Catalyst support for purification of exhaust gas, catalyst for purification of exhaust gas using the same, and method for producing the catalyst support for purification of exhaust gas

Patent metadata

Field	Value
Publication number	US-9409152-B2
Application number	US-201314410345-A
Country	US
Kind code	B2
Filing date	Jun 20, 2013
Priority date	Jun 20, 2012
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

Abstract

A catalyst support for purification of exhaust gas includes a porous composite metal oxide, the porous composite metal oxide containing alumina, ceria, and zirconia and having an alumina content ratio of from 5 to 80% by mass, wherein after calcination in the air at 1100° C. for 5 hours, the porous composite metal oxide satisfies a condition such that standard deviations of content ratios (as at % unit) of aluminum, cerium and zirconium elements are each 19 or less with respect to 100 minute areas (with one minute area being 300 nm in length×330 nm in width) of the porous composite metal oxide, the standard deviation being determined by energy dispersive X-ray spectroscopy using a scanning transmission electron microscope equipped with a spherical aberration corrector.

First claim

The invention claimed is:

1. A catalyst support for purification of exhaust gas comprising a porous composite metal oxide, the porous composite metal oxide containing alumina, ceria, and zirconia and having an alumina content ratio of from 5 to 80% by mass,
wherein the porous composite metal oxide is produced by:
introducing independently a first raw material solution and a second raw material solution directly into a region in which a shear rate is from 1000 to 200000 sec −1 , and homogeneously mixing the raw material solutions to obtain a colloidal solution of metal compounds, the first raw material solution containing an aluminum ion, a cerium ion, and a zirconium ion, and the second raw material solution containing a high-molecular dispersant having a weight average molecular weight of from 3000 to 15000,
adjusting a pH of the colloidal solution to between 3 and 5,
degreasing the colloidal solution after the pH adjustment or a suspension of metal compounds which is obtained by adding an organic amine to the colloidal solution after the pH adjustment, and then
subjecting the solution or the suspension to heat treatment at from 700 to 1050° C. in an oxidizing atmosphere, to obtain the porous composite metal oxide, and
wherein after calcination in air at 1100° C. for 5 hours, the porous composite metal oxide satisfies a condition such that standard deviations of content ratios (as at % unit) of aluminum, cerium and zirconium elements are each 19 or less with respect to 100 minute areas (with one minute area being 300 nm in length×330 nm in width) of the porous composite metal oxide, the standard deviation being determined by energy dispersive X-ray spectroscopy using a scanning transmission electron microscope equipped with a spherical aberration corrector.

2. The catalyst support for purification of exhaust gas according to claim 1 , wherein
the porous composite metal oxide after calcination in air at 1100° C. for 5 hours satisfies conditions such that
a total pore volume of pores having pore diameters within a range of from 1 nm to 0.1 μm is 0.1 cm 3 /g or more, the pore diameter being determined by a nitrogen adsorption method, and
a total pore volume of pores having pore diameters within a range of from 0.1 μm to 10 μm is 0.1 cm 3 /g or more, the pore diameter being determined by a mercury intrusion method.

3. The catalyst support for purification of exhaust gas according to claim 1 , wherein
the porous composite metal oxide after calcination in air at 1100° C. for 5 hours satisfies a condition such that a BET specific surface area determined by a nitrogen adsorption method is 2 m 2 /g or more.

4. The catalyst support for purification of exhaust gas according to claim 1 , wherein
the porous composite metal oxide after calcination in air at 1100° C. for 5 hours satisfies a condition such that standard deviations of content ratios (as at % unit) of aluminum, cerium and zirconium elements are each 18.5 or less with respect to the 100 minute areas, the standard deviation being determined by the energy dispersive X-ray spectroscopy.

5. A catalyst for purification of exhaust gas comprising:
the catalyst support for purification of exhaust gas according to claim 4 ; and
a noble metal supported on the catalyst support, wherein the porous composite metal oxide contains from 5 to 30% by mass of alumina, from 25 to 39% by mass of ceria, and from 33 to 51% by mass of zirconia.

