Commercial Catalyst Technologies

The main function of today’s commercial diesel catalyst is the control of diesel
particulates through the control of their organic fraction (SOF). Catalyst formulations have
been optimized to minimize generation of sulfate particulates. Lean NOx catalysts have also
been introduced for some applications. Different catalyst technologies are needed for the
temperature conditions of different emission test cycles, such as the US heavy-duty FTP cycle
or the European ECE+EUDC cycle.

INTRODUCTION

Most of modern commercial diesel catalysts are diesel oxidation catalysts (DOC) optimized
for the reduction of diesel particulate matter emissions through the removal of their heavy
organic fraction known as SOF. Certain emission regulations—for instance EU standards for
diesel passenger cars—also establish stringent limits on gaseous emissions of HC and CO,
which must be reduced in the catalyst as well, often with high efficiencies. Other regulations
—for instance US standards for heavy-duty engines—set CO and HC limits that are easily met
without a catalyst. Control of NO x emissions would be an extremely desirable function of the
diesel catalyst. While existing technologies cannot yet provide significant degrees of NO x
reduction, small NOx control functionality has been incorporated into commercial diesel
oxidation catalysts. Such catalysts, able to control all four regulated pollutants, are
sometimes referred to as “four-way catalysts”. Commercial diesel catalysts also reduce
several unregulated emissions, such as aldehydes and PAHs, as well as the diesel odor.

Mechanisms of catalytic PM emission control were explained when discussing the DOC
technology. In short, SOF can be removed in the DOC with very high efficiency through
catalytic oxidation and/or cracking. Storage and release of hydrocarbons in the catalyst
washcoat may also play an important role and influence the apparent PM conversion
efficiency. On the other hand, the carbonaceous fraction of diesel particulates—or dry soot—
is practically not oxidized in the catalyst. Thus, the potential for total particulate matter
(TPM) reduction depends on what fraction of TPM is composed of SOF (which, in turn,
depends on the engine technology and the emission test cycle). For example, if SOF forms
40% of the total particulate matter emission, the maximum possible conversion of TPM in
the catalyst is limited to about 40%.

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Oxidizing the SO2 to SO3 is a counterproductive process occurring in the diesel oxidation
catalyst which increases TPM emissions by the generation of sulfate particulates. The
fundamental problem in the development of catalysts for the removal of diesel particulates
has been to design a selective catalyst, i.e., one that will remove SOF without oxidizing SO 2.
Catalyst performance and its effectiveness in reducing PM emissions is strongly affected by
the following parameters:

 Sulfur content in the fuel (and in the lube oil in the case of ultra low sulfur fuels),

 SOF content of diesel particulates (and, thus, the engine test cycle),

 Exhaust gas temperature at catalyst inlet (and, thus, the engine test cycle and catalyst
location),

 Catalyst washcoat and precious metal system,

 Catalyst volume and substrate configuration (e.g., cell density).

As indicated, two of the above parameters—SOF content and exhaust temperature—critically

depend on the engine/vehicle test cycle. Modern diesel oxidation catalysts are tailored for
their applications and, most importantly, for the test cycle to be applied during the emission
certification or type approval process. Generally, catalytic oxidation rates of SO 2 increase
with temperature. Thus, the catalyst sulfate make becomes difficult to control over cycles
characterized by heavier load factors, that produce high exhaust temperatures. The SOF
content follows the exactly opposite tendency; the highest SOF content in the TPM is
measured at low engine loads and exhaust temperatures. Therefore, oxidation catalysts are
most effective in controlling diesel PM emissions over lightly loaded, low- to medium-
temperature test cycles. The catalyst light-off temperature presents the low temperature limit
for the catalyst effectiveness. As will be discussed, many modern DOCs include zeolite-based
HC traps which can extend the low temperature SOF activity by storing hydrocarbons in the
catalyst washcoat. Nevertheless, low light-off temperature is a very important and desirable
property of the diesel oxidation catalyst.

