Title of Invention

PALLADIUM-RHODIUM SINGLE-LAYER CATALYST

Abstract A one-layer three-way catalyst is described for the cleaning of the exhaust gases of internal combustion engines with outstanding activity and thermal stability. The catalyst comprises an active aluminum oxide, a first cerium/zirconium mixed oxide and a second cerium/zirconium mixed oxide. The first cerium/zirconium mixed oxide has a higher zirconium oxide content than the second mixed oxide. The first cerium/zirconium mixed oxide is catalytically activated with rhodium and the second cerium/zirconium mixed oxide with palladium.
Full Text Palladium-rhodium single-layer catalyst
Description
The invention relates to a three-way catalyst with outstanding catalytic activity and
aging stability for the cleaning of the exhaust gases of internal combustion engines.
Three-way catalysts are used in large numbers for the cleaning of the exhaust gases of
internal combustion engines operated under essentially stoichiometric conditions. They
are capable of converting the three significant pollutants from the engine, specifically
hydrocarbons, carbon monoxide and nitrogen oxides, simultaneously to harmless
components. Frequently, double-layer catalysts are used, which enable a separation of
different catalytic procedures and hence an optimal balance of the catalytic effects in the
two layers. Catalysts of this kind are described, for example, in EP 0 885 650 and
EP 1046 423.
Double-layer catalysts have the disadvantage that their production is more expensive
than that of single-layer catalysts. Moreover, double-layer catalysts have a tendency to
an increased exhaust gas backpressure compared to single-layer catalysts, which is at
the expense of the performance of the internal combustion engines and the fuel
consumption thereof. There have therefore always been efforts to obtain the good
catalytic properties of double-layer catalysts by means of single-layer catalysts, as far as
possible without tradeoffs. Single-layer three-way catalysts are known, for example,
from WO 98/09726, EP 1 138 382 and EP 1 541 220.
The constantly rising demands on reducing the emissions of internal combustion
engines necessitate constant further development of the catalysts with regard to catalytic
activity, aging stability and production costs. It was therefore an object of this invention
to provide a catalyst which has further-reduced lightoff temperatures and improved
thermal stability coupled with lower production costs compared to the prior art
catalysts.
This object is achieved by a catalyst according to the claims. The catalyst has a single
catalytically active coating on an inert catalyst support of ceramic or metal. The catalyst

is characterized in that it comprises an active aluminum oxide and a first and a second
cerium/zirconium mixed oxide, the first cerium/zirconium mixed oxide being activated
with rhodium and having a higher zirconium oxide content than the second
cerium/zirconium mixed oxide which is catalytically activated with palladium.
In the context of the present invention, the wording "a support material is activated with
a catalytically active element" means that the catalytically active element has been
deposited in highly disperse form on the surface of the support material accessible by
impregnation.
By virtue of the combination of the properties mentioned, the catalyst has very good
lightoff performance and possesses a high thermal stability. Moreover, the catalyst has a
low exhaust gas backpressure and the production costs thereof are lower than those of a
corresponding double-layer catalyst.
The active aluminum oxide and the cerium/zirconium mixed oxides are introduced into
the coating as pulverulent solids. The thermal stability of both mixed oxides can be
improved by stabilizing them with at least one oxide of the elements selected from the
group consisting of iron, manganese, tin, titanium, silicon, yttrium, lanthanum,
praseodymium, neodymium, samarium and mixtures thereof. The amount of the doping
elements, calculated as the oxide, is preferably between 1 and 15 and especially
between 5 and 10% by weight, based on the total weight of the stabilized mixed oxide.
The first cerium/zirconium mixed oxide preferably has a weight ratio of cerium oxide to
zirconium oxide of 0.5 to 0.1, and the second cerium/zirconium mixed oxide preferably
has a weight ratio of cerium oxide to zirconium oxide of 0.8 to 1.2. The specific surface
area of these materials is advantageously within a range between 50 and 100 m2/g.
The active aluminum oxide may be stabilized with 1 to 10% by weight of lanthanum
oxide, based on the total weight of aluminum oxide plus lanthanum oxide. A further
improvement in the thermal stability of the catalyst can be achieved when active
aluminum oxide and the cerium/zirconium mixed oxides are additionally impregnated
with strontium oxide and/or barium oxide.

