POLUTANTS PORDUCED BY ENGINES

In order to reduce emissions, modern engines carefully control the

amount of fuel they burn. They try to keep the air-to-fuel ratio very close to

the stoichiometric point, which is the ideal ratio of air to fuel. Theoretically,

at this ratio, all of the fuel will be burned using all of the oxygen in the air.

For gasoline, the stoichiometric ratio is about 14.7:1, meaning that for each

pound of gasoline, 14.7 pounds of air will be burned. The fuel mixture

actually varies from the ideal ratio quite a bit during driving. Sometimes the

mixture can be lean (an air-to-fuel ratio higher than 14.7), and other times

the mixture can be rich (an air-to-fuel ratio lower than 14.7).

AUTOMOBILE EMISSIONS

 Tailpipe emissions

 Evaporative emissions

 Life cycle emissions

Study of exhaust emissions and its control has been a matter of

concern from a long period for the engineers. The operating variables affect

the auto engine exhaust. The main variables for emitting pollution are HC,

CO and NOx. Previously the auto engineers control the pollution emission

by following ways.

1
  Controlling Air-Fuel ratio

 Controlling Engine Speed

 Proper Spark Timing

 Exhaust Back Pressure

 Valve Overlap

 Intake Manifold Pressure/ Vacuum

 Combustion Chamber Deposit Build Up

 Surface Temperature

 Surface to Volume Ratio

 Stroke to Bore Ratio

 Compression Ratio

 Effect Of Coolant Temperature

PROBLEM FORMULLATION (ADVANCE WORK)

A lot of research work has been done since 1940’s to check the

menace of pollution by automobiles. There are many techniques to control

the exhaust pollution through automobiles e.g.

 Exhaust Gas Recirculation

 Thermal Reactor

2
  Modification in Combustion System to Achieve Complete

Combustion

 Injection System

 Ignition System

 Carburetor

 After Burner

 Evaporative Emissions and Control

 Crankcase Emissions and Control

Now a day’s use of catalytic converter dominates all other techniques.

Catalytic converter is used in the tail pipe of the exhaust system so that the

level of obnoxious emissions from the engine is reduced before they are let

out to the atmosphere.

To evaluate the performance and design of catalytic converter is made

which predicts the catalytic converter performance. We can optimize

catalytic converter design by adjusting different parameters.

3
4
 NOMENCLATURE

 Gg Mass flow rate of the gases.

 Cb catalyst bed.

 Cj concentration of Species.

 CO Carbon monoxide.

 C Specific heat.

 Cp Specific heat at constant pressure.

 EGR Exhaust gas recirculation.

 E’ Activation Energy.

 HC Unburned Hydrocarbon.

 H Heat of reaction.

 h Heat transfer coefficient.

 K* Rate constant or equilibrium constant.

 Mg Molecular weight of gas.

 Nu Nusselt oxide.

5
 NO Nitric Oxide.

 NOx Oxides of nitrogen.

 pr Prandtl number.

 R Specific gas constant.

 Re Reynolds number.

 RGF Residual gas Fraction.

 Rj Rate of conversion of species.

 T Temperature.

 t Time.

 x Distance along the pipe axis.

 Y Mole fraction of fuel. gas

 ▲ Small change

 µ viscosity

 PPM Part per million.

 ρ Density

6
 deterioration of air quality is a major environmental problem in many

large urban centers in both developed and developing countries. Although

urban air quality in developed countries has been controlled to some extent

during the past two decades, in most of the developing countries it is

worsening and becoming a major threat to the health and welfare of people

and the environment. In our modern society, quality of life is greatly

measured by the amount of consumption of electricity or by the use of car.

Electricity generation and operation of vehicles mostly use fossil fuel. As

these fuels are burnt, huge quantity of lethal chemicals and poisonous

particulate matter are released as a part of emission into the surrounding

atmosphere due to incomplete combustion causing serious air pollution,

affecting public health. The contribution of motor vehicles to air pollution

7
was first recognized by Prof. Hazen Smit who discovered that the two

invisible vehicular emissions namely hydrocarbons and oxides of nitrogen

were responsible for the famous Los Angeles ‘photochemical smog’. These

gases interact with one another and other components of the atmosphere to

generate several harmful compounds viz. carcinogens. The auto exhaust also

affects our valuable cultural heritage, historical places/ monuments/

architecture and the environment. The number of vehicles in India has

increased from 1.86 million in 1971 to 32 million in 1996 and about 53

million in 2000. Meteorological and topographical conditions affect

dispersion and transport of these pollutants in ambient air.

The growth in population and growth in energy consumption per

person have combined together to give dramatic increase in both water and

air pollution problems. The mankind can survive without food and water for

few days, seldom the survival exists without air. Among several sources of

pollution, vehicles used in transportation sectors have a substantial share in

increasing atmospheric pollution.

It has been estimated that about 60 – 70% air pollution is from motor

vehicles. Almost all these are powered from I.C. engines which use fossil

fuel such as gasoline or diesel oil. The increases in two and three wheelers

are aggregated the problem further. In an average motor vehicle with no

8
emission control device (1, 3) the estimated values of annual production of

these pollutants is about 770 kg. of carbon monoxide; 240 kg. of unburned

hydrocarbons and 40 kg. of nitrogen oxides. This quantity increased

proportionately with the no. of vehicles.

1.1 EFFECT OF POLLUTANTS ON ENVIRONMENT

Vehicles equipment with petrol or diesel engines emit considerable

amount of carbon monoxide and unburned hydro carbons; Oxides of

nitrogen, compounds of lead oxides of sulphur etc. The air pollution due to

these pollutants effects adversely on materials, animals and human life .It

reduces visibility to a large extent causing traffic hazards. The vegetation

and plants are affected badly by sulphur dioxide, photo chemical smog and

lead.

1.2 EFFECTS OF AIR POLLUTANTS ON HUMAN HEALTH

Air pollutants emitted by motor vehicles have a number of adverse

effects on human health and ecology. Diseases such as silicosis,

pneumoconiosis, coniosis, allergy, asthma, inflammatory lung diseases,

infections and cases of mycotoxicosis and neurological or vascular disorders

9
have been associated with exposure to pollutants and bio aerosols (bacteria,

fungi and their by-products). Exposure by inhalation directly affects

respiratory, nervous and cardiovascular systems of humans, resulting in

impaired pulmonary functions, sickness and even death. Pollution hampers

the body normal immune system and consequently secondary diseases kill

the subject. Pollution is a hidden enemy of civilization. There are no specific

drugs for the diseases cause by the pollution. Pollutants thus give rise to

enormous health costs, in addition to the general discomfort and poor quality

of life in urban area.

Particulate matters cause breathing and pulmonary disorders like

asthma, bronchitis, lowering of the general immune system, cancer and long

term irreparable damage to the lungs. CO binds with hemoglobin to form

carboxyhemoglobin (COHb) which reduces the blood’s carrying capacity to

transport O2 to the tissues. SO2 is known to cause decreased lung functions

and a variety of respiratory diseases and increased risk of mortality and

morbidity. Adverse effects include coughing, phlegm, chest discomfort and

bronchitis. Nitrogen oxides-NO2 is linked with increased airway resistance

in asthmatics and decreased pulmonary function. NO2 has been associated

with respiratory illness in children (cough, runny nose, and sore throat).

Occupational exposure to NO2 range from inflammation of the mucous

10
membrane of the tracheobronchial tree to bronchitis, bronchopneumonia and

acute pulmonary edema. Lead prevents hemoglobin synthesis in red blood

cells in bone marrow, impairs liver and kidney function and causes

neurological damage. PAH are known as carcinogenic. Ozone-adverse

health effects include changes in pulmonary function, eye, nose and throat

irritation, coughing, throat dryness, thoracic pain, increased mucous

production, chest tightness, lassitude, malaise and nausea.

Chlorofluorocarbons-exposure to increased UV-B radiation is suspected to

increase the risk of skin cancer and eye illness especially cataract and to

adversely affect the immune system. Benzene – about 50% of inhaled

benzene is adsorbed. Part of the absorbed benzene is exhaled by respiration

and eliminated through the urinary tract. Benzene is accumulated in the fat

tissue and bone marrow. Benzene has toxic and carcinogenic effects. The

toxic effects are associated with central nervous system, hematological and

immunological systems. Higher exposure can damage the respiratory

tract, lung tissue and bone marrow and cause death. Carcinogenic effects

include leukemia.

Polyaromatic Hydrocarbons – PAH absorbed in the lungs and

intestines and metabolized in the human body, are mutagenic and

11
carcinogenic. Aldehydes-are absorbed in the respiratory and gastrointestinal

tracts and metabolized. Adverse health effects of HCOH include eye and

nose irritation, irritation of mucous membranes and alteration in respiration,

coughing nausea and shortness of breath. Lead (Pb) - Tetraethyl lead was

added to gasoline to increase the fuels octane number, which improves the

antiknock characteristics of the fuel in spark-ignition engines.

1.3 POLLUTANTS EMISSIONS FROM MOTOR VEHICLES

Emission from vehicles especially automobiles contribute

significantly two third of air pollution in the urban area. Main sources of

emission from automobiles are:

i) Volatile Organic Compounds (VOCs) / Evaporative Emissions- are HC

vapors lost constantly and directly to the atmosphere due to volatile nature

of petrol, mainly from the fuel line’s, fuel tank and carburetor depending

upon fuel composition, engine operating temperature and ambient

temperature. Losses from the carburetor, called Hot Soak Emissions, occur

when a hot engine is stopped. It should be noted that out of total emissions,

which are much more in case of petrol than diesel, 20-32% of the total

12
emissions are due to evaporation losses, of which the HCs happen to be the

chief constituents. These gases are also known as hydrocarbons and defined

as "volatile" because of their ability to evaporate quickly and easily into the

air. They react with nitrogen oxides in the presence of sunlight to produce

ground level ozone, a principle component of smog.

ii) Crankcase Emission (also called running loss emissions) – are unburnt

or partially burned fuel components that, under pressure, escape from the

combustion chamber, pass the pistons and enter the crankcase. This mixture

is called blow-by. The main constituent of blow-by emission is HCs. If

uncontrolled, it may constitute 13–25% of total emissions. Since, diesel

engines compress only air, blow-by contain very low levels of pollutants.

iii) Exhaust Emission- Automotive exhaust is the major source constituting

about 60% of the total emission. Automobile exhaust consists wide range of

pollutants from simple to carcinogenic substances such as (1) Hydrocarbons

(Unburnt), (2) Carbon monoxide, (3) Oxides of nitrogen (NOx), (4) Lead

oxides, (5) Particulate matters e.g. lead, carbon, alkaline earth compounds,

iron oxide, tar, oil, mist (6) Traces of aldehydes, esters, ethers, sulphur

dioxide, peroxides, ketones benzene (C6H6), 1, 3 butadiene, Poly Aromatic

13
Hydrocarbons (PAH), metal dust, asbestos fiber, dioxin, furan, ammonia,

organic acids , chlorofluorocarbons (CFCs) etc. .

Hydrocarbons and CO appears in the exhaust gas products of

incomplete combustion. Oxides of nitrogen result from the reaction of

nitrogen and oxygen contained in the combustion air at high temperature

prevailing during combustion. Further, many of these primary pollutants

react with each other to form secondary pollutants. Chief among these are

HC, CO, NOx when mixed with atmospheric water vapors in presence of

sunlight form ozone and variety of complex organic gases and resultant

particulates known as Photochemical Smog (Sharma, and Agnihotri, 1992).

Particulate Matter (PM) includes particles of soot, ash, and dirt that are

released from car exhaust. Particles are measured by their diameter and with

respect to smog; two sizes are of the most concern - PM10 and PM2.5.

Particulate matter and ground level ozone combine to make up smog.

Sulphur Dioxide (SO2) gas contributes to smog formation, but is

known better for combining with water molecules to form sulphuric acid and

producing acid rain. A comparative sulphur content in diesel fuel in different

countries and pollution arise from different parts of the automobiles are

given in Table-1.

14
Table 1: Maximum Permitted Sulphur Content in Automotive Diesel Fuel

E.C. Countries % Mass

U.K. 0.3
France 0.3
Germany 0.2
Italy 0.3
Others
Canada 0.5
Japan 0.5
Switzerland 0.2
South Korea 1.0
USA 0.5
India 0.5

1.4 EMISSION FROM GASOLINE VEHICLE

Gasoline- powered engines are of two types – 4 strokes and 2 strokes.

The exhaust consists of CO, HC, NOx, SO2 and partial oxides of aldehydes,

besides particulate matter, lead salts account for the larger chunk of all

pollution from gasoline-run vehicles.

The 2 stroke engine requires 2-T oil for lubrication of engine. Since the

burning quality of mineral based lubricating oil is very poor, major fraction

either remain unburned or burns partially and comes out through exhaust and

responsible for smoke emissions.

