Nano-structured particles with high thermal stability
View Patent ↗This invention relates to a composition comprising nano-structured metal oxide particles (particularly, zirconia) and at least one stabilizing agent, a method to produce the composition, and a method to produce the thermally stable nano-structured particles. The method to produce the nano-structured particles comprises first preparing a base solution and a nanoparticle precursor solution, then combining these solutions at a final pH 7 or greater to precipitate a colloidal hydrous oxide. The colloidal hydrous oxide is then treated with at least one silicate, phosphate, or aluminum phosphate stabilizing agent and dried. These nano-structured particle products have high thermal stability and are particularly advantageous in applications as catalysts or catalyst supports that operate at high temperatures.
1. A composition comprised of nano-structured metal oxide particles and at least one stabilizing agent, wherein said nano-structured metal oxide particles have a surface area of greater than or equal to 50 m 2 /g, are comprised of primary particles in the size range of 5 nm to 50 nm and are mesoporous, having a pore size distribution between 2 nm and 30 nm, wherein said nano-structured metal oxide particles are thermally stable at a temperature of at least 600° C. for at least 6 hours, and wherein said stabilizing agent is selected from the group consisting of silicate, phosphate, and aluminum phosphate.
2. The composition of claim 1 , wherein said nano-structured metal oxide particles comprise zirconia.
3. The composition of claim 2 , wherein said primary particles are of a size between 5 and 20 nm, have a surface area of greater than or equal to 70 m 2 /g and have a pore size distribution of about 2 nm to about 20 nm.
4. The composition of claim 3 , wherein said nano-structured metal oxide particles have a tetragonal-to-monoclinic phase transition temperature of about 600° C. or greater.
5. The composition of claim 4 , wherein at least 90% of said nano-structured metal oxide particles are in tetragonal crystalline form.
6. A catalyst comprised of the composition of claim 1 and at least one active ingredient selected from the group consisting of sulfates, vanadates, molybdates, tungstates, silica, alumina, metal oxides, metal salts and metals.
7. A catalyst comprised of the composition of claim 2 and at least one active ingredient selected from the group consisting of sulfates, vanadates, molybdates, tungstates, alumina, silica, metal oxides, metal salts and metals.
8. A method of producing a composition comprised of nanoparticle and at least one stabilizing agent, said method comprising aging nanoparticle precursors in a liquid suspension at a temperature of greater than or equal to 60° C. while maintaining a pH of greater than or equal to pH 7 and adding at least one stabilizing agent selected from the group consisting of silicate, phosphate, and aluminum phosphate.
9. The method according to claim 8 , wherein said nanoparticle precursors comprise at least one oxide selected from the group consisting of zirconia, hafnia, titania, tin oxide, ceria, niobium oxide or tantalum oxide.
10. A method of producing thermally stable nano-structured particles comprising: (a) preparing a precursor solution comprised of nanoparticle precursors and a base solution; (b) precipitating a colloidal hydrous oxide by combining said precursor solution with said base solution at a final pH of pH 7 or greater; (c) treating said colloidal hydrous oxide with at least one stabilizing agent selected from the group consisting of silicate, phosphate, and aluminum phosphate to form treated particles; and (d) drying said treated particles to form dried particles.
11. The method according to claim 10 , further comprising calcining said dried particles to form calcined particles.
12. The method according to claim 11 , wherein said calcining is conducted at a temperature of at least 600° C.
13. The method according to claim 12 , wherein said calcined particles are thermally stable at a temperature of at least 600° C. for at least 6 hours.
14. The method according to claim 10 , wherein said nanoparticle precursors comprise a zirconium salt solution or an organic zirconium compound.
15. The method according to claim 10 , wherein the said colloidal hydrous oxide is treated at a temperature of at least 80° C. and a pH of at least pH 9.
16. The method according to claim 10 , wherein said colloidal hydrous oxide is treated in a sealed autoclave at a temperature in the range of 80° C. to 150° C.