Usually, the catalyst support is a honeycomb with a volume V, which has parallel flow
channels for the exhaust gases of the internal combustion engine, the wall surfaces of
the flow channels being coated with the catalyst and the concentration of the palladium
based on the volume of the honeycomb being between 0.1 and 10g and the
concentration of the rhodium between 0.01 and 1 g. In a particular embodiment of the
catalyst, the first cerium/zirconium mixed oxide may also be catalytically activated with
palladium in addition to rhodium. In a further embodiment, both cerium/zirconium
mixed oxides may also be activated with platinum.
The noble metal concentrations which should actually be employed depend on the
desired pollutant conversions. The highest concentration values reported here are
required to comply with the strict emissions standards for SULEVs (SULEV = Super
Ultra-Low Emission Vehicles).
To coat the catalyst support with the catalytically active layer, it is necessary to prepare
a coating suspension which comprises all constituents of the desired catalytic layer
either directly or in the form of precursors thereof which are converted to their ultimate
form by the final calcination of the coating.
The two cerium/zirconium mixed oxides can be coated separately with precursor
compounds of rhodium or palladium by known impregnation processes. Preference is
given to using the water-soluble compounds rhodium nitrate and palladium nitrate. The
materials thus precoated can then be suspended in water together with aluminum oxide.
The suspension is ground in wet form until the solids of the suspension have a mean
particle size of about 3 to 5 µm. Thereafter, the honeycombs are coated with this
suspension by known methods, dried and calcined. This production process guarantees
that palladium and rhodium are deposited separately on different support materials.
In a preferred embodiment of the invention, the first cerium/zirconium mixed oxide is
first suspended in water. A solution of a precursor compound of rhodium, preferably
rhodium nitrate, is added to this suspension. Thereafter, the pH of the suspension is
raised to a value of about 6 with a base, for example tetraethylammonium hydroxide
(TEAH), in order to precipitate the rhodium nitrate. Subsequently, the second
cerium/zirconium mixed oxide is suspended in the suspension and a solution of a

precursor compound of palladium is added. This lowers the pH of the suspension into
the strongly acidic range. Further addition of a base raises the pH back to about 6 and
thus precipitates the palladium onto both mixed oxides. Thereafter, aluminum oxide is
added to the suspension and the suspension is finally, as already described, ground and
applied to the catalyst support body. The catalyst thus prepared does not contain any
alkaline earth metals.
Alternatively, a basic solution of barium hydroxide and/or strontium oxide can first be
initially charged. The first cerium/zirconium mixed oxide is added to this solution and
suspended in the solution. Thereafter, a solution of rhodium nitrate, for example, is
added to the suspension, which precipitates the rhodium onto the first cerium/zirconium
mixed oxide owing to the basicity of the suspension. Thereafter, the second
cerium/zirconium mixed oxide is supplied to the suspension, followed by a palladium
nitrate solution. Finally, aluminum oxide is added to the suspension and the suspension,
as already described, is ground and applied to the catalyst support body. Use of barium
hydroxide or strontium hydroxide as the base for the precipitation of rhodium nitrate
causes barium oxide or strontium oxide to remain in the coating after the final
calcination.
In the catalysts manufactured according to the last two production variants, both
rhodium and palladium are present on the particles of the first cerium/zirconium mixed
oxide.
The invention is illustrated in detail hereinafter with reference to the examples and the
figures. The figures show:
Figure 1: Comparison of the lightoff temperatures of a prior art catalyst with catalysts
according to different embodiments
Figure 2: Maximum conversions of the catalysts of figure 1
Comparative example
A catalyst according to EP 1 541 220 was prepared. To this end, a suspension of barium
sulfate in water was first prepared. 1% by weight nitric acid was added to this

