Method for producing acrylic acid from glycerol

Abstract

Disclosed is a method of preparing acrylic acid from glycerol, including: (a) preparing products including allyl alcohol from reactants including glycerol and carboxylic acid; (b) adding a heterogeneous catalyst and a basic solution to the product including allyl alcohol and then performing oxidation, thus preparing a mixture composed of 3-hydroxypropionic acid and acrylic acid; (c) dehydrating 3-hydroxypropionic acid of the mixture composed of 3-hydroxypropionic acid and acrylic acid, thus producing acrylic acid.

Claims

1. A method of comprising acrylic acid from glycerol, comprising: (a) preparing products including allyl alcohol from reactants comprising glycerol and carboxylic acid; (b) adding a heterogeneous catalyst and a basic solution to the product comprising allyl alcohol and then performing oxidation, thus preparing a mixture comprising 3-hydroxypropionic acid and acrylic acid; (c) dehydrating 3-hydroxypropionic acid of the mixture comprising 3-hydroxypropionic acid and acrylic acid, thus producing acrylic acid, wherein the heterogeneous catalyst of (b) is configured such that gold having a size of 5 nm or less is loaded on a carrier, and wherein the carrier is cerium oxide (CeO.sub.2).

2. The method of claim 1, further comprising separating the mixture comprising 3-hydroxypropionic acid and acrylic acid, before (c).

3. The method of claim 1, wherein (a) is performed at 220260 C. using glycerol and carboxylic acid in an amount of 0.52 equivalents relative to 1 equivalent of glycerol.

4. The method of claim 1, wherein the oxidation in (b) is performed at 10120 C. under a partial oxygen pressure of 0.0150 atm based on an absolute pressure by feeding oxygen or an oxygen-containing gas.

5. The method of claim 1, wherein the gold of the heterogeneous catalyst is used in an amount of 5 wt % or less based on a total dry weight of the carrier.

6. The method of claim 1, wherein in (b), the basic solution is prepared by mixing a basic compound containing an alkali metal or alkaline earth metal with water.

7. The method of claim 6, wherein the basic compound comprises at least one selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, and calcium hydroxide.

8. The method of claim 1, wherein in (a), the carboxylic acid is formic acid.

9. The method of claim 1, wherein an amount of allyl alcohol produced in (a) is 30 wt % or more based on a total weight of the product including allyl alcohol.

10. The method of claim 2, wherein separating the mixture comprising 3-hydroxypropionic acid and acrylic acid is performed using at least one process selected from the group consisting of extraction, crystallization, and distillation.

11. The method of claim 10, wherein the separated 3-hydroxypropionic acid or acrylic acid has a purity of 70% or more.

12. The method of claim 1, wherein (c) is performed at 70300 C.

13. The method of claim 1, wherein (c) is performed using an acidic catalyst or a basic catalyst.

14. The method of claim 13, wherein the acidic catalyst is a catalyst comprising a natural or synthetic silica material, acidic zeolite, heteropolyacid, and an acidic ion exchange resin; a metal phosphate catalyst comprising at least one selected from the group consisting of chromium, manganese, iron, cobalt, nickel, boron, lanthanum, calcium, strontium, barium, molybdenum, and ruthenium metals, and a metal phosphate catalyst loaded on a carrier comprising TiO.sub.2, Al.sub.2O.sub.3, SiO.sub.2, or SiO.sub.2Al.sub.2O.sub.3; at least one metal oxide selected from the group consisting of TiO.sub.2, Al.sub.2O.sub.3, SiO.sub.2, ZrO.sub.2, SnO.sub.2, Ta.sub.2O.sub.3, Nb.sub.2O.sub.5, and SiO.sub.2Al.sub.2O.sub.3; any one composite oxide selected from the group consisting of ZrO.sub.2SO.sub.4, ZrO.sub.2PO.sub.4, ZrO.sub.2WO.sub.3, ZrO.sub.2SiO.sub.2, TiO.sub.2SO.sub.4, TnO.sub.2SO.sub.4, H.sub.3PO.sub.4Al.sub.2O.sub.3, H.sub.3PO.sub.4SiO.sub.2, and H.sub.3PO.sub.4ZrO.sub.2; or a catalyst comprising at least one selected from the group consisting of inorganic acids, comprising hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.

