2/24/2014 Deactivation of Diesel Catalyst

DieselNet Technology Guide » Diesel Catalysts

www.DieselNet.com. Copyright © Ecopoint Inc. Revision 2002.05c

Deactivation of Diesel Catalyst

Abstract: The causes for the deactivation of diesel catalysts are thermal degradation and poisoning
by lubrication oil additives, as well as by sulfur. Phosphorus is the most common oil-derived catalyst
poison. Sulfur can be found uniformly distributed over the catalyst length and the washcoat depth,
while phosphorus is selectively adsorbed at the catalyst inlet and in a thin, outer washcoat layer.

Catalyst Durability
Thermal Deactivation
Poisoning

1. Catalyst Durability

1.1 Durability Requirements

Deactivation of the diesel catalyst causes gradual deterioration of its performance resulting in increased
emission levels from the vehicle. Most emission standards specify “emission durability” requirements,
defined as the minimum mileage and/or time period after which the engine is still expected to conform with
applicable emission limits. New emission standards typically increase the required emission durability
targets, putting higher demands on emission catalysts and emission control systems in general.

Most U.S. emission standards adopt a two-tier approach to emission durability, which involves (1)
emission warranty and (2) full life durability demonstration. Engine manufacturers warrant to the purchaser
that the engine is designed and built to conform with applicable emissions standards. The following are the
warranty periods for different classes of vehicles through the model year 2003:

5 years or 100,000 miles for heavy-duty diesel engines

5 years or 100,000 miles for medium-duty diesel engines
5 years or 50,000 miles for light-duty diesel engines.

As part of the engine emission certification process, manufacturers are required to demonstrate compliance
with emission standards over the “full useful life” of the engine. Useful engine lives are defined as follows:

8 years or 290,000 miles for heavy-duty diesel engines

8 years or 185,000 miles for medium-duty diesel engines
https://www.dieselnet.com/tech/cat_d_deactiv.php 1/8
2/24/2014 Deactivation of Diesel Catalyst

8 years or 110,000 miles for light-duty diesel engines.

Beginning in model year 2004, the EPA established increased useful life periods for all pollutants. The
revised requirements for the heavy duty diesel engine service class are 435,000 miles, 22,000 hours, or 10
years, whichever occurs first. Very durable catalyst technologies will be needed to meet these increased
requirements.

1.2 Determination of Catalyst Durability

Catalyst deactivation is usually a gradual process. The determination of catalyst durability involves testing of
a fresh catalyst, followed by the test of a catalyst that was aged over a given period of time. Based on the
measured performance, emission deterioration factors can be calculated for each of the pollutants by
dividing the emission result with the aged catalyst by that with the fresh catalyst. The knowledge of emission
deterioration factors, which can be determined not only for catalysts but also for the entire engine-
aftertreatment system, is necessary to provide the required engineering margins when designing emission
control systems.

Many catalysts exhibit a certain activity loss in the short, initial period of their operation. After this initial
activity loss, the catalyst performance remains stable over a long period of time. For this reason, new
catalysts should be “degreened” before emission tests. The catalyst degreening involves a short period of
aging performed usually on an engine dynamometer bench. Emission test results of “fresh catalysts” are
typically measured with degreened units. The duration and conditions of degreening vary greatly between
manufacturers and catalyst types. A quick degreening process may involve a few hours of operation under
a steady-state engine condition. More typically, the degreening lasts 10-20 hours (a 20 hour green aging at
a steady-state condition resulting in 375°C at the catalyst inlet was reported in a diesel oxidation catalyst
study [Henk 1992]). Some automotive catalysts are degreened over transient tests that are designed to
represent the equivalent of as much as 4,000 miles of real driving.

There are three methods of catalyst aging:

field aging,
engine bench aging, and
oven aging.

In the field aging, the catalyst is installed on a vehicle, such as a car, which is then operated over the desired
time period. Field aging is an expensive and time consuming method. A 50,000 mile catalyst aging on a car
requires several months of time and usually involves high costs of the car purchase/lease, operation (fuel,
...), and the driver expense. In order to minimize the time and cost, accelerated engine dynamometer aging
procedures have been developed. The catalyst is installed on an engine operated through a transient test,
which can simulate hundreds of miles of driving in one hour of testing. The test cycle must be designed to
provide high amount of “stress” to the catalyst, such as high exhaust temperatures, transients, or, in the case
https://www.dieselnet.com/tech/cat_d_deactiv.php 2/8
2/24/2014 Deactivation of Diesel Catalyst

of spark ignited engines, lean-rich cycling. The most challenging task in designing accelerated aging tests is
the determination of the equivalency between the real life mileage and the duration of the test. Ideally, the
equivalency is verified by comparing the performance loss of identical catalysts aged in the field and in the
bench test. Accelerated aging tests are very common in the development of automotive catalysts [Kisenyi
1998].

