U.S. patent application number 14/528139 was filed with the patent office on 2015-04-30 for three-way catalyst and its use in exhaust systems.
The applicant listed for this patent is Johnson Matthey Public Limited Company. Invention is credited to Hsiao-Lan CHANG, Hai-Ying CHEN, Kwangmo KOO, Jeffery Scott RIECK.
Application Number | 20150118119 14/528139 |
Document ID | / |
Family ID | 51982746 |
Filed Date | 2015-04-30 |
United States Patent
Application |
20150118119 |
Kind Code |
A1 |
CHANG; Hsiao-Lan ; et
al. |
April 30, 2015 |
THREE-WAY CATALYST AND ITS USE IN EXHAUST SYSTEMS
Abstract
A three-way catalyst is disclosed. The three-way catalyst
comprises a silver-containing extruded zeolite substrate and a
catalyst layer disposed on the silver-containing extruded zeolite
substrate. The catalyst layer comprises a supported platinum group
metal catalyst comprising one or more platinum group metals and one
or more inorganic oxide carriers. The invention also includes an
exhaust system comprising the three-way catalyst. The three-way
catalyst results in improved hydrocarbon storage and conversion, in
particular during the cold start period.
Inventors: |
CHANG; Hsiao-Lan; (Berwyn,
PA) ; CHEN; Hai-Ying; (Conshohocken, PA) ;
KOO; Kwangmo; (Wayne, PA) ; RIECK; Jeffery Scott;
(King of Prussia, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Johnson Matthey Public Limited Company |
London |
|
GB |
|
|
Family ID: |
51982746 |
Appl. No.: |
14/528139 |
Filed: |
October 30, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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61897543 |
Oct 30, 2013 |
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Current U.S.
Class: |
422/171 ;
422/169; 502/65; 502/74 |
Current CPC
Class: |
F01N 2570/14 20130101;
B01J 37/0018 20130101; B01J 37/0009 20130101; B01D 2255/2092
20130101; B01D 2255/502 20130101; B01J 23/63 20130101; F01N 3/035
20130101; B01D 53/9481 20130101; Y02T 10/22 20130101; B01D
2255/1025 20130101; B01J 23/10 20130101; B01J 23/40 20130101; B01D
2255/912 20130101; B01J 37/0207 20130101; B01D 2255/407 20130101;
B01D 2255/9022 20130101; B01J 23/464 20130101; B01J 37/0236
20130101; F01N 3/101 20130101; F01N 3/0814 20130101; B01D 2255/1021
20130101; B01J 29/7415 20130101; B01D 2255/40 20130101; F01N 3/2882
20130101; B01J 37/0215 20130101; B01J 35/0006 20130101; B01J 35/04
20130101; Y02T 10/12 20130101; B01J 37/0209 20130101; B01J 37/0244
20130101; B01D 2255/504 20130101; B01J 37/0217 20130101; B01J
37/0248 20130101; B01J 37/0201 20130101; B01J 37/082 20130101; B01D
2255/104 20130101; B01J 35/0013 20130101; B01J 35/006 20130101;
B01D 2255/1023 20130101; B01J 2229/186 20130101; B01D 2255/50
20130101; B01J 21/04 20130101; B01J 23/44 20130101; B01J 23/42
20130101; B01J 35/0073 20130101; B01D 53/945 20130101 |
Class at
Publication: |
422/171 ; 502/74;
502/65; 422/169 |
International
Class: |
B01J 29/74 20060101
B01J029/74; B01D 53/94 20060101 B01D053/94 |
Claims
1. A three-way catalyst comprising: (1) a silver-containing
extruded zeolite substrate; and (2) a catalyst layer disposed on
the silver-containing extruded zeolite substrate, wherein the
catalyst layer comprises a supported platinum group metal catalyst
comprising one or more platinum group metals and one or more
inorganic oxide carriers.
2. The three-way catalyst of claim 1 wherein the zeolite is
selected from the group consisting of a beta zeolite, a faujasite,
an L-zeolite, a ZSM zeolite, an SSZ-zeolite, an AEI framework
zeolite, a mordenite, a chabazite, an offretite, an erionite, a
clinoptilolite, a silicalite, an aluminum phosphate zeolite, a
mesoporous zeolite, a metal-incorporated zeolite, and mixtures
thereof.
