Methods for production and processing of a glycol reaction product obtained from hydrothermal digestion of cellulosic biomass solids

Patent metadata

Field	Value
Publication number	US-9353031-B2
Application number	US-201314067428-A
Country	US
Kind code	B2
Filing date	Oct 30, 2013
Priority date	Oct 31, 2012
Publication date	May 31, 2016
Grant date	May 31, 2016

Abstract

Hydrothermal digestion of cellulosic biomass solids may be conducted such that a glycol reaction product is formed for subsequent processing. Processing of a glycol reaction product may include a drying operation conducted prior to condensation of the glycol reaction product into higher molecular weight compounds. Methods for digesting cellulosic biomass solids to form a glycol reaction product can comprise: providing cellulosic biomass solids and a slurry catalyst in a hydrothermal digestion unit, the slurry catalyst being capable of activating molecular hydrogen; heating the cellulosic biomass solids in the hydrothermal digestion unit in the presence of the slurry catalyst, a digestion solvent, and molecular hydrogen, thereby forming a liquor phase comprising soluble carbohydrates; and performing a first catalytic reduction reaction on the soluble carbohydrates within the hydrothermal digestion unit, thereby at least partially converting the soluble carbohydrates into a reaction product comprising a glycol.

First claim

What is claimed is:

1. A method comprising:
providing cellulosic biomass solids;
converting the cellulosic biomass solids into a reaction product comprising a glycol, wherein converting the cellulosic biomass solids into the reaction product takes place in a hydrothermal digestion unit in the presence of a digestion solvent and a slurry catalyst capable of activating molecular hydrogen;
at least partially drying the reaction product, thereby forming a dried reaction product comprising a dried glycol; and
returning at least a portion of the dried glycol to the hydrothermal digestion unit.

2. The method of claim 1 , wherein at least about 5 percent by weight of the cellulosic biomass solids are converted into the glycol.

3. The method of claim 1 , wherein the dried glycol comprises about 35 wt. % or less water.

4. The method of claim 1 , further comprising:
separating the dried glycol from the dried reaction product.

5. The method of claim 1 , further comprising:
exposing the dried glycol or a product formed therefrom to a condensation catalyst; and
converting the dried glycol into a higher molecular weight compound using the condensation catalyst.

6. The method of claim 5 , wherein the condensation catalyst comprises a zeolite.

7. The method of claim 1 , wherein at least partially drying the reaction product takes place external to the hydrothermal digestion unit.

8. The method of claim 1 , wherein the slurry catalyst is distributed in the cellulosic biomass solids using fluid flow.

9. The method of claim 8 , wherein the slurry catalyst is circulated through a fluid circulation loop external to the hydrothermal digestion unit.

10. The method of claim 1 , wherein converting the cellulosic biomass solids into the reaction product further comprises heating the cellulosic biomass solids in the presence of the digestion solvent to form a liquor phase comprising soluble carbohydrates, and performing a first catalytic reduction reaction on the soluble carbohydrates to at least partially form the reaction product.

11. The method of claim 10 , further comprising:
removing at least a portion of the liquor phase from the hydrothermal digestion unit and recirculating at least a portion of the removed liquor phase thereto, the removed liquor phase also containing at least a portion of the slurry catalyst.

12. The method of claim 10 , further comprising:
performing a second catalytic reduction reaction on the liquor phase external to the hydrothermal digestion unit so as to increase a quantity of the glycol in the reaction product.

13. The method of claim 1 , wherein the slurry catalyst comprises a poison-tolerant catalyst.

14. The method of claim 13 , wherein the poison-tolerant catalyst comprises a sulfided catalyst.

15. The method of claim 1 , wherein the digestion solvent comprises an organic solvent and water.

16. The method of claim 15 , wherein the organic solvent comprises at least one solvent selected from the group consisting of ethanol, ethylene glycol, propylene glycol, glycerol, and any combination thereof.

