KR101634221B1 - Method for producing acrylic acid from glycerol - Google Patents

Abstract

(A) preparing a product comprising an allyl alcohol from a reactant comprising glycerol and a carboxylic acid;
(b) adding a heterogeneous catalyst and a basic solution to the product containing the allyl alcohol, and oxidizing the same to prepare a mixture containing 3-hydroxypropionic acid and acrylic acid;
(c) dehydrating 3-hydroxypropionic acid in the mixture of 3-hydroxypropionic acid and acrylic acid to prepare acrylic acid; To a process for producing acrylic acid from glycerol.

Description

The present invention relates to a method for producing acrylic acid from glycerol,

The present invention relates to a process for producing acrylic acid from glycerol, and more particularly to a process for producing acrylic acid from glycerol via 3-hydroxypropionic acid.

Currently, the most widely used method of producing acrylic acid is a process in which propylene produced in a petrochemical process is contacted with a molecular oxygen-containing gas to produce an oxidized product. Specifically, acrylic acid is produced by a two-step reaction consisting of a shearing step of mainly producing acrolein by gas phase oxidation of propylene with a molecular oxygen-containing gas, and a post-stage step of again oxidizing the reaction gas containing acrolein to produce acrylic acid .

On the other hand, there is a great interest in a method for producing acrylic acid by using a material derived from biomass as a raw material due to depletion of fossil fuel. Of the biomass-derived materials, glycerol is produced together as a by-product in the process of producing biodiesel from vegetable or animal oils. The technology for synthesizing biodiesel has already been commercialized, and the demand for it is increasing every year. Glycerol is available in large quantities and is considered an attractive raw material for the production of acrylic acid because it is an environmentally friendly and renewable raw material that can be safely stored or transported without explosion and toxicity hazards.

Therefore, a new method for producing acrylic acid using glycerol, which is a by-product of the biodiesel synthesis process, is urgently required.

KR 2009-0057612 A

The present invention provides a novel process for producing acrylic acid by using glycerol, which is a by-product of the biodiesel synthesis process, as a raw material for producing acrylic acid.

In order to solve the above-mentioned problems, the present invention provides a method for producing an allyl alcohol, comprising: producing a product containing allyl alcohol from a reaction product containing glycerol and a carboxylic acid; Adding a heterogeneous catalyst and a basic solution to a product containing the allyl alcohol and oxidizing the same to prepare a mixture containing 3-hydroxypropionic acid and acrylic acid; And dehydrating 3-hydroxypropionic acid in the mixture of 3-hydroxypropionic acid and acrylic acid to prepare acrylic acid; Lt; RTI ID = 0.0 > glycerol < / RTI >

The novel process for producing acrylic acid from glycerol of the present invention is advantageous in that it is eco-friendly and can be safely stored or transported because it uses glycerol, which is a by-product of the biodiesel synthesis process.

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

(A) preparing a product comprising an allyl alcohol from a reactant comprising glycerol and a carboxylic acid;

(b) adding a heterogeneous catalyst and a basic solution to the product containing the allyl alcohol, and oxidizing the same to prepare a mixture containing 3-hydroxypropionic acid and acrylic acid;

(c) dehydrating 3-hydroxypropionic acid in the mixture of 3-hydroxypropionic acid and acrylic acid to prepare acrylic acid; To a process for producing acrylic acid from glycerol.

Glycerol is a compound of the formula HOCH ₂ (CHOH) CH ₂ OH, also referred to as trihydroxypropane or glycerin. In the present invention, the purity of glycerol is not limited to the range of the present invention, but a purity of 80 wt% or more, preferably 90 wt% or more, and more preferably 95 wt% or more is used in order to reduce the production of reaction by-products.

In the present invention, glycerol can utilize by-products of the biodiesel production process, which is produced through an ester exchange reaction between a vegetable oil and an alcohol.

In the present invention, step (a) of producing a product containing allyl alcohol from a reaction product containing glycerol and carboxylic acid is carried out as shown in the following reaction formula (1).

[Reaction Scheme 1]

Since the glycerol and formic acid of the present invention react with each other at a ratio of 1: 1 as in the reaction scheme 1, the equivalent of the present invention is the same as the molar ratio.