15
TABLE-2 Emissions from Gasoline Vehicles

S.N. Source Amount of Emissions (%)

4-stroke 2-stroke
1 Crankcase blow by 20 -
2 Evaporative 20 3

Emissions
3 Exhaust Emissions 60 97

Table-3 Exhaust Emission from Indian Light Duty Gasoline Vehicle

The average INDIAN light-duty gasoline vehicle annually emits

approximately:

 4500 kg of CO2

 200 kg of CO

 20 kg of VOCs

 22 kg of NOX

 1 kg of SOX

 0.15 kg of PM10

 0.15 kg of PM2.5

16
 (based on data from the year 2000)

1.5 EMISSION FROM DIESEL VEHICLE

Due to low volatility, evaporative emissions are non-significant.

Though the concentration of CO and unburnt HC in the diesel exhaust are

rather low, they are compensated by high concentration of NOx. There are

smoke particles and oxygenated HC, including aldehydes and odour-

producing compounds.

1.6 MAJOR POLLUTANTS

Major pollutants from automobiles are:

(a) Unburned hydro carbons. (UBHC).

(b) Oxides of nitrogen (NOx).

(c) Carbon mono oxides.

(d) Lead compounds.

(e) Oxides of sulphur.

(a) Hydro carbon exhaust emissions arise from three sources;

17
(i) Wall quenching,

(ii) Incomplete combustion of charge.

(iii) Exhaust scavenging as in a two cycle engines.

(b) Formation of nitric oxide takes place within the combustion chamber

at the peak combustion temperature and remains there during expansion and

exhaust stroke in non equilibrium amount. When this Nitric oxide comes in

contact with atmospheric oxygen, other compounds of nitrogen may be

formed.

© Carbon monoxide is generated from the automobiles largely by old and

petrol vehicles, due to in complete combustion of organic matters. It has no

smelt; inactivates hemoglobin and can be very harmful because it shows no

physiological symptom or uncomforted. Human exposure to this for longer

than eight hours at a concentration of about 120 PPM should not be allowed

for more than one hour.

(d) Among anti knock additives TEL (Tetra ethyl lead (C2H5)4 Pb) is well

known. The effect of adding TEL is to reduce a non volatile combustion

product which tends to accumulate on the spark plug and cause the engine to

misfire. Therefore TEL is always blended with ethylene dibromide and

18
ethylene dichloride so that the lead compounds formed during combustion

are sufficiently volatile and are discharged through exhaust to atmosphere.

(e) Sulphur is present in the crude oil itself. During refining large amount

of sulphur is separated from the fuel. Still there remains some of its amount

in the fuel. It forms oxide of sulphur during combustion. These Oxides of

sulphur from exhaust go to atmosphere. This sulphur oxide may be

combined with sulphuric acid (H2SO4); a very corrosive secondary

pollutant.

CHAPTER-2

19
 AUTOMOTIVE ENGINE TYPES & AUTOMOTIVE POLLUTION

Spark-ignition and Diesel engines are the two most common

engines. Other types of engines are Rotary (Wankel) Engines, Gas-Turbine

(Brayton) Engines, Steam (Rankine) Engines, Stirling) Engines, Electric and

Hybrid Vehicles.

Spa

rk-ignition gasoline engines have either a 2-Stroke (the cycle is completed

in 2-strokes of the piston) or 4-Stroke design (the cycle is completed in 4-

strokes, Suction ►Compression ►Expansion or Power and ► Exhaust

Strokes of the piston). 2-stroke engines are cheaper, lighter and can produce

greater power output per unit of displacement, so they are widely used in

motorcycles, scooters and mopeds and small power equipment. It emits 20-

50% of their fuel unburned in the exhaust, resulting in high emissions and

poor fuel economy. All gasoline engines currently used in automobiles and

larger vehicles use the 4-Stroke design. Advanced 2-Stroke engines under

development would achieve lower emissions and fuel consumption than 4-

Stroke engines.

2.1 MODE OF VEHICLE OPERATION AND EMISSION RATES

20
 The vehicle operation is divisible into 4 modes or driving cycles: (i)

Idle / Start Mode - when the engine of vehicle has been started. It is yet

stationary. At this stage there is high level of HC and CO and very low level

of NOX, (ii) Acceleration- the emission of HC and CO come down with rise

in NOX levels, (iii) Cruise/Steady Mode-steady speed produces relatively

low concentration of HC and CO but high concentration of NO X and (iv)

Deceleration (a) free and while (b) applying brake- slow speed contributes

to more pollutants.

2.2 TYPES OF FUELS

Pollutant emissions from motor vehicles are determined by the

vehicle’s engine type and the fuel it uses. Ideal fuel must have certain

physical, chemical and combustion properties, such as high energy density,

good combustion qualities, high thermal stability, and low deposit forming

tendencies, compatibility with engine hardware, good fire safety, low

toxicity, low pollution, easy transferability and on-board vehicle storage.

Commonly use fuels are gasoline and diesel. Gasoline is a mixture of

hydrocarbon compounds which have been distilled from petroleum. Sulphur

21
is a constituent in oil; low sulfur oil is in great demand as a fuel because the

SO2 emission is reduced. Low sulphur oil is called “Sweet”.

Alternative fuels considered for vehicular use are natural gas (in

compressed or liquefied form, Natural gas contains the lighter aliphatic

compounds, largely methane, CH4. A typical gas would be 80-90% CH4 , 5

to 10 % ethane and the rest other compounds), liquefied petroleum gas

(LPG), methanol (made from natural gas, coal or biomass), ethanol (made

from grain or sugar) vegetable oils, hydrogen, synthetic liquid fuels derived

from the hydrogenation of coal and various blends such as gasohol.

2.3 AIR POLLUTANTS FROM MOTOR VEHICLES

The major pollutants emitted from gasoline fueled vehicles are CO,

HC, NOx and Pb while pollutants from diesel-fueled vehicles are particulate

matter (including smoke), NOX, SO2, Polyaromatic Hydrocarbons PAH.

The composition of automotive and diesel exhausts is characterized

by greater amounts of carbon monoxide and hydrocarbons than that of

emissions from other fuel burning processes. Factors for automotive and

diesel exhaust emission, in pounds per 1,000 gallons of fuel consumed

(Giver, 1972), are given in Table-4.

22
Table-4: Emission Factors for Gasoline Engines and Diesel Engines (lb/1000

gal of Fuel)

S. No. Pollutants Gasoline Diesel Engines

Engines
1 Particulates 11 110
2 Oxides of Sulphur 9 40
3 Oxides of Nitrogen 113 222
4 Carbon monoxide 2910 60
5 Hydrocarbons 524 180
6 Aldehydes 4 10
7 Organic acids 4 31
8 Ammonia 2 -----
9 Benzo(a) pyrene 0.3 g/1000 gal 0.4 g/1000 gal

Carbon monoxide (CO) - Colorless and odorless gas, slightly denser

than air. Residence time and turbulence in the combustion chamber, flame

temperature and excess O2 affect CO formation. Conversion of CO to CO 2 in

the atmosphere is slow and takes 2 to 5 months. In developing countries the

transport sector account for 53% of CO emissions and the residential and

commercial sectors, 46%.

Hydrocarbon Compounds (HC) - Compounds consisting of carbon

and hydrogen and include a variety of other volatile organic compounds

(VOCs). Most HCs are not directly harmful to health at concentrations found

23
in the ambient air. Through chemical reactions in the troposphere, however

they play an important role in forming NO 2 and O3 which are health and

environmental hazards. Among the various HC, methane (CH4) does not

participate in these reactions. Remaining HC, non methane hydrocarbons

(NMHC) are reactive in forming secondary air pollutants. NMHC are photo

chemically reactive.

Benzene and Polyaromatic Hydrocarbons (PAH) - Motor vehicles

emit toxic HC including benzene, aldehydes and polyaromatic hydrocarbons

(PAH). About 85 to 90% benzene emissions come from exhaust and the

remainder comes directly from gasoline evaporation and through distribution

losses. Toluene and xylene HC compounds are present in the gasoline

whereas aldehydes, 1, 3 butadiene are not present in gasoline, diesel fuel,

ethanol or methanol but are present in their exhaust emissions as partial

combustion products.

Note: PAH are emitted at a higher rate in exhaust of diesel-fueled vehicles

than gasoline –fueled vehicles.

24
 Nitrogen oxides (NOX) - includes nitric oxide (NO), nitrous oxide

( N2O), nitrogen dioxide (NO2), dinitrogen trioxide (N2O3) and nitrogen

pentoxide (N2O5). NO and NO2 collectively represented as NOX, are the

main nitrogen oxides emitted by vehicles. About 90% of these emissions are

in the form of NO. NO is produced in the vehicle engine by combustion of

nitrogen at high temperatures. NO2 formed by oxidation of NO, has a

reddish brown color and pungent odour.

In the atmosphere, NO2 involved in a series of reactions in the

presence of UV radiation that produce photochemical smog, reducing

visibility. It may also react with moisture to form nitric acid (HNO 3)

aerosols. In the lower atmosphere (troposphere), NO 2 forms O3 by reacting

with HC. In the upper atmosphere, it reacts with chlorine monoxide to form

chlorine nitrates. In developing countries, the transport sector accounts for

49% of NOX emissions and the power sector, 25%; the industrial sector,

11%; the residential and commercial sectors, 10% and other sources 5%.

Sulfur dioxide (SO2) - is a stable, nonflammable, nonexplosive,

colorless gas. In the atmosphere, SO X may be converted to sulfur trioxide

(SO3) by reacting with O2. SO2 and SO3 react with moisture in air to form

25
sulfurous (H2SO3) and sulfuric (H2SO4) acids may precipitate to earth as acid

rain. Sulphates may also be produced through reaction of these sulfur

compounds with metals present in particulate matter.

Ozone (O3) - in the lower (troposphere) layer, ground level ozone (GLO) is

formed by the reaction of VOCs and NOX with ambient O2 in the presence of

sunlight and high temperatures. GLO is a major constituent of smog in urban

areas and motor vehicles are the main emission source of its precursors. The

reactions that form GLO also produce small quantities of other organic and

inorganic compounds such as peroxyacetyl nitrate (PAN) and nitric acid.

GLO concentrations depend on the absolute and relative concentrations of

its precursors and the intensity of solar radiation, which exhibits diurnal and

seasonal variations. Thermal inversions increase GLO concentrations.

Particulate matter (PM) - consists of fine solids and liquid droplets

other than pure water that are dispersed in air. Total suspended particulates

are particles with an aerodynamic diameter of >70 m. PM with an

aerodynamic diameter of  10 m known as suspended inhalable particulate

matter/ Respirable Suspended Particulate Matter (RSPM) or PM 10, remains

in the atmosphere for longer periods because of its low settling velocity.

PM10 can penetrate deeply into the respiratory tract and cause respiratory

26
illness in humans. PM with an aerodynamic diameter of 2.5-10 m or less is

defined as fine particles (PM2.5), while the larger PM is called coarse

particles. Nearly all PM emitted by motor vehicles consists of fine particles

and a large fraction of these particles has an aerodynamic diameter less than

1m.

PM2.5 can also be formed in the atmosphere as aerosols from chemical

reactions that involve gases such as SO2, NOX and VOC. Sulfates, which are

commonly generated by conversion from primary sulfur emissions, make up

the largest fraction of PM2.5 by mass. PM2.5 can also form as a result of

solidification of volatile metals salts as crystals following cooling of hot

exhaust gases from vehicles in ambient air. Gasoline fueled vehicles have

lower PM emission rates than diesel–fueled vehicles. PM emissions from

gasoline fueled vehicles result from unburned lubricating oil and ash-

forming fuel and oil additives. PM emitted by diesel-fueled vehicles consists

of soot formed during combustion, heavy HC condensed or adsorbed on the

soot and sulfates. These emissions contain PAH. With the advancement of

emission control measures in engines, however, the contribution of soot has

been reduced considerably.

27
 Black smoke, associated with the soot portion of PM emitted by

diesel-fueled vehicles, is caused by O2 deficiency during the full combustion

or expansion phase. Blue, gray and white smokes are caused by the

condensed HC in the exhaust of diesel-fueled vehicles. Blue or gray smoke-

results from vaporized lubricating oil and white smoke occurs during engine

start-up in cold weather. Diesel fuel additives such as Ba, Ca and Mg reduce

smoke emissions but increase PM sulfate emissions. These additives may

also increase PAH emissions..

Chlorofluorocarbons (CFCs) - The source of CFC emissions from

motor vehicles is the Freon gases used in air conditioners. CFC emitted into

the atmosphere rise to the stratosphere layer within 10 years and are

estimated to remain there for 400 years. CFC molecules struck by UV

radiation release chlorine atoms, which destroy O3 by forming chlorine

monoxide. Furthermore, when a free O 2 atom reacts with a chlorine

molecule, an O2 molecule is formed and a chlorine atom is released to

destroy more O3.

