the calculated value is 80% or more.

[Equation 7]

(Yield,%) = (the number of moles of acrylic acid obtained in step (c)) / (the total number of moles of acrylic acid and 3-hydroxypropionic acid contained in the aqueous solution of step (a)) x 100

Therefore, it is excellent in economy.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

Manufacturing example

35 mg of a CeO 2 catalyst carrying nano-sized gold particles was placed in a solution of 17.24 mL of distilled water, 2.07 g of sodium hydroxide and 1.17 mL of allyl alcohol, and the solution was placed in a 50 mL glass reactor. The glass reactor was adjusted to a vacuum and high purity oxygen gas was charged to 3 bar and maintained at 3 bar during the reaction.

The glass reactor was then reacted at 50 < 0 > C for 12 hours. The catalyst and the salt were separated from the reaction solution to obtain a mixed aqueous solution of 3-HPA and AA.

Preparation Example  One

8 g of the mixed aqueous solution prepared in the above Production Example was added to a 20 mL vial, and then 8 g of trioctylamine was added as an organic extracting agent. The vials were vigorously stirred in a vortex mixer for 20 seconds and then stirred in an orbital shaker at 300 rpm for 2 hours. After stirring, the mixture was allowed to stand for 30 minutes until the layer separation completely took place. The aqueous phase and the organic phase were separated using a syringe and the volume and weight of each phase were recorded.

Preparation Example  2

Extraction was carried out in the same manner as in Preparation Example 1, except that methyl tertiary-butyl ether (MTBE) was used as the organic extractant in Preparation Example 1 above.

Preparation Example  3

100 g of phosphoric acid was added to a 500 mL three-necked flask, and then heated to 220 캜. The aqueous phase containing 21% by weight of 3-hydroxypropionic acid isolated in Preparation Example 1, while bubbling nitrogen through a gas distributor installed at the lower end of the reactor, was fed at a rate of 0.29 g / min Lt; / RTI > The vaporized product was passed through a condenser connected to the reactor, and a liquid reaction product was obtained in a flask installed at the end of the condenser.

Preparation Example  One

The concentration of 3-hydroxypropionic acid and acrylic acid present in the aqueous phase separated in Preparation Example 1 was analyzed by HPLC. The concentration of the organic phase was calculated on the basis of the amount obtained by subtracting the amount of 3-hydroxypropionic acid and acrylic acid present in the aqueous phase from the amounts of 3-hydroxypropionic acid and acrylic acid present in the first mixed solution. The partition coefficient (D AA ) of acrylic acid in the aqueous phase after extraction and the partition coefficient (D 3 -HPA ) of 3-hydroxypropionic acid are shown in Table 1 below. The extraction factor (E AA ) and the 3-hydroxypropionic acid extraction factor (E 3-HPA ) of the acrylic acid according to the following formulas 3 and 4 were calculated by the following formula 2 and shown in Table 1 below.

- Analysis conditions (HPLC)

Device: Waters 2690

Detector: Waters 2410 RI (Refractive Index) detector

Column: Agilent Hi-Plex H Column

Column temperature: 60 ° C

Mobile phase: DI water

Flow rate: 0.6 mL / min

[Equation 1]

Distribution coefficient (D) = concentration of substance in organic phase / concentration of substance in water phase

&Quot; (2) "

Separation factor (S) = partition coefficient of acetic acid (AA) / partition coefficient of 3-hydroxypropionic acid (3HPA)

&Quot; (3) "

Extraction factor (E) = Partition coefficient of substance (D) x Phase ratio (R)

&Quot; (4) "

Phase ratio (R) = flow rate of organic phase / flow rate of water phase

Preparation Example  2

The procedure of Preparation Example 1 was repeated, except that the aqueous phase separated in Preparation Example 2 was used.

division Preparation Example 1 Preparation Example 2 Extractant TOA MTBE Distribution coefficient D AA 4.888 3.271 D 3HPA 0.026 0.045 Flow rate (Kg / h) Aqueous 1000 1000 Organic 1000 1000 Extraction factor E AA 4.89 3.27 E 3HPA 0.03 0.04 Initial concentration (wt%) C AA , 0 2.83 5.75 C 3HPA , 0 2.97 5.99 Separation factor S 188 72.69

TOA: Trioctylamine / MTBE: Methyl tert-butyl ether

Preparation Example  3

The liquid phase reaction product prepared in Preparation Example 3 was analyzed by HPLC area% analysis of acrylic acid, 3-hydroxypropionic acid using liquid chromatography (Waters Alliance 2690). Acrylic acid conversion and 3-hydroxypropionic acid selectivity and yield of 3-hydroxypropionic acid were calculated using the following formulas 5 to 6. As a result, the conversion of 3-hydroxypropionic acid was 99.9%, and the yield of acrylic acid was 81.2%.

[Formula 5]

3-hydroxypropionic acid conversion rate (conversion%) = 100 x (molar amount of 3-hydroxypropionic acid before reaction - molar amount of 3-hydroxypropionic acid after reaction) / (3-hydroxypropionic acid Mol)

[Formula 6]

Acrylic acid yield (yield,%) = (3-hydroxypropionic acid conversion rate x acrylic acid selectivity) / 100

Example  One; ASPEN for Manufacturing Acrylic Acid Process simulation

The process for refining acrylic acid from a mixed aqueous solution of acrylic acid and 3-hydroxypropionic acid was carried out using ASPEN. The result and the flow rate of the material for each transfer line are shown in FIG. Trioctylamine (TOA) was used as an organic extractant for extraction. The yield of acrylic acid was calculated using Equation 7-1, and finally about 88% of acrylic acid was obtained.