3. The three-way catalyst of claim 1 wherein the zeolite is
selected from the group consisting of beta zeolite, ZSM-5, SSZ-33,
Y-zeolite, and mixtures thereof.
4. The three-way catalyst of claim 1 wherein the one or more
platinum group metals is selected from the group consisting of
platinum, palladium, rhodium, and mixtures thereof.
5. The three-way catalyst of claim 1 wherein the one or more
platinum group metals is palladium and rhodium.
6. The three-way catalyst of claim 1 wherein the one or more
inorganic oxide carriers is selected from the group consisting of
alumina, silica, titania, zirconia, ceria, niobia, tantalum oxides,
molybdenum oxides, tungsten oxides, and mixed oxides or composite
oxides thereof.
7. The three-way catalyst of claim 1 wherein the extruded zeolite
substrate is a flow-through substrate.
8. The three-way catalyst of claim 1 wherein the silver-containing
extruded zeolite substrate comprises from 1 to 700 g/ft.sup.3
silver.
9. An exhaust system for internal combustion engines comprising the
three-way catalyst of claim 1.
10. The exhaust system of claim 14 further comprising: a selective
catalytic reduction catalyst system; a particulate filter; a
selective catalyst reduction filter system; a NO.sub.x adsorber
catalyst; or combinations thereof.
Description
FIELD OF THE INVENTION
[0001] The invention relates to a three-way catalyst and its use in
an exhaust system for internal combustion engines.
BACKGROUND OF THE INVENTION
[0002] Internal combustion engines produce exhaust gases containing
a variety of pollutants, including hydrocarbons, carbon monoxide,
and nitrogen oxides ("NO.sub.x"). Emission control systems,
including exhaust gas catalysts, are widely utilized to reduce the
amount of these pollutants emitted to atmosphere. A commonly used
catalyst for gasoline engine applications is the "three-way
catalyst" (TWC). TWCs perform three main functions: (1) oxidation
of CO; (2) oxidation of unburnt hydrocarbons; and (3) reduction of
NO.sub.x to N.sub.2.
[0003] TWCs, like other exhaust gas catalysts, typically achieve
very high efficiencies once they reach their operating temperature
(typically, 200.degree. C. and higher). However, these systems are
relatively inefficient below their operating temperature (the "cold
start" period). As even more stringent national and regional
legislation lowers the amount of pollutants that can be emitted
from diesel or gasoline engines, reducing emissions during the cold
start period is becoming a major challenge. Thus, methods for
reducing the level of NO.sub.x and hydrocarbons emitted during cold
start condition continue to be explored.
[0004] For cold start hydrocarbon control, hydrocarbon (HC) traps
including zeolites as hydrocarbon trapping components have been
investigated. In these systems, the zeolite component adsorbs and
stores hydrocarbons during the start-up period and releases the
stored hydrocarbons when the exhaust temperature is high enough to
desorb hydrocarbons. The desorbed hydrocarbons are subsequently
converted by a TWC component either incorporated into the HC trap
or by a separate TWC placed downstream of the HC trap.
[0005] For instance, U.S. Pat. No. 5,772,972 discloses a hybrid
system of hydrocarbon trapping material and palladium based
three-way catalyst material. U.S. Pat. No. 6,617,276 teaches a
catalyst structure comprising a first layer consisting essentially
of a hydrocarbon-adsorbing zeolite and a K, Rb, or Cs active metal
that is impregnated on the zeolite, at least one additional layer
consisting essentially of at least one platinum group metal, and a
catalyst substrate on which the first layer and the one or more
additional layers are disposed. In EP 1129774, a hydrocarbon
adsorbing member is taught that comprises a zeolite having
SiO.sub.2:Al.sub.2O.sub.3 molar ratio of 100 or more and an average
primary particle diameter of 1 .mu.m or less of, and that it is
free from a monovalent metallic element. U.S. Pat. No. 6,074,973
teaches a catalyzed hydrocarbon trap material comprising palladium
and silver dispersed on a high surface area metal oxide support and
a zeolite material such as one or more of ZSM-5, Beta, Y, and other
suitable zeolites.