For the purpose of catalyst development and comparison of thermal stability between catalyst formulations,
oven aging is commonly used by catalyst manufacturers. Oven aging of diesel formulation is typically
performed over a number hours at elevated temperature—typically between 600 and 900°C—in a
controlled atmosphere containing oxygen and usually about 10% water vapor. As an example, oven aging
at 650°C (20 ppm SO2, 10% H2O, 10% O2, balance N2) and at 800°C was used in the development of
diesel SCR catalysts, with aging periods ranging from 48 to 100 hours [Gieshoff 2001][Gieshoff 2000].
Oven aging methods are fast and simple, but in most cases cannot be directly related to the emission
durability in real catalyst operation.

1.3 Sources of Deactivation

In general, there are several sources of catalyst deactivation, as discussed in the Catalyst Fundamentals
paper. In the following sections we discuss the two most important modes:

thermal degradation and

catalyst poisoning,

as applied to diesel catalysts.

2. Thermal Degradation

Thermal degradation is the most common mode of the loss of activity of spark ignition engine catalysts,
which may be exposed to temperatures in excess of 1000°C. In the diesel engine, both the exhaust
temperature and the temperature raise (exotherm) in the catalyst due to catalytic reactions are lower than
those in gasoline engines. The peak temperatures in the diesel catalyst rarely exceed 600°C. Since most of
the catalytic materials which were used in early diesel catalysts had been developed for high temperature
gasoline applications, thermal degradation of diesel catalysts was not considered a major problem in the
past. This notion has changed in view of the following considerations:

New diesel-specific materials have been introduced to catalyst formulations, which may require
thermal stabilization.
Catalysts used in low temperature applications have extremely demanding light-off temperature
requirements and cannot tolerate thermal deterioration.

https://www.dieselnet.com/tech/cat_d_deactiv.php 3/8
2/24/2014 Deactivation of Diesel Catalyst

Examples of materials introduced more recently for diesel catalysts include various zeolites or titania, which
are used in both diesel oxidation catalysts and NOx reduction catalysts such as SCR. It is well known that
the anatase form of titanium dioxide used in catalysts is thermally stable only up to about 500°C. In the
case of titania-based SCR catalysts, this temperature limit can be increased by stabilizing titania using
tungsten trioxide (WO3), as discussed in the SCR paper.

Another source of demand for good thermal durability of diesel catalysts comes from the low temperature
passenger car applications in the European Union. This application became even more challenging after
year 2000, when the initial warm-up period was eliminated from the ECE+EUDC test cycle used for
emission measurement. This test cycle is characterized by low engine loads, resulting in very low exhaust
temperatures over a long portion of the cycle, especially in the case of large passenger car engines of more
than 4 cylinders. The catalyst must provide reductions of gaseous emissions, including carbon monoxide,
with required CO light-off temperatures (t50) as low as 150°C. An important source of light-off
temperature deterioration (increase) in catalysts is loss of active sites due to sintering. Catalysts that have to
meet challenging light-off temperature demands, therefore, must be designed for excellent thermal stability.

3. Poisoning

3.1 Common Diesel Catalyst Poisons

A big challenge in the development of durable diesel catalysts is poisoning. There are two major sources of
catalyst poisons in diesel exhaust:

lube oil additives, including phosphorus (P), zinc (Zn), calcium (Ca), and sulfur (S)
additional quantities of sulfur (S) from the diesel fuel.

Since diesel engines burn larger quantities of oil than their gasoline counterparts, the diesel catalyst must be
more resistant to the oil and its additives. Under the cooler modes of operation, the unburnt oils and their
additives deposit within the catalyst washcoat. Unlike the organic portion of the oil, the additives remain
after the oil is catalytically oxidized. Such substances as phosphorus, zinc, and calcium oxide accumulate on
the surface or within the catalyst. Perhaps the most important of these poisons in phosphorous, the major
source of which has traditionally been the antiwear oil additive, zinc diethyldithiophosphate (ZDDP).
Phosphorus can accumulate at the surface of the washcoat, forming a permanent glaze layer which has a
masking effect on the catalyst. Phosphorus and other oil-derived poisons (other than sulfur) typically result
in an irreversible catalyst deactivation.

