Methods for making 1,3-dihydroxyacetone (DHA) from glycerol

• US 8,735,633 B2
• Filed: 07/14/2011
• Issued: 05/27/2014
• Est. Priority Date: 07/14/2010
• Status: Active Grant

• Current Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Original Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Inventors: Miller, Dennis, Hong, Xi, Lira, Carl, McGiveron, Omar
• Primary Examiner(s): Sullivan, Daniel
• Assistant Examiner(s): LAZARO, DOMINIC
• Application Number:
  US13/183,114
• Publication Number:
  US 20120014889A1
• Time in Patent Office: 1,048 Days
• Field of Search: None
• US Class Current: 568/391
• CPC Class Codes: C07C 45/60 in six-membered rings
• CPC Class Codes: C07C 49/17 containing hydroxy groups sugars C07H
• CPC Class Codes: C07D 317/20 Free hydroxyl or mercaptan
• CPC Class Codes: C07D 319/06 not condensed with other rings
• CPC Class Codes: Y02P 20/10 Process efficiency

Abstract

A method comprising reacting glycerol with acetaldehyde or 1,1-diethoxyethane to produce 1,3-dihydroxyacetone (DHA), without using fermentation or direct oxidation of the glycerol is provided. DHA is useful in various products, including as a sunless tanning agent.

Claims

1. A method comprising:

reacting glycerol with acetaldehyde or 1,1-diethoxyethane to produce 1,3-dihydroxyacetone (DHA), wherein the method comprises;

with an acid catalyst, forming glycerol acetal isomers from the glycerol and acetaldehyde or 1,1diethoxyethane, wherein at least one of the glycerol acetal isomers is a cis-5-hydroxy-2-methyl-1,3-dioxane isomer (cis-6 isomer);

separating the cis-6 isomer from the glycerol acetal isomers;

with an oxidation catalyst, oxidizing the cis-6 isomer to produce 2-methyl-1,3-dioxan-5-one (G-tone); and

combining the G-tone with water to produce 1,3-dihydroxyacetone (DHA), wherein the DHA is produced without using fermentation or direct oxidation of the glycerol.

2. The method of claim 1 wherein conversion of glycerol to DHA is at least 94%.

3. The method of claim 2 wherein the conversion is nearly 100%.

4. The method of claim 1 wherein the acid catalyst is a sulfuric acid catalyst.

5. The method of claim 1 wherein the glycerol acetal isomers further comprise trans-5-hydroxy-2-methyl-1,3-dioxane (trans-6 isomer), cis-4-hydroxymethyl-2-methyl-1,3dioxolane (cis-5 isomer), and/or trans-4-hydroxymethyl-2-methyl-1,3-dioxolane (trans-5 isomer), wherein the method further comprises converting the trans-6 isomer, the cis-5 isomer, the trans-5 isomer, or combinations thereof, to the cis-6 isomer.

6. The method of claim 1 wherein the oxidation catalyst is a homogeneous catalyst.

7. The method of claim 1 wherein the oxidation catalyst is a heterogeneous catalyst.

8. The method of claim 1 wherein the oxidation catalyst is a ruthenium catalyst, a palladium catalyst or a platinum catalyst.

9. The method of claim 8 wherein the ruthenium catalyst is a ruthenium (III) trichloride catalyst, a ruthenium dioxide catalyst, or a ruthenium tetraoxide catalyst.

10. The method of claim 8 wherein the oxidizing step further comprises adding an oxidizer.

11. The method of claim 10 wherein the oxidizer is selected from KBrO₃, NaBrO₃, NaClO, Ca(ClO)₂ and NaIO₄.

12. The method of claim 1 further comprising hydrolyzing and separating the G-tone to produce the DHA.

18. The method of claim 1 wherein the acid catalyst is a Brø

nsted acid catalyst.

19. The method of claim 1 wherein the acid catalyst is a cationic exchange resin.

20. The method of claim 1 wherein the oxidation catalyst is a chromium-based catalyst.

21. The method of claim 19 wherein the chromium-based catalyst is pyridinium chlorochromate.

22. The method of claim 8 wherein the platinum catalyst is a Pt—

Bi/C catalyst or a Pt/Al₂O₃ catalyst.

23. The method of claim 1 wherein the DHA is produced in a batch process in less than 20 hours.

24. The method of claim 1 further comprising drying the DHA to produce substantially pure DHA.

25. The method of claim 1 wherein a yield of G-tone is from about 50% to about 99% of theoretical yield.

26. The method of claim 25 wherein the yield is from about 77% to about 97%.

27. The method of claim 1 wherein the DHA is useful as a sunless tanning agent.

28. The method of claim 1 wherein the DHA is useful in wine, neutraceuticals, nutritional supplements, fungicides, plasticizers, cosmetics and combinations thereof.

13. A method comprising:

combining glycerol and acetaldehyde in a first reactor to produce glycerol acetal isomers and water together with unreacted acetaldehyde;

separating the glycerol acetal isomers from the unreacted acetaldehyde and water in an evaporator;

distilling the glycerol acetal isomers in a vacuum distillation column with an acid catalyst;

removing cis-5-hydroxy-2-methyl-1,3-dioxane isomer (cis-6 isomer) from the vacuum distillation column;

oxidizing the cis-6 isomer in a second reactor to produce 2-methyl-1,3-dioxan-5-one (G-tone); and

combining the G-tone with water in a reactive distillation column to produce 1,3dihydroxyacetone (DHA).

14. The method of claim 13 wherein the glycerol acetal isomers are continuously interconverted within the vacuum distillation column.

15. The method of claim 14 further comprising:

removing less volatile glycerol acetal isomers from the vacuum distillation column;

heating the less volatile glycerol acetal isomers to produce heated isomers;

exposing the heated isomers to an acid catalyst in a third reactor to produce equilibrated isomers; and

combining the equilibrated isomers with the glycerol acetal isomers exiting the evaporator.

16. The method of claim 15 wherein the unreacted acetaldehyde and water are separated in a vaporizer using flash distillation.

17. The method of claim 16 wherein separated acetaldehyde is provided to the first reactor.