Method for Direct Liquefaction of Biomass

• US 20180142162A1
• Filed: 11/20/2017
• Published: 05/24/2018
• Est. Priority Date: 11/21/2016
• Status: Active Application

• Current Assignee: Beijing Huashi United Energy Technology and Development Co., Ltd .
• Original Assignee: Beijing Huashi United Energy Technology and Development Co., Ltd .
• Inventors: LIN, Ke, LI, Lin, GUO, Lixin, CUI, Yongjun, JIANG, Lilong
• Granted Patent: US 10,260,004 B2
• Time in Patent Office: Days
• CPC Class Codes: B01D 3/10 Vacuum distillation B01D3/12 takes precedence
• CPC Class Codes: B01D 3/143 by two or more of a fractionation, separation or rectification step
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• 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 2300/42 Hydrogen of special source or of special composition
• CPC Class Codes: C10G 2300/44 Solvents
• CPC Class Codes: C10G 45/00 Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• CPC Class Codes: C10G 7/00 Distillation of hydrocarbon oils
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

The present invention discloses a method for direct liquefaction of biomass. The method comprises the following steps: (1) mixing a biomass, a hydrogenation catalyst and a hydrogen-donor solvent to prepare a biomass slurry; (2) carrying out a first liquefaction reaction with the biomass slurry and hydrogen gas to obtain a first reaction product; (3) carrying out a second liquefaction reaction with the first reaction product and hydrogen gas to obtain a second reaction product; (4) subjecting the second reaction product to a first gas-liquid separation at a temperature of 290-460 DEG C. to produce a first liquid phase and a first gas phase; (5) subjecting the first gas phase to a second gas-liquid separation at a temperature of 30-60 DEG C. to obtain a second liquid phase, and mixing the first liquid phase with the second liquid phase to obtain a liquid phase mixture; (6) carrying out a first distillation on the liquid phase mixture to obtain a light fraction and a heavy fraction; and (7) carrying out a second distillation on the heavy fraction to separate out a distillate oil and a residue, wherein the light fraction and the distillate oil are final liquid of the liquefaction. By utilizing the method for direct liquefaction of biomass, the obtained final liquid has a high yield and a low solid content of residue.

Claims

1. A method for direct liquefaction of biomass, comprising the following steps:

(1) mixing a biomass, a hydrogenation catalyst and a hydrogen-donor solvent to prepare a biomass slurry;

(2) carrying out a first liquefaction reaction with the biomass slurry and hydrogen gas to obtain a first reaction product;

(3) carrying out a second liquefaction reaction with the first reaction product and hydrogen gas to obtain a second reaction product;

(4) subjecting the second reaction product to a first gas-liquid separation at a temperature of 290-460 DEG C. to produce a first liquid phase and a first gas phase;

(5) subjecting the first gas phase to a second gas-liquid separation at a temperature of 30-60 DEG C. to obtain a second liquid phase, and mixing the first liquid phase with the second liquid phase to obtain a liquid phase mixture;

(6) carrying out a first distillation on the liquid phase mixture to obtain a light fraction and a heavy fraction; and

(7) carrying out a second distillation on the heavy fraction to separate out a distillate oil and a residue, wherein the light fraction and the distillate oil are final liquid of the liquefaction.

2. The method according to claim 1, wherein the step (1) comprises the following steps:

(a) drying the biomass to obtain a dried biomass, and crushing the dried biomass to obtain a crushed material;

(b) mixing the crushed material with the hydrogenation catalyst to obtain a mixture; and

(c) mixing the mixture with the hydrogen-donor solvent to prepare the biomass slurry.

3. The method according to claim 1, wherein in the step (1), a mass ratio of the biomass to the hydrogenation catalyst is 100:

(1-5);

the crushed material has a particle size of 5-2000 microns;

the hydrogenation catalyst has a particle size of 10-20 microns; and

the hydrogenation catalyst comprises at least one selected from a group consisting of the following catalysts;

(1) amorphous iron oxide and/or amorphous iron oxide hydroxide; and

(2) amorphous alumina loading an active component, wherein the active component comprises at least one selected from oxides of metals of group VIB, group VIIB and group VIII, and the active component has a content of 10-25 wt %.

4. The method according to claim 1, wherein in the step (2), reaction conditions for the first liquefaction reaction are as follows:

a reaction temperature is 300-470 DEG C.;

a reaction pressure is 13-25 MPa;

a gas-liquid ratio is 800-1500 NL/kg; and

a space velocity of the biomass slurry is 0.3-2 t/m³·

h.

5. The method according to claim 1, wherein in the step (3), reaction conditions for the second liquefaction reaction are as follows:

a reaction temperature is 300-470 DEG C.;

a reaction pressure is 13-25 MPa;

a gas-liquid ratio is 800-1500 NL/kg; and

a space velocity of the biomass slurry is 0.3-2 t/m³·

h.

6. The method according to claim 1, wherein in the step (6), the first distillation is carried out at a temperature of 260-400 DEG C. under a pressure of 0.1-0.7 MPa;

and

in the step (6), the second distillation is carried out at a temperature of 300-400 DEG C. under a pressure of 5-20 kPa.

