Catalyst Handbook The Right Chemistry For Tier 4pdf PDF

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Catalyst Handbook
The right chemistry for Tier 4
CAT_Booklet_FINAL.QXD 14/5/07 15:29 Page 3
A new type of
engine component
Catalytic exhaust aftertreatment is one of the key
technologies that will enable engines to meet the
forthcoming Tier 4 and equivalent standards.
The introduction of a new class of component is
always challenging, the more so when its function
and control is very different
to existing engine systems.
New to you,
but not to us
Catalysts have been used as a standard
component on cars for over 30 years and
Johnson Matthey supplied the world’s first
production batch in May 1974.
Since then, we have supplied
more than 500 million
autocatalysts, around one
third of all the catalysts
ever fitted to cars.
The Mark 1 Volkwagen Golf

launched in the USA in 1974.
It was one of the first mass
produced cars to be fitted
with an autocatalyst.
© Johnson Matthey plc 2007

The timetable for Tier 4 is tight, and the cost

of non-compliance is very high. The purpose
of this booklet is to describe the catalyst
technologies available and how Johnson
Matthey (JM) can work with you to achieve
the required emissions reductions while
maintaining, and in some cases improving,
the other features of diesel engines that
are valued by your customers.
01 Introduction
contents
03 Catalyst Technologies
09 JM’s Capabilities
17 Tier 4 Regulations
19 About Johnson Matthey

From on-road to non-road

Leaders in Diesel Catalyst Technology
Diesel cars were first fitted with Johnson Matthey catalysts and
catalysts in the early 1990s, since technologies have been inside
when tighter regulations and most of the particulate filter systems
increasing customer demands have retrofitted to heavy diesel engines
driven the development of engine and around the world. JM invented the
aftertreatment technologies together. CRT® diesel particulate filter (DPF)
system and more than 100,000 have
been sold for retrofit applications.
We are building on this success with
the introduction of the retrofit SCRT®
(CRT® + selective catalytic reduction
(SCR)) system for integrated control
of all regulated diesel pollutants.
Since 2005, tightening emissions

regulations for truck and bus engines
in Japan, Europe and the USA have led
to the introduction of particulate filters,
SCR systems and NOx adsorbers on new
heavy diesel engines. Johnson Matthey
has developed leading technology to
meet the requirements in all markets.
These types of catalysts are all in series
production at JM.
01 © Johnson Matthey plc 2007

From on-road to non-road
The non-road
Applications Challenge
Non-road machines represent a very
different challenge to on-road vehicles.
Indeed, it would be better to say that
NRMM represents many thousands
of different applications challenges.
Johnson Matthey has been supplying

and applying retrofit aftertreatment
systems to non-road machines for
more than 15 years. Therefore, we
have experience of the variety of
operating requirements, engine duty
cycles and packaging constraints found
in non-road machines. We know the
differences between a tractor and a
tracked excavator. And we know the
regulations. We are very well placed
to understand the requirements on
catalytic systems for Tier 4 compliance.
© Johnson Matthey plc 2007 02

Types of
catalyst
technology
An emission control catalyst is
usually a catalytic coating applied
to a ceramic or metallic substrate.
The catalyst has open channels and
the gases react as they pass through.
Some catalysts are designed to be
able to store reagents (e.g. oxygen,
ammonia) to enhance performance
or even to act as a chemical trap,
as in the case of NOx adsorbers.
A particulate filter is a physical trap.

The most common type is a ceramic
monolith like a catalyst substrate, but
with channels closed at alternate ends
so that the gases must pass through
the channel walls, leaving the soot
behind. These filters are nearly 100%
efficient for solid particles. Partial
filters, designed for a lower efficiency,
are also available. A DPF does not always
contain a catalyst, but catalysts are
used to burn the accumulated particulate.
Catalyst: a substance which when present in small amounts

increases the rate of a chemical reaction or process but which
is chemically unchanged by the reaction.

