Catalytic hydrothermal liquefaction for bio-oil production
Embodiments of a method for producing bio-oil include hydrothermal liquefaction of a biomass (e.g., a lignocellulosic biomass) feedstock to provide a process stream comprising crude oil and an aqueous fraction. The process stream is catalytically upgraded by contact with a sulfided-ruthenium catalyst, in the absence of added hydrogen, at a temperature and pressure effective to reduce an oxygen content of the crude oil, reduce a nitrogen content of the crude oil, reduce a total acid number of the crude oil, increase a H:C mole ratio of the crude oil, reduce a density of the crude oil, reduce a moisture content of the crude oil, reduce viscosity of the crude oil, or any combination thereof, thereby producing an upgraded oil and an upgraded aqueous fraction, which are subsequently separated. The catalytic upgrading process may be a plug-flow process and/or may be performed at or near liquefaction conditions.
1. A method for producing oil, comprising:
hydrothermally liquefying a lignocellulosic feedstock comprising (i) 5-30 wt % of a lignocellulosic biomass and (ii) water to produce a composition comprising a crude oil, an aqueous fraction, and inorganic solids;
separating the inorganic solids from the crude oil and the aqueous fraction to provide a process stream comprising the crude oil and the aqueous fraction;
contacting the process stream comprising the crude oil and the aqueous fraction with a sulfided-ruthenium catalyst, in the absence of added hydrogen, at an operating temperature and pressure effective to reduce an oxygen content of the crude oil, reduce a nitrogen content of the crude oil, reduce a total acid number of the crude oil, increase a H:C mole ratio of the crude oil, reduce a density of the crude oil, reduce a moisture content of the crude oil, reduce viscosity of the crude oil, or any combination thereof, thereby producing an upgraded oil and an upgraded aqueous fraction, wherein the sulfided-ruthenium catalyst comprises Ru, S, and a support, and has a Ru:S weight ratio within a range of from 10:1 to 25:1 prior to contact with the process stream; and
subsequently separating the upgraded oil and the upgraded aqueous fraction.
2. The method of claim 1 , wherein the sulfided-ruthenium catalyst comprises from 1-10 wt % ruthenium based on a combined mass of the ruthenium and the support.
3. The method of claim 2 , wherein contacting the process stream with the sulfided-ruthenium catalyst is performed at a liquid hourly space velocity, LHSV, of 0.5-30 hr −1 .
4. The method of claim 1 , wherein the support comprises partially graphitized carbon, activated carbon, rutile titania, or zirconia.
5. The method of claim 4 , wherein the support comprises partially graphitized carbon having a graphite structure content within a range of from 50 to 95 wt %.
6. The method of claim 1 , wherein contacting the process stream with the sulfided-ruthenium catalyst is performed at an operating temperature within a range of from 250° C. to 364° C.
7. The method of claim 6 , wherein contacting the process stream with the sulfided-ruthenium catalyst is performed at a pressure sufficient to maintain the process stream in liquid phase without forming a supercritical fluid.
8. The method of claim 7 , wherein the pressure is within a range of from 2.5 MPa to 4.5 MPa greater than a vapor pressure of the process stream at the operating temperature.
9. The method of claim 1 , wherein contacting the process stream with the sulfided-ruthenium catalyst is performed at an operating temperature within a range of from 340° C. to 360° C. and a pressure within a range of from 18 MPa to 22 MPa.
10. The method of claim 1 , wherein the method is a plug-flow process.
11. The method of claim 1 , wherein the lignocellulosic biomass comprises 20-40 wt % lignin based on the dry matter mass of the lignocellulosic biomass.
12. The method of claim 1 , wherein the lignocellulosic biomass comprises ≤1.5 wt % sulfur based on the dry matter mass of the lignocellulosic biomass.
13. The method of claim 1 , wherein the lignocellulosic feedstock comprises from 1 ppm to 1,000 ppm sulfur by weight.
14. The method of claim 1 , further comprising exposing a ruthenium catalyst to an aqueous solution comprising a sulfate salt, in the absence of added hydrogen, to produce the sulfided ruthenium catalyst.
15. The method of claim 14 , wherein the aqueous solution comprises from 100 ppm to 1000 ppm sulfate.
16. The method of claim 14 , wherein the ruthenium catalyst is exposed to the aqueous solution at an operating temperature within a range of from 250° C. to 364° C.
17. The method of claim 16 , wherein the ruthenium catalyst is exposed to the aqueous solution at a pressure that maintains the aqueous solution in liquid phase at the operating temperature without forming a supercritical fluid.
18. The method of claim 1 , wherein hydrothermally liquefying the lignocellulosic feedstock comprises subjecting the lignocellulosic feedstock to an effective liquefaction temperature and liquefaction pressure to thermally depolymerize organic constituents of the lignocellulosic biomass.
19. The method of claim 18 , wherein the effective liquefaction temperature is within a range of 250-364° C. and the effective liquefaction pressure is greater than a vapor pressure of the lignocellulosic feedstock at the effective liquefaction temperature.