Diesel car emissions in the European Union are tested over the ECE+EUDC cycle which is
characterized by low engine loads and maximum exhaust gas temperatures typically below
300-350°C. Under these conditions PM can be controlled effectively by the DOC, due to both
high SOF content in the particulates and relatively straightforward control of sulfate
formation in the catalyst. Catalytic PM emission reduction of as much as 60-70% may be
possible over the European driving cycle. Temperatures during the heavy-duty FTP transient

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cycle, which is used for the certification of truck and bus engines in the USA, average around
350°C. Catalytic particulate matter control might be difficult, especially on hot running
engines and advanced catalyst formulations are necessary. The possible degree of PM control
over the FTP transient test is in most cases limited to some 25%. Test cycles used for type
approvals of heavy-duty diesel engines in Europe—including the ESC, ETC, as well as the
pre-Euro 3 ECE R-49—are all characterized by heavy engine loads and high temperatures,
often in excess of 500°C. Catalytic PM control over these cycles is very difficult or impossible
due to both sulfate formation and low SOF content.

Figure 1. DOC Performance in Different Test Cycles

Performance of three catalyst formulations of increasing selectivity in three different test

cycles is illustrated in Figure 1 [Smedler 1995]. The catalyst formulations utilize the Pt/Al 2O3
system with base metal oxide additive to suppress sulfate formation. Catalyst 1 of the lowest
selectivity can effectively control PM emissions under the ECE+EUDC cycle but generates
high quantities of sulfate particulates when tested in the ECE R-49 test cycle (negative
conversions in the graph indicate an increase in TPM emissions). Even the most selective
catalyst 3 shows only a small TPM emission reduction over the ECE R-49.

Improvements in catalyst selectivity are always accompanied by a deterioration in their

activity. The decreasing performance for the oxidation of hydrocarbons and carbon
monoxide with increasing catalyst selectivity is well pronounced in Figure 1. The same three
catalyst formulations are compared in Figure 2 which illustrates the SO 2 activity as a function
of the CO light-off temperature. Catalyst 3 exhibits an excellent CO light-off of 180°C but
oxidizes about 90% of the sulfur dioxide. The selective catalyst 3 oxidizes less than 20% of
SO2 but its CO light-off is 260°C.

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 Figure 2. Activity vs Selectivity of DOC

Introduction of diesel fuels of decreased sulfur content makes the sulfate issue less
prominent, thus allowing for use of more active catalyst formulations. The sulfate make,
however, always needs to be evaluated in the context of existing PM emission standards.
Assuming 10 ppm S fuel plus an equivalent sulfur amount from the lube oil, an active DOC
can easily produce sulfates on the order of 0.01 g/bhp-hr (see DOC paper). This figure may
be insignificant when compared with the US 1994 PM standard of 0.1 g/bhp-hr, but is clearly
prohibitive in view of the US 2007 standard of 0.01 g/bhp-hr.

LIGHT DUTY ENGINES

The main area of DOC application in light-duty vehicles are EU cars, which are emission
tested for the type approval over the ECE 15 + EUDC driving schedule. This test involves four
repetitions of the slow, urban driving ECE segment, followed by one repetition of faster,
highway driving EUDC segment. Originally, the test was started after a 40 s warm-up period,
which was eliminated at the Euro 3 stage (2000). The new, cold-start version of the test is
referred to as the New European Driving Cycle (NEDC). In the USA, light duty vehicles are
emission certified over the FTP-75 test, which is characterized by somewhat higher engine
load factors than the European cycle (but still produces low exhaust temperatures in
comparison with tests for heavy-duty engines).

Exhaust gas temperatures from a number of diesel cars and light trucks (vehicles C and D)
are shown in Figure 3 [Lueders 1997]. Most of the data was collected over the cold-start
ECE+EUDC test (NEDC), as indicated in the chart. The T10 values, shown as the left end of
each bar, are defined as temperatures above which exhaust gas temperature is 90% of the

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time. The T90 values, shown as the right end of each bar, are defined as temperatures below
which exhaust gas temperature is 90% of the time.