When designing a catalyst, we make it active to give high

conversions from smaller catalysts and to make the best
use of precious metal.
We make it selective to ensure that it is active for the

desired reactions and does not produce undesirable
by-products.
And we make it durable to meet useful life requirements

and to minimise the durability factors that must be
applied to new systems. Designing durability requires
an understanding of how the catalyst will be used in its
application and the exhaust conditions that it will see
throughout its life. It also requires knowledge of the
deactivation mechanisms, both chemical and physical,
of each type of catalyst.
What are the properties of

a good catalyst
? © Johnson Matthey plc 2007 04
PM Control
Particulate filters are used to trap
Particulate Matter (PM). Catalysts are needed
to burn the PM collected in the trap, maintaining
the performance of the system. There are two ways
that catalysts can be used to keep DPFs clean, and these
are often used together.
Nitrogen dioxide (NO2) and oxygen (O2) can both be used to

combust the soot trapped in a filter. NO2 has the advantage that
it reacts with soot at the temperatures found in diesel exhaust.
The O2 reaction requires higher temperatures, but is much faster.
Soot Combustion Rate (CO2 Intensity)
0 100 200 300 400 500 600 700

o
Temperature C
Using
NO2 to regenerate
a particulate filter
NO2 reacts with soot trapped in a filter, making NO and CO2.
This reaction can occur from 200°C, so the temperatures found
in diesel exhaust streams are sufficient and no additional energy
is required. Some of the NOX emitted by an engine is NO2 and more
can be made by an oxidation catalyst designed to oxidise NO to NO2.
This system – an oxidation catalyst to make NO2 followed by a
particulate filter which is regenerated by the NO2 – is the CRT®
system, a Johnson Matthey invention.
Using the CRT® effect to regenerate a filter has two great advantages:
it is continuous (helping to maintain a low and even exhaust back
pressure) and it requires no additional energy.
Using
O2 to regenerate
a particulate filter
Particulate matter collected in a filter can be oxidised very quickly
using the oxygen (O2) in the exhaust gases. This reaction requires
higher temperatures (>550°C) than are reliably found in most diesel
engine applications, so some mechanism is required to raise the
temperature of the exhaust periodically.
An oxidation catalyst placed before the filter is a very efficient way of

doing this. When the filter needs regenerating, the hydrocarbon content
of the exhaust stream is increased. The catalyst burns the hydrocarbon,
producing the heat required. The catalyst can also be designed to make
NO2 during normal operation to provide additional regeneration.
The hydrocarbon enrichment can be achieved in-cylinder using electronic
fuel systems, or by injecting fuel directly into the exhaust system.

NOx Control
Converting NOx from the engine to nitrogen
requires a chemical reduction. Diesel exhaust
is an oxidising, not a reducing, environment.
There are two main strategies to achieve
NOx reduction.
Selective
catalyic reduction
An SCR system reduces NOx to nitrogen (N2) and is capable of more
than 90% conversion, depending on conditions. To achieve this reaction
in normal, lean (i.e. high oxygen, low hydrocarbon) diesel exhaust,
a chemical reductant is needed. In most systems, ammonia (NH3) is used,
and this is delivered as an aqueous solution of urea (“AdBlue” in Europe).
The urea decomposes in the exhaust stream to form ammonia, which
reacts with the NOx to make nitrogen and water.
An SCR system requires a means of storing the urea and injecting the
amount required to reduce the NOx emitted by the engine. Careful
control is needed for transient cycles. The SCR catalysts usually have an
oxidation catalyst , often called a slip catalyst, at the end as a guard to
ensure that no ammonia is emitted.

NOx adsorber
catalysts
NOx adsorber catalysts or NACs,
also known as lean NOx traps (LNTs), NOx Adsorber Catalyst - lean conditions
operate in two modes. In normal diesel
NO + 1/2 O2 CO2
exhaust conditions, they adsorb the
NOx from the exhaust gas, storing NO2
it chemically. In “rich” exhaust Pt
conditions, with little or no oxygen (O2) Rh
they release the stored NOx and react

it with components of the rich exhaust
gas - carbon monoxide (CO),
hydrocarbons (HC) and hydrogen (H2)
- to make nitrogen.
Like any trap, chemical or physical,

NACs have a finite capacity so the NOx Adsorber Catalyst - rich conditions
engine or some auxiliary system must
CO + HC + H2 NOx CO
create rich exhaust conditions at
intervals to regenerate the catalyst
and this reduces the stored NOx to Pt
Rh
nitrogen. NACs also store sulphur
and this reduces their capacity to trap
NOx, so periodic “desulphations”, N2 + CO2
requiring increased exhaust
temperatures, are necessary.