suspension and the pH was thus lowered to about 5. Thereafter, a γ-aluminum oxide
stabilized with 3% by weight of lanthanum oxide was added, followed by a
cerium/zirconium mixed oxide with a zirconium oxide content of 50% by weight, and
the pH was kept approximately constant by means of nitric acid during the addition.
After the addition of 10% by weight of sucrose, the suspension was ground, and then
palladium nitrate and rhodium nitrate were added. After a maturing time of one hour, a
cordierite honeycomb was coated with the suspension, dried and calcined. The
honeycomb had a cell density of 93 cm"2, a diameter of 14.4 cm and a length of
10.2 cm. The finished catalyst contained the following amounts of coating:
80 g/1 of lanthanum-stabilized aluminum oxide
75 g/1 of cerium/zirconium mixed oxide (70% by weight of zirconium oxide)
0.18 g/1 of rhodium (on all solid components)
0.88 g/1 of palladium (on all solid components)
Example 1
An inventive catalyst was prepared as follows:
A zirconium-rich cerium/zirconium mixed oxide (70% by weight of zirconium oxide)
was suspended in water, and then rhodium nitrate was stirred into the suspension.
TEAH was used to raise the pH of the suspension back to a value of about 6. Thereafter,
a cerium/zirconium oxide with 50% by weight of zirconium oxide was added to the
suspension, and palladium nitrate was stirred into the suspension. The pH was raised to
6 again with TEAH, before a y-aluminum oxide stabilized with 3% by weight of
lanthanum oxide was added to the suspension. Subsequently, the suspension was ground
and a honeycomb was coated therewith as in the comparative example, dried and
calcined. The finished catalyst contained the following amounts of coating:
80 g/1 of lanthanum-stabilized aluminum oxide
35 g/1 of first cerium/zirconium mixed oxide (70% by weight of zirconium
oxide)
40 g/1 of second cerium/zirconium mixed oxide (50% by weight of zirconium
oxide)

0.18 g/1 of rhodium (on first cerium/zirconium mixed oxide)
0.88 g/1 of palladium (on first and second cerium/zirconium mixed oxide)
Example 2
A further inventive catalyst was prepared as follows:
Barium hydroxide was dissolved in water. The cerium/zirconium mixed oxide with 70%
by weight of zirconium oxide was suspended in this solution, and rhodium nitrate was
added to the suspension. Thereafter, the cerium/zirconium oxide with 50% by weight of
zirconium oxide was dispersed in the suspension, and palladium nitrate was stirred into
the suspension. After the addition of the aluminum oxide, the pH was adjusted to the
value of 6 with acetic acid. Finally, the suspension was ground and a honeycomb was
coated therewith, dried and calcined as in the comparative example. The finished
catalyst contained the following amounts of coating:
80 g/1 of lanthanum-stabilized aluminum oxide
2 g/1 of barium oxide
35 g/1 of first cerium/zirconium mixed oxide (70% by weight of zirconium
oxide)
40 g/1 of second cerium/zirconium mixed oxide (50% by weight of zirconium
oxide)
0.18 g/1 of rhodium (on first cerium/zirconium mixed oxide)
0.88 g/1 of palladium (on first and second cerium/zirconium mixed oxide)
Testing of the catalysts
Before the testing, all catalysts were exposed to hydrothermal aging in a furnace at a
temperature of 985°C for the duration of 16 hours.
After the aging, the catalysts were examined on an engine test bench with regard to
lightoff temperatures and maximum conversions.
Figure 1 shows the comparison of the lightoff temperatures. The two inventive catalysts
have, after aging, significantly lower lightoff temperatures for the conversion of the HC
(hydrocarbon), CO (carbon monoxide) and NOx (nitrogen oxide) pollutants than the

comparative catalyst. The diagram of figure 2 shows the maximum conversions
achieved with the catalysts.
The catalysts had a backpressure of 18.3 mbar at a gas temperature of 30°C and an air
mass flow of 345 kg/h. This backpressure is about 15% below the backpressure of a
comparable double-layer catalyst.

