Catalysts for thermo-catalytic conversion of biomass, and methods of making and using
View Patent ↗Disclosed are catalyst compositions including zeolite and silica components, methods of making, and processes of using in the thermo-catalytic conversion of biomass. Such disclosed methods of making include: i) spray drying of the catalyst precursor slurry at a pH below 1, or ii) the removal of ions such as sodium from the binder material prior to spray drying the catalyst precursor slurry at a pH below 2.7, or iii) spray drying the catalyst precursor including a pore regulating agent followed by steam treating, or iv) some combination of i), ii) and iii).
1. A method of making a biomass conversion catalyst comprising:
a) preparing an aqueous slurry comprising a phosphorous-promoted zeolite and a silica precursor, wherein the zeolite is selected from the group consisting of ZSM-5, mordenite, beta, ferrierite, zeolite-Y, and combinations thereof;
b) spray drying said aqueous slurry at a pH equal to or less than about 2.7, thereby gelling said silica precursor and forming a biomass conversion catalyst in the form of particles;
c) wet impregnating the biomass conversion catalyst with phosphorous; and
d) drying the wet impregnated biomass conversion catalyst, forming a phosphorous-promoted biomass conversion catalyst.
2. The method of claim 1 wherein said aqueous slurry further comprises a clay; said zeolite is ZSM-5; and said silica precursor is at least one of silicic acid and polysilicic acid.
3. The method of claim 2 wherein said clay is kaolin, and said biomass conversion catalyst is free of or substantially free of amorphous alumina.
4. The method of claim 2 wherein said particles have: i) an average pore volume of pores ranging in diameter from about 80 to about 600 Å of at least about 0.025 cm 3 /g, and ii) an average pore volume of pores ranging in diameter from about 20 to about 80 Å of no more than about 0.08 cm 3 /g; wherein each of said average pore volumes in i) and ii) are obtained from the adsorption branch of the nitrogen isotherm, when measured per ASTM method D4222 at about 77° K, and discretized according to the BJH pore size distribution model.
5. A method of making a biomass conversion catalyst comprising:
a) preparing an aqueous slurry comprising: (i) a phosphorous-promoted zeolite, wherein the zeolite is selected from the group consisting of ZSM-5, mordenite, beta, ferrierite, zeolite-Y, and combinations thereof, (ii) a silica precursor which is substantially sodium free, and (iii) a pore regulating agent selected from the group consisting of ionic pore regulating agents, nonionic pore regulating agents, and combinations thereof;
b) spray drying said aqueous slurry at a pH equal to or less than about 2.7, thereby gelling said silica precursor and forming said biomass conversion catalyst into particles; wherein said particles have an average mesopore surface area (average MSA) less than or equal to about 50 m 2 /g, and wherein said biomass conversion catalyst has a salt concentration less than about 0.1 times the mass of said silica; and
c) promoting the biomass conversion catalyst with phosphorous.
6. The method of claim 5 wherein said aqueous slurry further comprises a clay; said zeolite is ZSM-5; said silica precursor is at least one of silicic acid and polysilicic acid; and wherein said biomass conversion catalyst is free of or substantially free of amorphous alumina.
7. The method of claim 5 wherein, prior to step a), a ZSM-5 material is treated with a phosphorous-containing compound to form a phosphorous promoted ZSM-5 which is used as said zeolite in said aqueous slurry.
8. The method of claim 5 wherein said particles have: i) an average pore volume of pores ranging in diameter from about 80 to about 600 Å of no more than about 0.020 cm 3 /g, and ii) an average pore volume of pores ranging in diameter from about 20 to about 80 Å of no more than about 0.010 cm 3 /g; wherein each of said average pore volumes in i) and ii) are obtained from the adsorption branch of the nitrogen isotherm, when measured per ASTM method D4222 at about 77° K, and discretized according to the BJH pore size distribution model.
9. The method of claim 5 wherein said aqueous slurry is spray dried in step b) at a pH equal to or less than about 1, thereby gelling said silica precursor and forming said biomass conversion catalyst into particles.
10. The method of claim 9 wherein said particles have: i) an average pore volume of pores ranging in diameter from about 80 to about 600 Å of at least about 0.01 cm 3 /g, and ii) an average pore volume of pores ranging in diameter from about 20 to about 80 Å of no more than about 0.03 cm 3 /g; wherein each of said average pore volumes in i) and ii) are obtained from the adsorption branch of the nitrogen isotherm, when measured per ASTM method D4222 at about 77° K, and discretized according to the BJH pore size distribution model.
11. The method of claim 9 wherein said aqueous slurry further comprises a clay; said zeolite is ZSM-5; and said silica precursor is at least one of silicic acid and polysilicic acid.
12. The method of claim 9 wherein, prior to step a), a ZSM-5 material is treated with a phosphorous-containing compound to form a phosphorous promoted ZSM-5 which is used as said zeolite in said aqueous slurry.
13. The method of claim 9 wherein following said spray drying step said biomass conversion catalyst is promoted with phosphorous.