Performance enhancement of a platinum-containing catalyst via exhaust gas hydrogen enrichment
The disclosure provides a platinum-containing three-way conversion (TWC) catalyst, and a system for treating an exhaust gas stream from a gasoline engine using the TWC catalyst. The system is configured to introduce controlled quantities of hydrogen gas into the exhaust gas stream upstream of the platinum-containing TWC 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.
1 . A platinum-containing three-way conversion (TWC) catalyst article effective to oxidize carbon monoxide and hydrocarbons and reduce nitrogen oxides in an exhaust gas stream from a gasoline engine, the platinum-containing TWC catalyst article comprising a substrate, a first catalyst composition disposed on at least a portion of the substrate, and a second catalyst composition disposed on at least a portion of the substrate, wherein the second catalyst composition comprises:
a first palladium component, wherein at least a portion of the first palladium component is impregnated on a first refractory metal oxide support, and at least another portion of the first palladium component is impregnated on a first oxygen storage component; and
a rhodium component impregnated on a second refractory metal oxide support; and
wherein the first catalyst composition comprises:
a second palladium component, wherein at least a portion of the second palladium component is impregnated on a third refractory metal oxide support, and at least another portion of the second palladium component is impregnated on a second oxygen storage component; and
a platinum component, wherein the platinum component is impregnated on the third refractory metal oxide support, or wherein the platinum component is impregnated on the second oxygen storage component.
2 . The platinum-containing TWC catalytic article of claim 1 , wherein the first refractory metal oxide support comprises alumina, zirconia, titania, ceria, or a combination thereof, and wherein the first refractory metal oxide support is optionally doped with a rare earth metal oxide, wherein the rare earth metal oxide is optionally selected from lanthanum oxide, praseodymium oxide, yttrium oxide, neodymium oxide, or any combination thereof.
3 . The platinum-containing TWC catalytic article of claim 2 , wherein the first refractory metal oxide support is lanthana-alumina, ceria-alumina, zirconia-alumina, ceria-zirconia-alumina, lanthana-zirconia-alumina, or lanthana-neodymia alumina.
4 . The platinum-containing TWC catalytic article of claim 1 , wherein the first oxygen storage component comprises ceria, zirconia, alumina, silica, titania, lanthana, baria, praseodymia, yttria, samaria, gadolinia, or a combination thereof.
5 . The platinum-containing TWC catalytic article of claim 1 , wherein the first oxygen storage component is a ceria-zirconia composite comprising zirconia in an amount from about 5 wt % to about 20 wt %, based on the total weight of the ceria-zirconia composite.
6 . The platinum-containing TWC catalytic article of claim 1 , wherein the rhodium component is present in an amount from about 0.05 wt % to about 5 wt %, based on the total weight of the second layer.
7 . The platinum-containing TWC catalytic article of claim 1 , wherein the second refractory metal oxide support comprises alumina, zirconia, titania, ceria, or a combination thereof, and wherein the second refractory metal oxide support is optionally doped with a rare earth metal oxide and optionally is lanthana-alumina, ceria-alumina, zirconia-alumina, ceria-zirconia-alumina, lanthana-zirconia-alumina, or lanthana-neodymia alumina.
8 . The platinum-containing TWC catalytic article of claim 1 , wherein the third refractory metal oxide support comprises alumina, zirconia, titania, ceria, or combinations thereof, and wherein the third refractory metal oxide support is optionally doped with a rare earth metal oxide, wherein the third refractory metal oxide support is optionally lanthana-alumina, ceria-alumina, zirconia-alumina, ceria-zirconia-alumina, lanthana-zirconia-alumina, or lanthana-neodymia alumina.
9 . The platinum-containing TWC catalytic article of claim 1 , wherein the second oxygen storage component comprises ceria, zirconia, alumina, silica, titania, lanthana, baria, praseodymia, yttria, samaria, gadolinia, or a combination thereof.
10 . The platinum-containing TWC catalytic article of claim 1 , wherein the oxygen storage component is a ceria-zirconia composite comprising zirconia in an amount from about 5 wt % to about 20 wt %, based on the total weight of the ceria-zirconia composite.
11 . The platinum-containing TWC catalytic article of claim 1 , wherein the first catalyst composition further comprises a rare earth metal oxide, an alkaline earth metal component, or both, wherein the rare earth metal oxide is optionally lanthanum oxide, praseodymium oxide, yttrium oxide, neodymium oxide, or any combination thereof.
12 . The platinum-containing TWC catalytic article of claim 11 , wherein the alkaline earth metal component is present in an amount from about 1 wt % to about 40 wt %, based on the total weight of the first layer.
13 . The platinum-containing TWC catalytic article of claim 12 , wherein the alkaline earth metal component comprises calcium, magnesium, strontium, barium, or a combination thereof, wherein the alkaline earth metal component is optionally barium sulfate.
14 . The platinum-containing TWC catalytic article of claim 1 , wherein the platinum component is impregnated on the third refractory metal oxide support or the second oxygen storage component.
15 . The platinum-containing TWC catalytic article of claim 1 , wherein the second catalyst composition comprises:
lanthana-doped alumina impregnated with a portion of the first palladium component;
ceria-zirconia impregnated with a portion of the first palladium component;
alumina impregnated with the rhodium component; and
lanthanum oxide.
16 . The platinum-containing TWC catalytic article of claim 1 , wherein the first catalyst composition comprises:
alumina impregnated with the platinum component and a portion of the second palladium component;
ceria-zirconia impregnated with a portion of the second palladium component;
lanthanum oxide; and
barium sulfate.