Formic acid is exemplified as carboxylic acid in Reaction Scheme 1, but it is not necessarily limited to formic acid. However, in the case of formic acid, since carbon dioxide is produced as an allyl alcohol production reaction by-product, it is preferable in that the by-products can be easily removed.

The formic acid may be prepared from a formate. The formate may be sodium formate or calcium formate. In particular, the sodium formate or calcium formate preferably utilizes sodium formate or calcium formate, which is a by-product produced during the production of polyhydric alcohol. The polyhydric alcohols include, but are not limited to, pentaerythritol, trimethylolethane, trimethylolpropane, neopentyl glycol, and the like.

The formic acid may be prepared from formic acid esters. The formic acid ester includes, but is not limited to, methyl formate, ethyl formate, and the like.

Since the step (a) causes oxidative decomposition of glycerol in an oxygen-containing gas atmosphere and carbonization may occur or yield may be lowered, the reaction is preferably carried out in an inert gas atmosphere, for example, helium, nitrogen or argon desirable.

Also, the step (a) can produce allyl alcohol from glycerol at a high yield by heating at 220 to 260 ° C, preferably 220 to 250 ° C, more preferably 230 to 250 ° C.

In the step (a), the equivalence of formic acid to 1 equivalent of glycerol is 0.5 to 3 equivalents, the preferable formic acid equivalent to improve the yield of allyl alcohol is 0.8 to 2 equivalents, more preferably the formic acid equivalent is 1.2 to 1 7 equivalents.

Since the step (a) of the present invention does not use the catalyst exemplified in ChemSus Chem 2012, Vol 5, pp 1401-1404, a byproduct such as propionaldehyde, 1,3-dihydroxyacetone, Without creating, Angew. Chem. Int. Ed. 2012, Vol 51, pp 8082-8086, which is free of rhenium catalysts, and is suitable for commercial mass production.

The content of the allyl alcohol produced in the step (a) is preferably 30% by weight or more based on the total weight of the product containing allyl alcohol.

In the present invention, the step (b) of adding a heterogeneous catalyst and a basic solution to the product containing allyl alcohol and then oxidizing the same to prepare a mixture containing 3-hydroxypropionic acid and acrylic acid may be carried out as shown in the following reaction formula .

[Reaction Scheme 2]

The allyl alcohol used as a reactant in the step (b) may be used in a concentrated form, but a solution containing a mixture of water and a base or a reaction by-product of the step (a) may be used. In this case, the concentration of allyl alcohol is 0.1 mol% to 90 mol%.

In the step (b), by injecting oxygen or an oxygen-containing gas, the reactivity of the oxidation reaction is improved and 3-hydroxypropionic acid and acrylic acid having a high yield can be obtained. The partial pressure of oxygen through the oxygen- or oxygen-containing gas can be arbitrarily set outside the combustion range and the explosion range in consideration of the concentration of the reactant and the reaction temperature. The partial pressure of oxygen is 1 to 50 atm, preferably 1 to 30 atm, more preferably 1 to 20 atm on the absolute pressure basis. The reaction temperature is not particularly limited as long as the reaction proceeds in a liquid phase, but it is 10 to 120 캜, preferably 20 to 100 캜, more preferably 30 to 90 캜.

The catalyst used in the step (b) is a heterogeneous catalyst having a size of 5 nm or less on the support. The heterogeneous catalyst, which is used in the present invention, means that the phase of the catalyst is different from that of the catalyst. And the catalyst can be easily separated from the product after the reaction.

To this end, the catalyst of the present invention may be characterized in that the support has a size of 5 nm or less, preferably 1 nm or less. When the size of the gold particles satisfies the above range, the effect of reactivity and selectivity is excellent. In addition, the smaller the size of the gold particles, the higher the yield of acrylic acid and 3-hydroxypropionic acid as the products. Particularly, when the size of the gold particles is 1 nm or less, the yield of acrylic acid as the main product is 50%, which is more preferable.

The gold may be contained in an amount of 5% by weight or less, preferably 0.0001-5% by weight based on the total dry weight of the support. When the amount of gold is included in the above content range, the use of gold as a precious metal is minimized while reactivity is maximized .

