Biomass treatment for hydrothermal hydrocatalytic conversion

• US 9,593,388 B2
• Filed: 12/18/2014
• Issued: 03/14/2017
• Est. Priority Date: 12/18/2013
• Status: Expired due to Fees

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Powell, Joseph Broun, Chheda, Juben Nemchand
• Primary Examiner(s): Mayes, Melvin C
• Assistant Examiner(s): CALL, DOUGLAS BRYANT
• Application Number:
  US14/574,971
• Publication Number:
  US 20150166682A1
• Time in Patent Office: 817 Days
• US Class Current: 1/1
• 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 2300/205 Metal content
• 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: Y02P 30/20 using bio-feedstock

Abstract

A selective removal of metal and its anion species 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 a detrimental metals and their anion species 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 to provide a bed of detrimental species-containing cellulosic biomass solids in said vessel, wherein said bed of cellulosic biomass solids has an interstitial volume that is the amount of liquid added to just cover the top of said bed of cellulosic biomass solids when the biomass solids are saturated with liquid;

c. introducing an acidic solution having a pH of at most 4 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% to at most about 40% of said interstitial volume;

d. subsequently to step c, introducing an aqueous solution having a pH of at least 5 from an inlet to said acidic 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 an acidic water effluent, wherein said acidic 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 acidic 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 acidic solution comprises an inorganic acid.

3. The method of claim 2 wherein the inorganic acid is nitric acid.

4. The method of claim 3 wherein the nitric acid is present in an amount of 0.01 wt % to 1 wt % based on the acidic solution.

5. The method of claim 2 wherein the inorganic acid is a phosphoric acid.

6. The method of claim 5 wherein the phosphoric acid is present in an amount of 0.01 wt % to 1 wt % based on the acidic solution.

7. The method of claim 2 wherein the inorganic acid is sulfuric acid.

8. The method of claim 7 wherein the sulfuric acid is present in an amount of 0.01 wt % to 1 wt % based on the acidic solution.

9. The method of claim 1 wherein the acidic solution comprises a carboxylic acid.

10. The method of claim 9 wherein the carboxylic acid is selected from the group consisting of acetic acid, levulinic acid, lactic acid, formic acid, propionic acid, and mixtures thereof.

11. The method of claim 9 wherein the carboxylic acid is present in an amount of 0.1 wt % to 5 wt % based on the acidic solution.

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

13. 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.

14. The method of claim 13 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.

15. The method of claim 1 wherein the inlet of steps c, d, and e are the same inlet.

16. The method of claim 1 wherein the inlet of step c and step e are a different inlet.

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).

18. A method for selective removal of a detrimental metals and their anion species 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 to provide a bed of detrimental species-containing cellulosic biomass solids in said vessel, wherein said bed of cellulosic biomass solids has an interstitial volume that is the amount of liquid added to just cover the top of said bed of cellulosic biomass solids when the biomass solids are saturated with liquid;

c. introducing an acidic solution having a pH of at most 4 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% to at most about 40% of said interstitial volume;

d. subsequently to step c, introducing an aqueous solution having a pH of at least 5 from an inlet to said acidic 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 an acidic water effluent;

e. introducing a base solution having a pH of at least 9 from an inlet to said washed 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% to at most about 40% of said interstitial volume;

f. subsequently to step e, introducing an aqueous solution having a pH of at most 8 from an inlet to said basic cellulosic biomass solids-containing vessel, thereby producing second washed cellulosic biomass solids having reduced detrimental species content compared to the detrimental species-containing cellulosic biomass solids and an basic water effluent;

g. wherein the combined amount of said acidic water effluent and 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)

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

i. 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;

j. recycling at least a first portion of the aqueous effluent to produce acidic solution;

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

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

19. The method of claim 18 wherein the base solution comprises a base selected from sodium hydroxide, potassium hydroxide or ammonia.

20. The method of claim 18 wherein the acidic solution comprises an inorganic acid or an organic acid.

21. The method of claim 18 wherein the organic solvent is a solvent used in the digestion and/or reaction zone.

22. The method of claim 18 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.

23. The method of claim 22 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.

24. The method of claim 18 wherein the inlet of steps c, d, e, f and h are the same inlet.

25. The method of claim 18 wherein the inlet of step c and step h are a different inlet.

26. The method of claim 18 wherein the loss of carbohydrate from the washing is less than 10% by weight, based on the carbohydrates present in the biomass (dry basis).

27. A method for selective removal of a detrimental metals and their anion species 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 to provide a bed of detrimental species-containing cellulosic biomass solids in said vessel, wherein said bed of cellulosic biomass solids has an interstitial volume that is the amount of liquid added to just cover the top of said bed of cellulosic biomass solids when the biomass solids are saturated with liquid;

c. introducing a base solution having a pH of at least 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% to at most about 40% of said 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 an basic water effluent;

e. introducing an acidic solution having a pH of at most 4 from an inlet to said washed 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% to at most about 40% of said interstitial volume;

f. subsequently to step e, introducing an aqueous solution having a pH of at least 5 from an inlet to said acidic cellulosic biomass solids-containing vessel, thereby producing second washed cellulosic biomass solids having reduced detrimental species content compared to the detrimental species-containing cellulosic biomass solids and an acidic water effluent;

g. wherein the combined amount of said acidic water effluent and 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)

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

i. 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;

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

k. recycling at least a first portion of the second aqueous effluent to produce acidic solution; and

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

28. The method of claim 27 wherein the base solution comprises a base selected from sodium hydroxide, potassium hydroxide or ammonia.

29. The method of claim 27 wherein the acidic solution comprises an inorganic acid or an organic acid.

30. The method of claim 27 wherein the organic solvent is a solvent used in the digestion and/or reaction zone.

31. The method of claim 27 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.

32. The method of claim 31 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.

33. The method of claim 27 wherein the inlet of steps c, d, e, f and h are the same inlet.

34. The method of claim 27 wherein the inlet of step c and step h are a different inlet.

35. The method of claim 27 wherein the loss of carbohydrate from the washing is less than 10% by weight, based on the carbohydrates present in the biomass (dry basis).