17 . The platinum-containing TWC catalytic article of claim 1 , wherein the first catalyst composition comprises:
alumina impregnated with a portion of the second palladium component;
ceria-zirconia impregnated with platinum and a portion of the second palladium component;
lanthanum oxide; and
barium sulfate.
18 . The platinum-containing TWC catalytic article of claim 1 , wherein the substrate is a metal or ceramic monolithic honeycomb substrate or a wall-flow filter substrate or a flow through substrate.
19 . The platinum-containing TWC catalytic article of claim 1 , wherein the first catalyst composition is disposed on the substrate as a first catalyst layer, and the second catalyst composition is disposed on the first catalyst layer.
20 . A system for treating an exhaust gas stream from a gasoline engine, the exhaust gas stream comprising carbon monoxide (CO), the system comprising:
the platinum-containing three-way conversion (TWC) catalyst article of claim 1 , located downstream of and in fluid communication with the gasoline engine;
a source of hydrogen gas (H 2 );
a feedback sensor located upstream from the platinum-containing TWC catalyst article and in contact with the exhaust gas stream; and
a control unit in communication with the feedback sensor;
wherein the system is configured to introduce H 2 from the H 2 source into the exhaust gas stream upstream of the platinum-containing TWC catalyst article during a cold-start period, and wherein the feedback sensor is configured to provide H 2 in the exhaust gas stream by modulating the H 2 introduction.
21 . The system of claim 20 , wherein the feedback sensor comprises a wide-band oxygen sensor (UEGO) and a temperature sensor.
22 . The system of claim 20 , wherein the source of H 2 is an on-board compressed hydrogen vessel or an on-board hydrogen generator.
23 . The system of claim 22 , 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 and is preferably an exhaust gas reformer comprising a catalytic reforming article located upstream from the catalytic article and in fluid communication with the exhaust gas stream.
24 . The system of claim 22 , wherein the on-board hydrogen generator 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.
25 . The system of claim 20 , further comprising a H 2 injection article upstream from the TWC 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 is configured to introduce H 2 from the H 2 source into the exhaust gas stream upstream of the catalyst article.
26 . The system of claim 20 , 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 TWC catalytic article is in a range from about 90° C. to about 190° C.
27 . The system of claim 20 , wherein, when a temperature of the exhaust gas stream upstream of or within the TWC 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 .
28 . The system of claim 20 , wherein the exhaust gas stream contains no greater than about 2 vol. % of H 2 , or no greater than about 0.5 vol. % of H 2 .
29 . The system of claim 20 , wherein the system is configured to introduce H 2 from the H 2 source into the exhaust gas stream to provide a given 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.
30 . The system of claim 29 , wherein Δλ is about −0.060, or about −0.014.
31 . A method of treating an exhaust gas stream from a gasoline engine, the method comprising:
contacting the exhaust gas stream with the platinum-containing TWC catalyst article of claim 1 , located downstream of the gasoline engine and in fluid communication with the exhaust gas stream;
introducing hydrogen gas (H 2 ) from a H 2 source into the exhaust gas stream upstream of the platinum-containing TWC catalyst article; and
controlling a concentration by volume of H 2 in the exhaust gas stream upstream from the platinum-containing TWC catalyst article, wherein controlling the concentration by volume of H 2 comprises modulating the H 2 introduction.
32 . The method of claim 31 , wherein controlling the concentration by volume of H 2 comprises introducing H 2 into the exhaust gas stream when a temperature of the exhaust gas stream upstream from or inside the TWC catalyst article is in a range from about 90° C. to about 550° C., or is in a range from about 90° C. to about 190° C.
33 . The method of claim 31 , wherein the H 2 is introduced for about 200 seconds.
34 . The method of claim 31 , 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 TWC catalyst article, and the temperature sensor is located upstream from or inside the TWC catalyst article, and both sensors are in contact with the exhaust gas stream; and
controlling a quantity of H 2 introduced using the signal.
35 . A method of enhancing the cold-start catalytic performance of a platinum-containing TWC catalyst article, wherein the platinum-containing TWC catalyst article comprises a substrate, a first catalyst layer disposed on the substrate, and a second catalyst layer disposed on the first layer, wherein the second catalyst layer comprises a second catalyst composition comprising:
a first palladium component, wherein at least a portion of the first palladium component is impregnated on a first refractory metal oxide support, and at least another portion of the first palladium component is impregnated on a first oxygen storage component; and
a rhodium component impregnated on a second refractory metal oxide support; and
wherein the first catalyst layer comprises a first catalyst composition comprising:
a second palladium component, wherein at least a portion of the second palladium component is impregnated on a third refractory metal oxide support, and at least another portion of the second palladium component is impregnated on a second oxygen storage component; and
a platinum component, wherein the platinum component is impregnated on the third refractory metal oxide support, or wherein the platinum component is impregnated on the second oxygen storage component;
the method comprising:
contacting the exhaust gas stream with the platinum-containing TWC catalyst article, located downstream of a gasoline engine and in fluid communication with an exhaust gas stream;
controlling a concentration by volume of H 2 in the exhaust gas stream for a period of time, wherein
controlling the concentration by volume of H 2 comprises introducing hydrogen gas (H 2 ) from a H 2 source into the exhaust gas stream upstream of the TWC catalyst article; and
modulating the H 2 introduction using a signal from a feed-back sensor.