5.

1 Diesel Oxidation Catalysts

Due to the higher A/F ratio, the three-way catalysts (TWC) used for stoichiometric-burn gasoline

engines are not able to efficiently operate in diesel engine exhaust. To achieve the same

emissions targets, diesel exhaust systems require multiple strategies. Typically, the first

component following the engine is the diesel oxidation catalyst (DOC). DOCs have been used

since 1967, where they were first used for indoor forklifts and underground mining vehicles

where air quality for workers was a major issue. As the name suggests, CO and hydrocarbon

reactions readily occur over the DOC, although total NO X emissions are not necessarily altered.

Initially, vehicle engine emissions regulations targeted only CO and hydrocarbons (HCs)

emissions, and when engine modifications alone could not reach the emissions limits of the 1970

Clean Air Act, many types of catalysts were investigated. Transition metals such as copper and

nickel and other base metals were too sensitive to fuel contaminants and lacked sufficient

thermal durability. Platinum group metals, including platinum (Pt) and palladium (Pd), showed

good oxidation performance along with good thermal durability, and as such have been used in

catalytic converters since their inception. Rhodium (Rh) is sometimes also added, primarily for

NOX reduction. In terms of diesel emissions, DOCs with precious metal components provide

high oxidation activity for CO, unburned hydrocarbons, and liquid hydrocarbons (soluble

organic fraction (SOF) components).

Diesel Oxidation Catalysts (DOC)as shown in the fig.1 are catalytic converters designed

specifically for diesel engines and equipment to reduce Carbon Monoxide (CO), Hydrocarbons

(HC) and Particulate Matter (PM) emissions. DOC's are simple, inexpensive, maintenance-free

and suitable for all types and applications of diesel engines.Modern catalytic converters consist

of a monolith honeycomb substrate coated with platinum group metal catalyst, packaged in a
stainless steel container. The honeycomb structure with many small parallel channels presents a

high catalytic contact area to exhaust gasses. As the hot gases contact the catalyst, several

exhaust pollutants are converted into harmless substances: carbon dioxide and water.

Fig.1 Diesel Oxidation Catalyst

The diesel oxidation catalyst is designed to oxidize carbon monoxide, gas phase hydrocarbons,

and the SOF fraction of diesel particulate matter to CO2 and H2O:

(i)

(ii)

(iii)

Reaction (i) describes the oxidation of carbon monoxide to carbon dioxide.Hydrocarbons are

oxidized to form carbon dioxide and water vapor, as described by reaction (ii). Reaction (iii)

describes the oxidation of SOF into carbon dioxide. Since carbon dioxide and water vapor are
considered harmless, the above reactions bring an obvious emission benefit. The oxidation of

HCs also results in a reduction of the diesel odor. Diesel exhaust contains sufficient amounts of

oxygen, necessary for the above reactions. The concentration of O 2 in the exhaust gases from

diesel engine varies between 3 and 17%, depending on the engine load. Typical conversion

efficiencies for CO and HC in the diesel oxidation catalyst are given in Figure 2. The catalyst

activity increases with temperature. A minimum exhaust temperature of about 200°C is

necessary for the catalyst to "light off". At elevated temperatures, conversions depend on the

catalyst size and design and can be higher than 90%.

Figure 2. Catalytic Conversion of Carbon Monoxide and Hydrocarbons

Conversion of diesel particulate matter is an important function of the modern diesel oxidation

catalyst. The catalyst exhibits a very high activity in the oxidation of the organic fraction (SOF)

of diesel particulates. Conversion of SOF may reach and exceed 80%. At lower temperatures,

say 300°C, the total DPM conversion is usually between 30 and 50% (Figure 3). At high
temperatures, above 400°C, a counterproductive process may occur in the catalyst. It is the

oxidation of sulfur dioxide to sulfur trioxide, which combines with water forming sulfuric acid:

A formation of the sulfate (SO 4) particulates occurs, outweighing the benefit of the SOF

reduction. Figure 3 shows an example situation, where at 450°C the engine-out and the catalyst

total Diesel Particulate Matter (DPM) emissions are equal. In reality the generation of sulfates

strongly depends on the sulfur content of the fuel as well as on the catalyst formulation. It is

possible to decrease DPM emissions with a catalyst even at high temperatures, provided suitable

catalyst formulation and good quality fuels of low sulfur contents are used. On the other

hand, diesel oxidationcatalyst used with high sulfur fuel will increase the total DPM output at

higher temperatures. This is why diesel catalysts become more widespread only after the

commercial introduction of low sulfur diesel fuel.

