Biomass treatment for hydrothermal hydrocatalytic conversion

Patent metadata

Field	Value
Publication number	US-9347178-B2
Application number	US-201414574453-A
Country	US
Kind code	B2
Filing date	Dec 18, 2014
Priority date	Dec 18, 2013
Publication date	May 24, 2016
Grant date	May 24, 2016

Abstract

A selective removal of 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 chlorine and phosphorus from a cellulosic biomass solids comprising:
a. providing a cellulosic biomass solids containing chorine and/or phosphorus;
b. introducing said cellulosic biomass solids into a base solution having a pH of greater than 9 at a temperature in the range of 0° C. to 60° C., in a first contact zone, thereby producing an base washed cellulosic biomass solids and basic water effluent wherein said basic water effluent is in the range of about 3 parts to about 0.5 parts relative to about 1 part of cellulosic biomass solids (dry basis);
c. introducing said base washed cellulosic biomass solids into an aqueous solution having a pH of at most 8, in a second contact zone, thereby producing water washed cellulosic biomass solids having reduced chorine and/or phosphorus content compared to the cellulosic biomass solids;
d. passing a gas and/or an organic solvent through said water washed cellulosic biomass solids, in a third contact zone, thereby producing a pretreated cellulosic biomass solids with reduced water content compared to the water washed cellulosic biomass solids and separated aqueous effluent;
e. recycling the separated aqueous effluent to the second contact zone to form at least a portion of the aqueous solution; and
f. transferring at least a portion of said treated cellulosic biomass solids to a digestion and/or reaction zone.

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

3. The method of claim 1 wherein the base solution comprises a base in an amount of less than 5 Normal and at least 0.01 Normal.

4. The method of claim 1 wherein the organic solvent is a solvent used in the digestion and/or reaction zone.

5. 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 the second contact zone to form at least a portion of the aqueous solution.

6. 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 the second contact zone to form at least a portion of the aqueous solution.

7. The method of claim 6 wherein, the oxygenated intermediate product steam comprises oxygenated hydrocarbons and water, and at least a portion of the water is separated and recycled to the second contact zone to form at least a portion of the aqueous solution.

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

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

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

11. The method of claim 5 wherein the solvent in step d) is the digestion solvent.

12. The method of claim 6 wherein the solvent in step d) is the digestion solvent.

13. The method of claim 7 wherein the second contact zone contains at least 2 vessels.

14. The method of claim 1 wherein the flow of the aqueous solution is in a pulse flow through the contact zone.

15. The method of claim 1 wherein the flow of the aqueous solution is in a continuous flow through the contact zone.

16. The method of claim 1 wherein steps b) and c) are conducted in one reactor.

17. 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

• C10G2300/4037

  In-situ processes · CPC title

• C10G1/065

  in the presence of a solvent · CPC title

• Y02P30/20

  using bio-feedstock · CPC title

• C10G2300/202

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

• C10G2300/4081

  Recycling aspects · CPC title