Development
and testing
Catalyst
Technology
Each new Johnson Matthey catalyst Coatings are developed specifically
formulation is the product of four to exploit the properties of different
decades of development experience substrate types.
and a fundamental understanding of
catalyst properties. Research into Test work starts in the laboratory
new types of catalysts and catalytic using bottled gases to simulate
properties is undertaken at JM’s own exhaust gas with precise control
research facilities. Teams around the of gas mix and temperature.
world develop new formulations to Testing then moves to engines for
meet the requirements of different performance and durability testing.
engines, regulations and applications.

Johnson Matthey has its own test

cells dedicated to diesel engine
testing in Europe, the USA and Japan,
and ageing
many capable of transient operation.
These cells are used to test and prove
catalysts; for catalyst ageing and for
collaborative development programmes
using customer engines. Our facility in
Detroit also performs contract testing
(see www.jmtesting.com).
Testing
JM develops proprietary catalyst-specific
accelerated ageing procedures for
its own and customer testing. These
are based on catalyst deactivation
mechanisms and are validated against
catalyst aged in real world operation
on vehicles and machines.

Systems technology
and applications
expertise
JM works to develop new
aftertreatment systems and makes
them available for new engines and
retrofitting. This work covers not
just the catalysts themselves, but the
operating principles of the whole
system. An example of this is the
CRT® (Continuously Regenerating Trap)
particulate filter system. Johnson
Matthey developed its operating
principle in the late 1980s. It has
been used in the majority of retrofit
particulate filter systems supplied
around the world and has also been
employed in many OEM applications.
Johnson Matthey won the Royal Academy
of Engineering MacRobert Award in 2000 JM’s work in this area has moved
for its CRT® technology, in recognition of an
outstanding innovation of benefit to society
beyond particulate filter systems
to include systems for NOx and NO2
control and integrated 4-way systems,
which simultaneously reduce emissions
of PM and NOx as well as CO and HC.

Having worked on retrofit applications

since the early 1990s, Johnson Matthey
has direct, hands-on experience in
the non-road market. This is based
primarily on particulate filter systems
for construction and materials handling
machines, but we also have experience of
other systems and of rail and agricultural
applications. This long experience
has given us an understanding of the
particular challenges of non-road mobile
machinery: the variable and sometimes
extreme duty cycles, the physical
demands placed on the exhaust system,
the packaging constraints, heat rejection,
performance monitoring and control.

1.0
CO
0.8
THC
NO
NOx
0.6
0.4
0.2
Points: Measured
Steady state conversions
Lines: Simulated
0.0
100 150 200 250 300 350 400 450 500
Inlet Temperature / °C
DOC light-off model validation
integration
Modelling
JM builds computer models of catalyst performance,
starting with the measured kinetics of individual
reactions over real catalysts. These are built up
into models capable of modelling fully transient
operation. Models are important tools in JM’s own
Systems catalyst development work but are also made
available to customers for their own system
development and calibration. This approach
is particularly valuable in the non-road market,
reducing the work required to check the performance
of whole engine systems over different ratings
and machine-specific duty cycles.

systems
Integrated
Catalytic systems for PM or NOx control almost
always contain more than one component. An SCR
system will have an oxidation catalyst after the SCR
catalyst and sometimes before. A particulate filter
usually has an oxidation catalyst before the filter
and a catalytic coating on the filter itself.
Systems to control PM and NOx are more than a

simple combination of PM filter and NOx control
system. It is best when the two are designed to
work together: NO2 from a PM filter can help an
SCR system downstream; NOx adsorber desulphation
cycles can be used to regenerate particulate filters.
To assist packaging, the components themselves can

be integrated, for example with SCR or NAC coatings
on particulate filters.