Figure 3. Exhaust Temperature in Light Duty Vehicles

A: 1.9 l IDI; B: 1.9 l TDI; C: 2.5 l DI; D: 2.5 l TDI; E: 1.9 l TDI; F: 1.9 l
TDI; G: 1.9 l TDI; H: 3 l IDI

While there is a certain variation between vehicles and engines, exhaust temperatures are
generally low, in some cases below 300°C. These low exhaust gas temperatures result in
relatively high SOF content in the TPM. At the same time, the sulfate make in the catalyst
becomes less critical than in high temperature applications, providing favorable conditions
for catalytic PM control. The major challenge facing catalyst developers is to develop durable
formulations of low light-off temperatures.

In the European Union, diesel oxidation catalysts were introduced on a number of Euro 2
(1996) and practically all Euro 3 (2000) diesel passenger car models. Commercial use of
catalysts was made feasible by the introduction of the 500 ppm sulfur limit in diesel fuel in
1996. The catalyst, in addition to the particulate matter removal, has to be effective in the
oxidation of gas phase hydrocarbons and carbon monoxide. The cool driving conditions
contribute to increased formation of odors from unburned hydrocarbons and aldehydes.
Although odors are not regulated, their control is also a desirable feature of the diesel car
catalyst. Since the Euro 2 stage, NOx emissions are controlled chiefly through exhaust gas
recirculation (EGR), but certain Euro 3/4 catalysts also incorporate some lean NO x reduction
activity.

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Diesel oxidation catalysts remain the major emission control component in Euro 4 (2005)
cars. In small-to-medium sized cars, Euro 4 limits can be met using the DOC + EGR
technology (i.e., without the need for diesel particulate filters for PM control). While the Euro
4 emission limits are more stringent than Euro 3, the DOC application becomes in many
respects easier due to the lower sulfur content in the fuel. The maximum sulfur content in
Euro 4 reference (type approval) diesel fuel, initially introduced as 50 ppm, was later lowered
to 10 ppm.

The configuration of first diesel catalyst systems in light duty vehicles featured a single
catalytic converter in the underfloor position. Elimination of the warm-up period in the
NEDC test cycle at the Euro 3 stage created more challenges related to cold-start emissions.
As a result, catalysts were moved closer to the exhaust manifold to expose them to the
highest possible exhaust temperatures. In some Euro 3/4 cars, catalyst systems include two
catalytic converters: a smaller close-coupled pre-catalyst, followed by the main converter in
the underfloor position [Renault 2001]. This configuration—resembling catalyst systems used
in many gasoline applications—was introduced mainly in large size engines, where catalyst
light-off and cold start issues are especially challenging. It was also proposed (but not
commercialized) that the pre-catalyst be moved upstream of the turbocharger to expose it to
even higher temperatures and maximize its performance [Reizig 2001][Saroglia 2002].

Advanced commercial catalysts for diesel cars can incorporate a number of technologies,
such as:

 oxidation catalyst,

 HC adsorber (trap),

 lean NOx catalyst.

Considering the need for simultaneous PM, CO and HC control, commercial catalyst
technologies for EU diesel cars are typically active Pt formulations on alumina-based
washcoats. While satisfactory PM and HC performance is possible using medium (say 10-20
g/ft3) Pt loadings in combination with HC adsorbers, high precious metal content gradually
became the main strategy to achieve durable low-temperature CO light-off. At the Euro 4
stage, platinum loadings as high as 80-100 g/ft 3 are not uncommon, with somewhat lower
loadings used in the two catalyst configuration (the diesel pre-catalyst is also Pt based,
contrary to the Pd pre-catalysts common in gasoline engines).

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In applications with higher sulfur levels (Euro 2-3), an important requirement of the DOC
formulation was sulfate suppression. This was achieved through the use of either sulfate
inhibitors (V2O5) or non-sulfating washcoat materials (TiO 2, SiO2, ZrO2). Catalyst selectivity
became less important in Euro 4 catalysts due to low sulfur content in the fuel.