CHAPTER-3

28
 CONTROL TECHNOLOGIES FOR POLLUTION EMISSION

Study of exhaust emissions and its control has been a matter of

concern from a long period for the engineers. The operating variables affect

the auto engine exhaust.

3.1 EFFECT OF OPERATING AND DESIGN VARIABLE ON HC &

CO EMISSION

3.1.1 Air-Fuel Ratio

For a fuel quality, concentrations of many of these pollutants

are influenced by such factors as the air-fuel ratio in the cylinder at the time

of combustion, ignition timing, combustion chamber geometry, engine

parameters (e.g. Speed, load and engines temperatures) and use of emission

control devices. Vehicles with electronic fuel injection engines maintain an

air-fuel ratio of about 14.7: 1 (i.e. burning of 1 lb of fuel about 14.7 lbs of air

is needed, which is the stoichiometric/ ideal ratio for the air-gasoline

mixture) to achieve complete combustion.

29
 Lean mixture (Higher Ratios) produces less HC & CO emissions

while Rich mixture (Lower Ratios) produces more CO & HC and low values

of NOx emissions from unburned or partially burned fuel. The air/fuel ratio

is adjusted taking into consideration the emission and efficiency of an

engine. It is seen that most of the gasoline operated engines are adjusted

within the air/fuel ratio of 12:16. The air/fuel ratio and ignition timing are

readily adjustable, both in design specifications and field tune up

adjustments.

3.1.2 Engine Speed

Emission concentration is markedly reduced at higher engine speed.

Primarily increase in engine speed improves the combustion process within

the cylinder by increasing turbulent mixing and eddy diffusion. This

promotes after oxidation of quenched layer. In addition increased exhaust

port turbulence at higher speeds promote exhaust system oxidation reactions

through deter mixing.

3.1.3 Spark Timing

It has been found that at a constant power of 13 BHP and 1500 rpm, a

retard of 10° from the manufacturers recommended setting of 30° BBDC

30
reduced HC emissions by 100 PPM, but increased fuel consumption of 10%.

The 100 PPM change for 10° retard suggests the importance of precise spark

timing and minimum distributor tolerance.

3.1.4 Exhaust Back Pressure

Increasing exhaust gases in the cylinder at the end of the cycle. If this

increase in residual does not increase the percentage dilution of the fresh

charge to a level where the combustion process is adversely affected, the HC

emission concentration will be lowered. The reduction arises from leaving

the tail end of the exhaust, which is rich in unburned hydrocarbons in the

cylinder. This tail is subsequently burned in next cycle.

3.1.5 Valve Overlap

It has similar effects as that of back pressure case. The charge is

further diluted with the residual gases. Slight valve overlap (about 2°)

provided minimum emission. Thus a slight amount of residual tail did lower

the average HC emission value. However a further increase in residual led to

an incomplete combustion and a HC emission increase.

31
3.1.6 Intake Manifold Pressure

At a fixed mixture ratio and speed with best power timing there is no

effect of engine horsepower on hydrocarbon or carbon mono oxide emission.

However because carburetor and distribute settings are variable in a vehicle,

there is a change in emission concentration as the throttle is varied at a

constant speed.

3.1.7 Combustion Chamber Deposit Build Up

Major source of combustion chamber deposit is TEL, fuel additive

used to suppress the combustion knock. Deposits act to increases. Deposits

also act as a sponge to trap raw fuel which remains unburned and adds to

exhaust hydrocarbons. Deposits build up also increases compression ratio

which in turn increases emission.

3.1.8 Surface Temperature

Combustion chamber surface temperature affects the UBHC emission

by changing the thickness of the combustion chamber quench layer and the

degree of after reaction. Went Worth (6) studied the effect of such changes

on hydrocarbon emissions of 0.35 to 0.58 PPM hexane per one degree

32
Fahrenheit (f) rise in combustion chamber surface temperature. In one test

an increase of 100°F decreased emissions by 37%

3.1.9 Surface to Volume Ratio

It is desirable to minimize the surface area of the combustion chamber

because hydrocarbons emissions arise primarily from quenching at the

chamber mixture, a thin layer of HC is left on the wall surface. Hence by

decreasing the surface area for the same volume of the combustion chamber

we can reduce this emission.

3.1.10 Stroke to Bore Ratio

Engine with small bore born and large stroke have lower surface to

volume ratio. But this modification is opposed due to increased frictional

losses in case of long stroke and practice is for short stroke for reduced

friction, increased power and economy.

3.1.11 Compression Ratio

A large reduction in surface to volume ratio can be affected by

decreasing compression ratio. This increases the clearance volume greatly

with little increase in surface area. However, reduced compression ratio

33
results in lower thermal efficiency and reduced engine power. A decrease in

compression ratio reduces hydrocarbon emissions a second way when C.R.

reduces, thermal efficiency is lowered and as a re result exhaust gas

temperature is increased which improves exhaust system after reactions.

3.2 EFFECT OF OPERATING AND DESIGN VARIABLE ON NOx

EMISSION

3.2.1 Equivalence Ratio

The equivalence ratio affects both the gas temperature and the

available oxygen during combustion. Theoretically an increase in the

equivalence ratio from 1 to 1.1 results in an increase in the maximum cycle

temperature of 100°F while o2 concentration occurs at an equivalence ratio

of 0.9. The maximum cycle temperature with this lean mixture is lower that

with a richer mixture, but the available oxygen concentration is much higher.

3.2.2 Spark timing

34
 Increase in spark advance at any load and speed results in an increase

in the no concentration.

3.2.3 Intake Manifold Vacuum

Increase in manifold vacuum decreases load and temperature and an

increase the mass of the residual gases, due to this ignition delay is increased

and flame speed is reduced. This results in increase in the time of

combustion. If the spark timing is kept constant the increase in manifold

vacuum would cause the greater part of the combustion process to occur

during the expansion stroke. This would result in decrease of maximum

temperature of cycle and a corresponding decrease in No concentration in

exhaust.

3.2.4Engine speed

An increase in engine speed has a little effect on ignition delay,

results in an increase in the flame speed due to turbulence and reduces heat

losses/cycle. This tends to raise compress and combustion temperature and

pressure. It spark timing is held constant a greater portion of this combustion

35
tends to occur during expansion where temperature and pressure are

comparatively low. This is slowest for burning mixture ratio 19:1. For richer

mixture, which burn faster, the effect of reduced heat losses at higher speed

predominates. This implies that an increase in the rate of no formation due to

reduced heat losses opposed by a reduction in the rate of no formation due to

late burning. For rich mixtures where combustion and NO formation are, the

former effect predominates. For lean mixtures where combustion and no

formation are rapid, the former effect predominates. For lean mixtures where

combustion and no formation are flow the later effect predominates.

3.2.5 Effect of Coolant Temperature

An increase in coolant temperature results in a reduction in the heat

lost to the cylinder walls and an increase in maximum gas temperature. This

results in an increase in No concentration and vice versa.

3.2.6 Humidity

An increase in the mixture humidity is mainly due to the drop in

maximum flame temperature which reduces No formation, Moore (7) has

calculated that 1% (by weight) of water vapour reduced a hydrogen-air

ethylene air flame temperature by 36°F. This reduced the initial rate of No

production by about 25%.

36
 CHAPTER-4

CONTROL TECHNOLOGIES FOR POLLUTION EMISSION

If we adjust above design and operating variables we can minimize

Exhaust emission pollution but we are not able to do so and to maintain the

equilibrium along different variables. The following techniques have been

used to reduce the exhaust emission:

4.1 Exhaust Gas Recirculation

A portion of the exhaust gas is recirculated to the cylinder intake

charge. This reduces the peak combustion temperature, since the inert gases

absorb a large quantity of heat. This also reduces the quantity of oxygen

available for combustion. The exhaust gas for recirculation is directly taken

from the stove area through an orifice; It passes through the butterfly control

valve for regulation of the rate and ducted down to the throttle shaft by

means of appropriate linkage and the amount of valve opening is recycle

exhaust is normally shut off during full throttle acceleration to prevent loss

of power when maximum performance is needed. There will be a little effect

37
on Nox emission even if the above arrangement is not made because Non

concentrations in idle and full throttle are already very low. Reduction of the

peak combustion temperature by EGR reduces the formation of Nox.

4.2 Thermal reactors

A thermal reactor is a chamber in the exhaust system designed to

provide sufficient residence time to allow appreciable homogeneous

oxidation of Co and hydrocarbon to occur. In order to improve co conversion

efficiency, the exhaust temperature is increased by spark retard. This

however, results in fuel economy loss. Thermal reactor consist of two

enlarged exhaust manifold which allow greater residence time for burning of

HC and CO with oxygen in the air, which is pumped. A cylindrical reactor

with a tangential entry from the exhaust manifold is attached to the engine.

Secondary air pumps inject fresh air into the reactor to keep a flame

constantly burning and thereby assuring complete combustion.

38
4.3 Modification in Combustion System to Achieve Complete

Combustion

The undesirable exhaust emission of vehicle is formed mainly within

the combustion process. Due to improper vaporization of fuel in inlet

manifold incomplete combustion results which leads to liberation of Co and

HC modification such as heating the inlet air(4), enhances the vaporization

of liquid gasoline and improve mixture distribution among the cylinder

resulting in a better. Combustion which reduce Hc and Co.

4.4 Injection System

The objective of the injection system is to atomize and distribute the

fuel throughout the air in the cylinder while maintaining prescribed fuel-air

rations. To accomplish these tasks a number of functional element might be

required within the system.

(a) Pumping elements: to move the fuel from fuel tank to cylinder.

(b) Metering element: to measure and supply the fuel at the rate

demanded by the speed and load.

39
 (c) Metering control: to adjust the rate of metering elements for changes

in load and speed of the engine.

(d) Mixture control: to adjust the ratio of fuel rate to air rate as demanded

by the load and speed.

(e) Distributing elements: to divide the metered furl equally among the

cylinders.

(f) Timing control to compensate for changes in temperature and

pressure of either air or fuel or engine that affects the elements of the

system.

(g) Ambient control: to compensate for changes in tem. And pressure of

either air or fuel or engine that affects the element of system.

(h) Mixing Element: to atomize that fuel and mix with air to from a

homogeneous mixture.

These changes ensure precise fuel metering in accordance with changing

engine requirements at low and high loads.

4.5 Ignition System

Ignition system modification is carried out for burning leaner air

fuel mixture. Lean mixtures have higher breakdown voltage than do slightly

rich mixtures. Good ignition depends upon the following reasons.

40
(a) Length of air gap of the spark plug the greater the gap, the larger is

the required breakdown voltage.

(b) Geometry of the gap: Pointed electrodes require less breakdown

voltage.

(c) The temperature of the electrodes and enclosed air fuel mixture: high

temperature allow lower breakdown voltage

(d) The density of mixture: higher density requires high breakdown

voltage.

(e) The leakage resistance of the insulator: carbon and metallic oxides

from electrically conductive coatings on the insulator which thus

shunt the secondary winding and reduce the maximum voltage that

the secondary can impress across the spark gap.

(f) The rate of increase of the voltage at the gap: if the ignition system

builds up the voltage at a rapid rate, the effect leakage will be

minimized and a Grater sparking voltage is available.

(g) The presence of ionized gases in the gap: Good ignition system also

depends on following point.

 A combustible mixture must present between the electrodes. For this

reason, a spark plug location near the intake valve is desirable,

41
 although opposed by the necessity to locate the plug near the hot

exhaust valve to avoid knock.

 A large gap increases the probability of regular firing, especially at

parts loads, when stratification from exhaust gas dilution is present.

 A high mixture density allows a greater amount of energy to be

liberated and probability of ignition is increased.

 Ignition is best secured with slightly rich mixtures, since a greater

release of energy is obtained.

 The position of the plug and the position of the electrodes relative to

the flow conditions in the chamber.

4.6 Carburetor

Main work of carburetor is to meter, atomize, vaporize and mix the

fuel with air. If carburetor modifications are such that to ensure precise fuel

metering in accordance with changing engine requirements at low and high

loads.

4.7 After Burner

42
 The after burners designed to oxidize UBHC and CO; includes a pre-

combustion chamber where secondary air and fuel are ignited by a spark to

provide thermal energy for the reaction.

4.8 Evaporative Emissions and Control

Diurnal and Hot soak emissions have been controlled by venting the

fuel tank to the atmosphere through a canister of activated carbon. The

volatile nature of gasoline can be minimized by keeping gasoline Reid Vapor

Pressure of 10 psi. Gasoline with an RVP of 11 psi will produce about twice

the evaporative emissions of gasoline with an RVP of 8.7 psi.

4.9 Crankcase Emissions and Control

Crankcase emission controls involve closing the crankcase vent port

and venting the crankcase to the air intake system via a check valve. In

newer model crankcase blow–by are controlled by recycling to the engine

through the intake system.

43
4.10 Catalytic converter

The principal of catalytic converter is to control the emission levels

of various pollutants by changing chemical characteristics of the exhaust

gases.