Manufacturing
technology
Johnson Matthey has ten TS16949-
certified manufacturing plants
around the world, with two more
under construction. JM’s proprietary
coating technology enables very
precise control over the amount of
washcoat and precious metal applied
to each part, giving consistent high
performance and efficient use of
raw materials. It also allows different
catalytic coatings to be applied to
different areas of the substrate,
further enhancing performance,
efficiency and, in some cases,
durability. It also enables more than
one function to be built into a single
component, reducing the complexity
and cost of the finished system.
JM is in full series production of diesel

oxidation catalysts for active filter
systems, catalysed particulate filters
for light and heavy duty engines, SCR
catalysts and NOx adsorbers.
Production
Precious metal
management
Most emission control catalysts for mobile applications contain precious
metals. Johnson Matthey is an acknowledged authority on precious
metal markets and sole marketing agent for Anglo Platinum Ltd,
the world’s largest producer of platinum group metals. JM is able to
advise customers on the methods of sourcing, pricing and managing
their precious metal requirements in the way that best suits their needs.
For further information on the platinum group metals markets,
visit www.platinum.matthey.com.
Johnson Matthey is also the world’s largest refiner of secondary platinum

group metals so, at the end of a machine’s life, we are able to recover the
precious metals from the exhaust catalysts and reuse them.

Regulations
US EPA non-road
emissions limits
Engines <56kW
Power <8kW 8-19kW
Tier 1 2 4 1 2 4
Year 2000 2005 2008 2000 2005 2008
CO 8.0 8.0 8.0 6.6 6.6 6.6
NMHC
10.5 7.5 7.5 9.5 7.5 7.5
NOx
PM 1.0 0.8 0.4 0.8 0.8 0.4
Power 19-37kW 37-56kW

Tier 1 2 4 4 1 2 4 4
Year 1999 2004 2008 2013 1998 2004 2008 2013
CO 5.5 5.5 5.5 5.5 - 5.0 5.0 5.0
NMHC -
9.5 7.5 7.5 4.7 7.5 4.7 4.7
NOx 9.2
PM 0.8 0.6 0.3 0.03 - 0.4 0.3 0.03
Original Tier 2/3 limit of 0.4g/kWh

may be used if 0.03g/kWh limit is
introduced in 2012.

Engines >56kW
Power 56-75kW
Tier 1 2 3 4a 4b
Year 1998 2004 2008 2012 2015
CO - 5.0 5.0 5.0 5.0
NMHC - 7.5 4.7 - 0.19
NOx 9.2 - - 3.4 0.4
PM - 0.4 0.4 0.02 0.02
Power 75-130kW
Tier 1 2 3 4a 4b
Year 1997 2003 2007 2012 2015
CO - 5.0 5.0 5.0 5.0
NMHC - - 0.19
6.6 4.0
NOx 9.2 3.4 0.4
PM - 0.3 0.3 0.02 0.02
Power 130-560kW
Tier 1 2 3 4a 4b
Year 1996 2001-3 2006 2011 2014
CO 11.4 3.5 3.5 3.5 5.0
NMHC 1.3 0.19
6.4-6.6 4.0
NOx 9.2 2.0 0.4
PM 0.54 0.2 0.2 0.02 0.02
Power 130-225kW 225-450kW 450-560kW

Year 2003 2001 2002
NMHC
6.6 6.4 6.4
NOx
Tier 4 phase-in Test cycles and fuels

Manufacturers may certify all their Tier 1-3: test cycle is the NRSC
engines according to the 4a and 4b (=ISO8178-C1) fuel sulphur <2000ppm
standards shown in the table.
Alternatively, they may phase in the Tier 4: engines must meet limits over
NOx + HC standard as follows: NRSC and NRTC fuel sulphur 7-15ppm;
NTE (not to exceed) limits apply
• 130-560kW engines PM/CO 100%
compliance from 2011; NOx/HC 50%
compliance in 2011-3
Notes
• 56-130kW engines PM/CO 100% These tables are intended for general guidance only.
compliance from 2012; NOx/HC 25% For full regulations, refer to the regulatory authorities.
compliance in 2012-4 Standards for engines >560kW not shown.