Traditionally, diesel fuels contained significant quantities of sulfur, several times higher than those present in
gasoline. Those high-sulfur fuels may be another source of catalyst deactivation (with ultra-low sulfur fuels,
the contribution from lube oil to sulfur dioxide levels in the exhaust gas may also become significant). Sulfur
poisoning is frequently reversible by high temperatures, under which the sulfur compounds decompose and
https://www.dieselnet.com/tech/cat_d_deactiv.php 4/8
2/24/2014 Deactivation of Diesel Catalyst

are released from the catalyst washcoat. However, due to the low diesel exhaust temperatures, in many
diesel engine applications the conditions needed for catalyst regeneration may never be reached.

According to a study conducted by Volkswagen/Degussa [Beckmann 1992], sulfur and the lube oil additives
(phosphorus) can produce cumulative poisoning effects of comparable magnitudes. The loss of catalyst
activity can be represented by its loss of carbon monoxide conversion efficiency (Table 1). Among three
engine aged samples of the same catalyst, the highest loss of activity was observed when both high sulfur
fuel and high phosphorus lubrication oil were used. Aging with low sulfur fuel (0.04% S) and high P oil
induced the same loss of activity as aging with low phosphorus oil (0.05% P) and high S fuel.

Table 1
Influence of Poisons on Catalyst Activity

Catalyst Sample S in Fuel, % P in Oil, % CO Conversion, %

Fresh 0.15 0.1 94
Aged 32 hrs 0.15 0.1 80
Aged 32 hrs 0.04 0.1 89
Aged 32 hrs 0.15 0.05 89

Certain poisons can be also derived from vehicle components. An important example is silicon (Si),
contained in sealants, washers, etc., which can enter the combustion chamber and/or the exhaust stream
being carried by the fuel or through out-gassing. Si was reported to be an effective poison of gasoline
catalysts [Gandhi 1986]. It can be reasonably expected that diesel catalysts, if exposed, would be also
deactivated by Si. This kind of poisoning is also known in engines operated with certain types of biogas
fuels which contain silicon compounds.

Contamination with silicon is apparent as crystalline deposits of SiO2, which in extreme cases may plug the
inlet face of the monolith. Silicon deactivation was reported to be reversible though washing in hydrofluoric
acid and ultrasonic treatment in soapy water [Eastwood 2000].

3.2 Distribution of Poisons

Diesel catalyst makers developed special test methods and conducted several studies to determine how
different poisons are deposited within the catalyst. Knowledge of the poison locations and their interactions
with the active catalytic sites allows the catalyst manufacturer to design more poison tolerant catalysts.

Figure 1 shows microprobe traces for S and P which were scanned across a 75 µm thick washcoat fillet
[Heck 1995]. Sulfur was found to accumulate throughout the entire depth of the washcoat, while the
phosphorus compounds were concentrated in the outer 15-20 microns. The washcoat interface with the
monolith is at about 75 µm, as is evident by the drop in the S profile to zero. Zn and Ca containing
compounds, not shown in Figure 1, were concentrated practically entirely at the washcoat surface, within
the outer 10-15 microns layer.

https://www.dieselnet.com/tech/cat_d_deactiv.php 5/8
2/24/2014 Deactivation of Diesel Catalyst

Figure 1. P and S Distribution in the Washcoat of an Aged Diesel Catalyst

The distribution of poisons across the washcoat thickness, as well as along the catalyst length, was also
investigated in the above mentioned work by Volkswagen/Degussa [Beckmann 1992]. Adsorption of sulfur,
carbon, phosphorus, and zinc were measured on a Pt-based diesel catalyst. The findings, which are in
general agreement with the data from Figure 1, can be summarized as follows:

Sulfur compounds, which included sulfites, sulfates, and thiosulfates, were uniformly distributed over
the catalyst length and the washcoat depth. The amount of S in the catalyst depended both on the
washcoat type and on the noble metal loading.
Carbon formed a separate layer at the washcoat surface. The amount of adsorbed carbon
decreased at higher noble metal loading but was independent of the washcoat technology.
Phosphorus was selectively adsorbed at the inlet side of the catalyst and in the outer layer of the
washcoat. The adsorption was independent of the washcoat technology or of the platinum loading.
Zinc was found only within the carbon layer and not within the washcoat.

