Process for manufacturing an upgraded bio-oil from black liquor
The present invention relates to a process for manufacturing an upgraded bio-oil derived from black liquor, comprising the following steps: —Providing black liquor, which comes from the pulp and paper manufacturing industry; —Subjecting black liquor to a pyrolysis treatment with formation of a pyrolyzed black liquor gas and a solid mass, which comprises char and salts; —Catalytic conversion of said pyrolyzed black liquor gas by contacting at least part of the latter with a bi-metallic modified zeolite catalyst with formation of the upgraded bio-oil, which comprises benzene, toluene, xylene (BTX), naphthalene and non-BTX products.
1. A process for manufacturing an upgraded bio-oil derived from a black liquor, comprising the following steps:
providing the black liquor;
subjecting the black liquor to a pyrolysis treatment and forming a pyrolyzed black liquor gas and a solid mass, wherein the solid mass comprises char and salts, and wherein the pyrolyzed black liquor gas comprises oxygenated compounds;
forming the upgraded bio-oil, which comprises benzene, toluene, xylene (BTX), naphthalene, and non-BTX products, through catalytic conversion of the pyrolyzed black liquor gas by contacting at least part of the pyrolyzed black liquor gas with a bi-metallic modified zeolite catalyst.
2. The process according to claim 1 , wherein a first metal of the bi-metallic modified zeolite catalyst is a transition metal selected from Group IIB of the periodic table and wherein a second metal of the bi-metallic modified zeolite catalyst consists of:
a. one metallic element selected from the Lanthanide series of the periodic table having an atomic number ranging from 57 to 60; or
b. a transition metal of Group IB of the periodic table; or
c. a transition metal of Group VIB of the periodic table.
3. The process according to claim 1 , wherein a zeolite has a silica alumina molar ratio from 5 to 300.
4. The process according to claim 1 , wherein a zeolite of the bi-metallic modified zeolite catalyst has an internal pore size distribution in the range of 4.5 to 12.
5. The process according to claim 1 , wherein said bi-metallic modified zeolite catalyst has a metal loading between 0.1-10 wt % on metal basis.
6. The process according to claim 1 , being an ex situ catalytic pyrolysis process, wherein said pyrolysis treatment is carried out in an upstream pyrolysis reactor and said catalytic conversion is performed in a downstream catalysis reactor.
7. The process according to claim 1 , wherein said pyrolysis treatment and/or said catalytic conversion is performed in an inert atmosphere.
8. The process according to claim 1 , wherein the pyrolysis treatment of black liquor is carried out at a temperature of 350° C. to 700° C.
9. The process according to claim 1 , wherein the catalytic conversion occurs at a temperature ranging from 200° C. and 1000° C.
10. The process according to claim 1 , wherein said black liquor is concentrated in a multistage evaporation process, in order to obtain a concentrated black liquor containing between 20 and 35 wt % of water.
11. The process according to claim 1 , wherein said black liquor derived from wood, which is selected from the group consisting of eucalyptus hardwood, southern hardwood, northern hardwood, northern softwood, southern softwood.
12. The process according to claim 1 , wherein said upgraded bio-oil has BTX/naphthalene weight ratio of up to 50.
13. The process according to claim 2 , wherein compounds or salts comprising said first metal and said second metal are both mixed and thereby incorporated into said zeolite.
14. The process according to claim 1 , wherein said catalytic conversion is performed until substantial deoxygenation of said upgraded bio-oil is reached.
15. The process according to claim 1 , wherein the first metal is zinc and the second metal is cerium.
16. The process according to claim 1 , wherein the first metal is zinc and the second metal is molybdenum.