Johnson Johnson Matthey is

a speciality chemicals
company focused on
Matthey its core skills in catalysts,
precious metals and
fine chemicals.
The group's principal

activities are the
manufacture of autocatalysts
About
and pollution control
systems, catalysts and
components for fuel cells,
pharmaceutical compounds,
process catalysts and fine
chemicals, and the refining,
fabrication and marketing
of precious metals.

Johnson Matthey has continued to develop its technology for almost

200 years, demonstrating the company’s ability to maintain world
leadership by adapting constantly to rapidly changing customer needs.
Rigorous in its own environmental policies, many of Johnson Matthey’s
products have a major beneficial impact on the environment and
enhance the quality of life for millions around the world.
JM’s Emission Control Technologies business is part of the Environmental

Technologies Division. It is the world leader in the development and
manufacture of emission control catalysts for internal combustion
engines. It provides exemplary customer service through a global
network of technology centres, manufacturing plants and sales offices,
local to customer needs.

United Kingdom USA Japan

Johnson Matthey Plc Johnson Matthey Johnson Matthey
Orchard Road 380 Lapp Road 5123-3 Kitsuregawa
Royston Malvern Sakura-shi
Hertfordshire PA 19355 Tochigi 329-1412
SG8 5HE USA Japan
UK
T (1) 610-971-3100 T (81) 286 86 5781
T (44) 1763 253000 F (1) 610-971-3116 F (81) 286 86 5791
F (44) 1763 256015
tier4@matthey.com
www.jmcatalysts.com/ect

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CAT_Booklet_FINAL.

QXD 14/5/07 15:29 Page 2

The Mark 1 Volkwagen Golf

© Johnson Matthey plc 2007

The timetable for Tier 4 is tight, and the cost

19 About Johnson Matthey

From on-road to non-road

Since 2005, tightening emissions

01 © Johnson Matthey plc 2007

From on-road to non-road

Johnson Matthey has been supplying

© Johnson Matthey plc 2007 02

A particulate filter is a physical trap.

Catalyst: a substance which when present in small amounts

03 © Johnson Matthey plc 2007

When designing a catalyst, we make it active to give high

We make it selective to ensure that it is active for the

And we make it durable to meet useful life requirements

What are the properties of

Nitrogen dioxide (NO2) and oxygen (O2) can both be used to

Soot Combustion Rate (CO2 Intensity)

0 100 200 300 400 500 600 700

An oxidation catalyst placed before the filter is a very efficient way of

© Johnson Matthey plc 2007 06

07 © Johnson Matthey plc 2007

they release the stored NOx and react

Like any trap, chemical or physical,

© Johnson Matthey plc 2007 08

09 © Johnson Matthey plc 2007

Johnson Matthey has its own test

© Johnson Matthey plc 2007 10

11 © Johnson Matthey plc 2007

Having worked on retrofit applications

© Johnson Matthey plc 2007 12

13 © Johnson Matthey plc 2007

Systems to control PM and NOx are more than a

To assist packaging, the components themselves can

© Johnson Matthey plc 2007 14

JM is in full series production of diesel

Johnson Matthey is also the world’s largest refiner of secondary platinum

© Johnson Matthey plc 2007 16

Power 19-37kW 37-56kW

Original Tier 2/3 limit of 0.4g/kWh

17 © Johnson Matthey plc 2007

Power 130-225kW 225-450kW 450-560kW

Tier 4 phase-in Test cycles and fuels

© Johnson Matthey plc 2007 18

Johnson Johnson Matthey is

The group's principal

19 © Johnson Matthey plc 2007

Johnson Matthey has continued to develop its technology for almost

JM’s Emission Control Technologies business is part of the Environmental

© Johnson Matthey plc 2007 20

United Kingdom USA Japan

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