7. The method according to claim 1, wherein the step (5) further comprises steps of collecting a second gas phase obtained after the second gas-liquid separation, mixing the second gas phase with the hydrogen gas in the step (2) and/or the step (3) to obtain a gas mixture, and introducing the gas mixture into a reaction system.

8. The method according to claim 1, further comprising steps of carrying out a hydrogenation reaction on the final liquid to obtain a hydrogenation product, and subjecting the hydrogenation product to a fractionation operation to obtain a light oil and a heavy oil;

and returning the heavy oil to the step (1) to be used as the hydrogen-donor solvent.

9. The method according to claim 8, wherein reaction conditions for the hydrogenation reaction are as follows:

a reaction temperature is 300-430 DEG C.;

a reaction pressure is 13-25 MPa;

a gas-liquid ratio is 800-1500 NL/kg;

a space velocity is 0.5-2 h<sup>−

1</sup>; and

the fractionation is carried out at a temperature of 280-390 DEG C.

10. The method according to claim 8, wherein before subjecting the hydrogenation product to the fractionation operation, further comprising steps of subjecting the hydrogenation product to a third gas-liquid separation to obtain a third gas phase and a third liquid phase;

and mixing the third gas phase with the hydrogen gas in the step (2) and/or the step (3) to obtain a gas mixture, and introducing the gas mixture into the reaction system, or discharging the third gas phase to the outside, and subjecting the third liquid phase to the fractionation operation.

11. The method according to claim 2, wherein in the step (1), a mass ratio of the biomass to the hydrogenation catalyst is 100:

(1-5);

the crushed material has a particle size of 5-2000 microns;

the hydrogenation catalyst has a particle size of 10-20 microns; and

the hydrogenation catalyst comprises at least one selected from a group consisting of the following catalysts;

(1) amorphous iron oxide and/or amorphous iron oxide hydroxide; and

(2) amorphous alumina loading an active component, wherein the active component comprises at least one selected from oxides of metals of group VIB, group VIIB and group VIII, and the active component has a content of 10-25 wt %.

12. The method according to claim 2, wherein in the step (2), reaction conditions for the first liquefaction reaction are as follows:

a reaction temperature is 300-470 DEG C.;

a reaction pressure is 13-25 MPa;

a gas-liquid ratio is 800-1500 NL/kg; and

a space velocity of the biomass slurry is 0.3-2 t/m³·

h.

13. The method according to claim 3, wherein in the step (2), reaction conditions for the first liquefaction reaction are as follows:

a reaction temperature is 300-470 DEG C.;

a reaction pressure is 13-25 MPa;

a gas-liquid ratio is 800-1500 NL/kg; and

a space velocity of the biomass slurry is 0.3-2 t/m³·

h.

14. The method according to claim 2, wherein in the step (3), reaction conditions for the second liquefaction reaction are as follows:

a reaction temperature is 300-470 DEG C.;

a reaction pressure is 13-25 MPa;

a gas-liquid ratio is 800-1500 NL/kg; and

a space velocity of the biomass slurry is 0.3-2 t/m³·

h.

15. The method according to claim 3, wherein in the step (3), reaction conditions for the second liquefaction reaction are as follows:

a reaction temperature is 300-470 DEG C.;

a reaction pressure is 13-25 MPa;

a gas-liquid ratio is 800-1500 NL/kg; and

a space velocity of the biomass slurry is 0.3-2 t/m³·

h.

16. The method according to claim 4, wherein in the step (3), reaction conditions for the second liquefaction reaction are as follows:

a reaction temperature is 300-470 DEG C.;

a reaction pressure is 13-25 MPa;

a gas-liquid ratio is 800-1500 NL/kg; and

a space velocity of the biomass slurry is 0.3-2 t/m³·

h.

17. The method according to claim 2, wherein in the step (6), the first distillation is carried out at a temperature of 260-400 DEG C. under a pressure of 0.1-0.7 MPa;

and

in the step (6), the second distillation is carried out at a temperature of 300-400 DEG C. under a pressure of 5-20 kPa.

18. The method according to claim 3, wherein in the step (6), the first distillation is carried out at a temperature of 260-400 DEG C. under a pressure of 0.1-0.7 MPa;

and in the step (6), the second distillation is carried out at a temperature of 300-400 DEG C. under a pressure of 5-20 kPa.

19. The method according to claim 2, wherein the step (5) further comprises steps of collecting a second gas phase obtained after the second gas-liquid separation, mixing the second gas phase with the hydrogen gas in the step (2) and/or the step (3) to obtain a gas mixture, and introducing the gas mixture into a reaction system.

20. The method according to claim 2, further comprising steps of carrying out a hydrogenation reaction on the final liquid to obtain a hydrogenation product, and subjecting the hydrogenation product to a fractionation operation to obtain a light oil and a heavy oil;

and returning the heavy oil to the step (1) to be used as the hydrogen-donor solvent.