The supported body is activated carbon (Activated Carbon), titanium oxide (TiO _2), aluminum oxide (Al ₂ O _3), silicon oxide (SiO _2), zinc oxide (ZnO _2), zirconium oxide (ZrO _2), manganese oxide ( MnO _2), iron oxide (Fe ₂ O _3), vanadium oxide (V ₂ O _5), tin oxide (SnO _2), tungsten oxide (WO ₃₎ and cerium oxide (at least one element selected from the group consisting of CeO ₂₎ May be used. More preferably, the support may be a composite oxide containing cerium oxide (CeO ₂ ) or cerium oxide, but is not limited thereto.

In addition, when the catalyst of the present invention is subjected to a special pretreatment, the catalyst durability is improved and can be reused many times. The pretreatment temperature is from 50 캜 to 500 캜, more preferably from 70 캜 to 400 캜. The pretreatment time is 10 minutes to 24 hours, more preferably 20 minutes to 20 hours. The gas used for the pretreatment may be a mixture of at least one of oxygen, nitrogen, helium and argon.

In the step (b), a basic solution is used. The basic solution serves to activate the reaction in the oxidation reaction of allyl alcohol. The basic solution may be prepared by mixing a basic compound containing an alkali metal or an alkaline earth metal with water. More specifically, the basic compound may include at least one selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, and calcium hydroxide.

The basic compound contained in the basic solution is preferably added in an amount of 0.01 to 10 molar equivalents based on 1 mol of the allyl alcohol, more preferably 2 to 8 molar equivalents. Depending on the amount of the basic compound, the conversion of allyl alcohol and the yield and selectivity of acrylic acid, 3-hydroxypropionic acid, glyceralic acid as a by-product are affected.

In the present invention, step (c) of dehydrating 3-hydroxypropionic acid in the mixture of 3-hydroxypropionic acid and acrylic acid to produce acrylic acid is carried out as shown in the following reaction formula (3).

[Reaction Scheme 3]

The 3-hydroxypropionic acid used as the reactant in the step (c) can be separated and purified from the mixture of 3-hydroxypropionic acid and acrylic acid prepared in the step (b), or 3-hydroxypropionic acid can be used by concentrating A mixture of hydroxypropionic acid and acrylic acid may be used as the reactant.

Therefore, in the present invention, it may further include separating the 3-hydroxypropionic acid and the acrylic acid mixture before the step (c). The step of separating the 3-hydroxypropionic acid and acrylic acid mixture is carried out as follows.

The step of separating the 3-hydroxypropionic acid and the acrylic acid mixture may use a method comprising at least one selected from extraction, crystallization and distillation.

Extraction can be carried out by separating 3-hydroxypropionic acid from the mixture of 3-hydroxypropionic acid and acrylic acid.

The solvent used for extraction may include at least one selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters, aromatic compounds and other organic solvents, but is not limited thereto.

Crystallization can be used as a method of separating 3-hydroxypropionic acid from the mixture of 3-hydroxypropionic acid and acrylic acid.

The crystallization can be performed by a suspension crystallization method or a layer crystallization method by using a difference in solubility of the mixture.

Distillation can be used by separating 3-hydroxypropionic acid from the mixture of 3-hydroxypropionic acid and acrylic acid.

The distillation can be operated under reduced pressure, atmospheric pressure and pressure by separating the mixture using the boiling point difference. 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 is provided in the distillation column to convert 3-hydroxypropionic acid to acrylic acid and to separate the mixture at the same time.

The purity of 3-hydroxypropionic acid isolated from the mixture of 3-hydroxypropionic acid and acrylic acid is preferably 70% or more.

In the step (c), dehydration is preferably performed using a catalyst, and an acidic catalyst or a basic catalyst may be used as the catalyst. For example, the acidic catalyst may be a catalyst comprising a natural or synthetic silica material or an acidic zeolite, heteropoly acid, acidic ion exchange resin as follows: Metal phosphate catalyst comprising chromium, manganese, iron, cobalt, nickel, boron, lanthanum, calcium, strontium, barium, molybdenum, one or more materials that are selected from ruthenium metal and _{TiO 2, Al 2 O 3,} SiO 2, A metal phosphate catalyst supported on a SiO ₂ -Al ₂ O ₃ 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 ; A catalyst containing at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid can be used.

On the other hand, as the basic catalyst, oxides or hydroxides of alkali metals or alkaline earth metals; Amines selected from the group consisting of trimethylamine, triethylamine or tridodecyl amine; And basic ion exchange may be used as the catalyst.