Figure 3. Catalytic Conversion of DPM

The diesel oxidation catalyst, depending on its formulation, may also exhibit some limited

activity towards the reduction of nitrogen oxides in diesel exhaust. NO x conversions of 10-20%
are usually observed. The NOx conversion exhibits a maximum at medium temperatures of about

300°C.

5.2 Diesel Particulate Filter

Diesel particulate filters operate by trapping soot particles from the engine exhaust, preventing

them from reaching the environment. Unlike a catalytic converter which is designed to reduce

gas-phase emissions flowing through the catalyst, the particulate filter is designed to trap and

retain the solid particles until the particles can be oxidized or burned in the DPF itself, through a

process called regeneration.

The most common diesel particulate filters in widespread use are cellular ceramic honeycomb

filters with channels that are plugged at alternating ends, as shown in Figure 1. The ends of the

filter, plugged in a checkerboard pattern, force the soot-containing exhaust to flow through the

porous filter walls. While the exhaust gas can flow through the walls, the soot particles are

trapped within the filter pores and in a layer on top of the channel walls. The honeycomb design

provides a large filtration area while minimizing pressure losses, and has become the standard,

so-called wall-flow filter for most diesel exhaust filtration applications. Ceramic materials are

widely used for particulate filters, given their good thermal durability, with the most common

ceramic materials being: cordierite, silicon carbide, and aluminum titanate.

Figure 1. Diesel particulate filter for heavy-duty vehicle (a), cross-section viewing showing
filtration processes within several DPF channels (b), and close-up view of particle capture
and build-up on the channel walls (c).
The details of the filtration process are illustrated in Figure 1(b), which shows the soot particles

trapped along the inlet channel, which is open at the front end but plugged at the back end. DPFs

contain several hundred channels or cells per square inch (cpsi), with the most common being

200 cpsi. Since half of the channels are plugged at the front of the DPF and the other half are

plugged at the back of the filter, only half of the filter channels accumulate soot or ash. That is,

only the channels open on the inlet side are exposed to the “dirty” exhaust flow, while the

channels open to the outlet side remain clean. Given the small pore size and design of the

honeycomb filters, DPFs can achieve a particle trapping efficiency of 99% or greater. Due to the

high trapping efficiency and DPF cell design, no visible soot or ash should pass through the filter

walls. Black streaks or visible soot in the outlet channels are a sure sign of filter failure.

Soot particles are captured and retained in the DPF through a combination of depth filtration

inside the filter pores and surface filtration along the channel walls. The inset in Figure

1(c) shows these two processes, where a small fraction of the soot initially accumulates in the

filter pores (1) and then subsequently builds a layer along the channel walls (2). As the soot load

in the filter increases, so too does the filter’s trapping efficiency, as the accumulated soot
provides an additional layer to trap incoming particles. The specific soot filtration mechanisms,

whether in the pores on the surface of the walls, plays an important role in determining the

overall increase in exhaust back pressure (or pressure drop across the filter), shown in Figure 2.

