Inorganic composite oxides and methods of making the same

Patent metadata

Field	Value
Publication number	US-10239045-B2
Application number	US-201415106486-A
Country	US
Kind code	B2
Filing date	Dec 23, 2014
Priority date	Dec 23, 2013
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

Described herein are methods for forming inorganic composite oxides. Such methods include combining, at a substantially constant pH of between about 5 and about 6.75 over a period of at least about 5 minutes, an acidic precursor composition and a basic composition to form a precipitate composition, wherein the acidic precursor composition comprises an alumina precursor, a ceria precursor, a zirconia precursor and optionally one or more dopant precursors; stabilizing the precipitate by increasing the pH of the precipitate composition to between about 8 and about 10; and calcining the stabilized precipitate to form an inorganic composite oxide. Also described are inorganic composite oxides formed using such methods.

First claim

We claim:

1. A method for forming an inorganic composite oxide, the method comprising:
combining, at a substantially constant pH of between about 5 and about 6.75 over a period of at least about 5 minutes, an acidic precursor composition and a basic composition to form a precipitate composition, wherein the acidic precursor composition comprises an alumina precursor, a ceria precursor, a zirconia precursor and optionally one or more dopant precursors;
stabilizing the precipitate by increasing the pH of the precipitate composition to between about 8 and about 10; and
calcining the stabilized precipitate to form an inorganic composite oxide.

2. The method according to claim 1 , wherein the substantially constant pH is maintained by (a) controlling a flow rate of the acidic precursor composition, the basic composition or both or (b) controlling a concentration of the acidic precursor composition, the basic composition or both or (c) controlling a flow rate and a concentration of the acidic precursor composition, the basic composition or both.

3. The method according to claim 1 , wherein the acidic precursor composition and the basic composition are combined at a substantially constant pH of between about 5.5 and about 6.5 over a period of between about 30 and about 90 minutes.

4. The method according to claim 1 , wherein the acidic precursor composition and the basic composition are combined at a substantially constant pH of about 6.5 over a period of between about 30 and about 90 minutes.

5. The method according to claim 1 , wherein the pH of the precipitate composition in the combining step does not vary by more than about 0.25.

6. The method according to claim 1 , wherein the pH of the precipitate composition in the combining step does not vary by more than about 0.1.

7. The method according to claim 1 , wherein the acidic precursor composition and the basic composition are combined at a temperature of between about 50° C. and about 200° C.

8. The method according to claim 1 , wherein the precipitate is stabilized by increasing the pH of the precipitate composition to between about 8 and about 9.

9. The method according to claim 1 , further comprising heating the precipitate composition to a temperature of between about 50° C. and about 200° C. for a period of time of between about 15 minutes and about 6 hours.

10. The method according to claim 1 , wherein the precipitate is calcined at a temperature between about 600 and about 1100° C. for a time period of between about 2 and about 4 hours.

11. The method according to claim 1 , wherein the precursor composition comprises one or more dopant precursors selected from yttrium precursor, lanthanum precursor, neodymium precursor, praseodymium precursor, gadolinium precursor, or mixtures thereof.

12. The method according to claim 1 , wherein the inorganic composite oxide has, after calcining at 900° C. for 2 hours, a BET surface area of at least about 70 m 2 /g, a pore volume of at least about 0.45 cm 3 /g, or both.

13. The method according to claim 1 , wherein the inorganic composite oxide, after aging at 1200° C. for 5 hours, exhibits minimal ceria-zirconia phase separation as measured by the absence of peak splitting in XRD.

14. The method according to claim 1 , wherein the inorganic composite oxide has, after aging at 1100° C. for 5 hours, a surface area of at least about 30 m 2 /g, ceria-zirconia crystallites with a crystallite size of less than about 16 nm, or both.

15. The method according to claim 1 , wherein the inorganic composite oxide exhibits, after calcination at 900° C. for 2 hours, a maximum reducibility temperature of less than about 570° C., as measured by TPR with a 10° C./min temperature rise in a 30 mL/minute flow of 10% H 2 in argon.

16. The method according to claim 1 , wherein the inorganic composite oxide exhibits, after calcination at 900° C. for 2 hours, an onset of ceria reducibility at a temperature of less than about 300° C., as measured by TPR with a 10° C./min temperature rise in a 30 mL/minute flow of 10% H 2 in argon.

17. The method according to claim 1 , wherein the inorganic composite oxide exhibits, after calcination at 900° C. for 2 hours, a half-maximal TPR width measurement of less than about 75° C., as measured by TPR with a 10° C./min temperature rise in a 30 mL/minute flow of 10% H 2 in argon.

18. The method according to claim 1 , wherein the inorganic composite oxide exhibits, after calcination at 900° C. for 2 hours, an absolute ceria reducibility of at least about 75%, as measured by TPR with a 10° C./min temperature rise in a 30 mL/minute flow of 10% H 2 in argon.

19. The method according to claim 1 , wherein the inorganic composite oxide exhibits, after calcination at 900° C. for 2 hours, an absolute ceria reducibility of at least about 85%, as measured by TPR with a 10° C./min temperature rise in a 30 mL/minute flow of 10% H 2 in argon.

Assignees

• Rhodia Operations

Inventors

• Zhao Qiang
• Southward Barry W L
• Francis Francis
• Ocampo Fabien

Classifications

• B01J37/03

  Precipitation; Co-precipitation · CPC title

• B01J23/10 Primary

  of rare earths · CPC title

• B01J21/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• C04B2235/3227

  Lanthanum oxide or oxide-forming salts thereof · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title