Reduction in Emissions with Catalytic Converters

Catalytic converters, fitted in series with the exhaust pipe of gasoline fueled vehicles, convert
over 90 percent of hydrocarbons (HC), carbon monoxide (CO) and nitrogen oxides (NOx)
from the engine into less harmful carbon dioxide (CO2), nitrogen and water vapour. Since
catalytic converters were first fitted to cars in 1974, more than 12 billion tons of harmful
exhaust gases have been prevented from entering the earths atmosphere. More than 96
percent of cars manufactured today are equipped with catalysts.


Figure 1. Catalytic converter
From: Davis Recycling Inc.


A catalytic converter (colloquially, "cat" or "catcon") is a device used to reduce the toxicity
of emissions from an internal combustion engine. Catalytic converters are also used on
generator sets, forklifts, mining equipment, trucks, buses, trains, and other engine-equipped
machines. A catalytic converter provides an environment for a chemical reaction wherein
toxic combustion by-products are converted to less-toxic substances.


Construction

Ceramic-core converter

The catalytic converter consists of several components:
1. The core, or substrate. The core is often a ceramic honeycomb in modern catalytic
converters, but stainless steel foil honeycombs are used, too. The honey-comb surface
increases the amount of surface area available to support the catalyst, and therefore is often
called a "catalyst support".
2. The washcoat. A washcoat is used to make converters more efficient, often as a
mixture of silica and alumina. The washcoat, when added to the core, forms a rough, irregular
surface, which has a far greater surface area than the flat core surfaces do, which then gives
the converter core a larger surface area, and therefore more places for active precious metal
sites. The catalyst is added to the washcoat (in suspension) before being applied to the core.
3. The catalyst itself is most often a precious metal. Platinum is the most active catalyst
and is widely used. It is not suitable for all applications, however, because of unwanted
additional reactions and/or cost. Palladium and rhodium are two other precious metals used.
Platinum and rhodium are used as a reduction catalyst, while platinum and palladium are used
as an oxidization catalyst.

Metal-core converter Ceramic-core converter



Several components of catalytic converter

Makrobereich Macro area Mikrobereich Micro area
Trger Core Zwischenschicht Washcoat
Katalysatorkontakt Catalyst

Types

Two-way
A two-way catalytic converter has two simultaneous tasks:

1. Oxidation of carbon monoxide to carbon dioxide: 2CO + O
2
2CO
2

2. Oxidation of unburnt hydrocarbons (unburnt and partially-burnt fuel) to carbon
dioxide and water: C
x
H
2x+2
+ 2xO
2
xCO
2
+ 2xH
2
O (a combustion reaction)

This type of catalytic converter is widely used on diesel engines to reduce hydrocarbon and
carbon monoxide emissions.

Three-way
Since 1981, three-way catalytic converters have been used in vehicle emission control
systems in North America and many other countries on roadgoing vehicles. A three-way
catalytic converter has three simultaneous tasks:

1. Reduction of nitrogen oxides to nitrogen and oxygen: 2NO
x
xO
2
+ N
2

2. Oxidation of carbon monoxide to carbon dioxide: 2CO + O
2
2CO
2

3. Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water: C
x
H
2x+2
+ 2xO
2

xCO
2
+ 2xH
2
O

These three reactions occur most efficiently when the catalytic converter receives exhaust
from an engine running slightly above the stoichometric point. This is between 14.6 and 14.8
parts air to 1 part fuel, by weight, for gasoline. The ratio for LPG, natural gas and ethanol
fuels is slightly different, requiring modified fuel system settings when using those fuels.
Generally, engines fitted with 3-way catalytic converters are equipped with a computerized
closed-loop feedback fuel injection system employing one or more oxygen sensors, though
early in the deployment of 3-way converters, carburetors equipped for feedback mixture
control were used. While a 3-way catalyst can be used in an open-loop system, NO
x
reduction
efficiency is low. Within a narrow fuel/air ratio band surrounding stoichometry, conversion of
all three pollutants is nearly complete. However, outside of that band, conversion efficiency
falls off very rapidly. When there is more oxygen than required, then the system is said to be
running lean, and the system is in oxidizing condition. In that case, the converter's two
oxidizing reactions (oxidation of CO and hydrocarbons) are favoured, at the expense of the
reducing reaction. When there is excessive fuel, then the engine is running rich. The reduction
of NO
x
is favoured, at the expense of CO and HC oxidation.