[0006] U.S. Appl. Pub. No. 2012/0117953 A1 teaches a three way
catalyst that comprises an extruded solid body comprising 10-100
weight percent of at least one binder/matrix component, 5-90 weight
percent of a zeolitic molecular sieve, a non-zeolitic molecular
sieve or a mixture of any two or more thereof, and 0-80 weight
percent of an optional stabilized ceria. The catalyst comprises at
least one precious metal and optionally at least one non-precious
metal, wherein: (i) the at least one precious metal is carried in
one or more coating layer(s) on a surface of the extruded solid
body; (ii) at least one metal is present throughout the extruded
solid body and at least one precious metal is also carried in one
or more coating layer(s) on a surface of the extruded solid body;
or (iii) at least one metal is present throughout the extruded
solid body, is present in a higher concentration at a surface of
the extruded solid body and at least one precious metal is also
carried in one or more coating layer(s) on the surface of the
extruded solid body. In addition, U.S. Appl. Pub. No. 2012/0308439
A1 teaches a cold start catalyst that comprises (1) a zeolite
catalyst comprising a base metal, a noble metal, and a zeolite, and
(2) a supported platinum group metal catalyst comprising one or
more platinum group metals and one or more inorganic oxide
carriers.
[0007] As with any automotive system and process, it is desirable
to attain still further improvements in exhaust gas treatment
systems, particularly under cold start conditions. We have
discovered a new three-way catalyst that provides enhanced cleaning
of the exhaust gases from internal combustion engines.
SUMMARY OF THE INVENTION
[0008] The invention is a three-way catalyst for use in an exhaust
system. The three-way catalyst comprises a silver-containing
extruded zeolite substrate. The three-way catalyst also comprises a
catalyst layer that is disposed on the silver-containing extruded
zeolite substrate. The catalyst layer comprises a supported
platinum group metal catalyst comprising one or more platinum group
metals and one or more inorganic oxide carriers. The invention also
includes an exhaust system comprising the three-way catalyst.
DETAILED DESCRIPTION OF THE INVENTION
[0009] The three-way catalyst of the invention comprises a
silver-containing extruded zeolite substrate.
[0010] The zeolite of the silver-containing extruded zeolite
substrate may be any natural or a synthetic zeolite, including
molecular sieves, and is preferably composed of aluminum, silicon,
and/or phosphorus. The zeolites typically have a three-dimensional
arrangement of SiO.sub.4, AlO.sub.4, and/or PO.sub.4 that are
joined by the sharing of oxygen atoms. The zeolite frameworks are
typically anionic, which are counterbalanced by charge compensating
cations, typically alkali and alkaline earth elements (e.g., Na, K,
Mg, Ca, Sr, and Ba) and also protons.
[0011] The zeolite is preferably a beta zeolite, a faujasite (such
as an X-zeolite or a Y-zeolite, including NaY and USY), an
L-zeolite, a ZSM zeolite (e.g., ZSM-5, ZSM-48), an SSZ-zeolite
(e.g., SSZ-13, SSZ-41, SSZ-33), an AEI framework zeolite, a
mordenite, a chabazite, an offretite, an erionite, a
clinoptilolite, a silicalite, an aluminum phosphate zeolite
(including metalloaluminophosphates such as SAPO-34), a mesoporous
zeolite (e.g., MCM-41, MCM-49, SBA-15), or mixtures thereof; more
preferably, the zeolites are beta zeolite, ZSM-5 zeolite, or
SSZ-33, or Y-zeolite. The zeolite is most preferably beta zeolite,
ZSM-5 zeolite, or SSZ-33.