Figure 2. Pressure drop evolution with soot accumulation in the DPF showing rapid initial
rise in pressure drop due to soot accumulation in the filter pores (1) followed by a gradual
increase as soot builds a layer along the walls (2).
The porosity of most commercial DPFs ranges from around 40% to 60%. The walls of these

filters contain a complex network of pores in the range of 10 – 30 micrometers (microns) in

diameter. In a new or clean DPF, the surface of the filter is exposed to the exhaust flow and soot

rapidly accumulates in the surface pores. Although only a small fraction of the total soot

accumulates in the filter micro-pores, it contributes to a steep rise in filter pressure drop shown

in Figure 2. Subsequent soot accumulation in the DPF forms a layer (cake layer) along the walls

of the channel, and results in a slower and more gradual rise in filter pressure drop. Depending

on the soot loading level and filter type, the pore accumulation can account for 50% of the filter

pressure drop, or more, in some cases. The non-linear response of the DPF to material
accumulation complicates the determination of filter soot or ash loading levels based on pressure

drop alone

5.2.1 Filter Regeneration

In order to reduce filter pressure drop due to soot accumulation, the filter is regenerated through

a processes the burns off (oxidizes) the soot. There are two broad categories of regeneration

processes, although most commercial applications use some combination of the two. This is

particularly true with vehicles or equipment experiencing extended periods of low exhaust

temperature operation, such as long periods of idle or low speed/load operating cycles.

Active Regeneration requires the addition of heat to the exhaust to increase the temperature of

the soot to the point at which it will oxidize in the presence of excess oxygen in the exhaust. The

combustion of soot in oxygen typically requires temperatures above 550 °C (1,000 °F). Since

these high temperatures generally fo not occur during normal engine operation, a number of

strategies are used to actively increase the exhaust temperature. Active regeneration systems

may include the use of a diesel burner to directly heat the exhaust entering the DPF or the use of

a diesel oxidation catalyst (DOC) to oxidize diesel fuel over the catalyst as a means for

increasing the DPF temperature. Use of the DOC also requires excess diesel fuel in the exhaust,

which may be accomplished through a fuel injector (hydrocarbon doser) mounted in the exhaust

upstream of the DOC, or through late in-cylinder post injection strategies. Other forms of active

regeneration include the use of electrical heating elements, microwaves, or plasma burners.

The use of a DOC in combination with some form of exhaust fuel dosing is the most common

active regeneration strategy currently used for on- and off-highway applications. The duration of

an active regeneration event generally ranges from 20 to 30 minutes on average, under normal
operating conditions. In some cases, such as severe DPF soot plugging, a parked regeneration

may be required, which can last up to several hours to slowly burn off the soot under more

controlled conditions. Regardless of the specific strategy, active regenerations always require

additional energy input (additional fuel) to heat the exhaust and the DPF to the required

temperature.

Passive Regeneration, as the name implies, does not require additional energy to carry out the

regeneration process. Instead, this strategy relies on the oxidation of soot in the presence of NO 2,

which can occur at much lower temperatures in the range of 250 °C to 400 °C (480 °F to

750 °F). A catalyst is used to convert NO present in the exhaust to NO 2. These catalysts require

the use of precious metals to facilitate the reaction, platinum (Pt), in particular, which adds

additional cost to the system. In some cases the catalyst coating is applied directly to the DPF, as

with a catalyzed DPF (C-DPF), or an upstream oxidation catalyst (DOC) may also be used.

Many commercial systems utilize a combination of a DOC and C-DPF. Use of the catalysts

allows NO2 to be produced and soot to be oxidized at temperatures which occur during normal

engine or vehicle operation.

In an ideal case, if engine operation results in a certain amount of time spent within this passive

regeneration “temperature window” then active regeneration may not be needed. In reality

however, low temperature operation may occur for extended periods of time, such as long

periods of idle or low load operation, particularly in cold climates, and some active regeneration

may still be needed. In the absence of active regeneration, periods of low temperature operation

may be supplemented by periods of high temperature operation (such as extended highway

driving) to induce passive regeneration.

In order to reduce fuel consumption, passive regeneration is preferred, although most

commercial systems still use active regeneration to varying degrees, depending on the drive

cycle and operating conditions. Regardless of the regeneration method, the oxidation of soot

(whether active or passive) results in incombustible material, or ash, which cannot be burned,

and remains in the DPF. Understanding the key differences between ash and soot, as well as

their impacts on DPF performance is important when selecting the most appropriate cleaning

method for the filter.

Why is this important for DPF ash cleaning?