Claims
1. A three-way catalyst consisting of a single catalytically active coating on an inert
catalyst support of ceramic or metal for the cleaning of the exhaust gases of
internal combustion engines,
characterized in that
the catalyst comprises an active aluminum oxide and a first and a second
cerium/zirconium mixed oxide, the first cerium/zirconium mixed oxide being
activated with rhodium and having a higher zirconium oxide content than the
second cerium/zirconium mixed oxide which is catalytically activated with
palladium.
2. The three-way catalyst as claimed in claim 1,
characterized in that
aluminum oxide and the cerium/zirconium mixed oxides are additionally surface
coated with strontium oxide or barium oxide.
3. The three-way catalyst as claimed in claim 1,
characterized in that
the cerium/zirconium mixed oxides are each stabilized with 1 to 15% by weight of
rare earth oxides, based on the total weight of the mixed oxides, the rare earth
oxides in each case being selected from the group consisting of iron, manganese,
tin, titanium, silicon, yttrium, lanthanum, praseodymium, neodymium, samarium
and mixtures thereof.
4. The three-way catalyst as claimed in claim 3,
characterized in that
the first cerium/zirconium mixed oxide has a weight ratio of cerium oxide to
zirconium oxide of 0.5 to 0.1 and the second cerium/zirconium mixed oxide has a
weight ratio of cerium oxide to zirconium oxide of 0.8 to 1.2.
5. The three-way catalyst as claimed in claim 4,
characterized in that
the active aluminum oxide is in each case stabilized with 1 to 10% by weight of
lanthanum oxide, based on the total weight of the aluminum oxide.

6. The three-way catalyst as claimed in claim 1,
characterized in that
the catalyst support is a honeycomb with a volume V, which has parallel flow
channels for the exhaust gases of the internal combustion engine, the wall surfaces
of the flow channels being coated with the three-way catalyst and the
concentration of the palladium based on the volume of the honeycomb being
between 0.1 and 10 g, and the concentration of the rhodium between 0.01 and 1 g.
7. The three-way catalyst as claimed in claim 6,
characterized in that
the first cerium/zirconium mixed oxide is also catalytically activated with
palladium in addition to rhodium.
8. The three-way catalyst as claimed in claim 7,
characterized in that
the first and second cerium/zirconium mixed oxides are also catalytically
activated with platinum in addition to palladium.
9. The use of the three-way catalyst as claimed in one of the preceding claims as a
close-coupled starter catalyst or as an underfloor main catalyst of a motor vehicle
equipped with a gasoline engine for cleaning the exhaust gases of the engine.

A one-layer three-way catalyst is described for the cleaning of the exhaust gases of internal combustion engines with outstanding activity and thermal stability. The catalyst comprises an active aluminum oxide, a first cerium/zirconium mixed oxide and a second cerium/zirconium mixed oxide. The first cerium/zirconium mixed oxide has a higher zirconium oxide content than the second mixed oxide. The first cerium/zirconium mixed oxide is catalytically activated with rhodium and the second cerium/zirconium mixed oxide with palladium.

Documents:

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Patent Number 269341
Indian Patent Application Number 2717/KOLNP/2009
PG Journal Number 43/2015
Publication Date 23-Oct-2015
Grant Date 16-Oct-2015
Date of Filing 27-Jul-2009
Name of Patentee UMICORE AG & CO.KG
Applicant Address RODENBACHER CHAUSSEE 4 63457 HANAU-WOLFGANG
Inventors:
# Inventor's Name Inventor's Address
1 ROESCH, MARTIN OLMEUTZER STRASSE 2A 63110 RODGAU
2 KLINGMANN, RAOUL 4662 SOUTH 203RD EAST AVENUE, BROKEN ARROW, OK 74014
3 LINDNER, DIETER ANTON-STORCH-STRASSE 14 63457 HANAU
4 RICHTER, JOERG-MICHAEL GLUCKSTRASSE 9 60318 FRANKFURT A.M.
PCT International Classification Number B01J23/44; B01D53/94; B01J23/46
PCT International Application Number PCT/EP2008/001450
PCT International Filing date 2008-02-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 07005548.8 2007-03-19 EPO