IP Library Granted Patent US 12,416,254
Granted Patent B2
US 12,416,254 · App. 18/024,833 · Granted Sep 16, 2025

Performance enhancement of a catalyst via exhaust gas hydrogen enrichment

Inventors: Shiang Sung (New York, NY); Chunxin Ji (Hillsborough, NJ); Pavel Ruvinskiy (Novosibirsk, RU)
Assignee: BASF MOBILE EMISSIONS CATALYSTS, LLC
F01N3/206F01N9/00F01N2240/30F01N2560/024F01N2560/025F01N2610/04F01N2900/0408
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Quick Facts
Patent No.
US 12,416,254
App. No.
18/024,833
Granted
Sep 16, 2025
Kind
B2
Abstract

The disclosure provides a system for treating an exhaust gas stream from a gasoline engine. The system is configured to introduce controlled quantities of hydrogen gas into the exhaust gas stream upstream of a catalyst article during a cold-start period. Further provided are related methods of treating such exhaust streams. Such systems and methods are useful in reducing a level of one or more of hydrocarbons, carbon monoxide, and nitrogen oxide in a gaseous exhaust stream from a gasoline engine.

Claims (89)

1. A system for treating an exhaust gas stream from a gasoline engine, the system comprising:

a catalyst article downstream of and in fluid communication with the gasoline engine, wherein the catalyst article comprises a substrate, a first catalyst layer disposed on the substrate, and a second catalyst layer disposed on the first catalyst layer, wherein:

the first catalyst layer comprises a first palladium component, a first refractory metal oxide support, and a first oxygen storage component, wherein at least a portion of the first palladium component is impregnated on the first refractory metal oxide support, and another portion of the first palladium component is impregnated on the first oxygen storage component; and

the second catalyst layer comprises a second palladium component, a second refractory metal oxide support, a second oxygen storage component, a rhodium component,

and a third refractory metal oxide support, wherein at least a portion of the second palladium component is impregnated on the second refractory metal oxide support, and another portion of the second palladium component is impregnated on the second oxygen storage component, and the rhodium component is impregnated on the third refractory metal oxide support;

a source of hydrogen gas (H 2 );

a feedback sensor located upstream from the catalyst article and in contact with the exhaust gas stream, wherein the feedback sensor comprises a wide-band oxygen sensor (UEGO) and a temperature sensor; and

a control unit in communication with the feedback sensor;

an H 2 injection article upstream from the catalyst article, upstream from the feedback sensor, in fluid communication with the exhaust gas stream and with the H 2 source, and in communication with the control unit; and wherein the H 2 injection article configured to introduce H 2 from the H 2 source into the exhaust gas stream upstream of the catalyst article;

wherein the system is configured to introduce H 2 from the H 2 source into the exhaust gas stream upstream of the catalyst article during a cold-start period, and wherein the system is configured to introduce H 2 from the H 2 source into the exhaust gas stream when the exhaust gas stream temperature upstream of or within the catalytic article is in a range from about 90° C. to about 190° C., wherein the feedback sensor is configured to provide H 2 in the exhaust gas stream by modulating the H 2 introduction;

wherein the system is configured to introduce H 2 from the H 2 source into the exhaust gas stream to provide a Δλ value of from about −0.014 to no more negative than about −0.345 for a period of time, wherein:

Δλ

=

λ

¯

-

λ°

;

λ° is a pre-defined value; and

λ is a running average air-to-fuel ratio of the exhaust gas stream, calculated for a length of time according to the formula:

λ

¯

=

i

=

1

N

λ

i

N

;

wherein (N) is the number of points comprised in this length of time, and λ i is the air-to-fuel ratio at each point.

2. The system of claim 1 , wherein the catalyst article is chosen from a three-way conversion (TWC) catalyst article, a four-way conversion catalyst article, a selective catalytic reduction (SCR) catalyst article, a direct oxidation catalyst article, an ammonia oxidation (AMOx) catalyst article, and a catalyzed soot filter (CSF) article or a combination thereof.

3. The system of claim 1 , wherein the source of H 2 is an on-board compressed hydrogen vessel, or an on-board hydrogen generator.

4. The system of claim 3 , wherein the on-board hydrogen generator comprises an alcohol reformer, an ammonia decomposition apparatus, an electrolysis apparatus, a fuel reformer, an exhaust gas reformer, or a combination thereof, or an exhaust gas reformer comprising a catalytic reforming article located upstream from the catalytic article and in fluid communication with the exhaust gas stream, or comprises at least one H 2 generating component comprising a dopant comprising nanoparticles of aluminum, nanoparticles of aluminum/nickel, nanoparticles of aluminum/silica, nanoparticles of aluminum/cobalt, nanoparticles of aluminum/magnesium, nanoparticles of alumina, nanoparticles of magnesium, nanoparticles of magnesium/nickel, nanoparticles of zinc, sodium borohydride, or a combination thereof, and wherein the at least one H 2 generating component is added to a gasoline fuel prior to combustion of said fuel in the gasoline engine.

5. The system of claim 1 , wherein, when a temperature of the exhaust gas stream upstream of or within the catalytic article is in a range from about 90° C. to about 550° C., the exhaust gas stream contains no greater than about 20 vol % of H 2 .

6. The system of claim 1 , wherein the exhaust gas stream contains no greater than about 2 vol % of H 2 .

7. The system of claim 1 , wherein Δλ is about −0.060.

8. The system of claim 1 , wherein Δλ is about −0.014.

9. The system of claim 1 , wherein the exhaust gas stream contains no greater than about 0.5 vol % of H 2 .

10. A method for reducing a level of one or more of hydrocarbons, carbon monoxide, nitrogen oxide, and particulate matter in a gaseous exhaust stream from a gasoline engine, the method comprising contacting the gaseous exhaust stream with the exhaust gas treatment system of claim 1 .

