Method for producing glycidol by successive catalytic reactions

Patent metadata

Field	Value
Publication number	US-9199950-B2
Application number	US-201414313153-A
Country	US
Kind code	B2
Filing date	Jun 24, 2014
Priority date	Feb 27, 2014
Publication date	Dec 1, 2015
Grant date	Dec 1, 2015

Abstract

Disclosed is a method for producing glycidol by successive catalytic reactions. The method includes a series of reactions for the preparation of glycerol carbonate from glycerol and the decarboxylation of the glycerol carbonate. Specifically, the method includes i) reacting glycerol with a dialkyl carbonate to prepare glycerol carbonate, and ii) subjecting the glycerol carbonate to decarboxylation wherein a base is added as a catalyst in step i) and is allowed to react with an acid to form a metal salt after step i), and the salt is used as a catalyst in step ii). According to the method, inexpensive and easy-to-purchase acid and base catalysts can be used to produce glycidol from glycerol, a by-product of biodiesel production, as a starting material in high yield with high selectivity in a convenient, simple, and environmentally friendly way. In addition, the method eliminates the need to separate the base catalyst.

First claim

What is claimed is:

1. A method for producing glycidol by successive catalytic reactions, comprising:
i) reacting glycerol with a dialkyl carbonate to prepare glycerol carbonate; and
ii) subjecting the glycerol carbonate to decarboxylation,
wherein a base is added as a catalyst in step i) and is allowed to react with an acid to form a metal salt after step i), and the salt is used as a catalyst in step ii).

2. The method according to claim 1 , wherein the base is selected from the group consisting of NaOH, KOH, LiOH, R 3 N (R is a C 2 -C 6 alkyl group), and mixtures thereof.

3. The method according to claim 1 , wherein in step i), the base catalyst is added in an amount of 0.005 moles to 0.05 moles per mole of the glycerol.

4. The method according to claim 1 , wherein step i) is performed at a temperature of 20° C. to 90° C.

5. The method according to claim 1 , wherein step i) is performed for 3 minutes to 120 minutes.

6. The method according to claim 1 , wherein in step i), the dialkyl carbonate reacts with the glycerol in a molar ratio of 1:1 to 12:1.

7. The method according to claim 1 , wherein the acid is selected from the group consisting of HNO 3 , HCl, H 3 PO 4 , CH 3 CO 2 H, H 2 CO 3 , HI, H 2 SO 4 , and mixtures thereof.

8. The method according to claim 1 , wherein step ii) is performed at a temperature of 140° C. to 200° C. and a pressure of 0.13 kPa to 6.67 kPa.

9. A method for producing glycidol by successive catalytic reactions, comprising:
i) reacting glycerol with a dialkyl carbonate to prepare glycerol carbonate; and
ii) subjecting the glycerol carbonate to decarboxylation,
wherein a base is added as a catalyst in step i) and is allowed to react with an acid to form a metal salt after step i), and the salt is used as a catalyst in step ii) and a Lewis acid metal salt is further added that is selected from the group consisting of Zn(NO 3 ) 2 , ZnCl 2 , MgCl 2 , AlCl 3 , and mixtures thereof.

10. The method according to claim 1 , wherein in step ii), the reaction is carried out in a solvent selected from the group consisting of polyethylene glycol dimethyl ether, dibenzyl ether, dibutyl phthalate, and mixtures thereof.

11. The method according to claim 1 , wherein steps i) and ii) are performed successively in the same reaction vessel.

12. The method according to claim 1 , wherein step ii) is performed in a continuous manner by which the final glycidol is continuously collected under reduced pressure.

13. The method according to claim 9 , wherein the base is selected from the group consisting of NaOH, KOH, LiOH, R3N (R is a C2-C6 alkyl group), and mixtures thereof.

14. The method according to claim 9 , wherein in step i), the base catalyst is added in an amount of 0.005 moles to 0.05 moles per mole of the glycerol.

15. The method according to claim 9 , wherein in step i), the dialkyl carbonate reacts with the glycerol in a molar ratio of 1:1 to 12:1.

16. The method according to claim 9 , wherein the acid is selected from the group consisting of HNO 3 , HCl, H 3 PO 4 , CH 3 CO 2 H, H 2 CO 3 , HI, H 2 SO 4 , and mixtures thereof.

17. The method according to claim 9 , wherein in step ii), the reaction is carried out in a solvent selected from the group consisting of polyethylene glycol dimethyl ether, dibenzyl ether, dibutyl phthalate, and mixtures thereof.

18. The method according to claim 9 , wherein steps i) and ii) are performed successively in the same reaction vessel.

19. The method according to claim 9 , wherein step i) is performed in a continuous manner by which the final glycidol is continuously collected under reduced pressure.

20. A method for producing glycidol by successive catalytic reactions, comprising:
i) reacting glycerol with a dialkyl carbonate to prepare glycerol carbonate; and
ii) subjecting the glycerol carbonate to decarboxylation,
wherein a base selected from the group consisting of NaOH, KOH, LiOH, R 3 N (R is a C 2 -C 6 alkyl group), and mixtures thereof is added as a catalyst in step i) and is allowed to react with an acid selected from the group consisting of HNO 3 , HCl, H 3 PO 4 , CH 3 CO 2 H, H 2 CO 3 , HI, H 2 SO 4 , and mixtures thereof to form a metal salt after step i), and the salt is used as a catalyst in step ii) and a Lewis acid metal salt is further added that is selected from the group consisting of Zn(NO 3 ) 2 , ZnCl 2 , MgCl 2 , AlCl 3 , and mixtures thereof.

Assignees

• Korea Inst Sci & Tech

Inventors

• Lee Hyun Joo
• Ahn Byoung Sung
• Lee Sang Deuk
• Jae Jungho
• Choi Ji Sik

Classifications

• C07D301/02 Primary

  Synthesis of the oxirane ring · CPC title

• C07D317/36

  Alkylene carbonates; Substituted alkylene carbonates · CPC title

• C07D303/14

  by free hydroxyl radicals · CPC title