BIOMASS TREATMENT FOR HYDROTHERMAL HYDROCATALYTIC CONVERSION

• US 20150167241A1
• Filed: 12/18/2014
• Published: 06/18/2015
• Est. Priority Date: 12/18/2013
• Status: Active Grant

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: POWELL, Joseph Broun, CHHEDA, Juben Nemchand
• Granted Patent: US 9,593,448 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C07C 1/24 by elimination of water
• CPC Class Codes: C07G 1/00 Lignin; Lignin derivatives
• CPC Class Codes: C08H 8/00 Macromolecular compounds derived from lignocellulosic materials pretreatment thereof B27N
• CPC Class Codes: C10G 1/065 in the presence of a solvent
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/4037 In-situ processes
• CPC Class Codes: C10G 2300/4081 Recycling aspects
• CPC Class Codes: C10G 3/42 Catalytic treatment
• CPC Class Codes: C10G 3/50 in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: C13K 1/02 obtained by saccharification of cellulosic materials manufacture of fodder A23K10/32
• CPC Class Codes: D21C 11/0028 Effluents derived from the washing or bleaching plants
• CPC Class Codes: Y02P 30/20 using bio-feedstock

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/hydrogenolysis/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

Claims

1. A method for selective removal of chlorine and phosphorus from a cellulosic biomass solids comprising:

a. providing a detrimental species-containing cellulosic biomass solids;

b. introducing said detrimental species-containing cellulosic biomass solids from an inlet into a treatment vessel, said cellulosic biomass solids having a true interstitial volume in said vessel;

c. introducing a base solution having a pH of greater than 9 from an inlet to said cellulosic biomass solids containing vessel at a temperature in the range of 0°

C. to 60°

C. in an amount to fill at least about 5% bed volume to at most about 40% bed volume of said true interstitial volume;

d. subsequently to step c, introducing an aqueous solution having a pH of at most 8 from an inlet to said basic cellulosic biomass solids-containing vessel, thereby producing washed cellulosic biomass solids having reduced detrimental species content compared to the detrimental species-containing cellulosic biomass solids and a 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 detrimental species-containing cellulosic biomass solids (dry basis);

e. introducing a removal stream comprising a gas stream or an organic solvent solution from an inlet to the vessel containing the washed cellulosic biomass solids thereby producing a pretreated cellulosic biomass solids with reduced water content compared to the water washed cellulosic biomass solids and an aqueous effluent;

f. discharging the pretreated cellulosic biomass solids from an outlet and transferring at least a portion of the discharged pretreated biomass solids to a digestion and/or reaction zone;

g. recycling at least a first portion of the aqueous effluent to produce base solution; and

h. recycling at least a second portion of the aqueous effluent as an aqueous solution.

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

3. The method of claim 2 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;

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.

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 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 form at least a portion of the aqueous solution.

8. 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).

9. The method of claim 2 wherein the loss of carbohydrate from the washing is less than 10% by weight, based on the carbohydrates present in the biomass (dry basis).