[0012] The extruded zeolite substrate may be formed by any known
means. Typically, the zeolite is extruded to form a flow-through or
filter substrate, and is preferably extruded to form a honeycomb
flow-through monolith. Extruded zeolite substrates and honeycomb
bodies, and processes for making them, are known in the art. See,
for example, U.S. Pat. Nos. 5,492,883, 5,565,394, and 5,633,217 and
U.S. Pat. No. Re. 34,804. Typically, the zeolite material is mixed
with a permanent binder such as silicone resin and a temporary
binder such as methylcellulose, and the mixture is extruded to form
a green honeycomb body, which is then calcined and sintered to form
the final extruded zeolite substrate.
[0013] The extruded zeolite substrate may be formed as a
flow-through or filter substrate. If formed as a flow-through
substrate, it is preferably a flow-through monolith having a
honeycomb structure with many small, parallel thin-walled channels
running axially through the substrate and extending throughout from
an inlet or an outlet of the substrate. The channel cross-section
of the substrate may be any shape, but is preferably square,
sinusoidal, triangular, rectangular, hexagonal, trapezoidal,
circular, or oval.
[0014] If formed as a filter substrate, the silver-containing
extruded zeolite substrate is preferably a wall-flow monolith
filter. The channels of a wall-flow filter are alternately blocked,
which allow the exhaust gas stream to enter a channel from the
inlet, then flow through the channel walls, and exit the filter
from a different channel leading to the outlet. Particulates in the
exhaust gas stream are thus trapped in the filter.
[0015] The zeolite may contain silver prior to extruding such that
the silver-containing extruded zeolite substrate is produced by the
extrusion procedure. If the zeolite contains silver prior to
extrusion, the silver may be added to the zeolite to form a
silver-containing zeolite by any known means, the manner of
addition is not considered to be particularly critical. For
example, a silver compound (such as silver nitrate) may be added to
the zeolite by impregnation, adsorption, ion-exchange, incipient
wetness, precipitation, or the like.
[0016] If an extruded zeolite substrate is first formed without
silver, the extruded zeolite monolith is then loaded with silver to
produce the silver-containing extruded zeolite substrate.
Preferably, the extruded zeolite monolith is subjected to an
impregnation procedure to load silver onto the zeolite
monolith.
[0017] Preferably, the silver-containing extruded zeolite substrate
comprises from 1 to 700 g/ft.sup.3 silver, more preferably from 10
to 200 g/ft.sup.3 silver.
[0018] The three-way catalyst also comprises a catalyst layer that
is disposed on the silver-containing extruded zeolite substrate.
The catalyst layer comprises a supported platinum group metal
catalyst. The supported platinum group metal catalyst comprises one
or more platinum group metals ("PGM") and one or more inorganic
oxide carriers. The PGM may be platinum, palladium, rhodium, or
combinations thereof, and most preferably palladium and rhodium.
The inorganic oxide carriers most commonly include oxides of Groups
2, 3, 4, 5, 13 and 14 elements. Useful inorganic oxide carriers
preferably have surface areas in the range 10 to 700 m.sup.2/g,
pore volumes in the range 0.1 to 4 mL/g, and pore diameters from
about 10 to 1000 Angstroms. The inorganic oxide carrier is
preferably alumina, silica, titania, zirconia, ceria, niobia,
tantalum oxides, molybdenum oxides, tungsten oxides, or mixed
oxides or composite oxides of any two or more thereof, e.g.
silica-alumina, ceria-zirconia or alumina-ceria-zirconia. Alumina
and ceria-zirconia are particularly preferred.
[0019] The supported platinum group metal catalyst may be prepared
by any known means. Preferably, the one or more platinum group
metals are loaded onto the one or more inorganic oxides by any
known means to form the supported PGM catalyst, the manner of
addition is not considered to be particularly critical. For
example, a palladium compound (such as palladium nitrate) may be
supported on an inorganic oxide by impregnation, adsorption,
ion-exchange, incipient wetness, precipitation, or the like. Other
metals may also be added to the supported PGM catalyst.
[0020] The supported PGM catalyst layer is disposed on the
silver-containing extruded zeolite substrate. The supported PGM
catalyst layer may be disposed on the silver-containing extruded
zeolite substrate by processes well known in the prior art.
Preferably, the supported platinum group metal catalyst is coated
onto the silver-containing extruded zeolite substrate using a
washcoat procedure to produce a three-way catalyst of the
invention.
