Hydrothermal hydrocatalytic treatment of biomass using water tolerant catalysts

Patent metadata

Field	Value
Publication number	US-9469822-B2
Application number	US-201314133704-A
Country	US
Kind code	B2
Filing date	Dec 19, 2013
Priority date	Dec 19, 2012
Publication date	Oct 18, 2016
Grant date	Oct 18, 2016

Abstract

A method of hydrothermal hydrocatalytic treating biomass is provided. Lignocellulosic biomass solids is provided to a hydrothermal digestion unit in the presence of a digestive solvent, and a supported hydrogenolysis catalyst containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into an alumina support, which support is predominantly alpha alumina; (ii) heating the lignocellulosic biomass solids and digestive solvent in the presence of hydrogen, and supported hydrogenolysis catalyst thereby forming a product solution containing plurality of oxygenated hydrocarbons, said alumina support having a specific surface area of up to about 30 m 2 /g and said catalyst retaining a crush strength of at least 50% after being subjected to an aqueous phase stability test compared with before the aqueous phase stability test or a crush strength of at least 0.25 kg after being subjected to an aqueous phase stability test.

First claim

We claim:

1. A method comprising: (i) providing lignocellulosic biomass solids in a hydrothermal digestion unit in the presence of a digestive solvent, and a supported hydrogenolysis catalyst comprising (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into an alumina support, which support is predominantly alpha alumina; (ii) heating the lignocellulosic biomass solids and digestive solvent in the presence of hydrogen, and supported hydrogenolysis catalyst thereby forming a product solution containing plurality of oxygenated hydrocarbons, said alumina support having a specific surface area of up to about 30 m 2 /g and said catalyst retaining a crush strength of at least 50% after being subjected to an aqueous phase stability test compared with before the aqueous phase stability test.

2. The method of claim 1 wherein the lignocellulosic biomass solids is heated to a temperature in the range of 180° C. to less than 300° C.

3. The method of claim 1 wherein the catalyst retains aqueous phase stability of at least 60% after being subjected to an aqueous phase stability test.

4. The method of claim 1 wherein the alumina support have a specific surface area in the range of 1 to 30 m 2 /g.

5. The method of claim 4 wherein the alumina support have a specific surface area in the range of 3 to 15 m 2 /g.

6. The method of claim 5 wherein the alumina support have a specific surface area in the range of 5 to 10 m 2 /g.

7. The method of claim 3 wherein the catalyst retains aqueous phase stability of at least 80% after being subjected to an aqueous phase stability test.

8. The method of claim 1 wherein at least a portion of the digestive solvent is comprised of the oxygenated hydrocarbons from the product solution.

9. The method of claim 1 wherein the alumina support comprises at least 90% alpha-alumina.

10. The method of claim 9 wherein the alumina support comprises at least 95% alpha-alumina.

11. A method comprising: (i) providing a lignocellulosic biomass solids (ii) contacting the biomass solids with a digestive solvent to form a pretreated biomass containing soluble carbohydrates; (iii) contacting the pretreated biomass with hydrogen at a temperature in the range of 180° C. to less than 300° C. in the presence of a supported hydrogenolysis catalyst comprising (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into an alumina support, which support is predominantly alpha alumina, to form a plurality of oxygenated products, said alumina support having a specific surface area of up to about 30 m 2 /g and said catalyst retaining a crush strength of at least 50% after being subjected to an aqueous phase stability test compared with before the aqueous phase stability test.

12. The method of claim 11 wherein the lignocellulosic biomass solids is heated to a temperature in the range of 180° C. to less than 300° C.

13. The method of claim 11 wherein the catalyst retains aqueous phase stability of at least 60% after being subjected to an aqueous phase stability test.

14. The method of claim 11 wherein the alumina support have a specific surface area in the range of 1 to 30 m 2 /g.

15. The method of claim 14 wherein the alumina support have a specific surface area in the range of 3 to 15 m 2 /g.

16. The method of claim 15 wherein the alumina support have a specific surface area in the range of 5 to 10 m 2 /g.

17. The method of claim 13 wherein the catalyst retains aqueous phase stability of at least 80% after being subjected to an aqueous phase stability test.

18. The method of claim 11 wherein at least a portion of the digestive solvent is comprised of the oxygenated hydrocarbons from the product solution.

19. The method of claim 11 wherein the alumina support comprises at least 90% alpha-alumina.

20. The method of claim 19 wherein the alumina support comprises at least 95% alpha-alumina.

21. A method comprising: (i) providing lignocellulosic biomass solids in a hydrothermal digestion unit in the presence of a digestive solvent, and a supported hydrogenolysis catalyst comprising (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into an alumina support, which support is predominantly alpha alumina; (ii) heating the lignocellulosic biomass solids and digestive solvent in the presence of hydrogen, and supported hydrogenolysis catalyst thereby forming a product solution containing plurality of oxygenated hydrocarbons, said alumina support having a specific surface area of up to about 30 m 2 /g and said catalyst having a crush strength of at least 0.25 kg after being subjected to an aqueous phase stability test.

22. The method of claim 21 wherein the lignocellulosic biomass solids is heated to a temperature in the range of 180° C. to less than 300° C.

23. The method of claim 21 wherein the catalyst having a crush strength of at least 0.4 kg.

24. The method of claim 21 wherein the alumina support have a specific surface area in the range of 1 to 30 m 2 /g.

25. The method of claim 24 wherein the alumina support have a specific surface area in the range of 3 to 15 m 2 /g.

26. The method of claim 25 wherein the alumina support have a specific surface area in the range of 5 to 10 m 2 /g.

27. The method of claim 21 wherein at least a portion of the digestive solvent is comprised of the oxygenated hydrocarbons from the product solution.

28. The method of claim 21 wherein the alumina support comprises at least 90% alpha-alumina.

29. The method of claim 28 wherein the alumina support comprises at least 95% alpha-alumina.

30. A composition comprising:
(a) lignocellulosic biomass;
(b) hydrogenolysis catalyst comprising (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into an alumina support, which support is predominantly alpha alumina, having a specific surface area of up to about 30 m 2 /g and said catalyst retaining a crush strength of at least 50% after being subjected to an aqueous phase stability test compared with before the aqueous phase stability test;
(c) water; and
(d) digestive solvent.

31. The composition of claim 30 wherein the alumina support have a specific surface area in the range of 1 to 30 m 2 /g.

32. The composition of claim 30 wherein the hydrogenolysis catalyst further comprises (d) phosphorus.

33. The composition of claim 30 wherein the alumina support comprises at least 90% alpha-alumina.

34. A composition comprising:
(a) lignocellulosic biomass;
(b) hydrogenolysis catalyst comprising (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into an alumina support, which support is predominantly alpha alumina, having a specific surface area of up to about 30 m 2 /g and said catalyst having a crush strength of at least 0.25 kg after being subjected to an aqueous phase stability test;
(c) water; and
(d) digestive solvent.

35. The composition of claim 34 wherein the alumina support have a specific surface area in the range of 1 to 30 m 2 /g.

36. The composition of claim 34 wherein the hydrogenolysis catalyst further comprises (d) phosphorus.

37. The composition of claim 34 wherein the alumina support comprises at least 90% alpha-alumina.

Assignees

• Shell Oil Co

Inventors

• Powell Joseph Broun
• Komplin Glenn Charles
• Smegal John Anthony
• Johnson Kimberly Ann

Classifications

• B01J21/04 Primary

  Alumina · CPC title

• B01J23/882

  and cobalt · CPC title

• B01J23/88

  Molybdenum · CPC title

• B01J23/86

  Chromium · CPC title

• C10G3/50

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