[Equation 7-1]

Yield of acrylic acid (yield,%) = (moles of acrylic acid finally obtained) / (total number of moles of acrylic acid and 3-hydroxypropionic acid contained in FEED) x 100

Example  2; ASPEN for Manufacturing Acrylic Acid Process simulation

The process for purifying acrylic acid from a mixed aqueous solution of acrylic acid and 3-hydroxypropionic acid was carried out using ASPEN, and the result and the flow rate of the material for each transfer line are shown in FIG. Methyl tert-butyl ether (MTBE) was used as the organic extractant for the extraction. The yield of acrylic acid was calculated using Equation 7 above, and finally about 86% of acrylic acid was obtained.

1 to 13 transferring lines 100 extraction device 200 3-hydroxypropionic acid purification device 300 dehydration reaction device 400 acrylic acid purification device 500 organic extraction agent recovery device

Claims (12)

(a) an organic phase containing acrylic acid and an organic phase containing 3-hydroxypropionic acid (3-hydroxypropionic acid, 3-HPA) using an organic extractant in an aqueous solution containing acrylic acid and 3-hydroxypropionic acid Separating the aqueous phase comprising the aqueous phase;
(b) converting the aqueous phase containing 3-hydroxypropionic acid (3-HPA) obtained in the step (a) into an aqueous phase containing acrylic acid through dehydration; And
(c) obtaining acrylic acid in a mixed solution of the acrylic acid-containing organic phase obtained in the step (a) and the aqueous phase containing acrylic acid obtained in the step (b). The method according to claim 1,
Wherein the organic extractant used in step (a) comprises at least one selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters, tertiary amines and aromatic compounds. The method according to claim 1,
The organic extractant used in step (a) may be ethyl acetate (EA), methyl isobutyl ketone (MIBK), methyl tert-butyl ether (MTBE), triisobutyl ether (1-octanol: OCT) selected from the group consisting of trioctylamine (TOA), 2-ethylhexanol: 2EH, n-butanol: BuOH and 1-octanol ≪ / RTI > or more. The method according to claim 1,
Wherein the mass ratio of the aqueous solution of step (a) to the organic extractant is from 1:20 to 20: 1. The method according to claim 1,
Wherein the step (c) is a step of obtaining acrylic acid by a method of distillation or crystallization. The method according to claim 1,
Further comprising the step of isolating and obtaining an organic extractant in the mixed solution of step (c). The method according to claim 1,
The dehydration reaction of step (b)
Wherein the reaction is carried out by adjusting one or more conditions selected from the group consisting of a catalyst, a liquid phase or a phase change of gas phase, a reaction temperature and a reaction time. The method of claim 7,
Wherein the catalyst is an acidic catalyst or a basic catalyst. The method of claim 8,
The acidic catalyst
A catalyst comprising at least one selected from a natural gypsum material, a synthetic gypsum material, an acidic zeolite, a heteropoly acid, and an acidic ion exchange resin; A metal phosphate catalyst comprising at least one material selected from chromium, manganese, iron, cobalt, nickel, boron, lanthanum, calcium, strontium, barium, molybdenum and ruthenium metal; TiO 2, Al 2 O 3, SiO 2, SiO 2 -Al 2 O 3 on a metal phosphate catalyst supporting carrier; At least one metal oxide selected from TiO 2 , Al 2 O 3 , SiO 2 , ZrO 2 , SnO 2 , Ta 2 O 3 , Nb 2 O 5 and SiO 2 -Al 2 O 3 ; ZrO 2 -SO 4 , ZrO 2 -PO 4 , ZrO 2 -WO 3 , ZrO 2 -SiO 2 , TiO 2 -SO 4 , TnO 2 -SO 4 , H 3 PO 4 -Al 2 O 3 , H 3 PO 4 -SiO 2 and H 3 PO 4 -ZrO 2 ; And inorganic acids including at least one selected from hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; ≪ / RTI > wherein the catalyst is a catalyst comprising at least one selected from the group consisting < RTI ID = 0.0 > of: < / RTI > The method of claim 8,
The basic catalyst
Oxides of alkali metals; Hydroxides of alkali metals; Oxides of alkaline earth metals; Hydroxides of alkaline earth metals; Amines containing at least one member selected from the group consisting of trimethylamine, triethylamine, trihexylamine, trioctylamine and tridodecylamine; And a basic ion-exchange resin. The method for producing acrylic acid according to claim 1, wherein the catalyst is a catalyst comprising at least one substance selected from the group consisting of an alkali metal salt and a basic ion-exchange resin. The method of claim 7,
Wherein the reaction temperature of step (b) is 70 to 300 < 0 > C. The method according to claim 1,
Wherein the yield of acrylic acid is 80% or more as calculated by Formula 7 below.
[Equation 7]
(Yield,%) = (the number of moles of acrylic acid obtained in step (c)) / (the total number of moles of acrylic acid and 3-hydroxypropionic acid contained in the aqueous solution of step (a)) x 100
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Publication number Priority date Publication date Assignee Title
WO2022114519A1 (en) * 2020-11-27 2022-06-02 주식회사 엘지화학 Method for producing catalyst for dehydrogenation of 3-hydroxypropionic acid, catalyst for dehydrogenation of 3-hydroxypropionic acid, and method for producing acrylic acid using same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7279598B2 (en) 2003-06-26 2007-10-09 Xiangsheng Meng Process for separating and recovering 3-hydroxypropionic acid and acrylic acid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7279598B2 (en) 2003-06-26 2007-10-09 Xiangsheng Meng Process for separating and recovering 3-hydroxypropionic acid and acrylic acid

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WO2022114519A1 (en) * 2020-11-27 2022-06-02 주식회사 엘지화학 Method for producing catalyst for dehydrogenation of 3-hydroxypropionic acid, catalyst for dehydrogenation of 3-hydroxypropionic acid, and method for producing acrylic acid using same

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