Zeolite-based hydrocarbon traps became another standard component in many modern

diesel oxidation catalysts. Zeolites are used to enhance the low temperature hydrocarbon
performance through storage of HCs in the catalyst washcoat [Leyrer 1996]. The general idea is
to adsorb (store) the hydrocarbons which are produced during low temperature operation
and release them when a certain adsorber temperature is reached. It is essential that the
adsorbing material is capable of dragging the stored hydrocarbons into a temperature range
where the true catalytic oxidation of the HCs starts. Otherwise the hydrocarbons would
desorb at temperatures before they can be destroyed at the active sites of the catalyst without
any advantage in the overall hydrocarbon removal.

Some catalysts also incorporate a limited NO x reduction activity, on the order of 15%. These
formulations typically utilize lean NOx activity of the Pt/Al2O3 system. They also incorporate
zeolite HC traps to provide increased HC levels within the lean NO x catalyst temperature
window, thus enhancing NOx reduction over the Pt catalyst.

An example catalyst incorporating various functionalities is a Pt/zeolite/alumina formulation

developed by ASEC (Delphi) [Sawyer 1998]. The catalyst washcoat is composed of zeolites and
alumina. The zeolites must be capable of trapping diesel HCs at temperatures below about
250°C and releasing them at above 250°C. The required temperature durability is 750-
850°C. The preferred types of zeolite are beta and Y, with Si/Al ratio of 5-50 and pore size of
about 0.6 nm. A mixture of two zeolites can be used, one of pore size above 0.6 nm to trap
longer chain hydrocarbons, the other with smaller pores to trap shorter chain HCs. γ-
alumina is added to the washcoat to improve adhesion of the zeolite to substrate, as well as to
aid in the oxidation of CO. Typical washcoat loadings are 90-100 g/dm 3 zeolite and about 15
g/dm3 alumina. The noble metal is in most cases pure Pt. While the described metal loadings
are around 10 g/ft3, it is believed that higher Pt content may be needed in commercial Euro
3/4 applications to achieve high and durable CO conversion rates.

In applications where sulfate make is a problem vanadium oxide is used as sulfate

suppressant. Typical vanadium loading is 5 g/ft 3 (as V metal). For the 10 g/ft 3 Pt loading, this
is equivalent to a V/Pt ratio of about 2 by mole or 0.5 by mass. Loadings of both Pt and V are

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varied depending on the application. In some catalysts described by ASEC, Pt loadings were
decreased to as little as 5 g/ft3 and V loadings were increased to as much as 60 g/ft 3.

The combined adsorption/catalytic oxidation effect on the apparent HC conversion in the

Pt/zeolite/alumina catalyst is illustrated in Figure 4 [Kharas 1998]. Three oxidation catalysts
incorporating zeolite HC traps were tested on a quasi-steady state engine dynamometer test.
The exhaust temperature was increased stepwise during the test. Diesel fuel was injected into
the exhaust gas to maintain an HC1/NOx ratio of 10.

Figure 4. Performance of HC Trap/Catalyst Systems

The HC conversion observed below approximately 200°C is attributed to adsorption into the
micropore volume of the zeolite. The declining HC conversions are likely caused by gradual
saturation of the trap adsorption capacity. Catalytic oxidation is the HC removal mechanism
at higher temperatures. In catalyst A, desorption apparently preceded catalyst light-off,
resulting in a negative HC conversion around 190°C. Catalysts B and C showed increasingly
better HC adsorption/desorption characteristics.

The zeolite HC trap technology is compatible with the lean NO x activity of Pt/Al2O3 catalysts.
These catalysts promote selective reactions between HC and NO x. Therefore, their NOx
conversion increases with increasing HC/NO x ratio in the exhaust gas. Zeolites that would
desorb hydrocarbons at temperatures of maximum NO x reduction activity can enhance the
lean NOx function of the catalyst. This catalyst strategy has been adopted in several systems
for Euro 3 cars. An example of the four-way performance of the Pt/zeolite/alumina catalyst is
shown in Figure 5. The overall emission reduction of the catalyst over the NEDC cycle was
HC - 92%, CO - 90%, NOx - 19%, and PM - 71% [Kharas 1998].