The reaction temperature in the step (c) is 70 to 300 ° C, preferably 100 to 280 ° C. The pressure can be any of reduced pressure, atmospheric pressure, and pressurized condition, and the production yield of acrylic acid from 3-hydroxypropionic acid can be 90% or more, preferably 92% or more, more preferably 95% or more.

Also, in the present invention, the above-mentioned three-step reaction may be carried out in any one of reactors selected from the group consisting of a batch reactor, a semi-batch reactor, a continuous stirred tank reactor, a plug flow reactor, a stationary phase reactor and a fluidized bed reactor, Lt; / RTI >

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.

Example

Preparation of oxidation catalyst

[Synthesis Example]

12 mg of HAuCl ₄ .3H ₂ O was dissolved in 100 ml of distilled water and the pH of the solution was adjusted to 10 with 0.2 M aqueous sodium hydroxide solution. Thereafter, 190 mg of cerium oxide was dispersed in the solution, and the solution was kept at 70 ° C. for 1, 3, 6, and 12 hours while stirring, and then subjected to filtering, washing and drying to obtain a catalyst.

Preparation of allyl alcohol from glycerol (step a)

[Example 1]

27.6 g (300 mmol) of glycerol and 20.71 g (450 mmol) of formic acid were charged into a flask reactor (F1) under helium atmosphere, and the temperature of the reaction was raised to 230 ° C. at a rate of 230 ° C./hr while slowly stirring, .

[Example 2]

Allyl alcohol was prepared in the same manner as in Example 1, except that 11.04 g (240 mmol) of formic acid was added.

From allyl alcohol, 3- Hydroxypropionic acid  And acrylic acid (step b)

[Example 3]

2.07 g of sodium hydroxide and 17.24 ml of distilled water were mixed with 1.17 ml of allyl alcohol. At this time, sodium hydroxide per mole of allyl alcohol was 3 mole. While stirring the mixed solution slowly, 30 mg of the oxidation catalyst prepared by maintaining the synthesis time in the synthesis example for 1 hour was added to the mixed solution.

3-Hydroxypropionic acid and acrylic acid were prepared by introducing oxygen of 3 atm into the reactor, raising the temperature of the reactor to 50 캜 and reacting for 24 hours.

[Example 4]

3-hydroxypropionic acid and acrylic acid were prepared in the same manner as in Example 3, except that the oxidation catalyst prepared by maintaining the synthesis time for 3 hours in the synthesis example was used.

[Comparative Example 1]

The reaction was carried out in the same manner as in Example 3, except that the catalyst prepared from only gold particles without a carrier was added to the mixed solution.

[Comparative Example 2]

The reaction was carried out in the same manner as in Example 3, except that the catalyst prepared using the activated carbon carrier was added to the mixed solution.

3- From hydroxypropionic acid  Production of acrylic acid (step c)

[Example 5]

After adding 100 g of phosphoric acid to 3-hydroxypropionic acid, it was heated to 180 占 폚. A 50 wt% aqueous solution of 3-hydroxypropionic acid was added dropwise to the reactor at a rate of 0.5 g / min while bubbling nitrogen through a gas distributor installed at the bottom of the reactor. The vaporized product was passed through a condenser connected to the reactor and then collected in a flask installed at the end of the condenser.

[Example 6]

8 g of the TiO ₂ catalyst was charged into a fixed-bed reactor, and the reactor temperature was heated to 180 ° C., and then a 10 wt% aqueous solution of 3-hydroxypropionic acid was injected from the top of the reactor at a rate of 3.0 g / hr . The product was passed through a condenser installed at the bottom of the reactor and then collected in a flask.

Experimental Example

Conversion rates and selectivities of the reactants produced in the above Examples and Comparative Examples were analyzed as follows.

The concentrations of allyl alcohol and unreacted glycerol prepared in the step (a) were analyzed by gas chromatography (GC 6890N, Agilent).

Using the results thus obtained, the conversion of glycerol, allyl alcohol selectivity, and allyl alcohol yield were calculated using the following formulas 1 to 3, and the results are shown in Table 2.

