Method of producing lower alcohols from glycerol

• US 7,663,004 B2
• Filed: 03/24/2005
• Issued: 02/16/2010
• Est. Priority Date: 04/22/2002
• Status: Active Grant

• Current Assignee: Renewable Alternatives LLC, Curators of the University of Missouri (University of Missouri)
• Original Assignee: Renewable Alternatives LLC, Curators of the University of Missouri (University of Missouri)
• Inventors: Sutterlin, William Rusty, Dasari, Mohanprasad, Suppes, Galen J.
• Primary Examiner(s): Price; Elvis O
• Application Number:
  US11/088,603
• Publication Number:
  US 20050244312A1
• Time in Patent Office: 1,790 Days
• Field of Search: 568/862, 568/861
• US Class Current: 568/862
• CPC Class Codes: C07C 29/145 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 29/60 by elimination of -OH groups, e.g. by dehydration C07C29/34 takes precedence
• CPC Class Codes: C07C 31/205 1,3-Propanediol; 1,2-Propanediol
• CPC Class Codes: C07C 45/52 by dehydration and rearrangement involving two hydroxy groups in the same molecule
• CPC Class Codes: C07C 49/17 containing hydroxy groups sugars C07H

Abstract

A reactive-separation process converts glycerin into lower alcohols, having boiling points less than 200° C., at high yields. Conversion of natural glycerin to propylene glycol through an acetol intermediate is achieved at temperatures from 150° to 250° C. at a pressure ranging from 1 and 25 bar. The preferred applications of the propylene glycol are as an antifreeze, deicing compound, or anti-icing compound. The preferred catalyst for this process in a copper-chromium powder.

Claims

1. A process for converting glycerol to acetol with high selectivity, comprising the steps of:

combining a glycerol-containing feedstock with a catalyst that is capable of dehydrating glycerol to form a reaction mixture;

heating the reaction mixture at an effective temperature to allow dehydration of the glycerol at a pressure not exceeding 25 bar, said effective temperature being less than 250°

C.,

the step of heating the reaction mixture being performed while limiting hydrogen reagent to form predominately acetol as the dehydration product of glycerol, and

removing the acetol from the reaction mixture in vapor form by action of a stripper gas.

2. The process of claim 1, wherein the glycerol-containing feedstock used in the step of combining contains from 0% to 15% water in glycerol by weight.

3. The process of claim 1, wherein the catalyst used in the step of combining is a heterogeneous catalyst selected from the group consisting of palladium, nickel, rhodium, copper, zinc, chromium and combinations thereof.

4. The process of claim 1, wherein the stripper gas used in the step of removing the acetol comprises hydrogen.

5. The process of claim 4, comprising a step of condensing the vapor form of acetol to yield a liquid acetol reaction product.

6. The process of claim 1, wherein the effective temperature used in the heating step ranges from 180°

C. to 240°

C.

7. The process of claim 6, wherein the pressure used in the heating step ranges from 0.5 to 3 atmospheres.

8. The process of claim 5, wherein the step of condensing occurs using a condenser operating at a temperature ranging from 0°

C. to 140°

C.

9. The process of claim 8, wherein the condenser operates at a temperature ranging from 25°

C. to 60°

C.

10. The process of claim 4, comprising a subsequent step of contacting the acetol with a hydrogen co-reagent to promote conversion of glycerol to propylene glycol.

11. The process of claim 10, comprising a step of recycling unused hydrogen from the condenser back to the subsequent step reaction mixture.

12. The process of claim 11, wherein the reaction time of the subsequent step reaction ranges from 0.2 to 24 hours.

13. The process of claim 12, wherein the reaction time of the subsequent step reaction ranges from 1 to 6 hours.

14. The process of claim 1 further comprising

combining hydrogen with the acetol to provide a reaction mixture in the presence of a catalyst that is capable of hydrogenating acetol;

and

heating the reaction mixture to a temperature ranging from 50°

C. to 250°

C. and a pressure ranging from 1 and 25 bar to convert the acetol to propylene glycol.

15. The process of claim 14, wherein the acetol used in the step of combining contains from 0% to 35% water by weight.

16. The process of claim 14, wherein the catalyst used in the step of combining is a heterogeneous catalyst selected from the group consisting of palladium, nickel, rhodium, copper, zinc, chromium and combinations thereof.

17. The process of claim 14, wherein the temperature used in the heating step ranges from 150°

C. to 220°

C.

18. The process of claim 14, wherein the pressure used in the heating step ranges from 10 to 20 bar.