[0021] A representative process for preparing the three-way
catalyst using a washcoat procedure is set forth below. It will be
understood that the process below can be varied according to
different embodiments of the invention.
[0022] The washcoating procedure is preferably performed by first
slurrying finely divided particles of the supported platinum group
catalyst in an appropriate solvent, preferably water, to form the
slurry. Additional components, such as transition metal oxides,
binders, stabilizers, or promoters may also be incorporated in the
slurry as a mixture of water soluble or water-dispersible
compounds. The slurry preferably contains between 10 to 70 weight
percent solids, more preferably between 30 to 50 weight percent.
Prior to forming the slurry, the supported platinum group catalyst
particles are preferably subject to a size reduction treatment
(e.g., milling) such that the average particle size of the solid
particles is less than 20 microns in diameter.
[0023] The silver-containing extruded zeolite substrate may then be
dipped one or more times into the slurry or the slurry may be
coated on the substrate such that there will be deposited on the
silver-containing extruded zeolite substrate the desired loading of
catalytic materials. Alternatively, a slurry containing only the
inorganic oxide(s) may first be deposited on the zeolite
catalyst-coated substrate to form an inorganic oxide-coated
substrate, followed by drying and calcination steps. The platinum
group metal(s) may then be added to the inorganic oxide-coated
substrate by any known means, including impregnation, adsorption,
or ion-exchange of a platinum group metal compound (such as
platinum nitrate).
[0024] Preferably, the entire length of the silver-containing
extruded zeolite substrate is coated with the slurry so that a
washcoat of the supported platinum group catalyst covers the entire
surface of the substrate.
[0025] After the silver-containing extruded zeolite substrate has
been coated with the supported platinum group catalyst slurry, the
coated substrate is preferably dried and then calcined by heating
at an elevated temperature to form the three-way catalyst.
Preferably, the calcination occurs at 400 to 600.degree. C. for
approximately 1 to 8 hours.
[0026] The invention also includes an exhaust system for internal
combustion engines comprising the three-way catalyst. The exhaust
system preferably comprises one or more additional after-treatment
devices capable of removing pollutants from internal combustion
engine exhaust gases.
[0027] Preferably, the exhaust system comprises a close-coupled
catalyst and the three-way catalyst of the invention. The
close-coupled catalyst is located upstream of the three-way
catalyst. Preferably, a particulate filter may also be added to
this system. The particulate filter may be located downstream of
the close-coupled catalyst and upstream three-way catalyst, or the
particular filter may be located downstream of the three-way
catalyst.
[0028] Close-coupled catalysts are well known in the art.
Close-coupled catalysts are typically utilized to reduce
hydrocarbon emissions during cold start period following the start
of the engine when the temperature, as measured at the three-way
catalyst, will be below a temperature ranging from about 150 to
220.degree. C. Close-coupled catalysts are located within the
engine compartment, typically adjacent to the exhaust manifold and
beneath the hood, so that they are exposed to high temperature
exhaust gas immediately exiting the engine after the engine has
warmed up.
[0029] The close-coupled catalyst preferably comprises a substrate
structure coated with a catalyst layer of a heat-resistant
inorganic oxide containing at least one noble metal selected from
Pt, Pd and Rh. The heat-resistant substrate is typically a monolith
substrate, and preferably a ceramic substrate or metallic
substrate. The ceramic substrate may be made of any suitable
heat-resistant refractory material, e.g., alumina, silica, titania,
ceria, zirconia, magnesia, zeolites, silicon nitride, silicon
carbide, zirconium silicates, magnesium silicates, aluminosilicates
and metallo aluminosilicates (such as cordierite and spodumene), or
a mixture or mixed oxide of any two or more thereof. The metallic
substrate may be made of any suitable metal, and in particular
heat-resistant metals and metal alloys such as titanium and
stainless steel as well as ferritic alloys containing iron, nickel,
chromium, and/or aluminum in addition to other trace metals
(typically, rare earth metals).