[Formula 1]

Glycerol conversion rate (conversion,%) = 100 x (molar amount of glycerol before reaction - molar amount of glycerol after reaction) / (molar amount of glycerol before reaction)

[Formula 2]

Allyl alcohol selectivity (%) = 100 (molarity of produced allyl alcohol) / (molar amount of glycerol reacted)

[Formula 3]

Allyl alcohol yield (yield,%) = (glycerol conversion x allyl alcohol selectivity) / 100

The liquid reaction product prepared in the step (b) was analyzed by HPLC area% analysis of allyl alcohol, acrylic acid and 3-hydroxypropionic acid using liquid chromatography (YL9100 HPLC, Young Lin Instrument Co.) . The conversion of allyl alcohol, the yield of 3-hydroxypropionic acid, and the yield of acrylic acid were calculated using the following formulas 4 to 6, respectively.

[Formula 4]

Allyl alcohol conversion (conversion,%) = 100 x (mole of allyl alcohol before reaction - mole of allyl alcohol after reaction) / (mole of allyl alcohol before reaction)

[Formula 5]

3-Hydroxypropionic acid yield (yield,%) = 100 x (molar amount of produced 3-hydroxypropionic acid) / (molar amount of allyl alcohol before reaction)

[Formula 6]

Yield of acrylic acid (yield,%) = 100 x (molar amount of acrylic acid produced) / (molar amount of allyl alcohol before reaction)

The liquid reaction product prepared in the step (c) was analyzed by HPLC area% analysis of acrylic acid and 3-hydroxypropionic acid using liquid chromatography (YL9100HPLC, Young Lin Instrument Co.). Acrylic acid conversion, 3-hydroxypropionic acid selectivity and 3-hydroxypropionic acid yield were calculated using the following formulas 7 to 9.

[Equation 7]

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

[Equation 8]

Acrylic acid selectivity (yield,%) = 100 x (molar amount of acrylic acid produced) / (molar amount of 3-hydroxypropionic acid reacted)

[Equation 9]

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

A transmission electron microscope (JEM-2100, JEOL) was used to measure the gold particle size of the oxidation catalyst prepared according to the synthesis example of the above Example. When the synthesis time was 1, 3, 6, 12 hours, the average size of gold particles was less than 5 nm. The gold of the oxidation catalyst was 5 wt% or less based on the total dry weight of the support.

Experimental Example  1: Experimental results in step (a)

Table 1 shows the glycerol conversion, allyl alcohol selectivity and allyl alcohol yield for the reaction of step (a) for producing allyl alcohol from glycerol. The higher the mole number of formic acid added to the reaction, the higher the glycerol conversion. The lower the mole number of formic acid, the lower the glycerol conversion but the higher the allyl alcohol selectivity.

Glycerol conversion,% Allyl alcohol selectivity,% Allyl alcohol yield,% Example 1 95 85 80.7 Example 2 72 89 64.1

Experimental Example  2: Experimental results in step (b)

The conversion of allyl alcohol, the yield of 3-hydroxypropionic acid and the yield of acrylic acid for the reaction of step (b) for preparing 3-hydroxypropionic acid and acrylic acid from allyl alcohol are shown in Table 2. As the reaction time increased, the yield of 3 - hydroxypropionic acid and the yield of acrylic acid increased. As in Comparative Example 1 and Comparative Example 2, when the carrier was not used or the activated carbon carrier was used, the yield of 3-hydroxypropionic acid and the yield of acrylic acid were greatly decreased.

Allyl alcohol conversion,% 3-hydroxy
Propionic acid yield,% Acrylic acid yield,% Example 3 100 28.4 51.1 Example 4 100 24.1 43.1 Comparative Example 1 49.6 4.2 0.0 Comparative Example 2 100 18.5 0.8

Experimental Example  3: Experimental results in step (c)

Hydroxypropionic acid conversion, acrylic acid selectivity, and acrylic acid yield for the reaction of step (c) for preparing acrylic acid from 3-hydroxypropionic acid are shown in Table 3. < tb >< TABLE > When the acidic catalyst was used as in Example 5 and Example 6, the yield of acrylic acid was 90% or more.