15. The method of claim 13, wherein the basic catalyst is a catalyst comprising at least one selected from the group consisting of alkali metal or alkaline earth metal oxides and hydroxides; amines comprising trimethylamine, triethylamine and tridodecyl amine; and basic ion exchange resins.

16. The method of claim 13, wherein (c) is performed using any one reactor or a reactor combination of two or more 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.

17. The method of claim 1, wherein in (c), acrylic acid is produced at a yield of 80% or more from 3-hydroxypropionic acid.

Description

EXAMPLE

Preparation of Oxidation Catalyst

Synthesis Example

(1) 12 mg of HAuCl.sub.4.3H.sub.2O was dissolved in 100 mL of distilled water, and pH of the solution was adjusted to 10 using a 0.2 M sodium hydroxide aqueous solution. Subsequently, 190 mg of cerium oxide was dispersed in the solution, and the resulting solution was maintained at 70 C. for 1, 3, 6, and 12 hr with stirring. The solution was filtered, washed and dried to obtain the catalyst.

Preparation of Allyl Alcohol from Glycerol Step (a)

Example 1

(2) In a flask reactor (F1) in a helium atmosphere, 27.6 g (300 mmol) of glycerol and 20.71 g (450 mmol) of formic acid were placed, and heated to 230 C. at a rate of 230 C./hr with slow stirring, yielding allyl alcohol.

Example 2

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

Preparation of 3-Hydroxypropionic Acid and Acrylic Acid from Allyl Alcohol Step (b)

Example 3

(4) 1.17 mL of allyl alcohol was mixed with 2.07 g of sodium hydroxide and 17.24 mL of distilled water. As such, sodium hydroxide was used in an amount of 3 mol relative to 1 mol of allyl alcohol. While the mixed solution was slowly stirred, 30 mg of the oxidation catalyst prepared maintaining the solution for 1 hr in Synthesis Example was added.

(5) While oxygen, of which partial pressure was 3 atm was injected into the reactor, the temperature of the reactor was elevated to 50 C. and then the reaction was carried out for 24 hr, yielding 3-hydroxypropionic acid and acrylic acid.

Example 4

(6) 3-hydroxypropionic acid and acrylic acid were prepared in the same manner as in Example 3, with the exception that the oxidation catalyst prepared by maintaining the synthesis time for 3 hr in Synthesis Example was used.

Comparative Example 1

(7) The reaction was carried out in the same manner as in Example 3, with the exception that the catalyst prepared using only gold particles without a carrier was added to the mixed solution.

Comparative Example 2

(8) The reaction was carried out in the same manner as in Example 3, with the exception that the catalyst prepared using an activated carbon carrier was added to the mixed solution.

Preparation of Acrylic Acid from 3-Hydroxypropionic Acid Step (c)

Example 5

(9) 3-hydroxypropionic acid was added with 100 g of phosphoric acid, and then heated to 180 C. While bubbling nitrogen via a gas distributor placed at the bottom of the reactor, a 50 wt % of 3-hydroxypropionic acid aqueous solution was added slowly at a rate of 0.5 g/min into the reactor. The vaporized product was passed through a condenser connected to the reactor, and then the condensate was collected in a flask placed at the end of the condenser.

Example 6

(10) 8 g of a TiO.sub.2 catalyst was loaded in a fixed-bed reactor, the temperature of the reactor was elevated to 180 C., and then a 10 wt % of 3-hydroxypropionic acid aqueous solution was fed from the top of the reactor at a rate of 3.0 g/hr. The product was passed through a condenser placed at the end of the reactor and then collected in a flask.

Test Example

(11) The reaction products obtained in the above examples and comparative examples were analyzed for calculation of conversion and selectivity as follows.

(12) The concentration of allyl alcohol prepared in the step (a) and unreacted glycerol was analyzed using gas chromatography (GC 6890N, Agilent).

