Biomass treatment for hydrothermal hydrocatalytic conversion

Patent metadata

Field	Value
Publication number	US-9399836-B2
Application number	US-201414575112-A
Country	US
Kind code	B2
Filing date	Dec 18, 2014
Priority date	Dec 18, 2013
Publication date	Jul 26, 2016
Grant date	Jul 26, 2016

Abstract

A selective removal chlorine and phosphorus that are detrimental to subsequent hydrothermal hydrocatalytic conversion from the biomass feed prior to carrying out catalytic hydrogenation/hydrogenolyzis/hydrodeoxygenation of the biomass in a manner that does not reduce the effectiveness of the hydrothermal hydrocatalytic treatment while minimizing the amount of water used in the process is provided.

First claim

What is claimed is:

1. A method for selective removal of at least a portion of detrimental metals and their anions from a detrimental species-containing cellulosic biomass solids comprising:
a. providing a first portion of cellulosic biomass solids being contacted by a first dispersed or semi-continuous liquid phase and first continuous gas phase at a temperature in the range of about 0° C. to about 60° C. in a first contact zone wherein the liquid phase comprises base solution having a pH of greater than 9 wherein the flux of the first liquid phase is at least 1 kg/(m 2 s);
b. providing said first dispersed or semi-continuous liquid phase treated cellulosic biomass solids being contacted by a second dispersed or semi-continuous liquid phase and second continuous gas phase at a temperature in the range of about 0° C. to about 60° C. in a second contact zone wherein the liquid phase comprises an aqueous solution having a pH of at most 8 wherein the flux of the second liquid phase is at least 1 kg/(m 2 s);
c. removing the first dispersed or semi-continuous liquid phase from the first contact zone as a basic effluent;
d. recovering the second dispersed or semi-continuous liquid phase from the second contact zone as aqueous effluent;
e. recycling at least a portion of the aqueous effluent as a portion of the liquid phase in the first contact zone;
f. transferring at least a portion of said second dispersed or semi-continuous liquid phase treated cellulosic biomass solids to a digestion and/or reaction zone.

2. The method of claim 1 wherein the first contact zone and the second contact zone are in one vessel.

3. The method of claim 1 wherein the first contact zone and the second contact zone are in separate vessels.

4. The method of claim 1 wherein both first liquid phase and second liquid phase flow downward.

5. The method of claim 4 wherein the first gas phase is static gas blanket to maintain pressure.

6. The method of claim 4 wherein the first gas phase is flowing concurrently with the first liquid phase.

7. The method of claim 4 wherein the first gas phase is flowing counter-currently with the first liquid phase.

8. The method of claim 1 wherein the biomass and the liquid phase is flowing counter-currently.

9. The method of claim 1 wherein the first gas phase and the second gas phase is the same.

10. The method of claim 1 wherein the flux of the first liquid phase is at least 3 kg/(m 2 s).

11. The method of claim 1 wherein the flux of the second liquid phase is at least 3 kg/(m 2 s).

12. The process of claim 1 wherein the base solution comprises a base selected from potassium hydroxide, sodium hydroxide or ammonia.

13. The method of claim 12 wherein the base solution comprises a base in an amount of less than 5 Normal and at least 0.01 Normal.

14. The method of claim 1 wherein, in the digestion and/or reaction zone, the treated cellulosic biomass is contacted with a hydrothermal hydrocatalytic catalyst in the presence of hydrogen in the presence of a digestion solvent thereby producing an intermediate oxygenated product stream comprising oxygenated hydrocarbons and water; and at least a portion of the water is separated and recycled to form at least a portion of the aqueous solution.

15. The method of claim 1 wherein, in the digestion and/or reaction zone, the treated cellulosic biomass is contacted with a hydrothermal hydrocatalytic catalyst in the presence of hydrogen in the presence of a digestion solvent thereby producing an intermediate oxygenated product stream; at least a portion of the oxygenated intermediate product stream is converted to a hydrocarbon product stream comprising hydrocarbons and water; and at least a portion of the water is separated and recycled to form at least a portion of the aqueous solution.

16. The method of claim 15 wherein, the oxygenated intermediate product steam comprises oxygenated hydrocarbons and water, and at least a portion of the water is separated and recycled to form at least a portion of the aqueous solution.

17. The method of claim 1 wherein the aqueous solution is in-situ generated.

18. The method of claim 1 wherein the gas is selected from the group consisting of air, hydrogen, nitrogen, steam, organic vapors, and mixtures thereof.

19. The method of claim 1 wherein the gas is pressurized up to 100 bar.

20. The method of claim 1 further comprising passing a gas and/or an organic solvent through said second dispersed or semi-continuous liquid phase treated cellulosic biomass prior to transferring to a digestion and/or reaction zone.

21. The method of claim 14 wherein the organic solvent is the digestion solvent.

22. The method of claim 1 further comprising passing a gas and/or an organic solvent through said second dispersed or semi-continuous liquid phase treated cellulosic biomass prior to transferring to a digestion and/or reaction zone.

23. The method of claim 22 wherein the organic solvent is the digestion solvent.

24. The method of claim 1 wherein the loss of carbohydrate from the washing is less than 10% by weight, based on the carbohydrates present in the biomass (dry basis).

Assignees

• Shell Oil Co

Inventors

• Powell Joseph Broun
• Chheda Juben Nemchand

Classifications

• C08H8/00

  Macromolecular compounds derived from lignocellulosic materials {(pretreatment thereof B27N)} · CPC title

• C10G1/065

  in the presence of a solvent · CPC title

• C10G2300/1014

  of vegetal origin · CPC title

• C13K1/02

  obtained by saccharification of cellulosic materials (manufacture of fodder A23K10/32) · CPC title

• C10G2300/202

  Heteroatoms content, i.e. S, N, O, P · CPC title