GLYCIDOL SYNTHESIS METHOD

• US 20180319756A1
• Filed: 07/28/2016
• Published: 11/08/2018
• Est. Priority Date: 07/30/2015
• Status: Active Grant

• Current Assignee: Fundacion Tecnalia Research & Innovation (Fundación Tecnalia Corporación Tecnológica)
• Original Assignee: Fundacion Tecnalia Research & Innovation (Fundación Tecnalia Corporación Tecnológica)
• Inventors: OCHOA GOMEZ, Jose Ramon, GOMEZ DE MIRANDA JIMENEZ DE ABERASTUI, Olga, BLANCO PEREZ, Noelia, MAESTRO MADURGA, Belen, PRIETO FERNANDEZ, Soraya
• Granted Patent: US 10,640,478 B2
• Time in Patent Office: Days
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 21/066 Zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 21/10 Magnesium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 23/02 of the alkali- or alkaline earth metals or beryllium
• CPC Class Codes: B01J 23/04 Alkali metals
• CPC Class Codes: B01J 23/10 of rare earths
• CPC Class Codes: B01J 23/14 of germanium, tin or lead
• CPC Class Codes: B01J 23/20 Vanadium, niobium or tantalum
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C07D 301/02 Synthesis of the oxirane ring
• CPC Class Codes: C07D 303/14 by free hydroxyl radicals

Abstract

The invention relates to a method for obtaining glycidol in a semi-continuous or continuous manner by decarboxylating glycerol carbonate at reduced pressure, at a temperature less than or equal to 130° C. and in the presence of alkoxide catalysts of alkaline metals and alkaline earth metals, metal oxides, mixed metal oxides, metal stannates and mixed metal stannates, all of which optionally supported via SiO₂, γ-Al₂O₃, MgO and ZrO₂.

Claims

1. A method for producing glycidol by decarboxylating glycerol carbonate, which comprises the steps:

a) Placing into contact, optionally in the presence of an organic solvent, glycerol carbonate with a catalyst selected from the group consisting of (C₁-C_n) alkoxides of alkaline metals and alkaline earth metals, metal oxides, mixed metal oxides, metal stannates, mixed metal stannates and mixtures thereof, wherein the catalyst is optionally supported via a support selected from the group consisting of SiO₂, γ

-Al₂O₃, MgO and ZrO₂; and

b) Carrying out the reaction at a temperature less than or equal to 130°

C. at reduced pressure to continuously separate the glycidol formed by evaporation.

2. The method according to claim 1, wherein the catalysts are (C₁-C_n) alkoxides of alkaline metals and alkaline earth metals and are selected from the group consisting of sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide.

3. The method according to claim 1, wherein the catalysts are metal oxides and are selected from the group consisting of oxides of alkaline metals and alkaline earth metals and metals selected from zirconium, niobium, scandium, yttrium, lanthanum, zinc, cerium and tin, optionally supported via SiO₂, γ

-Al₂O₃, MgO and ZrO₂.

4. The method according to claim 1, wherein the catalysts are mixed metal oxides and are selected from the group consisting of mixtures of two or more alkaline metal oxides and alkaline earth metals and metals selected from zirconium, niobium, scandium, yttrium, lanthanum, zinc, cerium and tin, optionally supported via SiO₂, γ

-Al₂O₃, MgO and ZrO₂.

5. The method according to claim 1, wherein the catalysts are stannates and are selected from the group consisting of metal stannates and mixed metal stannates of alkaline metals and alkaline earth metals, optionally supported via SiO₂, γ

-Al₂O₃, MgO and ZrO₂.

6. The method according to claim 5, wherein the metal stannates and mixed metal stannates of alkaline metals are from sodium and potassium.

7. The method according to claim 1, wherein the concentration of catalyst is comprised between 0.001% and 10%, in percentage by weight with respect to the glycerol carbonate.