[0030] The substrate is preferably a flow-through substrate, but
may also be a filter substrate. The flow-through substrates
preferably have a honeycomb structure with many small, parallel
thin-walled channels running axially through the substrate and
extending throughout the substrate. If the substrate is a filter
substrate, it is preferably a wall-flow monolith filter. The
channels of a wall-flow filter are alternately blocked, which allow
an exhaust gas stream to enter a channel from the inlet, and then
flow through the channel walls, and exit the filter from a
different channel leading to the outlet. Particulates in the
exhaust gas stream are thus trapped in the filter.
[0031] The catalyst layer of the close-coupled catalyst is
typically added to the substrate as a washcoat that preferably
comprises one or more inorganic oxides and one or more platinum
group metals. The inorganic oxide most commonly includes oxides of
Groups 2, 3, 4, 5, 13 and 14 elements. Useful inorganic oxides
preferably have surface areas in the range 10 to 700 m.sup.2/g,
pore volumes in the range 0.1 to 4 mL/g, and pore diameters from
about 10 to 1000 Angstroms. The inorganic oxide is preferably
alumina, silica, titania, zirconia, niobia, tantalum oxides,
molybdenum oxides, tungsten oxides, rare earth oxides (in
particular ceria or neodymium oxide), or mixed oxides or composite
oxides of any two or more thereof, e.g. silica-alumina,
ceria-zirconia or alumina-ceria-zirconia, and can also be a
zeolite. The PGMs comprise one or more of platinum, palladium, and
rhodium. The close-coupled catalyst may contain other metals or
metal oxides as well.
[0032] In another useful embodiment, the exhaust system may also
preferably comprise a conventional oxidation catalyst component and
the three-way catalyst of the invention. In this configuration, the
exhaust system will preferably contain valves or other
gas-directing means such that during the cold-start period (below a
temperature ranging from about 150 to 220.degree. C., as measured
at the three-way catalyst, the exhaust gas is directed to contact
the three-way catalyst before flowing to the conventional oxidation
catalyst component. Once the after-treatment device(s) reaches the
operating temperature (about 150 to 220.degree. C., as measured at
the three-way catalyst), the exhaust gas flow is then redirected to
contact the conventional oxidation catalyst component prior to
contacting the three-way catalyst. A particulate filter may also be
added to this by-pass system. U.S. Pat. No. 5,656,244, the
teachings of which are incorporated herein by reference, for
example, teaches means for controlling the flow of the exhaust gas
during cold-start and normal operating conditions.
[0033] The conventional oxidation catalyst component is preferably
a conventional TWC catalyst that comprises a substrate coated with
a TWC layer. The substrate is typically a monolith substrate, and
preferably a ceramic substrate or metallic substrate, and is
preferably a flow-through substrate but may also be a filter
substrate. The TWC catalyst layer preferably comprises a supported
platinum group metal catalyst that comprises one or more platinum
group metals ("PGM") and one or more inorganic oxide carriers, as
described above.
[0034] The following examples merely illustrate the invention.
Those skilled in the art will recognize many variations that are
within the spirit of the invention and scope of the claims.
EXAMPLE 1
Preparation of Catalysts of the Invention
[0035] Catalyst 1A: Ag on extruded beta zeolite+Pd--Rh layer
[0036] A beta zeolite monolith (formed by extruding beta zeolite
into a honeycomb monolith, and containing 55% beta zeolite; see,
e.g., U.S. Pat. Nos. 5,492,883, 5,565,394, and 5,633,217) is
impregnated with an aqueous silver nitrate solution, followed by
drying, and calcining by heating at 500.degree. C. for 4 hours to
achieve a Ag loading of 150 g/ft.sup.3.
[0037] The Ag/beta zeolite monolith is then coated with a typical
TWC layer consisting of alumina and ceria-zirconia mixed oxides as
the supports for Pd and Rh. The Pd loading is 76.5 g/ft.sup.3 and
the Rh loading is 8.5 g/ft.sup.3. The supported coated substrate is
dried, and then calcined by heating at 500.degree. C. for 4
hours.