Understanding the design and operation of the DPF to collect and trap particles, whether in the

pores or on the surface, has a large impact on how easily the particles can later be removed. Soot

is fundamentally different from ash in that the soot can be oxidized and removed through

regeneration, while the ash is incombustible and remains in the DPF until the DPF is serviced for

ash cleaning.

5.3 Selective Catalyst Reduction

NOx emission from diesel engines causes deleterious effects on human health and the

environment. Due to high thermal efficiency and low CO emissions, the use of diesel engines has

been increasing in number. This in turn increases the global emissions, among which nitrogen

oxides is the main pollutant. In Europe, stringent emission norms of Euro 5 and Euro 6 have

forced the OEMs to focus on NOx reduction. The limits for NOx as per Euro 5 and Euro 6 are

0.18 g/km and 0.08 g/km. To satisfy such lower limits, an after-treatment device like SCR or

Lean NOx Trap (LNT) is required in heavy duty vehicles when the emissions exceed 0.08 g/km

of NOx. The reduction of NOx is more challenging in the lean combustion environment of diesel
engines. In an attempt to reduce NOx in the exhaust gas to harmless N 2, technologies such as

SCR, SNCR (Selective Non-Catalytic Reduction) and LNT have been explored. Among these,

the SCR which is a proven technology for NOx emission control relies on a catalyst. It makes

use of a reductant and produces 95+ % NOx reduction efficiency. The different reducing agents

used are NH3 /urea, HC and H2.

SCR method is suitable for heavy duty and low duty applications due to its higher NOx reduction

potential.The SCR system involves several components packaged together with other parts of the

emissions control system. Each manufacturer has its own variations of the type and sequencing

of different components in the system.

The design of SCR technology is such that it permits nitrogen oxide (NOx) reduction reactions to

take place in an oxidizing atmosphere. It is called "selective" because it reduces levels of NOx

using ammonia as a reductant within a catalyst system. The chemical reaction is known as

"reduction" where the DEF(Diesel emission fluid) is the reducing agent that reacts with NOx to

convert the pollutants into nitrogen, water, and tiny amounts of CO 2. The DEFis rapidly broken

down to produce the oxidizing ammonia in the exhaust stream.

In spite of the challenging parameters such as urea dosing, mixing and proper decomposition to

NH3 and spray preparation, the SCR technology has been successfully introduced in the design

passenger car market. In urea SCR, the chemical reactions take place at lower temperature of

200- 400ºC with the aid of a catalyst bed. Urea is injected in liquid form. DEF is an aqueous

solution with 32.5% urea content and 67.5% de- ionized water. 32.5% of urea is chosen to be

optimum since it provides the lowest re-crystallization temperature (-11°C). The commercial

names for aqueous urea solution are DEF in Canada and Adblue in Europe. The decomposition

of urea into NH3 takes place in 3 steps: evaporation, thermal decomposition and hydrolysis.

In equation (1) the water droplets evaporate from the urea water solution and results in molten

urea.

NH2 -CO-NH2 (aqueous) → NH2 -CO-NH2 (molten) + H2O (gas) (1)

Equation (2) represents the thermal decomposition of molten urea to NH 3 and HNCO. This

process starts around 152°C.

NH2 -CO-NH2 (molten) → NH3 (gas)+ HNCO (gas) (2)

The above two reactions do not require any catalyst and takes place in the decomposition tube.

Equation (3) represents the hydrolysis of isocyanic acid to NH 3 and CO2 in the presence of a

catalyst.