Except catalytic converter above method require additional changes

in the engine design. In the exhaust gas recirculation method, is basically to

reduce the concentration of only one specie i.e. Nox. and may increase the

concentration of other constituents. Thermal reactors need additional

combustion chamber and spark ignition systems which make it more

expensive. This may also increase the combustion of fuel.

In modern practice catalytic converter has been effectively used

because it has some additional benefits e.g.

 No additional fuel is necessary to initiate or sustain reaction.

 Temperature inside the catalyst zone is lower, which reduces the

problem of construction material.

 System is self initiating at exhaust gas temperature and does not need

spark plug or other device.

 System operates even at low level of HC and CO.

44
5.1 Historical Background

Air pollution problems became serious in 1940s and many nations

took a serious view of it and some legislation was introduced since then in

1968 most of the automobile. Manufacturers started introducing some from

of emission control devices, such as catalytic converters. There were studied

extensively in 1957-64 and again appeared in 1990s when it was recognized

to get large reductions in pollutants from the exhaust. Various materials such

as platinum or its group metals have been used for reduction of pollutants.

Besides of them oxides of base metals, such as copper, nickel, chromium

and magnise were also used as oxidizing catalyst, which had shown

significant reduction in pollutants.

Base metal alloys such as copper-nickel, and copper-Zink were

successfully used as a catalyst. These alloys along with noble metals

supported on alumina formed a dual catalyst system the reducing catalyst for

reducing nitrogen oxides has been kept in first half of the converter and the

second half is packed with oxidation catalyst. This would give out some

45
oxygen for oxidation reactions in the second half, so as to improve the

reduction mechanism.

Three way catalyst systems generally known as T.W.C. have been

come into operation and are being widely used. A three way catalyst system

is employed to promote the oxidation and reduction reactions

simultaneously. The converter contains a catalytic element in a cylindrical

block with a large number of channels forming a honey comb structure. The

active material, platinum and pollodinum, platinum and rhodium in different

combinations are dispersed over the outer surface of alumina. When the

exhaust gases pass over the honey comb structure they would be in contact

with the catalyst and would get oxidized and reduced simultaneously.

Gandhi Blum berg et alHansel Baruah Hammerle and many others

evaluated the three way catalyst system under different operating conditions

and the performance of a T.W.C. catalytic converter has been found very

encouraging for reduction of pollutants, improved fuel economy and a

negligible loss of engine power.

It has also been felt that duel catalyst system would be better than

T.W.S. for certain operations. Whether it is a three way catalyst or a dual

catalyst system the catalyst used are made of noble metals like platinum,

46
palladium and rhodium which are very expensive and application to

automobile industry in the country would mean additional cost.

Ching H.wu and Hammerle then presented a solution for the

development of a low cost stable T.W.C, System. This consists of cheaper

palladium in one half and platinum and rhodium in second half to give an

improved performance of converter at a comparative cheaper cost. The

operation of three way catalyst requires a very close control of air fuel ratio

in the vicinity of the stoichiometric air- fuel ratio. This requires sophisticated

electronically operated closed loop feed back control. T.W.C. system gets

poisoned by lead, phosphorous and sulphur dioxide which are also present in

exhaust gases. This deactivates the catalyst and requires a replacement cost.

Therefore, the necessity of a low cost thermally stable catalyst preferably

from indigenous sources for the reduction of the pollutants having same

activation period as that of other noble metals. Base metal oxides such as

copper oxide, iron oxide, chromium oxide, and magnese oxide can easily be

used for reduction. Copper and Ni alloy

known as Monel, is available in sheet form and could be easily which is

indigenously available can also be used as a catalyst. This has got a tendency

to promote oxidation and reduction of the pollutants. For an automobile

industry, the primary consideration of selecting a catalyst is its cost

47
effectiveness and availability of material. A newly (1993) searched

compound ‘Econogreen’ has been used as catalytic converter and it is given

pollution control check certificate.

Galen et al. investigated the alternatives to the Rhodium. With

World-wide growth of the automotive emissions control market, concerns

about future cost and availability of catalytic metals, particularly Rhodium,

have also grown. These factors have led to an increased interest in catalyst

formulations which might allow reduced Rh usage or the complete removal

of Rh from the catalyst without compromising the performance of the

emission control system. They had tested a set of catalyst to examine Ru, Ir,

and Pd as alternative to Rh, either alone or in combination with Pt. They

found that addition of Pd (or Rh) always improves the activity of Pt/Pd

system over Pt/Rh formulation.

Porter ‘Doyle et al. have studied the performance characteristics of

oxidation catalyst in heavy duty application and reviewed the optimization

process required to match the system to the application. They reviewed the

recent research by Svenska emissions Teknik A B and Recardo to investigate

the potential and performance characteristics of catalysts for the application

together with a critical examination of the matching process require to

48
optimize the engine and catalyst as a system. They concluded a sound

judgment to meet the 1994 standards of emissions from automobiles.

Suresh T. Gulati published a paper on the development and successful

application of ceramic catalytic converters for controlling automotive

exhaust emission. They designed the high surface area to meet both

performances, durability requirement. They followed a step by step design

process for each of the converter components. The initial design stage

focuses on understanding automakers requirements and optimizing

component design commensurate with them. The intermediate stage

Involves laboratory testing of converter component in simulated

environment and ensuring component compatibility from durability point of

view. The final design stage addresses the critical tests on converter

assembly to ensure performance and field durability. They also examined the

necessary trade-offs and associated design modification and evaluates their

impacts on warranty cost on system failure. They focused on integrated

design approach for failure free operation of catalytic converter over the

vehicles like them. Hurley et al. studied about electrically heated catalyst to

meet stringent California and federal 1993/94 emission standards. They

focused specific attention on the cold start characteristics of the vehicles

emission system. Specially that of the catalyst. From test data it is evident

49
that major portion of the total H C and Co emission occur within the first

two minutes of the driving cycle. Of The use of an electrically heated

catalyst (EHC) is shown to be advantageous in lowering cold start emissions

during this portion of the drive cycle. They showed the effect on emissions

from the stand point of EHC location, catalyst volume, and engine

calibration in an overall emission improvements have been at a premium, i.e.

lower fuel economy, additional vehicle weight, power consumption, and yet

to be totally accessed EHC durability.

Martin j. Heimrich added some improvement in the Hurley’s efforts

for electrically heated catalyst. In his Study he injected air ahead of an

electrically heated catalyst during cold start operation. He continuously

recorded raw exhaust emissions. Analysis was used to determine air

injection calibration and oxidation reduction trade offs. Improved control of

non methane hydrocarbons (NMHC), benzene, and carbon mono oxide (co)

emission control was maintained by the use of carefully controlled air

injection flow rate and schedule. They determined that heating an

automobile exhaust emission catalyst prior to cold start operation may not be

sufficient in itself. Supplemented oxygen may be required for improved

emission control.

50
 Douglas J. ball and Robert Gattack gave a theory about the diesel

exhaust catalysis using an oxidation flow-through type catalyst to reduce

particulate emission. They discussed about converter design, catalyst support

materials and the use of nodle metals for light and heavy duty applications.

They performed experiments to determine the sulphur storage and release

characteristics of alumina and silica catalyst support materials and the ability

of platinum and palladium to oxidize so2 to sulfate particulate.

Mitsure et algave a technique to reduce Nox in diesel engine exhaust.

Copier iron exchanged z sm-5 zeolite catalyst, which reduces nitrogen

oxides (Nox) in the presence of oxygen and hydrocarbons, was applied to

actual diesel engine exhaust. Copper ion exchanged zsm-5 zeolite effectively

reduced Nox by 25% in normal engine operation and by 80% when

hydrocarbons in the exhaust were increased. Water in the exhaust gas

decreased the NOx reduction efficiency but oxygen and sulphur appeared to

have only a small effect. Maximum NOx reduction was observed at 400°c

irrespective of hydrocarbon species.

Masaaki Takiguchi et al. gave a technique to reduce the NOx from

diesel engines with NH3 as reducing agent NH3 is one of the most useful

compounds that react with NOx selectively on a catalyst, such as v2o5- Ti

o2, under oxygen containing exhaust gas. However ammonia can not be

51
stored because of its toxicity for the small power generation in populated

areas or for the diesel vehicles. This system is constructed from the

hydrogen generation by fuel reformer, the NH3 synthesizer, SCR catalyst for

NOx reduction and the gas injection system of reformed gas into the

cylinder.

R. Beckmann et alexplained the working and use of a precious metal

based, flow-through type diesel oxidation catalyst. He paid much attention to

the durability of the diesel oxidation catalyst and especially to the influence

of poisoning elements on the catalytic activity. Starting from 1984 an

increasing number of diesel passenger cars in Europe have been equipped

with this type of precious metal based catalyst. The main function of this

flow-through type catalyst, containing precious metal, are the conversion of

the gaseous pollutants carbon mono-oxide and hydrocarbon as well as the

oxidation of hydro carbon components absorbed on the soot. Therefore it is

possible to reduce the amount of particulates emitted by the diesel oxidation

catalyst in such a way that it selectively catalyzes the oxidation of carbon

containing components at the low exhaust gas temperature typical for diesel

engine at partial load operation, and that it does not oxidize sulphur dioxide

or nitrogen oxides in the range of high exhaust gas temperature occurring at

full load.

52
 Makoto Horiache studied the effects of flow-through type of oxidation

catalysts on the particulates reduction of 1990’s diesel engines. The

reduction behavior of diesel particulate and so F by flow through type

oxidation catalysts was investigated under steady and dynamic engine

conditions using a current fuel (S.Content;0.38% by wt.). Each catalyst gave

40-90%, soluble organic fraction (SOF) reduction at exhaust gas temperature

between 100°C to 500°C. SOF is absorbed on catalyst surface at lower

temperature and is decomposed at the higher temperature PT only load

catalyst which has high SO2 oxidation ability resulted in a low total

particulate reduction due to high sulfate formation at higher temperature

even when low sulphur fuel was used.

Paul Zeienka did research work on reduction of diesel exhaust

emissions by using oxidation catalysts. Research describes the result work

concerning the investigation and optimization of oxidation catalysts for

diesel engines, especially for passenger cars and light duty trucks.

53
5.2 UNLEADED PETROL CAN NOT PLUG POLLUTION

WITHIOUT CATALYTIC CONVERTER

A Catalytic converter (CC) is placed inside the tailpipe through which

deadly exhaust gases containing unburnt fuel, CO, NOx and air are emitted.

The function of the CC is to convert these gases into CO 2, water and N2.

Unleaded petrol if used with catalytic converters could check pollution.

Unleaded petrol has a low density and therefore, it evaporates fast.

Currently, it is compulsory for all automobiles plying on roads in US

and Japan to have catalytic converters as they use unleaded petrol. In India,

the government has made catalytic converters mandatory for registration of

new cars. But what about old cars whose engine can get damaged due to

prolonged use and two-wheelers and three wheelers which account for 60%

of vehicular pollution?

5.3 PROBLEMS IN USE OF CATALYTIC CONVERTER

Nobel metals like platinum, rhodium and palladium required to make

good catalytic converters is also not available in India. To increase the

efficiency of fuel, benzene is added to petrol. In leaded petrol, the benzene

54
content was 5% which have been brought down to 3% in unleaded petrol.

Interestingly, the permissible euro limits are just 1% for benzene.

5.4 TYPES OF CATALYTIC CONVERTER

The catalytic converter is one of the most effective emission control

devices available. Two types of catalytic converters are commonly used in

automotive engines.

 Two-way catalytic converters (Oxidation) - used in diesel- fueled

vehicles can reduce CO emission by 80% and a large portion of HC

present in particulate matter emissions.

 Three-way Catalytic Converters (Oxidation–Reduction)- installed

on gasoline fueled vehicles can reduce CO and HC emissions by

about 90% and NOX emission by 70% from uncontrolled levels.

 Lean nitrogen-oxide Catalyst- is a new type of catalytic converter

which reduces NOX emissions in lean conditions where a three-way

catalyst is ineffective.

55
5.4.1 A TWO-WAY CATALYTIC CONVERTER HAS

TWOSIMULTANEOUS TASK:

1. oxidationof carbon monoxide to carbon dioxide: 2CO + O2 → 2CO2

2. Oxidation of unburnt hydrocarbons (unburnt and partially-burnt fuel)

to carbon dioxide and water: 2CxHy + (2x+y/2)O2 → 2xCO2 + yH2O

This type of catalytic converter is widely used on diesel engines to reduce

hydrocarbon and carbon monoxide emissions. They were also used on spark

ignition (gasoline) engines in USA market automobiles up until 1981, when

they were replaced by three-way converters due to regulatory changes

requiring reductions on NOx emissions.

Reduction of the NOx emissions requires an additional step. Platinum

catalysis can be used. Instead of catalysis, a true reactant — diesel fuel or

ammonia pyrolyzed in situ from urea— can be used to reduce the NO x into

nitrogen.