11. A method of treating an exhaust gas stream from a gasoline engine, the method comprising:

contacting the exhaust gas stream with a catalyst article located downstream of the gasoline engine and in fluid communication with the exhaust gas stream, wherein the catalyst article comprises a substrate, a first catalyst layer disposed on the substrate, and a second catalyst layer disposed on the first catalyst layer, wherein:

the first catalyst layer comprises a first palladium component, a first refractory metal oxide support, and a first oxygen storage component, wherein at least a portion of the first palladium component is impregnated on the first refractory metal oxide support, and another portion of the first palladium component is impregnated on the first oxygen storage component; and

the second catalyst layer comprises a second palladium component, a second refractory metal oxide support, a second oxygen storage component, a rhodium component, and a third refractory metal oxide support, wherein at least a portion of the second palladium component is impregnated on the second refractory metal oxide support, and another portion of the second palladium component is impregnated on the second oxygen storage component, and the rhodium component is impregnated on the third refractory metal oxide support;

introducing hydrogen gas (H 2 ) from a H 2 source via an H 2 injection article into the exhaust gas stream upstream of the catalyst article, upstream from a feedback sensor, in fluid communication with the exhaust gas stream and with the H 2 source into the exhaust gas stream upstream of the catalyst article, wherein the feedback sensor comprises a wide-band oxygen sensor (UEGO) and a temperature sensor; and

controlling a concentration by volume of H 2 in the exhaust gas stream upstream from the catalyst article, wherein controlling the concentration by volume of H 2 comprises modulating the H 2 introduction, wherein controlling comprises introducing H 2 into the exhaust gas stream when a temperature of the exhaust gas stream upstream from or inside the catalyst article is in a range from about 90° C. to about 550° C., or from about 90° C. to about 190° C.;

introducing H 2 into the exhaust gas stream; and

providing a Δλ value no more negative than about −0.345 for a period of time, wherein:

Δλ

=

λ

¯

-

λ°

;

λ° is a pre-defined value; and

λ is a running average air-to-fuel ratio of the exhaust gas stream, calculated for a length of time according to the formula:

λ

¯

=

i

=

1

N

λ

i

N

;

wherein (N) is the number of points comprised in this length of time, and λ i is the air-to-fuel ratio at each point.

12. The method of claim 11 , wherein the catalyst article is chosen from a three-way conversion (TWC) catalyst article, a four-way conversion catalyst article, a selective catalytic reduction (SCR) catalyst article, a direct oxidation catalyst article, an ammonia oxidation (AMOx) catalyst article, and a catalyzed soot filter (CSF) article or a combination thereof.

13. The method of claim 11 , wherein the H 2 is introduced for about 200 seconds.

14. The method of claim 11 , wherein modulating the H 2 introduction comprises:

obtaining a signal from a feedback sensor, a temperature sensor, or a combination thereof, wherein the feedback sensor is located upstream from the catalyst article, the temperature sensor located upstream from or inside the catalyst article, and both sensors are in contact with the exhaust gas stream; and

controlling a quantity of H 2 introduced using said signal.

15. The method of claim 14 , wherein the exhaust gas stream contains no greater than about 20 vol % of H 2 , no greater than about 2 vol % of H 2 , or no greater than about 0.5 vol % of H2.

16. The method of claim 14 , wherein the exhaust gas stream contains no greater than about 2 vol % of H 2 .

17. The method of claim 14 , wherein the exhaust gas stream contains no greater than about 0.5 vol % of H 2 .

18. The method of claim 11 , wherein Δλ is about −0.060.

19. The method of claim 11 , wherein Δλ is about −0.014.

20. The method of claim 11 , wherein introducing H 2 further comprises generating H2 during the combustion of gasoline in the gasoline engine, wherein generating H 2 comprises adding at least one H 2 generating component to the gasoline prior to combustion.

21. The method of claim 20 , wherein the at least one H 2 generating component comprises a dopant comprising nanoparticles of aluminum, nanoparticles of aluminum/nickel, nanoparticles of aluminum/silica, nanoparticles of aluminum/cobalt, nanoparticles of aluminum/magnesium, nanoparticles of alumina, nanoparticles of magnesium, nanoparticles of magnesium/nickel, nanoparticles of zinc, sodium borohydride, or a combination thereof.

22. The method of claim 21 , further comprising a vehicle, wherein the vehicle comprises the gasoline engine and the catalyst article.

23. The method of claim 22 , wherein the at least one H 2 generating component is added to the gasoline on board the vehicle, or is added to the gasoline externally to the vehicle.

24. The method of claim 11 , wherein introducing H 2 further comprises generating H 2 , wherein generating H 2 comprises contacting the exhaust gas stream with an exhaust gas reforming catalyst.

Assignments (2)
NUNC PRO TUNC ASSIGNMENT Recorded Aug 8, 2024
From: BASF CORPORATION
To: BASF MOBILE EMISSIONS CATALYSTS LLC
Reel/Frame 068518/0394 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 6, 2023
From: SUNG, SHIANG; JI, CHUNXIN; RUVINSKIY, PAVEL
To: BASF CORPORATION
Reel/Frame 062890/0906 →
Continuity (2)
Provisional Application 63075550 · Sep 8, 2020
Related Publication 20240287926A1 · Aug 29, 2024
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