17. The method of claim 16 , wherein the digestion solvent comprises glycerol and water.

18. The method of claim 17 , wherein the digestion solvent further comprises a monohydric alcohol.

19. The method of claim 1 , wherein the cellulosic biomass solids are converted into the reaction product in the presence of a solvent.

20. The method of claim 19 , wherein the solvent comprises an organic solvent and water.

21. The method of claim 20 , wherein the organic solvent comprises at least one solvent selected from the group consisting of ethanol, ethylene glycol, propylene glycol, glycerol, and any combination thereof.

22. The method of claim 21 , wherein the solvent comprises glycerol and water.

23. The method of claim 22 , wherein the solvent further comprises a monohydric alcohol.

24. The method of claim 1 , wherein at least partially drying the reaction product comprises a distillation to separate water from the glycol.

25. A method comprising:
providing cellulosic biomass solids and a slurry catalyst in a hydrothermal digestion unit, the slurry catalyst being capable of activating molecular hydrogen;
heating the cellulosic biomass solids in the hydrothermal digestion unit in the presence of the slurry catalyst, a digestion solvent, and molecular hydrogen, thereby forming a liquor phase comprising soluble carbohydrates;
performing a first catalytic reduction reaction on the soluble carbohydrates within the hydrothermal digestion unit, thereby at least partially converting the soluble carbohydrates into a reaction product comprising a glycol; and
at least partially drying the reaction product, thereby forming a dried reaction product comprising a dried glycol, wherein the dried glycol comprises about 35 wt. % or less water.

26. The method of claim 25 , wherein at least about 5 percent by weight of the cellulosic biomass solids are converted into the glycol.

27. The method of claim 25 , wherein the slurry catalyst is distributed in the cellulosic biomass solids using fluid flow.

28. The method of claim 27 , wherein the slurry catalyst is circulated through a fluid circulation loop external to the hydrothermal digestion unit.

29. The method of claim 25 , wherein at least partially drying the reaction product takes place external to the hydrothermal digestion unit.

30. The method of claim 29 , further comprising:
returning at least a portion of the dried glycol to the hydrothermal digestion unit.

31. The method of claim 25 , wherein at least partially drying the reaction product comprises a distillation to separate water from the glycol.

32. The method of claim 25 , further comprising:
exposing the dried glycol or a product formed therefrom to a condensation catalyst; and
converting the dried glycol into a higher molecular weight compound using the condensation catalyst.

33. The method of claim 25 , further comprising:
separating the dried glycol from the dried reaction product.

34. The method of claim 25 , further comprising:
performing a second catalytic reduction reaction on the liquor phase external to the hydrothermal digestion unit so as to increase a quantity of the glycol in the reaction product.

35. The method of claim 25 , wherein the slurry catalyst comprises a poison-tolerant catalyst.

36. The method of claim 35 , wherein the poison-tolerant catalyst comprises a sulfided catalyst.

37. The method of claim 25 , wherein the digestion solvent comprises an organic solvent and water.

38. The method of claim 37 , wherein the organic solvent comprises at least one solvent selected from the group consisting of ethanol, ethylene glycol, propylene glycol, glycerol, and any combination thereof.

39. The method of claim 38 , wherein the digestion solvent comprises glycerol and water.

40. The method of claim 39 , wherein the digestion solvent further comprises a monohydric alcohol.

41. The method of claim 25 , further comprising:
removing at least a portion of the liquor phase from the hydrothermal digestion unit and recirculating at least a portion of the removed liquor p

Assignees

• Shell Oil Co

Inventors

• Powell Joseph Broun
• Johnson Kimberly Ann

Classifications

• C10G2400/02

  Gasoline · CPC title

• C10G3/56

  suspended in the oil, e.g. slurries, ebullated beds · CPC title

• C07C31/202

  Ethylene glycol · CPC title

• C10G3/50

  in the presence of hydrogen, hydrogen donors or hydrogen generating compounds · CPC title

• C07C31/205

  1,3-Propanediol; 1,2-Propanediol · CPC title