Hydrothermal hydrocatalytic treatment of biomass using water tolerant catalysts
View Patent ↗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 a group 4 metal oxide support; (ii) heating the lignocellulosic biomass solids and digestive solvent in the presence of hydrogen, and the supported hydrogenolysis catalyst thereby forming a product solution containing plurality of oxygenated hydrocarbons, 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.
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 containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a group 4 metal oxide support; (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 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 group 4 metal oxide support is a stabilized form.
5. The method of claim 1 wherein the group 4 metal oxide support is zirconia.
6. The method of claim 1 wherein the group 4 metal oxide support is titania.
7. The method of claim 1 wherein the metal loading per unit volume of the catalyst comprising the outer 30% of the catalyst volume, is more than 25% greater than the metal loading averaged over the entire catalyst volume and mass.
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. 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 containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a group 4 metal oxide support, to form a plurality of oxygenated products, 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.
10. The method of claim 9 wherein the catalyst retains a crush strength of at least 60% after being subjected to an aqueous phase stability test.
11. The method of claim 9 wherein the group 4 metal oxide support is a stabilized form.
12. The method of claim 9 wherein the group 4 metal oxide support is zirconia.
13. The method of claim 9 wherein the group 4 metal oxide support is titania.
14. The method of claim 9 wherein the metal loading per unit volume of the catalyst comprising the outer 30% of the catalyst volume, is more than 25% greater than the metal loading averaged over the entire catalyst volume and mass.
15. The method of claim 10 wherein at least a portion of the digestive solvent is comprised of the oxygenated hydrocarbons from the product solution.
16. 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 containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a group 4 metal oxide support; (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 catalyst having a crush strength of at least 0.25 kg after being subjected to an aqueous phase stability test.
17. The method of claim 16 wherein the lignocellulosic biomass solids is heated to a temperature in the range of 180° C. to less than 300° C.
18. The method of claim 16 wherein the catalyst having a crush strength of at least 0.4 kg.
19. The method of claim 16 wherein the group 4 metal oxide support is a stabilized form.
20. The method of claim 16 wherein the group 4 metal oxide support is zirconia.
21. The method of claim 16 wherein the group 4 metal oxide support is titania.
22. The method of claim 16 wherein the metal loading per unit volume of the catalyst comprising the outer 30% of the catalyst volume, is more than 25% greater than the metal loading averaged over the entire catalyst volume and mass.
23. The method of claim 16 wherein at least a portion of the digestive solvent is comprised of the oxygenated hydrocarbons from the product solution.
24. 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 a group 4 metal oxide support, 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.
25. The composition of claim 24 wherein the group 4 metal oxide support is a stabilized form.
26. The composition of claim 24 wherein the group 4 metal oxide support is zirconia.
27. The composition of claim 24 wherein the group 4 metal oxide support is titania.
28. The composition of claim 24 wherein the metal loading per unit volume of the catalyst comprising the outer 30% of the catalyst volume, is more than 25% greater than the metal loading averaged over the entire catalyst volume and mass.
29. 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 a group 4 metal oxide support, 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.
30. The composition of claim 29 wherein the group 4 metal oxide support is a stabilized form.
31. The composition of claim 29 wherein the group 4 metal oxide support is zirconia.
32. The composition of claim 29 wherein the group 4 metal oxide support is titania.
33. The composition of claim 29 wherein the metal loading per unit volume of the catalyst comprising the outer 30% of the catalyst volume, is more than 25% greater than the metal loading averaged over the entire catalyst volume and mass.