Oxygen storage

Three-way catalytic converters can store oxygen from the exhaust gas stream, usually when
the air fuel ratio goes lean. When insufficient oxygen is available from the exhaust stream the
stored oxygen is released and consumed. This happens either when oxygen derived from NO
x

reduction is unavailable or certain maneuvers such as hard acceleration enrich the mixture
beyond the ability of the converter to compensate.


Pollutant conversion depending of air-fuel ratio

Schadstoffumsatz Pollutant conversion Bereich des Oxida. Area of oxi-cat.
Bereich unger. Drei Area of unregulated
3way Cat
Sauerstoffmangel oxygen deficiency
(rich)
geregelter regulated Sauerstoffberschu Excess oxygen
(lean)


3way catalytic converter for gasoline engines
Luft Air Katalytischer Konv. Catalytic converter
Abgas Exhaust gas Lambda-Sonde Oxygensensor
Luftmengenmesser Air-flow meter Motortemperatur Engine temperature
Motor Engine Drosselklappenst. Throttle position
Einspritzzeit Time of injection Drehzahl Speed


Unwanted reactions

Unwanted reactions can occur in the three-way catalyst, such as the formation of odiferous
hydrogen sulfide and ammonia. Formation of each can be limited by modifications to the
washcoat and precious metals used. It is difficult to eliminate these byproducts entirely.

For diesel engines

For compression-ignition (i.e., diesel) engines, the most commonly used catalytic converter is
the diesel oxidation catalyst. This uses excess O
2
(oxygen) in the exhaust gas stream to
oxidize CO (carbon monoxide) to CO
2
(carbon dioxide) and HC (hydrocarbons) to H
2
O
(water) and CO
2
. These converters often reach 90% efficacy, virtually eliminating diesel odor
and helping to reduce visible particulates (soot), however they are incapable of reducing NO
x

as chemical reactions always occur in the simplest possible way, and the existing O
2
in the
exhaust gas stream would react first.

To reduce NO
x
on a compression ignition engine, the chemical composition of the exhaust
must first be changed. Two main techniques are used: selective catalytic reduction (SCR) and
NO
x
(NO
x
) traps (or NOx Absorbers).

Diesel engine exhaust contains relatively high levels of particulate matter (soot), consisting in
large part of elemental carbon. Catalytic converters cannot clean up elemental carbon, though
they will remove up to 90% of the soluble organic fraction, so particulates are cleaned up by a
soot trap or diesel particulate filter (DPF).

Instead of catalysis, a reagent such as ammonia pyrolyzed in situ from urea, is sometimes
used to reduce the NO
x
into nitrogen.

For lean-burn engines

For lean burn spark ignition engines, an oxidation catalyst is used in the same manner as in a
diesel engine.

Installation

Many vehicles have a pre-catalyst located close to the engine's exhaust manifold. This heats
up quickly due to its proximity to the engine, and reduces cold-engine emissions by burning
off hydrocarbons from the extra-rich mixture used in a cold engine.

Damage

Poisoning

Catalyst poisoning occurs when the catalytic converter is exposed to exhaust containing
substances that coat the working surfaces, encapsulating the catalyst so that it cannot contact
and treat the exhaust. The most notable contaminant is lead, so vehicles equipped with
catalytic converters can only be run on unleaded gasoline.

Phosphorus is another catalyst contaminant. Although phosphorus is no longer used in
gasoline, it was until recently widely used in engine oil antiwear additives.

Depending on the contaminant, catalyst poisoning can sometimes be reversed by running the
engine under a very heavy load for an extended period of time. The increased exhaust
temperature can sometimes liquefy or sublimate the contaminant, removing it from the
catalytic surface. However, removal of lead deposits in this manner is usually not possible due
to lead's high boiling point.

Meltdown

Any condition that causes abnormally high levels of unburned hydrocarbons raw or
partially-burnt fuel to reach the converter will tend to significantly elevate its temperature,
bringing the risk of a meltdown of the substrate and resultant catalytic deactivation and severe
exhaust restriction. Vehicles equipped with OBD-II diagnostic systems are designed to alert
the driver of a misfire condition.

