METHOD OF PRODUCING LOWER ALCOHOLS FROM GLYCEROL

• US 20100019192A1
• Filed: 10/31/2006
• Published: 01/28/2010
• Est. Priority Date: 10/31/2005
• Status: Abandoned Application

• Current Assignee: Renewable Alternatives LLC, Curators of the University of Missouri (University of Missouri)
• Original Assignee: Curators of the University of Missouri (University of Missouri)
• Inventors: Sutterlin, William Rusty, Suppes, Galen J.
• Application Number:
  US12/278,634
• Publication Number:
  US 20100019192A1
• Time in Patent Office: Days
• US Class Current: 252/73
• 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
• CPC Class Codes: C09K 5/20 Antifreeze additives therefor, e.g. for radiator liquids for application to surfaces C09K3/18; inhibiting corrosion by liquids C23F11/00
• CPC Class Codes: C12C 11/02 Pitching yeast

Abstract

A reactive-separation process converts glycerin into lower alcohols, having boiling points less than 2000 C, at high yields. Conversion of natural glycerin to propylene glycol through an acetol intermediate is achieved at temperatures from 150° to 2500 C at pressures 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.

Claims

1. A process for converting glycerol to a product at high selectivity to a mixture of acetol and propylene glycol in any combination and at low selectivity to ethylene glycol, comprising:

contacting a gas phase reaction mixture with a heterogeneous catalyst,

wherein the gas phase reaction mixture contains essentially no liquid and has a partial pressure of glycerol between 0.01 and 0.5 bars of glycerol; and

establishing a temperature in a range from 80°

C. to 300°

C. to facilitate a reaction.

2. The process of claim 1, wherein the gas phase reaction mixture includes hydrogen at a partial pressure of hydrogen in a range from 0.01 and 25 bars of hydrogen.

3. The process of claim 2 wherein the range of partial pressure of hydrogen is from 0.01 to 0.1 bar of hydrogen to facilitate dominantly the production of acetol product with high selectivity.

4. The process of claim 3, comprising a step of condensing process effluent vapors to yield liquid acetol.

5. The process of claim 4, including a step of further reacting the liquid acetol.

6. The process of claim 5, wherein the step of further reacting includes introducing a hydrogen-containing gas to the liquid acetol at sufficient partial pressure for catalyzed reaction with the acetol to form propylene glycol as the second reaction product.

7. The process of claim 5, wherein the temperature used in the step of further reacting is in a range between 80°

C. to 150°

C.

8. The process of claim 6, further comprising a step of removing the propylene glycol from the liquid by action of the gas under conditions of partial pressure that facilitate selective removal of propylene glycol.

9. The process of claim 8, further comprising a step of condensing the propylene glycol from the gas in a second condenser to provide liquid propylene glycol

10. The process of claim 9, wherein the step of further reacting yields unused hydrogen and further comprising a step of recycling the unused hydrogen back to the liquid acetol.

11. The process of claim 2 wherein the range of partial pressure of hydrogen is greater than 0.1 bar to facilitate increased production of propylene glycol.

12. The process of claim 1, wherein the heterogeneous catalyst used in the step of contacting contains at least one element from Groups I or VIII of the Periodic Table, ruthenium, copper, chromite, and combinations thereof.

13. The process of claim 1, wherein the total pressure of reaction is between 0.02 and 25 bars.

14. The process of claim 1 where the partial pressure of glycerol is

less than glycerol'"'"'s dew point partial pressure in the reaction mixture and

greater than one fourth the dew point partial pressure in the reaction mixture.

15. The process of claim 14 where the partial pressure of glycerol is greater than half the dew point partial pressure in the reaction mixture.

16. The process of claim 1, wherein the temperature used in the step of establishing is in a range from 150°

C. to 250°

C.

17. The process of claim 1, wherein the temperature used in the step of establishing is in a range from 185°

C. to 240°

C.

