Method for producing acrylic acid from glycerol

Patent metadata

Field	Value
Publication number	US-9546124-B2
Application number	US-201414892849-A
Country	US
Kind code	B2
Filing date	Jun 27, 2014
Priority date	Jun 27, 2013
Publication date	Jan 17, 2017
Grant date	Jan 17, 2017

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.

First claim

The invention claimed is:

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 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 220˜260° C. using glycerol and carboxylic acid in an amount of 0.5˜2 equivalents relative to 1 equivalent of glycerol.

4. The method of claim 1 , wherein the oxidation in (b) is performed at 10˜120° C. under a partial oxygen pressure of 0.01˜50 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 70˜300° 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 2 , Al 2 O 3 , SiO 2 , or SiO 2 —Al 2 O 3 ; at least one metal oxide selected from the group consisting of 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 ; any one composite oxide selected from the group consisting of 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 ; 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.

Assignees

• Lg Chemical Ltd

Inventors

• Lee Won Jae
• Choe Yong-Jin
• Nam Hyun
• Kong Myungjin

Classifications

• B01J23/52

  Gold · CPC title

• C07C51/377

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} · CPC title

• C07C51/25

  of unsaturated compounds containing no six-membered aromatic ring · CPC title

• B01J23/66

  Silver or gold · CPC title

• C07C29/60

  by elimination of -OH groups, e.g. by dehydration (C07C29/34 takes precedence) · CPC title