HNCO (gas) + H2O(gas) → NH3(gas) + CO2 (gas) (3)

In general, one mole of urea generates 2 moles of NH 3. Overdosing of urea is practiced to fully

utilize the SCR catalyst. Also, the exhaust conditions of the engine vary with respect to flow rate,

composition and temperature. Due to these factors, there is a risk of NH 3 slip especially at high
temperature operating conditions. Euro VI norms regulates NH 3 emissions. Hence there is a need

to oxidize NH3 to N2 by a downstream Ammonia slip catalyst (ASC). Precious Group Metals

(PGM) based components are used in ASC. An efficient ASC should have high activity over a

wide range of flow rates, temperature and gas composition. Some undesirable reactions such as

conversion of NH3 into N2O or NO also occurs based on PGM loading. Hence it is important for

an ASC to have high selectivity to N 2. Metal or metal oxides supported on SiO 2, TiO2, zeolites or

carbon based materials are the explored catalysts. The catalysts can resist SO 2 poisoning. The

major drawback of this method is handling of large quantities of NH 3 because NH3 is toxic and

corrosive. The SCR reactions are classified as standard, fast and slow reaction based on NH 3, NO

and NO2 availability.

4NH3 + 4NO + O2 → 4N2 + 6 H2O (4)

8NH3 + 6 NO2 → 7N2 + 12H2O (5)

4NH3 + 2NO + 2NO2 → 4N2 + 6H2O (6)

2NH3 + 2NO2→ NH4NO3 + N2 + H2O (7)

Equation (4) represents standard SCR reaction in which the ratio of NH 3 and NO is 1:1 and some

moles of O2 are consumed. Equation (5) represents slow SCR reaction where pure NO 2 takes

place in the reaction. Equation (6) represents fast SCR reaction with NO and NO 2 ratio of 1:1.

Besides these reactions, certain undesirable reactions also occurs which limits the NOx

conversion. At lower temperatures below 200º C, NO 2 in the exhaust gas forms Ammonium

Nitrate according to the reaction in equation (7).

5.4 Ammonia Slip Catalyst

The conversion of nitrogen oxides (NO X) of a SCR system highly depends on the availability of

ammonia (NH3) generated from the injected AdBlue® (32.5% aqueous urea solution).In theory

the optimal NH3/NOX ratio with 1:1 (ANR [Ammonia NO X Ratio] = 1) is given by the reaction

stoichiometry. In practice the non-uniform ammonia distribution throughout the catalyst and the

oxidation of ammonia at high temperatures in a SCR system leads to a higher ANR (ANR > 1) to

achieve the maximum NOX conversion. An ANR > 1 usually results in an ammonia slip due to

the fact that some channels of the honeycomb structured catalyst substrate get more ammonia

than required for the SCR reaction and this excess gas passes through the catalyst. Especially if it

is required to realize NOX conversion larger than 90 % or during dynamic operation cycles, the

ammonia slip becomes an issue.

Implementing an ASC downstream of the SCR to oxidize extra ammonia that slips past the SCR

enables extra ammonia dosing, i.e., higher than the stoichiometric amount required, helping to

reach maximum NOx conversion. Gaseous ammonia has a very low smell threshold of approx.

15 ppm causing unpleasant odors and also leads to irritation of eyes and the respiratory system of

a human being.The ammonia slip catalyst (ASC) is designed for this purpose. It typically

contains a SCR catalyst with an oxidation catalyst like Pt/Al 2O3.The task of the ammonia slip

catalyst is the selective oxidation of the ammonia slip (NH 3) to harmless nitrogen (N2) and water

(H2O) and therefore avoiding smell and health risks.

2 NH3 + 3/2 O2 → N2 + 3 H2O

In combination with an adapted dosing strategy of urea, ASC technology enables to raise the

overall SCR conversion of the system due to a higher applicable ANR ratio without the

disadvantage of high ammonia slip. A customized catalyst design mostly prohibits the oxidation

of ammonia to laughing gas (N2O) or nitrogen oxide (NO).

2 NH3 + 2 O2 → N2O + 3 H2O

2 NH3 + 5/2 O2 → 2 NO + 3 H2O

The conversion of nitrogen oxides (NO X) of a SCR system highly depends on the availability of

ammonia (NH3) generated from the injected AdBlue® (32.5% aqueous urea solution).