Environmental impact

Catalytic converters have proven to be reliable and effective in reducing noxious tailpipe
emissions. However, they may have some adverse environmental impacts in use:

The requirement for a rich burn engine to run at the stoichiometric point means it uses
more fuel than a "lean burn" engine running at a mixture of 20:1 or less. This increases the
amount of fossil fuel consumed and the carbon dioxide emissions of the vehicle. However,
NO
x
control on lean burn engines is problematic and difficult.
Although catalytic converters are effective at removing hydrocarbons and other
harmful emissions, most of exhaust gas leaving the engine through a catalytic converter is
carbon dioxide (CO
2
), one of the greenhouse gases cause of global warming. Additionally, the
U.S. Environmental Protection Agency (EPA) has stated catalytic converters are a significant
and growing cause of global warming, due to their release of nitrous oxide (N
2
O), a
greenhouse gas over 300 times more potent than carbon dioxide.
Catalytic converter production requires palladium and/or platinum; part of the world
supply of these precious metals is produced near the Russian city of Norilsk, where the
industry (among others) has caused Norilsk of most polluted places.

Diagnostics

Various jurisdictions now legislate on-board diagnostics to monitor the function and condition
of the emissions control system, including the catalytic converter. On-board diagnostic
systems take several forms.

Temperature sensors

Temperature sensors are used for two purposes. The first is as a warning system, typically on
2-Way catalytic converters such as are still sometimes used on LPG forklifts. The function of
the sensor is to warn of catalytic converter temperature above the safe limit of 750 C
(1,380 F). More recent catalytic converter designs are not as susceptible to temperature
damage and can withstand sustained temperatures of 900 C (1,650 F). Temperature sensors
are also used to monitor catalyst functioning - usually two sensors will be fitted, with one
before the catalyst and one after to monitor the temperature rise over the catalytic converter
core. For every 1% of CO in the exhaust gas stream the exhaust gas temperature will rise by
100C.

The efficiency (light off temperature) of catalytic converter begins over 200 C and is
depending of exhaust gas component.


Efficiency depending of temperature
Wirkungsgrad Efficiency

Oxygen sensors

The Oxygen sensor is the basis of the closed loop control system on a spark ignited rich burn
engine, however it is also used for diagnostics. In vehicles with OBD II, a second oxygen
sensor is fitted after the catalytic converter to monitor the O
2
levels.

NO
x
sensors

NO
x
sensors are extremely expensive and are generally only used when a compression
ignition engine is fitted with a selective catalytic reduction converter, or a NO
x
adsorber
catalyst in a feedback system.


Principle of oxygen sensor
1 Air 4 Electrolyte 7 Probevoltage
2 Exhaust gas 5 Spinelbed
3 Housing 6 Internal electrode


References:
1. www.automotiverecycling.net
2. Wilhelm Wolsing: Abgasemissionen aus Kraftfahrzeugen und deren Kontrolle durch
Katalysatoren. Engelhard Kali-Chemie GmbH, 1989
3. Brandt, Erich; Wang, Yanying; Grizzle, Jessy (September 2000), "Dynamic Modeling
of a Three Way Catalyst for SI Engine Exhaust Emission Control", IEEE Transactions
on Control Systems Technology 8 (5): 767-776, ISSN 1063-6536,
ftp://www.eecs.umich.edu/people/grizzle/papers/TWC98.pdf
4. Owen Ullman (June 14, 1976). "Catalytic converter still controversial after two years
of use". The Bulletin.
5. Keith Tanner. Mazda MX-5 Miata. Motorbooks. p. 120.
6. Wright, Matthew. "What Exactly is a Catalytic Converter? The Science Behind
Catlytic Converters". About.com. http://autorepair.about.com/od/glossary/ss/how-
it_catalyti_3.htm. Retrieved 2009.
7. Le Treut H, Somerville R, Cubasch U, Ding Y, Mauritzen C, Mokssit A, Peterson T
and Prather M (2007) (PDF). Historical Overview of Climate Change Science In:
Climate Change 2007: The Physical Science Basis. Contribution of Working Group I
to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change
(Solomon S, Qin D, Manning M, Chen Z, Marquis M, Averyt KB, Tignor M and Miller
HL, editors). Cambridge University Press. pp. 5,10. http://ipcc-
wg1.ucar.edu/wg1/Report/AR4WG1_Print_Ch01.pdf. Retrieved 2009-01-18.