Considering the distribution of oil derived poisons in the catalyst, poison tolerant catalysts can be designed
by locating the active catalytic species in protected depths within the washcoat. The washcoat must also be
designed to be chemically inert to the poisons. Furthermore, the washcoat pore structure should be
designed to tolerate large amounts of the fouling materials to prevent pore blockage and the subsequent
pore diffusion limitations that result.

The main catalyst can be protected (at least to some degree) from poisons which adsorb selectively at the
inlet side by an upstream guard catalyst. Guard catalysts, commonly known in the chemical processing
industry and also used in stationary engine applications, are “blank”, non-precious metal containing
catalysts designed to provide adsorption capacity for poisons. Replacement of a poison-saturated guard
catalyst is much more cost-effective than replacing a poisoned precious metal catalyst. Guard catalysts can
be coated with alumina washcoat, or else with coatings optimized for the adsorption of particular poisons.

https://www.dieselnet.com/tech/cat_d_deactiv.php 6/8
2/24/2014 Deactivation of Diesel Catalyst

3.3 Restoring Catalyst Activity

In some cases the activity of a poisoned catalyst can be restored, at least in part. As mentioned before,
certain poisons (e.g., sulfur) may be driven off the catalyst washcoat through exposure to high
temperatures, either on the engine or in an oven. Many cases of catalyst fouling or masking can be
remedied by cleaning of the catalyst. Catalyst cleaning, not usual with small catalysts in mobile engine
applications, is a commonplace procedure in stationary applications using large and expensive catalysts
[Miratech 2004].

There are three groups of catalyst cleaning methods:

Air cleaning
Washing (in water or solvents)
Chemical washing

Fouling and ash buildup can sometimes be cleared using either compressed air or vacuum. The preferred
method in the case of ash accumulation is to simply vacuum the catalyst face. Washing using water or other
solvents can restore catalyst activity by removing poisons, masking, fouling or inhibiting agents, provided
such agents are soluble in the solvent. The most simple washing procedure is to rinse the catalyst using
water or, better, deionized water. More effective cleaning procedures use various chemicals to remove
poisons. An alkaline (high pH) wash may be very effective in removing organic resins, residues, and some
deposits resulting from lube oil contamination. For many inorganic substances, an acidic (low pH) wash will
be more effective. Solutions of EDTA (ethylenediaminetetraacetic acid), a commonly known chelating
agent, are sometimes used as acidic catalyst wash. Washing should be performed in consultation with the
catalyst manufacturer, as chemicals may cause damage to the catalyst or its substrate.

References
Beckmann, R., et al., 1992. “A New Generation of Diesel Oxidation Catalysts”, SAE Technical Paper 922330, doi:10.4271/922330
Eastwood, P., 2000. “Critical Topics in Exhaust Gas Aftertreatment”, Research Studies Press, Baldock, Hertfordshire, England
Gandhi, H.S., et al., 1986. “Silicon Contamination of Automotive Catalysts”, SAE Technical Paper 860565, doi:10.4271/860565
Gieshoff, J., et al., 2000. “Improved SCR Systems for Heavy Duty Applications”, SAE Technical Paper 2000-01-0189,
doi:10.4271/2000-01-0189
Gieshoff, J., et al., 2001. “Advanced Urea SCR Catalysts for Automotive Applications”, SAE Technical Paper 2001-01-0514,
doi:10.4271/2001-01-0514
Heck, R.M ., R.J. Farrauto, 1995. “Catalytic Air Pollution Control: Commercial Technology”, Van Nostrand Reinhold, New York
Henk, M .G., W.B. Williamson, R.G. Silver, 1992. “Diesel Catalysts for Low Particulate and Low Sulfate Emissions”, SAE Technical
Paper 920368, doi:10.4271/920368
Kisenyi, J.M ., et al., 1998. “Correlation between Dynamometer- and Vehicle-Aged Catalysts for Automotive Lean-Burn
Applications”, SAE Technical Paper 980934, doi:10.4271/980934
M iratech, 2004. “M IRATECH Catalyst Services”, Product/service brochure; M iratech Corporation, Tulsa, OK, USA,
http://www.miratechcorp.com/fireapp-content/uploads/2013/07/M IRATECH_Catalyst_Services.pdf

https://www.dieselnet.com/tech/cat_d_deactiv.php 7/8
2/24/2014 Deactivation of Diesel Catalyst

###

https://www.dieselnet.com/tech/cat_d_deactiv.php 8/8