In theory the optimal NH3/NOX ratio with 1:1 (ANR [Ammonia NO X Ratio] = 1) is given by the

reaction stoichiometry. In practice the non-uniform ammonia distribution throughout the catalyst

and the oxidation of ammonia at high temperatures in a SCR system leads to a higher ANR

(ANR > 1) to achieve the maximum NOX conversion. An ANR > 1 usually results in an

ammonia slip due to the fact that some channels of the honeycomb structured catalyst substrate

get more ammonia than required for the SCR reaction and this excess gas passes through the

catalyst. Especially if it is required to realize NO X conversion larger than 90 % or during

dynamic operation cycles, the ammonia slip becomes an issue.

Gaseous ammonia has a very low smell threshold of approx. 15 ppm causing unpleasant odors

and also leads to irritation of eyes and the respiratory system of a human being.

The task of the ammonia slip catalyst is the selective oxidation of the ammonia slip (NH 3) to

harmless nitrogen (N2) and water (H2O) and therefore avoiding smell and health risks.

2 NH3 + 3/2 O2 → N2 + 3 H2O

In combination with an adapted dosing strategy of urea, INTERKAT´s ASC technology enables

our customers to raise the overall SCR conversion of their systems due to a higher applicable

ANR ratio without the disadvantage of high ammonia slip. An additional benefit of our ASC is

the oxidation of carbon monoxide (CO) and hydrocarbons (HC) e.g. formaldehyde (CH 2O)

passing the SCR catalysts. A customized catalyst design mostly prohibits the oxidation of

ammonia to laughing gas (N2O) or nitrogen oxide (NO).

2 NH3 + 2 O2 → N2O + 3 H2O

2 NH3 + 5/2 O2 → 2 NO + 3 H2O

Even the best SCR catalyst will not achieve maximum NOx reductions in a system with non-

uniform NH3 distribution. For stationary engines, significant variation in load, exhaust flow rate

and NOx concentration make it difficult to deliver NH3 to the catalyst in the 1:1 ammonia NOx

ratio (ANR) required by reaction stoichiometry. Non-uniform NH3 distribution can result in

incomplete NOx conversion where localized ANR is low, and in NH3 slip where ANR is high.

To overcome the difficulty of attaining ideal stoichiometry, Johnson Matthey developed

advanced ASC technology that combines highly active oxidation catalyst and SCR catalyst

functions to improve NOx reduction while maintaining low NH3 slip. This technology was first

proven on thousands of mobile engines and is now successfully operating on stationary engines.

The ASC allows continuous operation at higher ANR, compensating for non-uniform NH3

distribution and boosting NOx conversion while maintaining low NH3 slip. As an added bonus,

the ASC delivers CO conversion which is not achieved over SCR catalyst alone. The SCR+ASC

are usually installed in a single housing which results in lower material costs.
ASC improves overall SCR system performance:

• ASC allows operation at higher ANR with low NH3 slip

• Better NOx and HC conversions with SCR+ASC

• CO forms from HCs over the SCR catalyst alone

• CO conversion achieved with SCR+ASC

The advanced ASC is very selective to N2 which means that almost all of the NH3 slip is

converted to N2 rather than NOx. The ASC also converts hydrocarbons and CO to CO2. The

overall performance of the SCR catalyst system is improved by addition of ASC. And better

SCR performance can mean reduced catalyst volume, which translates to lower system costs.

ASC converts NH3 to N2, not back to NOx:

• Nearly complete conversion of NH3 slip

• Formation of NOx and N2O, very low

• ASC is highly selective for N2

• HC is converted to CO2, no CO formed

In the previous section, NH3 oxidation was referred to as an undesired reaction, which is true in

terms of NOx reduction. However, it is also undesired to have any NH3 slip through the catalyst

and be emitted into the atmosphere. If any NH3 remains unreacted after the NOx reduction is

complete, it can be oxidized to N2 and H2O. The ammonia slip catalyst (ASC) is designed for

this purpose. It typically contains a SCR catalyst with an oxidation catalyst like Pt/Al2O3

Implementing an ASC downstream of the SCR to oxidize extra ammonia that slips past the SCR

enables extra ammonia dosing, i.e., higher than the stoichiometric amount required, helping to

reach maximum NOx conversion. The overall reaction on the ASC to oxidize NH3 to N2 is:

2𝑁𝐻3 + 1.5𝑂2 → 𝑁2 + 3𝐻2𝑂 (4)

At high temperatures, Pt catalysts are not selective to N2, and the production of N2O or NOx

can occur via the following side reactions:

2𝑁𝐻3 + 2𝑂2 → 𝑁2𝑂 + 3𝐻2𝑂 (5)

𝑁𝐻3 + 1.5𝑂2 → 𝑁𝑂 + 1.5𝐻2𝑂 (6)

𝑁𝐻3 + 2𝑂2 → 𝑁𝑂2 + 1.5𝐻2𝑂 (7)

Dual layered ASCs combine the oxidation functionality of the Pt/Al2O3 and the NOx reduction

functionality of an SCR catalyst.[71,72] The premise for this dual layered or dual functional

catalyst design is that the ammonia diffuses through the top SCR layer and the oxidation

reactions, 4–7, occur over the oxidation catalyst on the bottom, then the products diffuse back

through the zeolite towards the gas phase. The undesired oxidation products (NOx) produced in

Reactions 5–7 react with ammonia diffusing into the zeolite to produce N2, via the SCR
Reactions 1–3 discussed in the previous section. This chemistry was captured nicely in a model

of a layered SCR/oxidation catalyst configuration,[73] where the intra-layer NO and NH3

concentration profiles were calculated at different temperatures. At 250 °C both NH3 and NO

concentrations decreased through the layers, while at a higher temperature (500 °C) the NO

concentration gradient flipped in the bottom oxidation layer leading to a maximum NO

concentration at the interface of the layers due to the undesired NO formation from NH3

oxidation at high temperatures. In a dual layer SCR/oxidation catalyst study, a dual layer

Fe/zeolite SCR and Pt/Al2O3 oxidation catalyst was tested along with a single layer oxidation

catalyst for comparison, [70] and modelled using a previously developed mechanistic kinetic

model.[74] Both modelling and experiment showed that the top SCR layer introduced diffusion

limitations, which had a significant negative impact on the ammonia oxidation in the bottom

Pt/Al2O3 layer, the extent of which depended on the SCR layer thickness.[70] When the SCR

catalyst loading was reduced, ammonia oxidationincreased. Furthermore, ammonia conversion

was improved at lower gas space velocities, supporting the diffusion limitation hypothesis. As

the washcoat thickness of the SCR layer was increased, the ammonia conversion decreased, but

the selectivity to N2 increased. Another modelling study corroborated that the top SCR layer

thickness is an important parameter for NH3 conversion and product selectivity.[75] This

introduces an exercise in optimization with regards to the catalyst design parameters; the

washcoat loading for both catalyst layers is crucially important. Based on the diffusion

limitations identified from these studies, improving the diffusivity of the SCR washcoat layer

would improve ammonia conversion and maintain N2 selectivity. Another possible benefit of the

layered configuration would be NO oxidation to NO2 in the bottom layer, which would promote

fast SCR reactions on the SCR top layer, though this modelling study concluded that this
pathway does not play a significant role with the catalyst’s current NO oxidation capacity.[70]

Overall, this study showed that the dual layered design showed higher N2 selectivity, but lower

NH3 conversion than the oxidation catalyst alone.

In a separate modelling study, different configurations of the oxidation and SCR components

were evaluated:[76] (i) oxidation catalyst only, (ii) physical mixture of oxidation and SCR

components in a single washcoat, (iii) oxidation catalyst on top and SCR catalyst on the bottom,

and (iv) SCR on top and the oxidation catalyst on the bottom. The authors concluded that the

beneficial interaction between oxidation and SCR layers was best with the SCR catalyst on top

and oxidation catalyst on bottom, but high performance was also observed with the two catalysts

mixed in the same washcoat. Two of the modelling conditions are shown in Figures 11a–b and

12a–b, the difference being the presence of NO2 in the feed gas. These results show that the dual

layer SCR top/oxidation catalyst bottom case gave the best N2 selectivity at a higher

temperature. Similarly, there was an experimental study that evaluated the differences observed

between the dual layered Fe-ZSM-5 SCR/Pt-Al2O3 ASC monoliths versus a homogenous

mixture of the two components.[77] Modelling of this type of system was validated with

experiments.[78] Experimentally, ammonia oxidation on the mixed catalysts showed similar

NH3 conversion but lower N2 yield than the dual layered monoliths. Important findings from

this study include the ability to estimate the effective diffusivity of ammonia through the catalyst

layers, and the model was able to well predict qualitative trends in the data.