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 Figure 5. Four-Way Activity of a Pt/Zeolite/Alumina Catalyst

The maximum NOx reduction activity of the Pt catalyst occurs at about 200 - 250°C. For this
reason the catalyst would “lose” its lean NOx activity when tested on a hotter test cycle, such
as those used for heavy-duty engines. However, the low temperature HC performance benefit
due to the zeolite can be easily applied in catalysts for heavy-duty engines. In fact, very
similar catalyst technology has been offered in certain aftermarket catalysts for occupational
health and safety applications (mining, engines operated indoors, etc.). These catalysts can
offer superior HC and diesel odor control at low temperatures, e.g. during operation with
frequent engine idling. It should be remembered that the zeolite adsorber catalysts have a
limited HC adsorption capacity and are truly effective only under transient engine
conditions, such as those in diesel powered cars during city driving. Under low temperature
steady state operation or testing, the HC emissions would be removed only by a fresh catalyst
and for a limited time, until the zeolites are saturated.

As durable catalyst light-off and cold start performance remain a challenge, catalyst
manufacturers continuously develop formulations of improved low temperature activity. To
close this section, we should mention one of such more recent catalysts, disclosed by Degussa
(OMG), which uses platinum on alumina/silica washcoat with lead (Pb) as a promoter to
enhance low temperature performance [Klein 2000a].

HEAVUY DUTY ENGINES

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The main area of diesel oxidation catalyst use on new heavy-duty engines are US truck and
bus applications, which are emission certified over the heavy-duty FTP Transient test. At the
medium to high temperatures observed during that cycle—as illustrated in Figure 6—
particulate matter emissions can be controlled by a catalyst with suppressed sulfate make. In
1994, when the 0.1 g/bhp-hr PM emission standard was introduced by the US EPA (in
coordination with 500 ppm sulfur diesel fuel), several models of truck and urban bus diesel
engines in the USA were equipped with catalytic converters. The use of catalysts then
gradually declined, as the 0.1 g PM standard could be met on advanced, electronically
controlled engines without catalysts. DOCs, however, continued to be used on urban bus
engines, which have more stringent PM standard of 0.05 g/bhp-hr. Starting in October 2002,
DOCs were introduced again on certain 2004-compliant engines, such as the Caterpillar
ACERT engines.

Figure 6. Exhaust Gas Temperature Over FTP Transient Cycle

Model year 1999, heavy-duty, DI, turbocharged, intercooled diesel

engine

The only required function of the catalyst on US truck and bus engines has been the control
of PM emission; no CO or HC activity has been needed as the respective emission standards
are fairly relaxed and are easily met by diesel engines without aftertreatment. Due to the
higher exhaust temperatures over the FTP test (as compared to the light-duty applications),
highly selective catalysts with good sulfate make control are required. These selective
catalysts have reduced activity, resulting in a certain performance penalty. Many of these
catalysts, especially the base metal formulations, can have very low CO and HC activity.
Considering also the decreased SOF content (relative to LD engines), the degree of PM
emission reduction over the FTP test is limited to about 25%, with many commercial
catalysts providing as little as about 10% of PM benefit.

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Active high Pt loading catalysts generate too much sulfate over the FTP test. Several
alternative catalyst strategies or their combinations have been pursued for the US heavy-duty
truck engines:

 base metal catalyst,

 platinum catalyst with low precious metal content and sulfate suppressants,

 palladium catalyst.

Platinum catalyst activity towards the oxidation of SO 2 increases with the precious metal
loading. Maintaining low Pt loading, such as between 0.1 and 5 g/ft 3, produces catalysts with
suppressed sulfate formation. Pt catalysts of medium metal loadings, such as 10 g/ft 3, are still
viable on the FTP test, provided a sulfate suppressant is added (such as vanadium).
Palladium catalysts were also used of Pd loadings in the range of 40-60 g/ft 3. Washcoat
formulations are optimized to include various base metal oxides which inhibit sulfate make
or exhibit catalytic properties towards the reduction of SOF emissions.

A low Pt catalyst with a catalytically active base metal oxide has been developed and
commercialized by Engelhard [Farrauto 1997]. In its first generation, the catalyst washcoat was
composed of high surface area, stabilized alumina and ceria in approximately equal loadings.
Alumina and ceria may be mixed together and form one layer, or may be applied as two
separate washcoat layers. The particulate matter performance of the catalyst is explained by
catalytic activity of ceria. The SOF fraction of diesel particulates is removed over the cerium
oxide catalyst through a mixed cracking and oxidation mechanism. Platinum content is
apparently not important (or has little importance) for the PM removal function of the
catalyst but is necessary for the conversion of gas-phase HC and CO.

