Mixed oxide with improved reducibility

Patent metadata

Field	Value
Publication number	US-11964255-B2
Application number	US-201917278374-A
Country	US
Kind code	B2
Filing date	Sep 23, 2019
Priority date	Sep 24, 2018
Publication date	Apr 23, 2024
Grant date	Apr 23, 2024

Abstract

Disclosed are a mixed oxide composition based on zirconium and cerium exhibiting a high reducibility, the process for preparing it and its use in the field of catalysis.

First claim

The invention claimed is:

1. A mixed oxide comprising zirconium, cerium, lanthanum, iron, and optionally at least one rare-earth element other than cerium and lanthanum (RE), the mixed oxide having the composition:
between 18.0 wt % and 45.0 wt % of cerium;
between 1.0 wt % and 15.0 wt % of lanthanum;
up to 15.0 wt % of the rare-earth element(s) (RE(s)) other than cerium and lanthanum;
between 0.05 wt % and 0.25 wt % of iron;
the remainder as zirconium;
these proportions being given by weight of oxide relative to the mixed oxide as a whole, the mixed oxide exhibiting the following properties after calcination in air at 1100° C. for 4 hours:
a BET specific surface area of at least 25 m 2 /g;
a maximum reducibility temperature (T max ) of at most 530° C.

2. The mixed oxide according to claim 1 , further comprising hafnium.

3. The mixed oxide according to claim 2 , wherein the proportion of hafnium is less than or equal to 2.5 wt %, this proportion being given by weight of oxide relative to the mixed oxide as a whole.

4. The mixed oxide according to claim 1 , wherein the mixed oxide consists of or consists essentially of a combination of the oxides of zirconium, cerium, lanthanum, iron, optionally of at least one rare-earth element other than cerium and lanthanum, and optionally of hafnium, having the following composition:
between 18.0 wt % and 45.0 wt % of cerium;
between 1.0 wt % and 15.0 wt % of lanthanum;
up to 15.0 wt % of the rare-earth element(s) (RE(s)) other than cerium and lanthanum;
between 0.05 wt % and 0.25 wt % of iron;
between 0 and 2.5 wt % of hafnium;
the remainder as zirconium;
these proportions being given by weight of oxide relative to the mixed oxide as a whole, the mixed oxide exhibiting the following properties after calcination in air at 1100° C. for 4 hours:
a BET specific surface area of at least 25 m 2 /g;
a maximum reducibility temperature (T max ) of at most 530° C.

5. The mixed oxide according to claim 1 , wherein the elements Zr, Hf (if any), Ce, La, Fe and RE (if any) that constitute the mixed oxide are present in the mixed oxide as oxides or as oxides and also partially in the form of hydroxides or oxyhydroxides.

6. The mixed oxide according to claim 1 , wherein the proportion of cerium is between 18.0 wt % and 42.0 wt %.

7. The mixed oxide according to claim 1 , wherein the proportion of lanthanum is between 3.0 wt % and 12.0 wt %, or between 1.0 wt % and 7.0 wt %.

8. The mixed oxide according to claim 1 , wherein the total proportion of the rare-earth element(s) other than cerium and other than lanthanum is up to 10.0 wt % or at least 10.0 wt %.

9. The mixed oxide according to claim 8 , wherein the proportion of iron is greater than 0.15 wt %.

10. The mixed oxide according to claim 8 , wherein the mixed oxide comprises yttrium with a proportion of at least 10.0 wt %.

11. The mixed oxide according to claim 1 , wherein the mixed oxide has one of the following compositions C1-C3:
composition C1
between 18.0 wt % and 22.0 wt % of cerium;
between 3.0 wt % and 7.0 wt % of lanthanum;
between 3.0 wt % and 7.0 wt % of yttrium;
between 0.05 wt % and 0.25 wt % of iron;
the remainder as zirconium;
composition C2
between 28.0 wt % and 32.0 wt % of cerium;
between 3.0 wt % and 7.0 wt % of lanthanum;
between 3.0 wt % and 7.0 wt % of yttrium;
between 0.05 wt % and 0.25 wt % of iron;
the remainder as zirconium;
composition C3
between 38.0 wt % and 42.0 wt % of cerium;
between 3.0 wt % and 7.0 wt % of lanthanum;
between 3.0 wt % and 6.0 wt % of yttrium;
between 0.05 wt % and 0.25 wt % of iron;
the remainder as zirconium.

12. The mixed oxide according to claim 1 , wherein the proportion of iron is between 0.10 wt % and 0.20 wt % or strictly greater than 0.10 wt % (>0.10 wt %).

13. The mixed oxide according to claim 1 , wherein the proportion of zirconium is at least 45.0 wt %.

14. The mixed oxide according to claim 1 , comprising an amount of Na in the mixed oxide less than 150 ppm, or an amount of Na in the mixed oxide comprised between 10 ppm and 150 ppm, this amount being given by weight (ppm) and relative to the mixed oxide as a whole.

15. The mixed oxide according to claim 1 , comprising an amount of C1 in the mixed oxide lower than 100 ppm, or an amount of C1 in the mixed oxide comprised between 1 ppm and 100 ppm, this amount being given by weight (ppm) and relative to the mixed oxide as a whole.

16. The mixed oxide according to claim 1 , wherein the mixed oxide exhibits after calcination in air at 1000° C. for 4 hours, a BET specific surface area of at least 50 m 2 /g, a total consumption of hydrogen (V H2 ) of at least 17 mL/g mixed oxide, this volume being determined between 200° C. and 800° C., or a total pore volume (TPV) which is between 0.20 and 0.40 mL/g, the total pore volume being measured by N 2 porosimetry.

17. The mixed oxide according to claim 1 , wherein T max is between 460° C. and 530° C.

18. The mixed oxide according to claim 1 , wherein the mixed oxide exhibits a specific surface area which is at least 70 m 2 /g.

19. A composition comprising the mixed oxide according to claim 1 mixed with at least one mineral material.

20. The composition according to claim 19 , wherein the mineral material is selected from the group consisting of alumina, titanium oxide, cerium oxide, zirconium oxide, silica, spinels, zeolites, silicates, crystalline silico-aluminum phosphates and crystalline aluminum phosphates.

21. A catalytic converter for treating motor vehicle exhaust gases comprising a catalytically active coating layer formed from a composition according to claim 19 and deposited on a solid support.

Assignees

• Rhodia Operations

Inventors

• Ifrah Simon
• Bisson Laure Jeanne Simone
• Faure Benjamin
• Jorge Coelho Marques Rui Miguel
• Li Wei
• Zhu Ling

Classifications

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/56

  Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional [3D] monoliths · CPC title

• B01J21/066 Primary

  Zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• B01J6/001

  Calcining · CPC title