(13) Based on such measurement results, glycerol conversion, allyl alcohol selectivity, and allyl alcohol yield were calculated using Equations 1 to 3 below. The results are shown in Table 2 below.
Glycerol conversion (%)=100(mol of glycerol before reactionmol of glycerol after reaction)/(mol of glycerol before reaction)[Equation 1]
Allyl alcohol selectivity (%)=100(mol of produced allyl alcohol)/(mol of reacted glycerol)[Equation 2]
Allyl alcohol yield (%)=(glycerol conversionallyl alcohol selectivity)/100[Equation 3]

(14) For the liquid reaction product obtained in the step (b), HPLC area % of allyl alcohol, acrylic acid and 3-hydroxypropionic acid was analyzed using liquid chromatography (YL9100 HPLC, Young Lin Instrument Co.). Allyl alcohol conversion, 3-hydroxypropionic acid yield, and acrylic acid yield were calculated using Equations 4 to 6 below.
Allyl alcohol conversion (%)=100(mol of allyl alcohol before reactionmol of allyl alcohol after reaction)/(mol of allyl alcohol before reaction)[Equation 4]
3-Hydroxypropionic acid yield (%)=100(mol of 3-hydroxypropionic acid produced)/(mol of allyl alcohol before reaction)[Equation 5]
Acrylic acid yield (%)=100(mol of acrylic acid produced)/(mol of allyl alcohol before reaction)[Equation 6]

(15) For the liquid reaction product obtained in the step (c), HPLC area % of acrylic acid and 3-hydroxypropionic acid was analyzed using liquid chromatography (YL9100 HPLC, Young Lin Instrument Co.). Acrylic acid conversion, 3-hydroxypropionic acid selectivity, and 3-hydroxypropionic acid yield were calculated using Equations 7 to 9 below.
3-Hydroxypropionic acid conversion (%)=100(mol of 3-hydroxypropionic acid before reactionmol of 3-hydroxypropionic acid after reaction)/(mol of 3-hydroxypropionic acid before reaction)[Equation 7]
Acrylic acid selectivity (%)=100(mol of produced acrylic acid)/(mol of reacted 3-hydroxypropionic acid)[Equation 8]
Acrylic acid yield (%)=(3-hydroxypropionic acid conversionacrylic acid selectivity)/100[Equation 9]

(16) The gold particle size of the oxidation catalyst obtained in Synthesis Example was measured using a transmission electron microscope (JEM-2100, JEOL). When the synthesis time was 1, 3, 6, and 12 hr, the average particle size of gold was 5 nm or less. Also, the amount of gold of the oxidation catalyst was 5 wt % or less based on the total dry weight of the carrier.

Test Example 1

Test Results in the Step (a)

(17) The glycerol conversion, allyl alcohol selectivity and allyl alcohol yield in the step (a) for preparing allyl alcohol from glycerol are shown in Table 1 below. As the mol of formic acid was higher, the glycerol conversion was increased. On the other hand, as the mol of formic acid was lower, the glycerol conversion was decreased but the allyl alcohol selectivity was increased.

(18) TABLE-US-00001 TABLE 1 Glycerol Allyl alcohol Allyl alcohol Conversion, % Selectivity, % Yield, % Ex. 1 95 85 80.7 Ex. 2 72 89 64.1

Test Example 2

Test Results in the Step (b)

(19) The allyl alcohol conversion, 3-hydroxypropionic acid yield and acrylic acid yield in the step (b) for preparing 3-hydroxypropionic acid and acrylic acid from allyl alcohol are shown in Table 2 below. As the synthesis time was longer, the 3-hydroxypropionic acid yield and the acrylic acid yield were increased. In Comparative Examples 1 and 2 without the use of a carrier or with the use of an activated carbon carrier, the 3-hydroxypropionic acid yield and the acrylic acid yield were remarkably decreased.

(20) TABLE-US-00002 TABLE 2 Allyl alcohol 3-Hydroxypropionic acid Acrylic acid Conversion, % Yield, % Yield, % Ex. 3 100 28.4 51.1 Ex. 4 100 24.1 43.1 C. Ex. 1 49.6 4.2 0.0 C. Ex. 2 100 18.5 0.8

Test Example 3

Test Results in the Step (c)

(21) The 3-hydroxypropionic acid conversion, acrylic acid selectivity and acrylic acid yield in the step (c) for preparing acrylic acid from 3-hydroxypropionic acid are shown in Table 3 below. In Examples 5 and 6 using the acidic catalyst, the acrylic acid yield was 90% or more.

(22) TABLE-US-00003 TABLE 3 3-Hydroxypropionic acid Acrylic acid Acrylic acid Conversion, % Selectivity, % Yield, % Ex. 5 97 94 91.1 Ex. 6 95 96 91.2