Curiously, the regulations regarding hydrocarbons vary according to the

engine regulated, as well as the jurisdiction. In some cases, "non-methane

hydrocarbons" are regulated, while in other cases, "total hydrocarbons" are

regulated. Technology for one application (to meet a non-methane

56
hydrocarbon standard) may not be suitable for use in an application that has

to meet a total hydrocarbon standard. Methane is not toxic, but is more

difficult to break down in a catalytic converter, so in effect a "non-methane

hydrocarbon" standard can be considered to be looser. Since methane is a

greenhouse gas, interest is rising in how to eliminate emissions of it.

5.4.2THREE-WAY CATALYTIC CONVERTERS (OXIDATION-

REDUCTION)

Ensuring good quality air is essential for the protection of public

health. Governments worldwide have adopted a range of increasingly

demanding measures to curb air pollution with a particular focus on the

emissions from motor vehicles. An important part of this strategy has been

the development of the three-way catalytic converter to remove exhaust

pollutants such as carbon monoxide, unburnt hydrocarbons and nitrogen

oxides. This unit takes an in-depth look at the construction of this converter

for petrol-driven vehicles and investigates the catalytic chemistry taking

place at the molecular level. It is assumed that you already have a scientific

background.

57
The three-way catalytic converter

58
5.4.2.1 COMPOSITION

The current three-way catalyst, shown schematically in Figure 1, is

generally a multicomponent material, containing the precious metals

rhodium, platinum and (to a lesser extent) palladium, ceria (CeO 2), γ-

alumina (Al2O3), and other metal oxides. It typically consists of a ceramic

monolith of cordierite (2Mg.2Al2O3. 5SiO2) with strong porous walls

enclosing an array of parallel channels. A typical monolith has 64 channel

openings per cm2 (400 per in2), This design allows a high rate of flow of

exhaust gases Cordierite is used because it can withstand the high

temperatures in the exhaust, and the high rate of thermal expansion

encountered when the engine first starts – typically, the exhaust gas

temperature can reach several hundred degrees in less than a minute.

Metallic monoliths are also used, particularly for small converters, but these

are more expensive.

59
 Figure 1. Schematic diagram of the three-way catalytic converter.

To achieve a large surface area for catalysis, the internal surfaces of

the monolith are covered with a thin coating (30–50 μm) of a highly porous

material, known as the washcoat (Figure 2). The total surface area is now

equivalent to that of about two or three football pitches. The washcoat

generally consists of alumina (70–85%) with a large surface area, with

oxides, such as BaO, added as structural promoters (stabilizers to maintain

surface area) and others, for example CeO2, as chemical promoters. This

system becomes the support for the precious metal components (Pt, Pd and

60
Rh). These metals constitute only a small fraction (1–2%) of the total mass

of the washcoat, but they are present in a highly dispersed form. They are

generally applied by deposition from solution, although they may instead be

introduced during formation of the washcoat itself. Exact catalyst

formulations are, as one might expect, closely guarded secrets. Some

compositions use all three metals; others use Rh together with only one of

the other two, typically Pt, as in the present generation of Pt-Rh converters

used in the UK, in which Pt constitutes 80–90% of the total precious metal

mass

Figure 2. Electron micrograph of a cross section of a ceramic monolith

coated with an alumina washcoat

61
5.4.2.2 CATALYST PERFORMANCE

Figure 3 shows the difference in the emission levels for CO, VOC and

NOx for a vehicle, with and without a three-way catalytic converter. It is

evident that the catalytic converter reduces the emissions of all three classes

of pollutants quite dramatically over a wide range of speeds. Before we

discuss the data in any detail, a few words about how they were obtained are

in order.

62
 Figure 3 Emission levels for CO, VOC and NOx for petrol-engine vehicles

as a function of speed, with (green) and without (black) a three-way catalytic

converter.

Federal and European Test Procedures are used to test emissions from

a complete ‘finished’ converter and engine together, to ensure that a new car

model, for instance, will meet the current emissions legislation. Some sort of

smaller-scale testing is obviously required in the laboratory. In the research

and development of automotive catalysts, activity testing fulfils the function

of screening and comparing novel and modified catalysts, and examining

their performance under different conditions. The process of screening must

provide a reliable means of identifying materials that will perform as active,

selective and durable catalysts under automotive conditions. The approach

usually taken is to measure conversion of the pollutants as a function of

temperature, using a simulated exhaust-gas mixture flowing through a bed of

powdered catalyst: the flow-rate has to be high enough to mimic the

‘through-put’ or space velocity of a catalytic converter (typically a contact

time for the gases with the catalyst of 72 milliseconds is used). The test is

then repeated using a different simulated exhaust-gas to represent a different

engine mode. Ageing studies are performed by exposing the catalyst to

different and often extreme conditions, for varying lengths of time.

63
 Figure 4 Activity of a three-way catalyst for the simultaneous

conversion of CO (black), NOx (solid green) and the hydrocarbon propene

(C3H6) (dotted green)

Figure 4 shows a typical graph of catalytic performance over the

normal range of operating temperature, 100–600 °C. Until the incoming

gases have heated the catalyst to around 250–300 °C, the activity of the

catalyst is low. This temperature, at which the efficiency of the catalyst

rapidly increases, is known as the light-off temperature. Until this

temperature is reached, the catalyst is not working at full efficiency, and so

CO, NOx and hydrocarbons will all be emitted from the exhaust pipe in

significant amounts. This problem is known as cold start. Ideally the light-

off temperature should be as low as possible.

64
5.4.2.3 Exhaust Emission Characteristics

Before we consider how the three-way catalyst functions in any detail,

it is important to understand how the emissions of CO, HC and NO x, from

the engine depend on the ratio of air (A) to fuel (F) – the air/fuel ratio (or

A/F ratio). The significance of this will become clear when we see that the

ratio at which the three-way catalytic converter operates is crucial for its

success.

Taking octane (C8H18) to be the only constituent of fuel, and assuming

that air is 20% O2 by volume, estimate the stoichiometric A/F ratio (mass

ratio) required for total combustion to occur. At this stage neglect the effect

of NO as an oxidant. Comment on the difference between the value you

obtain and the experimental value of 14.7:1 (Use the following relative

atomic masses: C, 12.01; H, 1.01; O, 16.00; N, 14.01.)

The stoichiometric equation for the complete combustion of octane

can be written as follows:

C8H18 + 121/2O2 = 8CO2 + 9H2O

So combustion of 1 mol of octane will require 12.5 mol of oxygen.

65
Assuming air to be approximately 20% O2 and 80% N2 (by volume), the

mass of air required will be 12.5 (32.00 + 4 × 28.02) g = 1801 g.

The mass of 1 mol of octane is (8 × 12.01 + 18 × 1.01) g = 114.26 g.

Thus, the A/F mass ratio for complete combustion is:

A/F = 1801/114.26

= 15.8:1

Figure 5 The effect of changing air/fuel ratio on the levels of NOx (solid

green), CO (black) and HC (dotted green) produced in the engine. The

diagram also shows qualitatively how the engine power output changes with

the A/F ratio.

66
 This is as close as you would expect to the experimental value of

14.7:1, because we have used a very simplified system. We had not included

NO as an oxidant or the other hydrocarbons, CO or H2 as reductants, and we

have used octane, not the real mix of hydrocarbons in petrol.

A general relationship between levels of CO, HC and NO x released

from the engine and the A/F ratio is shown in Figure 5. At A/F ratios

somewhat above stoichiometric (14.7:1) – that is, when the engine is

operating under fuel-lean, net oxidizing conditions – low levels of HC and

CO are produced in the engine, and there is a peak in NO x concentration. At

higher A/F values, NOx falls, but the hydrocarbon concentration increases as

the engine begins to misfire.

67
Figure 6 Activity of a three-way catalyst for the simultaneous conversion of

NOx (solid green), CO (black) and HC (dotted green) as a function of the

air/fuel ratio. The shaded area defines the window for conversions of 80%

and above for all three pollutants. (Note that, for clarity, the A/F ratios are

expressed as the amount of air per unit of fuel, e.g. 14.7 instead of 14.7: 1.

We shall use this notation for the rest of this unit.)

When the exhaust gas is close to its stoichiometrically balanced

composition, at an A/F ratio of about 14.7:1, the concentrations of oxidizing

gases (NO and O2) and reducing gases (HC and CO) are matched; in theory,

it should then be possible to achieve complete conversion to produce only

CO2, H2O and N2. This is, of course, the objective of the three-way catalytic

converter, and so, ideally, it should be operated in a narrow band, or

window, close to the stoichiometric ratio, within which it will promote

simultaneously the nearly complete reduction of NOx to N2 and the nearly

complete oxidation of CO and HC to CO 2 and H2O. Figure 6 shows the

catalyst conversion efficiency for all three classes of pollutants as a function

of A/F ratio, with the dotted lines defining the window for conversions of

80% and above.

68
 Using the information given in Figures 5 and 6, explain the changes

in conversion efficiency seen for all three pollutants when the A/F value is

(a) greater than the window for optimum conversion, and (b) less than the

window for optimum conversion.

(a) Figure 5 shows that over the narrow range of A/F ratios covered in

Figure 6 the amounts of CO and HC emitted form the engine decrease as

A/F increases. As there is a simultaneous increase in the total amount of

oxidants (air + NOx), the overall conversion of CO and HC increases to

approach effective completion at the stoichiometric ratio, and then remains

constant in the net oxidizing conditions beyond that point. The sharp fall in

NOx conversion for A/F values approaching and above stoichiometric is

understandable in terms of the virtual elimination of reductions in this

region. Because the system is unable to remove all of the NO x, we would

expect to see an increase in NOx emissions from the exhaust. The three-way

catalytic converter is therefore unsuitable for engines that run lean.

(b) At A/F ratios below the window value there is less NO x and more

HC and CO present in the mixture expelled from the engine (Figure 5). All

the NOx present will react over the catalyst, so the NO x conversion will still

is high (as seen in Figure 6). However, we see a decrease in catalyst

69
efficiency for destroying HC and CO, as there are insufficient oxidants

present for complete conversion. We would therefore expect to see an

increase in the HC and CO levels emitted from the exhaust.

Obviously in both cases, in the absence of the three-way converter the levels

of CO, HC and NOx emitted for the exhaust would be much higher.

Engine control systems have been developed to include an oxygen

sensor (or lambda, λ, sensor as it is sometimes called), and an electronic

module to regulate the A/F ratio, so that the exhaust composition is kept

within the window for optimum conversion. However, because there are

time delays in the A/F correction, the ratio cycles very rapidly between

slightly fuel-rich and slightly fuel-lean, oscillating about the

stoichiometrically balanced composition (14.7 ± 0.3) at a typical frequency

of 1 cycle per second. Minimizing the amplitude of the oscillation increases

the effectiveness of the converter.

70
5.4.2.4 The Chemical Reactions

Introduction

Since its development, the three-way catalyst has been exposed to the

full spectrum of techniques available for the characterization of catalytic

materials. The data provided can be correlated with the results of activity

tests and kinetic measurements, which provide information on the

performance of the catalyst. This reveals that although the catalyst functions

as a composite material, it can be divided into distinct groups of catalytic

centers that provide several different types of site, active for one or more of

the many different reactions. The participation of a particular type of site at

any given moment will depend on the conditions experienced by the

catalyst; for example, whether the gases are a net reducing, stoichiometric,

or oxidizing mixture.

Measurements of intrinsic kinetics are usually carried out on simple

gas mixtures to allow activation energies and reaction orders to be calculated

for specific reactions. The data can often contribute to an understanding of

the mechanisms by which the surface reactions occur. They are also used to

71
create reaction models that will predict the performance of the catalyst under

various anticipated conditions.

The overall reaction scheme is complicated, with many contributing

processes. The strategy of the three-way catalyst is to simultaneously

remove CO, HC and NOx, and our treatment will accordingly be divided into

three subsections. The desired reactions can be expressed in simple terms as

follows:

Removal of CO

CO oxidation:

Water-gas shift (WGS) reaction:

Removal of hydrocarbons

Hydrocarbon oxidation:

For example:

72
Steam reforming:

Removal of NO (plus CO or HC (not shown))

CO + NO redox reaction:

Or with hydrogen:

Any number of these reactions may be occurring simultaneously as

the A/F ratio goes through its cycle about the stoichiometric composition.

The following subsections will look more closely at the removal of each of

the pollutants under various conditions, and will also examine the role of the

catalyst components.

The supported commercial catalyst is the one most difficult to study

because of its complexity, with a large number of different components – Pt,

Rh, Al2O3, CeO2, BaO, etc. – present in one catalyst. It is therefore often

simpler to study model systems, such as Pt/Al2O3 or Rh/CeO2, and if certain

73
surface-science techniques are to be used, the ‘catalyst’ under study has to be

even simpler – a particular face of a metal single crystal. These studies, often

performed under ultrahigh vacuum (UHV), are far removed from the real

catalyst system and the conditions it experiences. Hence, it cannot be

assumed automatically that the results will be directly relevant to what is

actually happening in a converter fitted to an operational vehicle.