8. The method according to claim 1, wherein the concentration of catalyst is comprised between 0.001% and 1%, in percentage by weight with respect to the glycerol carbonate.

9. The method according to claim 1, wherein the working pressure is less than or equal to 2 kPa.

10. The method according to claim 1, wherein the working pressure is less than or equal to 1 kPa.

11. The method according to claim 1, wherein the working pressure is comprised between 0.2 kPa and 1 kPa.

12. The method according to claim 1, wherein the temperature of the reaction is in the range of 100 to 130°

C.

13. The method according to claim 1, which is carried out in a semi-continuous manner.

14. The method according to claim 1, which is carried out in a continuous manner.

15. The method according to claim 1, wherein the catalysts are metal oxides and are selected from the group consisting of oxides of alkaline metals and alkaline earth metals and metals selected from zirconium, niobium, scandium, yttrium, lanthanum, zinc, cerium and tin, optionally supported via SiO₂, γ

-Al₂O₃, MgO and ZrO₂; and

wherein the concentration of catalyst is comprised between 0.001% and 1%, in percentage by weight with respect to the glycerol carbonate.

16. The method according to claim 1, wherein the catalysts are metal oxides and are selected from the group consisting of oxides of alkaline metals and alkaline earth metals and metals selected from zirconium, niobium, scandium, yttrium, lanthanum, zinc, cerium and tin, optionally supported via SiO₂, γ

-Al₂O₃, MgO and ZrO₂;

wherein the concentration of catalyst is comprised between 0.001% and 1%, in percentage by weight with respect to the glycerol carbonate; and

wherein the working pressure is less than or equal to 1 kPa.

17. The method according to claim 1, wherein the catalysts are metal oxides and are selected from the group consisting of oxides of alkaline metals and alkaline earth metals and metals selected from zirconium, niobium, scandium, yttrium, lanthanum, zinc, cerium and tin, optionally supported via SiO₂, γ

-Al₂O₃, MgO and ZrO₂;

wherein the concentration of catalyst is comprised between 0.001% and 1%, in percentage by weight with respect to the glycerol carbonate;

wherein the working pressure is less than or equal to 1 kPa; and

wherein the temperature of the reaction is in the range of 100 to 130°

C.

18. The method according to claim 1, wherein the catalysts are metal oxides and are selected from the group consisting of oxides of alkaline metals and alkaline earth metals and metals selected from zirconium, niobium, scandium, yttrium, lanthanum, zinc, cerium and tin, optionally supported via SiO₂, γ

-Al₂O₃, MgO and ZrO₂;

wherein the concentration of catalyst is comprised between 0.001% and 1%, in percentage by weight with respect to the glycerol carbonate;

wherein the working pressure is less than or equal to 1 kPa;

wherein the temperature of the reaction is in the range of 100 to 130°

C.; and

which is carried out in a semi-continuous manner.

19. The method according to claim 1, wherein the catalysts are stannates and are selected from the group consisting of metal stannates and mixed metal stannates of alkaline metals and alkaline earth metals, optionally supported via SiO₂, γ

-Al₂O₃, MgO and ZrO₂;

wherein the metal stannates and mixed metal stannates of alkaline metals are from sodium and potassium; and

wherein the concentration of catalyst is comprised between 0.001% and 1%, in percentage by weight with respect to the glycerol carbonate.

20. The method according to claim 1, wherein the catalysts are stannates and are selected from the group consisting of metal stannates and mixed metal stannates of alkaline metals and alkaline earth metals, optionally supported via SiO₂, γ

-Al₂O₃, MgO and ZrO₂;

wherein the metal stannates and mixed metal stannates of alkaline metals are from sodium and potassium;

wherein the concentration of catalyst is comprised between 0.001% and 1%, in percentage by weight with respect to the glycerol carbonate;

wherein the working pressure is less than or equal to 1 kPa;

wherein the temperature of the reaction is in the range of 100 to 130°

C.; and

which is carried out in a semi-continuous manner.