6. The catalyst for purification of exhaust gas according to claim 5 , wherein
the noble metal is palladium.

7. The catalyst support for purification of exhaust gas according to claim 1 , wherein
the porous composite metal oxide after calcination in air at 1100° C. for 5 hours satisfies a condition such that standard deviations of content ratios (as at% unit) of cerium and zirconium elements are each 15 or less with respect to the 100 minute areas, the standard deviation being determined by the energy dispersive X-ray spectroscopy.

8. A catalyst for purification of exhaust gas comprising:
the catalyst support for purification of exhaust gas according to claim 1 ; and
a transition metal supported on the catalyst support, wherein the porous composite metal oxide contains from 30 to 80% by mass of alumina.

9. The catalyst for purification of exhaust gas according to claim 8 , wherein
the transition metal is copper.

10. A method for producing a catalyst support for purification of exhaust gas comprising a porous composite metal oxide containing alumina, ceria, and zirconia, the method comprising the steps of:
preparing a first raw material solution containing an aluminum ion, a cerium ion, and a zirconium ion so that an alumina content ratio of the porous composite metal oxide can be from 5 to 80% by mass;
preparing a second raw solution containing a high-molecular dispersant having a weight average molecular weight of from 3000 to 15000;
introducing independently the first raw material solution and the second raw material solution directly into a region in which a shear rate is from 1000 to 200000 sec −1 , and homogeneously mixing the raw material solutions to obtain a colloidal solution of metal compounds;
adjusting a pH of the colloidal solution to between 3 and 5; and
degreasing the colloidal solution after the pH adjustment and subjecting the solution to heat treatment at from 700 to 1050° C. in an oxidizing atmosphere, to obtain the porous composite metal oxide.

11. The method for producing a catalyst support for purification of exhaust gas according to claim 10 , wherein
at least one of the first and second raw material solutions further contains a low-molecular dispersant having a molecular weight of from 40 to 200.

12. The method for producing a catalyst support for purification of exhaust gas according to claim 11 , wherein
the low-molecular dispersant is contained in the first raw material solution.

13. A method for producing a catalyst support for purification of exhaust gas comprising a porous metal composite metal oxide containing alumina, ceria and zirconia, the method comprising the steps of:
preparing a first raw material solution containing an aluminum ion, a cerium ion, and a zirconium ion so that an alumina content ratio of the porous composite metal oxide can be from 5 to 80% by mass;
preparing a second raw solution containing a high-molecular dispersant having a weight average molecular weight of from 3000 to 15000;
introducing independently the first raw material solution and the second raw material solution directly into a region in which a shear rate is from 1000 to 200000 sec −1 , and homogeneously mixing the raw material solutions to obtain a colloidal solution of metal compounds;
adjusting a pH of the colloidal solution to between 3 and 5;
adding an organic amine to the colloidal solution and performing gelation treatment to obtain a suspension of metal compounds; and
degreasing the suspension and subjecting the suspension to heat treatment at from 700 to 1050° C. in an oxidizing atmosphere, to obtain the porous composite metal oxide.

14. The method for producing a catalyst support for purification of exhaust gas according to claim 13 , wherein
at least one of the first and second raw material solutions further contains a low-molecular dispersant having a molecular weight of from 40 to 200.

15. The method for producing a catalyst support for purification of exhaust gas according to claim 14 , wherein
the low-molecular dispersant is contained in the first raw material solution.

Assignees

• Toyota Chuo Kenkyusho Kk
• Toyota Motor Co Ltd

Inventors

• Kumatani Naoki
• Morikawa Akira
• Konishi Kae
• Sato Kimitoshi
• Tanabe Toshitaka
• Suda Akihiko
• Miura Masahide
• Chinzei Isao
• Suzuki Hiromasa
• Nobukawa Takeshi
• Hayashi Takahiro

Classifications

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J23/83

  with rare earths or actinides · CPC title

• B01D2255/9207

  Specific surface · CPC title

• B01D2255/20761

  Copper · CPC title