3-hydroxy
Propionic acid conversion,% Acrylic acid selectivity,% Acrylic acid yield,% Example 5 97 94 91.1 Example 6 95 96 91.2

Claims (24)

(a) preparing a product comprising an allyl alcohol from a reactant comprising glycerol and a carboxylic acid;
(b) adding a heterogeneous catalyst and a basic solution to the product containing the allyl alcohol, and oxidizing the same to prepare a mixture containing 3-hydroxypropionic acid and acrylic acid,
The heterogeneous catalyst is prepared by preparing a mixture comprising 3-hydroxypropionic acid and acrylic acid, wherein the cerium oxide (CeO ₂ ) carrier has a size of 5 nm or less. And
(c) dehydrating 3-hydroxypropionic acid in the mixture of 3-hydroxypropionic acid and acrylic acid to prepare acrylic acid; ≪ RTI ID = 0.0 > glycerol. ≪ / RTI > delete The method according to claim 1,
And separating the 3-hydroxypropionic acid and the acrylic acid mixture before the step (c). The method according to claim 1,
The method for producing acrylic acid from glycerol according to claim 1, wherein, in step (a), 0.5 to 2 equivalents of a carboxylic acid is added to 1 equivalent of glycerol and the reaction is carried out at 220 to 260 ° C. The method according to claim 1,
The oxidation of the step (b) is carried out by introducing oxygen or an oxygen-containing gas, and the partial pressure of oxygen is 0.01 to 50 atmospheres based on the absolute pressure, and the reaction is carried out at 10 to 120 ° C. Way. The method according to claim 1,
Wherein the heterogeneous catalyst comprises 5 wt% or less of gold based on the total dry weight of the carrier. delete delete The method according to claim 1,
Wherein the basic solution charged in step (b) is prepared by mixing a basic compound containing an alkali metal or an alkaline earth metal with water to produce acrylic acid from glycerol. The method of claim 9,
Wherein the basic compound comprises at least one selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide and calcium hydroxide. The method according to claim 1,
Wherein in step (a), the carboxylic acid is formic acid. The method of claim 11,
Wherein the formic acid is prepared from a formate or a formate ester. The method of claim 12,
Wherein the salt of the formic acid is a by-product produced in the course of the production of polyhydric alcohols. 14. The method of claim 13,
Wherein the polyhydric alcohol is at least one selected from the group consisting of pentaerythritol, trimethylolethane, trimethylolpropane, neopentyl glycol, and the like. The polyhydric alcohol may be at least one selected from the group consisting of pentaerythritol, trimethylolethane, trimethylolpropane, neopentyl glycol, Way. The method of claim 12,
Wherein the formic acid ester is methyl formate or ethyl formate. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the content of the allyl alcohol produced in the step (a) is 30 wt% or more based on the total weight of allyl alcohol-containing products. The method of claim 3,
Wherein the step of separating the 3-hydroxypropionic acid and the acrylic acid mixture comprises using at least one selected from extraction, crystallization and distillation. 18. The method of claim 17,
Wherein the purity of the separated 3-hydroxypropionic acid or acrylic acid is 70% or more. The method according to claim 1,
Wherein the step (c) is carried out at 70 to 300 ° C. The method according to claim 1,
Wherein the step (c) comprises using an acidic catalyst or a basic catalyst. The method of claim 20,
The acidic catalyst may be a natural or synthetic silica material or a catalyst comprising an acidic zeolite, heteropoly acid, acidic ion exchange resin; Metal phosphate catalyst comprising chromium, manganese, iron, cobalt, nickel, boron, lanthanum, calcium, strontium, barium, molybdenum, one or more materials that are selected from ruthenium metal and _{TiO 2, Al 2 O 3,} SiO 2, A metal phosphate catalyst supported on a SiO ₂ -Al ₂ O ₃ 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 ; Wherein the catalyst is a catalyst comprising at least one substance selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. The method of claim 20,
The basic catalyst may be an oxide of an alkali metal or an alkaline earth metal, or a hydroxide; Amines selected from the group consisting of trimethylamine, triethylamine or tridodecyl amine; Wherein the catalyst is a catalyst comprising at least one substance selected from the group consisting of basic ion exchange and basic ion exchange. The method of claim 20,
The step (c) may be carried out in any reactor selected from the group consisting of a batch reactor, a semi-batch reactor, a continuous stirred tank reactor, a plug flow reactor, a fixed bed reactor and a fluidized bed reactor, or a mixed reactor ≪ RTI ID = 0.0 > 1, < / RTI > The method according to claim 1,
Wherein the yield of acrylic acid production from 3-hydroxypropionic acid in step (c) is 80% or more.