Removal of CO

Under fuel-lean conditions (excess O2), the oxidation of CO has been

studied over a very large range of single crystals and model noble metal

catalysts, one of the most intensively investigated examples being the

Pd(111) surface. Although this metal is not a component of the current three-

way catalyst used in the UK, it is worth considering the results in some

detail for a number of reasons. The reaction on metals such as Pt is in many

ways similar to that on Pd and, in any case, palladium is already being

incorporated into future generations of catalytic converter, particularly for

the US market. Most notable, however, is the fact that this is one of the few

cases in which surface-science techniques have successfully revealed the

details of a ‘real-world’ catalytic mechanism. Specifically, we will see how

74
surface studies of the adsorption of CO and oxygen on Pd (111) – both

individually and together – have led to the current understanding of the

mechanism of CO oxidation.

LEED results for the adsorption of CO on Pd (111), obtained at room

temperature and below, have been interpreted in terms of the structural

models shown in Figure 7. One of the significant observations from this

work is the readiness with which one arrangement of CO on the surface

evolves into another. Thus at a surface fractional coverage of θ = 1/3 (Figure

7a), the CO occupies a hollow site where it can bind to three Pd atoms. As θ

is increased to 1/2 (Figure 7b), CO moves out of the hollow to a bridging site,

where it binds to two Pd atoms. Finally, at θ = 2/3 (Figure 7c), a hexagonal

structure forms, in which half of the CO molecules reoccupy hollow sites,

while the remainder bind to single Pd atoms at terminal sites. The readiness

with which the CO molecules can reposition themselves suggests that the

activation energy for surface migration in the chemisorbed state is low, and

that CO is a highly mobile species under catalytic conditions.

Oxygen adsorbs dissociatively on Pd (111), and the O atoms are found

to be less mobile on the surface than CO molecules. The structure of the

chemisorbed layer at maximum coverage is shown in Figure 8.

75
Figure 7 Structural models for the adsorption of CO on Pd(111) at a surface

fractional coverage of (a) θ=1/3; (b) θ=1/2; and (c) θ=2/3.

Identify the adsorbate structure shown in Figure 8 in terms of the (m×n)

notation, and determine the fractional surface coverage, θ, of oxygen atoms.

Figure 8 The surface structure of O atoms adsorbed on Pd(111) at maximum

surface coverage

The unit meshes of the substrate (1 × 1) structure and of the adsorbate

structure are shown in Figure 8A. Evidently, the latter is (2 × 2) in the (m ×

76
n) notation, so the full description of this structure should be Pd (111) (2 ×

2)–O.

For adsorption on a single crystal surface, the fractional surface coverage is

given by

θ = x/ (m × n)

Where x is the number of adsorbate species within the (m × n)

adsorbate unit mesh. In this case (Figure 8A), O atoms occur only at the

corners of the mesh, so the latter contains a total of (4 × 1/4) = 1 atom. Hence

θ = 1/ (2 × 2) = 1/4

77
 Figure 8A the surface structure of O atoms adsorbed on Pd (111) at

maximum surface coverage, showing the substrate unit mesh and the

adsorbate unit meshes.

We might now assume that when CO and O2 are adsorbed together

during the oxidation reaction, the properties of the system will be a simple

combination of those of the two molecules adsorbed separately. The surface

layer would then consist of mobile CO (maximum coverage, θ = 2/3) within a

fixed lattice of O atoms (maximum coverage, θ = 1/4). The fact that this is not

the case, as we shall see below, demonstrates an important point. Because of

mutual interactions, the behavior of two (or more) co-adsorbed species very

often differs from their behavior when adsorbed separately.

In the case of CO and O 2, the order in which adsorption is carried out

is significant. If CO is adsorbed first, to a coverage greater than one-third of

a monolayer (θ = 1/3), subsequent oxygen adsorption is completely blocked.

With lower coverages of CO, dissociative oxygen adsorption does occur; but

the two species form separate domains on the surface (Figure 9a). Oxidation

will then take place only at the boundaries between domains, and so it will

be relatively slow.

78
Figure 9 Schematic representation of domains of CO (ad) and O (ad) on Pd

(111). (a) Separate domains (CO adsorbed first); (b) mixed domains (O2

adsorbed first).

When oxygen is adsorbed first to its maximum coverage, θ = 1/4,

subsequent CO adsorption occurs readily and compresses the O atoms into

domains in which the local coverage reaches θ = 1/3. At first, the adsorbed

CO is found in separate areas (as when CO is adsorbed first), but as more is

added mixed domains form, containing both CO and O, each at a local

coverage of θ = 1/2 (Figure 9b).

These mixed domains bring CO (ad) and O (ad) into intimate contact,

with the O atoms at twice the surface concentration possible in the absence

of CO. Thus, the stoichiometry is now that required for the oxidation

reaction. Moreover, an electronegative O atom will withdraw charge from

the surface. In turn, the surface will withdraw charge from neighboring Pd–

CO bonds, weakening them and so making the CO more readily available

79
for reaction. The net result is that the mixed domain is highly reactive and

generates CO2 at temperatures far below room temperature.

Having thus established that, on Pd (111), rapid CO oxidation can

occur by way of a Langmuir–Hinshelwood type process (a surface reaction

between two adsorbed species), we are almost in a position to propose a

detailed mechanism. First, however, we must consider the possibility of an

alternative Eley–Rideal type mechanism, in which the rate-limiting step

involves reaction between an adsorbed species and a molecule in the gas

phase. In this case, there are two such possibilities:

We can make a decision about reaction 9 on the basis of the

information provided in Figure 10. A Pd(111) surface presaturated with a

quarter of a monolayer of O atoms was exposed to a beam of gaseous CO,

and the surface coverages and the oxidation rate were monitored with time.

Figure 10 shows that the rate became significant only after a population of

CO had built up on the surface, and it reached a maximum when the

coverages of O and CO were approximately equal. This is clear evidence for

80
a Langmuir–Hinshelwood process. If reaction 9 had been operative, the rate

would have been high initially, and would have fallen continuously as the

oxygen layer was consumed by the reaction.

Figure 10 Changes in the rate of CO2 formation from CO and in the surface

density of oxygen and CO on Pd(111). The surface was precovered with a

quarter of a monolayer of oxygen atoms at time zero, and then exposed to a

constant stream of CO at a pressure of 7.9×10−11 atm.

Given the research effort that was involved, the mechanism finally

proposed for CO oxidation on Pd(111) is deceptively simple:

81
 Although the exact nature of the surface intermediates is still not

known, the depth of understanding of the catalytic mechanism is quite an

accomplishment. But just how relevant are these surface studies to the

practical catalysis taking place in the converter?

Indeed, Figure 12 shows that in the case of rhodium there is excellent

agreement between the rates of CO oxidation over a Rh(111) single crystal

surface and over a Rh/Al2O3 catalyst.

82
Figure 12 Comparison of the rates for CO oxidation measured over Rh(111)

(black) and over 0.01 mass % Rh/Al2O3 (green) at p(CO)=p(O2)=0.01 atm,

as a function of temperature.

Although the sequence of elementary steps is quite simple, the overall

kinetics of the CO oxidation reaction is not. The non-uniformity of the

surface, and the segregation of the reactants in surface domains, complicates

83
the detailed modelling of the kinetics. The exception is the special case of

low surface coverages of CO and O atoms, when they are found to be

randomly distributed over the surface and so satisfy one of the criteria for

applicability of the Langmuir isotherm. Under these circumstances,

Langmuir–Hinshelwood kinetics can be applied.

Figure 13 shows the comparative performance of single-metal

catalysts for the oxidation of CO at a fixed temperature. Evidently, all three

of the platinum groups metals present in automotive catalysts are active for

CO oxidation. In addition, results have shown that Rh may improve low-

temperature activity. In the current (1996) three-way catalyst used in the UK,

in which Pt constitutes 80–90% of the noble metal composition and Rh the

remainder, it is the Pt that is mainly responsible for CO oxidation. Under

stoichiometric or slightly fuel-rich (reducing) conditions, where there is

insufficient oxygen present to oxidise all of the CO, conversion can also

occur by one of the following routes:

84
Figure 13 Comparison of catalytic activity for CO oxidation at 400 °C for Pt,

Pd and Rh at different A/F ratios

 Via the CO + NO redox reaction (reaction 6). This will be

discussed in detail in section 4.4,

 via the water-gas shift reaction (equation 2), because H2O

is present in the exhaust gases as a product of

combustion:

The water-gas shift reaction is catalyzed by Pt and/or Rh, with ceria

acting as an excellent promoter. Pt/CeO2–Al2O3 and Pt-Rh/CeO2–Al2O3 are

particularly active combinations for the removal of CO under slightly fuel-

85
rich conditions. The hydrogen produced in this reaction will react, in

preference to CO, with any oxygen present. Hence, although the water-gas

shift reaction removes CO, it also inhibits CO oxidation by producing

hydrogen, which will remove any O2 present:

Removal of hydrocarbons

Figure 14 shows a comparative study for hydrocarbon oxidation over

single-metal catalysts: it can be seen that Rh, Pd and Pt all give high

conversions for A/F ratios at and above stoichiometric. Again (as in the case

of CO), in the current (1996) UK three-way catalytic converter, Pt is the

main component responsible for oxidation of the hydrocarbons. On noble

metal surfaces, alkane adsorption is dissociative, whereas unsaturated and

aromatic hydrocarbons adsorb either dissociatively or associatively as -

complexes. The subsequent oxidation process is thought to be considerably

more complicated than the oxidation of CO, and we shall not consider it in

any detail.

86
 When the engine exhaust gas composition is reducing (fuel-rich),

hydrocarbons compete effectively with CO for oxygen, and they can also

react with water vapour to produce CO and H 2 – a reaction known as steam

reforming:

Figure 14 Comparison of catalytic activity for HC oxidation at 400 °C for Pt,

Pd and Rh at different A/F ratios

This is catalyzed by Rh and/or Pt with ceria and, as in the case of the

water-gas shift reaction; the combination Pt–Rh/CeO 2–Al2O3 is particularly

87
active. As we noted earlier, the H 2 produced may react preferentially with

any O2 present, thus reducing the amount of oxygen available to react with

hydrocarbons and CO. In addition, the CO produced adds to the burden of

carbon monoxide to be removed.

Removal of NO

Laboratory experiments have shown that, under the conditions in the

catalytic converter, the decomposition of NO to O2 and N2 over noble metal

catalysts is too slow to be significant. When the A/F ratio is stoichiometric

(or below stoichiometric), NO can be removed by reduction with CO and/or

hydrocarbons. For simplicity we shall consider only reduction with CO, as

with the oxidation reaction, the situation with hydrocarbons is considerably

more complicated.

In principle, a variety of products can be formed, specifically:

In addition, H2 produced from the water-gas shift or steam reforming

reactions can reduce NO to N2, N2O or NH3:

88
 The NOx activities of Rh, Pt and Pd are shown in Figure 15. It is

evident that Rh has the highest activity, particularly under net reducing

conditions (low A/F). So why is Rh superior? To answer this question, we

need to consider the mechanism of the reaction.

Figure 15 Comparison of catalytic activity for NOx reduction at 400 °C over

Rh, Pt and Pd at different A/F ratios.

89
 The catalytic reduction of NO by CO and/or H 2 over a variety of

surfaces has been the subject of a great deal of research. Application of

various surface-science techniques has provided some understanding of the

elementary steps involved, but the exact mechanism is still controversial.

One view is that the first step is the dissociative chemisorption of NO. (You

should note that although we describe this as dissociative chemisorption

strictly it does not meet the definition, as NO is in fact first adsorbed

associatively and then dissociates on the surface.) The O atoms produced are

then removed by the reducing agents CO or H2. The N atoms can combine to

give N2, react with chemisorbed NO to give N2O (particularly important at

low temperatures), or react with chemisorbed H atoms to form NH 3. These

and other processes that may be involved are listed below.

Adsorption

Dissociation

NO (ad) N(ad) + O(ad)

90
 In the following steps we have assumed, for simplicity, that all

products are desorbed as quickly as they are produced. You should

recognize, however, that adsorbed species, no matter how transient, will be

formed initially.

Surface reactions and desorption

Reactions with hydrogen

Figure 16 compares the rate of the NO–CO reaction over an Rh (111) single

crystal with that over a Rh/Al2O3-supported catalyst.

91
 Figure 16 Comparison of the rates for the NO–CO reaction measured over

Rh(111) (black) and over 0.01 mass % Rh/Al2O3 (green) at

p(CO)=p(NO)=0.01 atm, as a function of temperature

This seems to be the case, particularly at higher temperatures. At

lower temperatures, the concentration of NO (ad) increases and reactions 22

and 23 would then be expected to contribute to N atom removal.