There are also studies evaluating Cu-zeolite SCR catalysts as part of the ASC design. Recalling

the work on dual-SCR systems, the Cu-zeolite catalysts have good SCR performance at low

temperatures, and then at a high temperature there is selectivity loss due to ammonia oxidation.

A recent pair of studies characterized the performance of Cu-exchanged on two zeolite supports,
ZSM-5 and SSZ-13, as part of the ASC.[79,80] In the first of these studies, the dual layered

catalyst with a top layer of Cu-ZSM-5 and a bottom layer of Pt/Al2O3 was prepared and

compared to a commercial ASC catalyst containing Pt and Fe-zeolite.[79] The suggested Pt

loading on an ASC is constrained to less than 353 g/m3 (10 g/ft3 ). Increasing the zeolite loading

on top of the Pt containing ammonia oxidation catalyst, similar to the previous studies, also

caused a reduction in the overall ammonia conversion due to diffusion limitations. The zeolite

loading also impacted the product selectivity at temperatures above 400 °C; the higher the zeolite

loading the higher the N2 yield. This again showed there is some trade-off in performance with

layer thickness, and there exists some optimum loading where the ammonia conversion will be

sufficiently high with an acceptable N2 yield. Compared to the commercial Fe-Pt-zeolite catalyst

in that work, the dual layered Cu-zeolite over Pt/Al2O3 showed better performance at low

temperatures (200–350 °C) in terms of selectivity to N2. This was attributed to the better SCR

performance of the Cu-zeolite at low temperatures compared to a Fe-zeolite SCR catalyst. This

was later validated in a study evaluating a dual layer Pt/Al2O3 bottom layer/top layer Cu/SSZ-13

SCR monolith, comparing the performance to a homogeneous mixture of the two catalyst

components and also to a dual layer catalyst with the homogeneous mixture as the bottom layer

instead of a pure oxidation layer (called a hybrid).[80] NH3 conversion and product selectivity

results of dual-layer, mixed, and hybrid catalysts are shown in Figures 13 and 14, with the

difference being the presence of NO in the feed gas. For both conditions, while the monolith with

the homogeneous mixture had higher overall NH3 conversion, as would be expected with the

lower overall diffusion issues to the oxidation sites, the dual layer catalyst had the higher NOx

conversion (higher N2 yield). For the hybrid monolith, the benefits of both dual layer and

homogenously mixed configurations were realized; high NH3 conversion and high N2 yield
were achieved. It is important to test both conditions, as during real engine operation some NOx

may slip past the SCR catalyst upstream of the ASC.

In the implementation of NH3 SCR technology, all the NH3 needs to be reacted to N2 whether

through reactions with NOx over the SCR catalyst or with O2 over the oxidation catalyst. Cu and

Fe SCR catalysts have been considered for use in the dual layer or dual zone configuration in an

ASC to convert otherwise unreacted NH3. The monolith design in either case is intuitive, the

oxidation catalyst or a mixture of oxidation/SCR catalysts should be the bottom layer/back zone

and the top layer/front zone should be the SCR catalyst to avoid oxidizing the NH3 before it is

able to participate in NOx reduction reactions. The layered configuration or the zoned

configuration using a mixture of oxidation/SCR catalyst at the back zone has the advantage of

reducing any NOx formed from high-temperature NH3 oxidation. The oxidation catalyst can also

improve the NO:NO2 ratios to promote fast SCR reactions. These designs have been successful

in improving NH3 conversion, NOx reduction and N2 selectivity making it a promising

technology for NOx reduction.