The performance of the ceria catalyst was evaluated by steady state testing on a Cummins
6BT DI turbocharged diesel engine having a 5.9 liter displacement and rated at 190 hp
[Farrauto 1997]. Three catalyst samples S4, S5, and S6 contained 0.0, 0.5, and 2.0 g/ft 3 Pt
respectively and were coated on 400 cpsi cordierite substrates of 229 mm (9") diameter and
152 mm (6") long (6.25 liter). A catalyst washcoat comprised of a gamma-alumina undercoat
at a loading of 61 g/dm3 (1.0 g/in3) was coated with a top layer comprised of 64 g/dm 3 (1.05
g/in3) gamma-alumina plus 55 g/dm3 (0.90 g/in3) alumina-stabilized ceria (2.5% Al2O3). The
catalyst samples were subjected to about 25 hours of engine aging prior to testing. Selected
test results are shown in Figure 7 and Figure 8.

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 Figure 7. Effect of Pt Loading on TPM Removal

Figure 7 presents the effect of Pt loading on the TPM conversion. It is apparent that catalysts
with different metal loadings show a very similar PM removal effectiveness indicating that
the role of platinum is negligible in the SOF removal mechanism. Negative TPM conversions
at temperatures above 500°C indicate increased particulate emissions due to the formation
of sulfates in the catalysts. All catalyst samples, including the Pt-free formulation (S4), make
sulfates at very high temperatures.

There is a well pronounced relationship between Pt loading and gaseous HC conversion, as

shown in Figure 8. The Pt-free formulation S4 is relatively inactive with maximum HC
conversion of about 40%. The 2 g/ft3 Pt formulation S6 exhibits a substantial improvement
with HC efficiency around 80%. Additional testing demonstrated very little performance
improvement when Pt loading was further increased beyond 2 g/ft 3. Conversion of CO
showed trends which were very similar to those recorded with hydrocarbons. These results
indicate that the function of platinum in the ceria catalyst is to enhance the gas-phase (HC +
CO) catalyst performance.

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 Figure 8. Effect of Pt Loading on Gas Phase HC Removal

The ceria catalyst showed SOF performance even at low exhaust temperatures (<200°C),
presumably due to storage of hydrocarbons in the catalyst washcoat. A 1000 hour engine
testing demonstrated satisfactory durability of the ceria catalyst, despite its low platinum
content. However, in many real-life applications Pt loadings higher than 2 g/ft 3 are used,
such as 5 g/ft3 or higher. The reason for higher Pt loadings are (1) increased durability and
(2) increased conversion efficiency, especially for CO and gaseous HC.

A second generation of this ceria catalyst additionally incorporates beta zeolite, which further
enhances the HC storage function for improved low temperature performance [Yavuz 2001].
The washcoat is composed of equal amounts of the zeolite, alumina, and alumina-stabilized
ceria. The preferred Pt loading according to the examples in the patent appears to be 2.5
g/ft3.

Diesel catalyst technologies have not been used to control PM emissions at high exhaust gas
temperatures, such as encountered over the EU test cycles for HD engines. Sulfates produced
over the catalyst during the high engine load modes would more than offset any SOF removal
benefit. A system with temperature controlled catalyst which was once proposed for ECE R-
49 applications is shown in Figure 9 .

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 Figure 9. Temperature Controlled Catalyst

Exhaust gas temperatures upstream (T1) and downstream (T2) of the catalyst would be
continuously monitored by an electronic control unit (ECU). When temperatures exceeded
380°C the exhaust gases would bypass the catalyst preventing excessive formation of
sulfates. Systems of this type were never commercialized, as emission standards for heavy-
duty engines were met without aftertreatment. Considering the low SOF content on high
temperature cycles, the PM emission reduction benefit of the catalyst would be likely very
limited.

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