92
 The elementary steps 21–23 all require surface mobility of N atoms

(to encounter either NO (ad) or other adsorbed N atoms). Although this

process may occur on surfaces that are extensive on the atomic scale, such as

those of single crystals or large supported crystallites, it has been argued that

such mobility will be insignificant on or between the small highly dispersed

particles of Rh in the automotive catalyst. Therefore, we might expect the

rate-limiting steps and the observed kinetics in the cases of Rh(111) and

supported Rh to be different. The Arrhenius-type plots in Figure 16 confirm

that this is so: over Rh/Al2O3, the reaction has higher activation energy (the

plot in Figure 16 has a larger gradient) and a lower rate (at a given

temperature) than over Rh (111).

What then is the rate-limiting step with the supported catalyst? One

suggestion is NO dissociation (reaction 19) but there is a more radical

alternative, involving a different overall mechanism. Infrared spectra for NO

adsorbed on Rh/Al2O3 (Figure 17) show bands at 1 743 cm−1 and 1 825 cm−1,

which have been taken as evidence of a dinitrosyl species, O=N–N=O,

formed by reaction 26:

93
 This step provides a means, other than diffusion of N (ad), of

accomplishing the most important task in the reduction of NO, namely the

pairing of two nitrogen atoms on the surface. Once formed, the dinitrosyl

species is thought to lose its two oxygen atoms by way of an N 2O

intermediate; for example:

Figure 17 Infrared spectra, recorded at 300 K, for NO adsorbed on Rh/Al2O3

as a function of NO coverage, increasing from spectrum A to spectrum D.

94
The bands at 1 743 cm−1 and 1 825 cm−1 have been assigned to the dinitrosyl

species O=N–N=O.

To summaries Whichever mechanism is correct – NO pairing to form

a dinitrosyl species, or NO dissociation followed by N-atom combination

and N2 desorption – both require catalytic sites that can not only bind NO

but also donate charge to the adsorbate. In the first case, this charge would

be used to coordinate the two NO molecules. In the second case, it would be

transferred into the partially vacant 2 * antibonding orbital of NO (Figure

18), weakening the N–O bond and hence facilitating dissociation.

On examining the electronic structures of the noble metals, that of

rhodium is found to be particularly suitable for facilitating charge transfer to

adsorbed NO, with the uppermost occupied electron levels of the metal at

higher energy than the partially vacant 2 * antibonding orbital of NO

(Figure 18). For Pt (and also Pd), however, the situation is reversed. Vacant

metal levels lie at energies below that of NO 2 *, so charge will drain from

this orbital to the surface, strengthening the N–O bond.

95
 This picture provides an appealingly simple explanation for the

observation that rhodium is the most active of the noble metals for NO x

removal, particularly under-net reducing conditions (Figure 15). In fact, not

only do Pt and Pd show lower activities, they are also less selective, with Pt,

for example, promoting ammonia formation (reaction 17). Rhodium is

therefore the essential ingredient in the automotive catalyst for NO x control.

Because it is so active, the amount required is small – about 0.1 mass % of

the catalyst, or 0.1–0.2 g, highly dispersed over the surface – but even so,

catalytic converters account for around 90% of world rhodium demand (see

Box 1).

Figure 18 (a) The partial orbital energy-level diagram of molecular NO. (b)

Schematic energy-level diagram showing the highest occupied level of Rh

and the lowest vacant level of Pt, in relation to the 2π* molecular orbital of

NO.

96
Postscript

It is important to remember that the reactions discussed in sections

4.2–4.4, and often studied separately, occur simultaneously in the presence

of all the other exhaust constituents. This may have an effect on the

efficiency of the individual reactions. For example, kinetic experiments have

demonstrated that NO has a strong inhibiting effect on the rate of the

reaction of CO with O2: Figure 19 illustrates the point for a Rh/Al2O3

catalyst.

Figure 19 The temperature dependence of CO conversion rates over 0.01

mass % Rh/Al2O3 in CO–O2, CO–NO–O2 and CO–NO mixtures The

concentration of each of the reactants was 0.5 vol % in all cases.

97
The role of CeO2

Figure 20 shows the effect on performance of adding CeO 2 to a Pt catalyst

for three-way catalytic conversion.

Figure 20 The effects of adding CeO2 to a Pt catalyst in terms of the

simultaneous conversion of CO, HC and NOx. The green lines show the

conversions for the Pt catalyst with CeO2 and the black lines those without.

Thus, ceria, which is added with the alumina in the washcoat, is an

essential ingredient of the three-way catalyst. It plays a number of roles:

98
1: Ceria is a structural promoter, stabilising the precious metals and alumina

against sintering and particle growth. Figure 21 emphasises this point.

Figure 21 The variation of dispersion stability as a function of ageing

temperature, with (green) and without (black) the addition of CeO2 to 0.9

mass % Pt/Al2O3

Ceria also stabilises the γ-Al2O3 used in the support, inhibiting a phase

change to -Al2O3, which has a lower surface area. (Lanthanum oxide and/or

barium oxide are also often added as stabilizers to help maintain the surface

area of γ-Al2O3.)

2: Ceria is known to be able to pick up and store oxygen from the gas phase

under fuel-lean operating conditions (excess oxygen) – thus promoting the

99
reduction of NO to N2 – and to release it under fuel-rich conditions (excess

fuel), for reaction with CO, H2 or hydrocarbons. Thus, it effectively dampens

the variations in the A/F ratio as the exhaust gas mixture cycles about

stoichiometry, thereby helping to keep operation within the desired window

for optimum conversion over the catalyst.

3: As we have seen in section 4.2, the ceria also enhances the water-gas shift

activity of Pt–Rh three-way catalysts, and hence promotes CO removal via

the following reaction under fuel-rich conditions:

The point is illustrated by the results shown in Table 1 for CO conversion

under fuel-rich conditions. Increasing the ceria content of the catalyst in the

absence of water has no effect, but when water is present the water-gas shift

reaction becomes increasingly important. (Addition of ceria also leads to an

improvement in activity for steam reforming.)

100
 Table 1 CO conversion for a 1.08 mass % Pt-Rha catalyst on γ-Al2O3

with 1.5, 4.0 and 8.0 mass % Ce levels, under fuel-rich conditions,

with and without water present. (aPt 0.9 mass % and Rh 0.18

mass %.)

CO conversion/%
With H2O Without H2O
1.5 mass % Ce 54 49
4.0 mass % Ce 64 49
8.0 mass % Ce 70 49

4: Enhanced conversions of CO, C3H6 and NO at low temperatures have also

been observed for Pt/CeO2 catalysts that have undergone a reducing

pretreatment. This is believed to be due to an interaction between Pt and

CeO2 induced by the reduction, causing an increase in the number and

activity of the active sites.

Chemical reactions: summary

1. Surface studies of the adsorption of CO and O2 on single

crystals and model catalysts have led to the development

of a possible mechanism for the oxidation of CO.

Dissociatively adsorbed O atoms undergo a surface

reaction with adsorbed CO, to form CO2.

101
2. Under slightly fuel-rich conditions, where there is

insufficient oxygen present for complete oxidation, CO

can be removed by the water-gas shift reaction, using

water produced in the combustion process in the engine.

This is promoted by ceria.

3. Hydrocarbons can be removed by oxidation or by

reaction with water (a process known as steam

reforming).

4. Both CO and hydrocarbons can be removed by reaction

with NO under stoichiometric or fuel-rich conditions.

The NO-CO redox reaction is believed to proceed either

by dissociation of NO(ad) followed by N atom

combination, or by pairing of NO(ad) to give a dinitrosyl

species, followed by dissociation. Whatever the detailed

mechanism, Rh is particularly active for this reaction, and

as such is currently an essential ingredient of the three-

way catalyst.

5. Ceria plays a number of important roles in the three-way

catalyst: it is a structural promoter, stabilising both the

noble metals and the support against particle growth and

102
 sintering; it is an oxygen-storage component, storing

oxygen under fuel-lean conditions, and releasing it under

fuel-rich conditions; it is a promoter for the water-gas

shift and steam reforming reactions and it can enhance

the low-temperature activity of the catalyst after certain

types of pretreatment

What are the major roles proposed for the different components of the

Pt-Rh/CeO2–Al2O3 three-way catalyst?

The major roles proposed for the different components of the Pt-Rh/CeO2–

Al2O3 three-way catalyst can be summarised as follows:

Platinum

 CO oxidation

 HC oxidation

 steam reforming and water-gas shift reactions (with

CeO2)

Rhodium

103
  CO–NO redox reaction

 steam reforming and water-gas shift reactions (with

CeO2)

Ceria

 oxygen storage

 structural promoter maintaining both metal and

support surface areas

 chemical promoter for the water-gas shift and steam

reforming reactions

 enhancement in low-temperature activity of Pt after

reducing pretreatment

In Figures 13, 14 and 15, Pd in its fresh state is seen to be superior to

Pt for the conversion of all three pollutants. Considering the properties we

require of a catalyst, what possible reason can you suggest for the current

widespread use of Pt in three-way catalysts, rather than Pd?

Pd is in fact cheaper than Pt (Box 1), so the reason for using Pt is not an

economic one. The principal properties we require of a catalyst are activity,

selectivity and stability. Because we have seen that the first two of these are

104
at least as good for Pd as for Pt, this should lead us to consider the third,

stability. In fact, as we shall discover in section 5.3, Pd has a high

susceptibility to poisons, especially lead and sulfur. In addition, it sinters in

reducing atmospheres, and can also form an alloy with Rh, reducing the

activity of the latter.

5.4.2.5 Catalyst Deterioration

Introduction

In the UK, three-way catalysts must currently (1996) meet emission

standards for a life of 50,000 miles; however, research efforts and legislation

are set to double this requirement in the very near future to the current US

standard of 100,000 miles. The catalysts do deactivate with use. Indeed the

ability to withstand mild deactivation is built into the design of the catalyst,

and into the entire emission control system in the vehicle. This is done by

setting up vehicles at efficiencies well above the legal requirements at low

mileage, so that as the catalyst slowly deactivates, it will still meet the

emission standards.

However, the catalyst may be exposed to conditions that result in

more severe deactivation above and beyond that which is ‘allowed for’ in its

lifetime. The major causes of deterioration are thermal damage (due to

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exposure of the catalyst to high temperatures), and poisoning by

contaminants in the exhaust (notably phosphorus, lead and sulfur). Research

aimed at detecting deterioration and trying to understand its nature, has

included post-mortem examinations of used catalysts, and simulated ageing

studies, in which the catalyst is exposed to high temperatures or catalyst

poisons.

Thermal effects

Exhaust catalysts usually operate in the temperature range 150–600

°C, but they can experience temperatures of up to 1000 °C. The conditions

that can produce such high temperatures include repeated misfire (resulting

in the oxidation of large amounts of unburned fuel over the catalyst) and

high driving speeds. In addition, very high temperatures may be experienced

if the catalyst is ‘close coupled’ to the engine, which is one of the possible

solutions to the cold-start problem. Although commercial catalysts are

designed to withstand occasional high-temperature operation prolonged and

repeated exposure to temperatures in excess of 800 °C, especially under

oxidizing conditions, have a number of serious effects.

High temperatures may affect all the components of the catalyst. The

noble metal particles may sinter (recall Figure 21 in section 4.6), resulting in

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a decrease in the fraction of the metal available for catalytic reactions. Such

sintering particularly affects the low-temperature activity of the catalyst. It

can be countered to some extent by the addition of ceria as a structural

promoter, which also stabilises the alumina support against sintering.

However, the ceria may itself undergo crystallite growth at elevated

temperatures. This can be inhibited by the addition of barium and zirconium,

as shown by the comparison in Figure 22: it is apparent that barium and

zirconium help to stabilize the catalytic activity.

Figure 22 Comparison of catalytic activity for a Pt–Rh/CeO2 catalyst with

(green) and without (black) the addition of Ba and Zr, after ageing at

A/F=16.5 at 950 °C for 40 hours.

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 At very high temperatures the support may itself sinter or even

undergo a phase change, affecting the total surface area. Mechanical loss of

catalyst support material may also occur in cases where the washcoat shrinks

and cracks, causing it to separate from the monolith (Figure 23a). Again, the

problem can be overcome by incorporating so called ‘phase stabilizers’ –

examples include barium and lanthanum – into the washcoat (Figure 23b).

At excessively high temperatures the ceramic monolith may even melt,

forming additional channels that may allow the exhaust gases to pass

through the converter without contacting the catalyst.

Figure 23 Optical micrographs of a washcoat after exposure to high

temperatures. In (a) sintering has caused severe shrinkage, whereas in (b) the

addition of ‘phase stabilisers’ has prevented shrinkage cracking.