EXAMPLE 2
Comparative Catalyst Preparation
[0038] Comparative Catalyst 2A: Extruded beta zeolite+Pd--Rh
layer
[0039] Comparative Catalyst 2A is prepared according to the same
procedure as Catalyst 1A with the exception that the extruded beta
zeolite is not impregnated with silver.
[0040] Comparative Catalyst 2B: Cordierite substrate+Pd--Rh
layer
[0041] Comparative Catalyst 2B is prepared according to the same
procedure as Catalyst 1A with the exception that a cordierite
substrate monolith is used in place of the Ag/beta zeolite
monolith.
EXAMPLE 3
Laboratory Testing Procedures and Results
[0042] All the catalysts are tested on core samples (2.54
cm.times.8.4 cm) of the flow-through catalyst-coated substrate.
Fresh catalyst and aged catalyst are both tested. Catalyst cores
are aged under flow-through conditions in a furnace under
hydrothermal conditions (5% H.sub.2O, balance air) at 800.degree.
C. for 80 hours. The cores are then tested for hydrocarbon
adsorption in a laboratory reactor, using a feed gas stream that is
prepared by adjusting the mass flow of the individual exhaust gas
components. The gas flow rate is maintained at 21.2 L min.sup.-1
resulting in a Gas Hourly Space Velocity of 30,000 h.sup.-1
(GHSV=30,000 h.sup.-1).
[0043] The catalysts are pretreated at 650.degree. C. in a gas flow
of 2250 ppm O.sub.2, 10% CO.sub.2, 10% H.sub.2O, and the balance
nitrogen, before cooling to room temperature. Following the
pretreatment, the catalyst undergoes a HC adsorption step in which
the catalyst is contacted for 30 seconds with a HC-containing gas
consisting of 1500 ppm (C.sub.1 basis) HC (17 vol. % toluene, 24
vol. % isopentane, and 59 vol. % propene), 1000 ppm NO, 1000 ppm
CO, 2250 ppm O.sub.2, 10% H.sub.2O, 10% CO.sub.2 and the balance
nitrogen. The HC adsorption step is then followed by a HC
desorption period in which the catalyst is subjected to a
desorption gas consisting of 200 ppm (C.sub.1 basis) HC, 300 ppm
O.sub.2, 10% H.sub.2O, 10% CO.sub.2 and the balance nitrogen.
[0044] The results on the fresh and aged catalysts for the HC
emissions during the adsorption period and oxidation period, as
well as total HC removed, are shown in Table 1.
EXAMPLE 4
Engine Testing Procedures
[0045] Full-sized catalysts of Example 1A and Comparative Examples
2A and 2B are evaluated on a 2.4 L gasoline vehicle. In each of the
tests, a commercial Pd--Rh TWC catalyst is placed in the
close-coupled position upstream of the Example catalysts. The CCC
TWC catalyst contains 405 g/ft.sup.3 Pd and 15 g/ft.sup.3 Rh in the
front zone, and 105 g/ft.sup.3 Pd and 15 g/ft.sup.3 Rh in the rear
zone. Each of the systems is aged for 150 hours with the Example
catalyst bed temperature peaking at 800.degree. C. The tailpipe
total HC (THC) emissions of the systems under FTP 75 testing
protocol are shown in Table 2. Catalyst 1A removes additional 4
mg/mile THC as compared to the two Comparative Examples.
[0046] The results are shown in Table 2.
TABLE-US-00001 TABLE 1 NO.sub.x Storage Capacity Results % HC
adsorbed % HC oxidized Total % HC Catalyst (30 sec; 80.degree. C.)
(80-650.degree. C.) removed 1A Fresh 93.1 78.1 81.3 Aged 90.4 62.6
68.8 2A* Fresh 83.5 70.4 73.4 Aged 71.7 61.7 63.9 2B* Fresh 7.8
69.8 55.9 Aged 9.2 65.4 53.3 *Comparative Example
TABLE-US-00002 TABLE 2 Engine Testing Results showing Total
Hydrocarbon (THC) Emission Cumulative Tailpipe THC Catalyst
(mg/mile) 1A 10 2A * 14 2B * 14 * Comparative Example
* * * * *