18. The process of claim 1 wherein the gas phase reaction mixture contains water in an amount of 1 part by mass water for every 0.333 to 1 parts glycerol and hydrogen is present at a hydrogen to glycerol molar ratio between 0.1:

1 and 15;

1.

19. The process claim 18, wherein the temperature used in the step of establishing is in a range between 250°

C. to 300°

C.

20. The process of claim 1, wherein the partial pressure of hydrogen used in the step of contacting is in a range from 3 to 25 bars of hydrogen.

21. The process of claim 1, wherein the partial pressure of hydrogen used in the step of contacting is in a range from 0.1 to 5 bars of hydrogen.

22. A system for converting glycerol to a product at high selectivity to a mixture of acetol and propylene glycol in any combination and at low selectivity to ethylene glycol, comprising:

means for contacting a gas phase reaction mixture with a heterogeneous catalyst,

wherein the gas phase reaction mixture contains essentially no liquid and has a partial pressure of glycerol between 0.01 and 0.5 bars of glycerol; and

means for establishing a temperature in a range from 80°

C. to 300°

C. to facilitate a reaction.

23. The system of claim 22, wherein the means for contacting includes means for providing the gas phase reaction mixture with hydrogen at a partial pressure of hydrogen in a range from 0.01 and 25 bars of hydrogen.

24. The system of claim 23 wherein the range of partial pressure of hydrogen is from 0.01 to 0.1 bar of hydrogen to facilitate dominantly the production of acetol product with high selectivity.

25. The system of claim 24, comprising a means for condensing process effluent vapors to yield liquid acetol.

26. The system of claim 25, including means for further reacting the liquid acetol.

27. The system of claim 26, wherein the means for further reacting includes means for introducing a hydrogen-containing gas to the liquid acetol at sufficient partial pressure for catalyzed reaction with the acetol to form propylene glycol as the second reaction product.

28. The system of claim 27, wherein the temperature used in the means for further reacting is in a range between 80°

C. to 150°

C.

29. The system of claim 27, further comprising means for removing the propylene glycol from the liquid by action of the gas under conditions of partial pressure that facilitate selective removal of propylene glycol.

30. The system of claim 29, further comprising means for condensing the propylene glycol from the gas in a second condenser to provide liquid propylene glycol

31. The system of claim 29, wherein the means for further reacting yields unused hydrogen and further comprising means for recycling the unused hydrogen back to the liquid acetol.

32. The system of claim 22 wherein the range of partial pressure of hydrogen is greater than 0.1 bar to facilitate increased production of propylene glycol.

33. The system of claim 22 wherein the heterogeneous catalyst used in the means for contacting contains at least one element from Groups I or VIII of the Periodic Table, ruthenium, copper, chromite, and combinations thereof.

34. The system of claim 22, wherein the total pressure of reaction is between 0.02 and 25 bars.

35. The system of claim 22 where the partial pressure of glycerol is

less than glycerol'"'"'s dew point partial pressure in the reaction mixture and

greater than one fourth the dew point partial pressure in the reaction mixture.

36. The system of claim 35 where the partial pressure of glycerol is greater than half the dew point partial pressure in the reaction mixture.

37. The system of claim 22, wherein the temperature used in the means for establishing is in a range from 150°

C. to 250°

C.

38. The system of claim 22, wherein the temperature used in the means for establishing is in a range from 185°

C. to 240°

C.

39. The system of claim 22, wherein the gas phase reaction mixture contains water in an amount of 1 part by mass water for every 0.333 to 1 parts glycerol and hydrogen is present at a hydrogen to glycerol molar ratio between 0.1:

1 and 15;

1.

40. The system claim 39, wherein the temperature used in the means for establishing is in a range between 250°

C. to 300°

C.

41. The system of claim 22, wherein the partial pressure of hydrogen used in the means for contacting is in a range from 3 to 25 bars of hydrogen.

42. The system of claim 22, wherein the partial pressure of hydrogen used in the means for contacting is in a range from 0.1 to 5 bars of hydrogen.