High temperatures can also promote damaging interactions between

the noble metals, resulting in the formation of a less active alloy, or between

a noble metal and base metals in the washcoat support. In particular, it has

been established that Rh begins to penetrate the surface of γ-Al 2O3 at

108
temperatures greater than 600° C by a solid state reaction between Rh 2O3

and γ-Al2O3. This subsurface penetration and loss of active Rh can be slowed

down if the reactivity of the support is minimized by first supporting the Rh

on zirconium, ZrO2, and then incorporating the resulting powder into the γ-

Al2O3 washcoat. Figure 24 shows the dramatic effect this can have on the

catalytic activity of a Rh/γ-Al 2O3 catalyst. Unfortunately, the incorporation

of Rh/ZrO2 into three-way catalysts requires complex manufacturing

methods, which are not yet suitable for high-speed production. An

alternative approach has been suggested by work that indicates that the

Rh/Al2O3 interaction may occur preferentially at the grain boundaries of the

support. Ceria can be incorporated as a stabilizer into the alumina in an

attempt to preferentially block this interaction.

Figure 24 Schematic comparison of the catalytic activity of (a) Rh/γ-Al2O3

and (b) [Rh/ZrO2]/γ-Al2O3 after thermal treatment at 1 100 °C in air for 1 h.

The activity of the ZrO2-supported catalyst (b) remains virtually intact after

109
 the calcinations, whereas that of the standard Rh/γ-Al2O3 catalyst (a) is

seriously diminished.

The Effect of Poisons

Lead

The use of catalytic converters was one of the major contributors to

the phasing-in of unleaded petrol. Lead in petrol is a severe poison for the

catalyst, and there have been many stories, particularly in the early days of

the converter, of people disabling the catalyst by misfiling. Figure 25 shows

how the activity of a typical three-way catalyst is impaired during, and

following, intermittent operation with leaded fuel (0.26 g l−1) during 15,000

miles of vehicle operation. The efficiency of a control vehicle (unleaded

petrol only) was virtually unchanged at 94% for hydrocarbons, 95% for CO

and 66% for NOx. Following the misfiling, the CO-conversion efficiency

(Figure 25a) decreased, but subsequently recovered to an acceptable level.

By contrast, the conversion efficiencies for the hydrocarbons (Figure 25b),

and especially NOx (Figure 25c), did not recover to passable values, and

hence did not meet the emission regulations current at the time (1986).

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 Figure 25 Effect of intermittent use of leaded petrol (black points) on

catalyst efficiency (for a typical three-way catalyst) for the conversion of (a)

CO (b) HC and (c) NOx.

Of the various noble metal components, Pd is the most sensitive to lead

poisoning. Its activity decreases when there are just trace amounts in the

fuel. Rh is slightly less susceptible, and Pt is by far the most resistant. Clues

to the mechanism of lead poisoning have come from model systems, which

are amenable to detailed surface analysis

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Figure 26 Electron probe elemental maps of Pt/γ-Al2O3 after exposure to Pb

for 24 hours at 700 °C. Electron probe microanalysis (EPMA) is based on

the emission of ‘characteristic’ X-ray photons following the ionization of

atoms by high-energy electrons. EPMA allows quantitative determination of

the composition of solids with a resolution of the order of 1 μm. The whiter

the area on the map, the higher the concentration of the element under study.

The X-ray spectrophotometer is a common attachment on scanning and

transmission electron microscopes.

This deposition of lead specifically onto the noble metal is believed to

occur because the molecules that ‘carry’ the lead out of the engine, probably

halides or oxyhalides, decompose on the noble metal, leaving the lead on the

surface.

The fact that Pt is more resistant to lead poisoning than Rh or Pd is

largely due to an indirect effect. The small amount of sulfur also present in

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fuel can act as a scavenger for lead. Provided that the sulfur is in its

hexavalent oxidation state (SVI), in the form of SO3, it can combine with lead

oxide to form a stable lead sulfate, which, although a poison itself, is not

site-specific. Only Pt, however, is a good catalyst for the oxidation of SO 2

(produced from sulfur in the combustion reaction, and present in the exhaust

mixture) to SO3: indeed, it is used for this purpose in the industrial

production of sulfuric acid.

Phosphorus

Phosphorus is recognized as a potential poison for automotive

catalysts. The phosphorus level in fuel is generally very low (2×10 −5 g l−1),

but it is present in higher concentrations in engine oils (1.2 g l−1).

Phosphorus derived from the engine oil is believed to react with the alumina

support, and also to reduce the activity of the noble metal component. This

deactivation is particularly important for Pd, with which phosphorus may

form an alloy. At the time of writing, phosphorus levels in engine oil are

becoming an issue, and oils with reduced levels are appearing on the market.

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Sulfur

Deactivation

The presence of sulfur in the exhaust gas mixture causes a reduction

in the activity of the three-way catalyst, particularly for the water-gas shift

and steam reforming reactions – processes that are important mechanisms

for the removal of CO and hydrocarbons under fuel-rich conditions. Sulfur

also decreases the efficiency of NOx removal. The deleterious effect of

exposure to SO2 on the catalytic activity of a commercial monolithic catalyst

(Pt–Rh/CeO2–Al2O3) is evident in Figure 27. Notice, however, that the

conversion efficiency recovers quite rapidly once the sulfur has been

removed from the gas stream. This is significant because it suggests that a

change in the sulfur content of fuel (average 208 mg l−1 in the UK), could

achieve a reduction in emissions from vehicles currently in use.

The general resistance of Pt and Rh to sulfur poisoning, and their

ability to recover from it, were two of the factors in the original decision in

the 1970s to use noble metals rather than the less active, but cheaper, base-

metal oxidation catalysts. (In terms of the more stringent legislation now in

114
force, let alone that which will apply in the future, it is unlikely that base-

metal activity (or durability) would be sufficient to meet emission control

requirements, even if all the sulfur in fuel were to be removed.) Pd is more

susceptible to long-term damage, and it is this susceptibility to poisoning

that limits its use in the UK at the moment. Pd-only catalysts are, however,

under development for the US market – where there are stricter controls over

the contaminant levels in fuel.

Some understanding of the mechanism of catalyst deactivation by

sulfur has been obtained by examining the effects of SO 2 on the surface area

of metals The physical adsorption of N2 can be used to determine the ‘total’

surface area of a catalyst. The capacity of a supported metal catalyst to

chemisorb CO can be used as a measure of the free metal surface area. It is

typically expressed as the ratio CO/M, where CO is the amount of CO

chemisorbed by a fixed mass of catalyst (proportional to the number of

surface metal atoms), and M is the metal content of the catalyst (proportional

to the total number of metal atoms). The higher the value of CO/M, the

higher the surface area of the metal. Table 2 gives values of the CO

chemisorption capacity of a Pt–Rh/CeO2–Al2O3 model catalyst after ageing

in a fuel-rich mixture, in the presence and absence of SO2.

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 Table 2 Effect of fuel-rich ageing on the metal-surface area (expressed

as CO/M) for a Pt–Rh/CeO2–Al2O3 catalyst, in the presence and

absence of SO2. The value of CO/M for a fresh sample is 0.79.

Ageing
CO/M after ageing
temperature/°C
In the presence of In the absence of

SO2 SO2
400 0.20 0.78
550 0.12 0.69
700 0.10 0.39

Because the effects are not permanent, this sulfur species is

presumably relatively weakly adsorbed. As a result it is desorbed, and the

activity of the catalyst is regenerated, when the gas-surface equilibrium is

shifted in favour of the gas-phase by removal of SO2 from the gaseous

mixture (Figure 27).

The production of hydrogen sulfide

Recently, there has been a great deal of interest in the interactions of

sulfur with the three-way catalyst, not so much because of its impact on

activity, but rather because of a smelly side-effect. Ever since catalytic

116
converters were introduced, the odour of hydrogen sulfide (H2S), described

as ‘smelling like rotten eggs’, has been an issue. This is particularly

noticeable when a car in front accelerates after idling (at traffic lights or a

roundabout, say) or decelerates sharply after cruising. After combustion in

the engine, sulfur in the fuel is released to the exhaust gases as SO2. Under

fuel-rich (reducing) conditions, this is converted into H2S over Pt, the

suggested mechanism involving the formation of the metal sulfide as a

reaction intermediate. It has been found, however, that the amounts of H2S

generated when engine conditions become fuel-rich, following prolonged

running under fuel-lean (or oxidising) conditions, are larger than expected.

The catalyst can apparently ‘store’ sulfur under lean conditions and release it

under rich conditions.

The noble metals do not retain any sulfur under these conditions.

However, adsorption studies with both model catalysts and the commercial

(fully formulated) catalyst have shown that sulfur storage under lean

conditions can occur by interaction of SO2 with both CeO2 and Al2O3 in the

support. Under typical conditions, CeO2 provides the preferred adsorption

sites, and the sulfur storage by the catalyst has been found to increase with

increasing Ce content. XPS studies (some results of which are collected in

Table 3) have been used to study the nature of the species involved.

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Table 3 XPS data recorded for various cerium and sulfur compounds.

Sample History Binding energy/eV

Ce 3d S 2p
CeO2 550 °C, air 881.7 –
CeO2 20 °C, SO2 881.6 168.0
CeO2 550 °C, SO2 882.8 168.8
Ce(NO3)3.6H2O 883.3 –
SVI compounds – 168.5–168.9
SIV compounds – 166.3–167.9

Hence, interpretation of the XPS data suggests that, at room

temperature, SO2 is adsorbed on CeO2, possibly to form a sulfite species

(that is, a species containing SIV). At 550 °C the CeIV oxide, CeO2, appears to

participate in a redox reaction with SO2; the sulfur is oxidised to SVI and the

cerium is reduced to CeIII, possibly resulting in the formation of cerium(III)

sulfate, Ce2(SO4)3.

The sulfate/sulfite species formed under fuel-lean conditions with the

cerium and aluminium in the support decompose in fuel-rich conditions to

release the SO2/SO3 species, which are then converted into H2S over the

118
noble metal component of the catalyst. Catalysts that do not contain noble

metals do not produce H2S.

Although it has been known for some time that automobile exhaust

catalysts can produce H2S in fuel-rich exhaust streams, there has been an

increase in the levels emitted in recent years. This is believed to be a

consequence of the considerable improvements made in catalyst activity

over the years. However, during one study into this effect, it was noted that

H2S emissions from ‘engine-aged’ catalysts, that is, those that had been ‘on

the road’ for 50,000 miles, were much lower than those from the fresh

catalyst. In addition, the H2S ‘spikes’ when going from lean to rich

conditions were found to be much smaller on the engine-aged catalyst.

Examination of an aged catalyst revealed traces of the usual poisons,

including S and Pb from the fuel, and phosphorus (and zinc) from the engine

oil. This suggested that at least one of these components can reduce the

storage of sulfur by the Pt–Rh/CeO2–Al2O3 system. Phosphorus appears to

be a likely candidate, because it has been found that phosphorus-doped Pt–

Rh/CeO2–Al2O3 catalysts exhibit a lower capacity for adsorption of SO2 than

an undoped reference catalyst. This suggests that the phosphorus is

somehow ‘interfering’ with the component of the catalyst that adsorbs the

119
SO2 – the ceria. Indeed, it has been proposed that a Ce–P–O species

(possibly CePO4) is formed, which is more stable than, and hence inhibits

the formation of, a Ce–S–O species (for example, Ce2(SO4)3). This would

have the effect of reducing the storage capabilities of the ceria, and hence of

reducing the size of the H2S spike on going from lean to rich conditions.

To summaries In view of the discussion above, it would seem that

several different strategies could be used to reduce H2S emissions: (i)

decreasing the Ce surface area (however, this will have detrimental effects

on the catalyst activity); (ii) improving the A/F control; (iii) reducing the

sulfur content of the fuel; (iv) including an H2S scavenger in the catalyst (in

the USA nickel is used, but in Europe this is prohibited because of concern

that it could lead to the formation and release of carcinogenic nickel

carbonyl).

Catalyst deterioration: summary

1. An ability to withstand mild deactivation is built into the

design of the catalytic converter. However, severe

deactivation could prevent the system from meeting

emissions legislation.

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2. The major causes of deactivation are thermal damage and

poisoning.

3. High temperatures may cause sintering of the metals

and/or the support; this can be prevented to some extent

by the addition of ceria as a structural promoter.

Damaging interactions between the noble metals, or with

the support, can also occur at high temperatures. The

interaction between Rh2O3 and γ-Al2O3 can be slowed

down by first supporting the Rh2O3 on ZrO2.

4. Lead is a severe poison, particularly for Pd, and is

believed to associate with the noble metal.

5. Phosphorus from engine oil can contaminate the catalyst

and cause deactivation.

6. Sulfur present in fuel has two major undesirable effects.

It can cause deactivation of the catalyst, and it also leads

to generation of H2S.

7. Sulfur is oxidised to SO2, which is believed to block sites

on the metal surface, forming a weakly adsorbed species

that is desorbed when the sulfur is removed from the gas

stream.

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 8. Sulfur can also be stored under fuel-lean conditions by

Al2O3, and especially CeO2, in the support, and released

as H2S under fuel-rich conditions. The sulfur is believed

to be stored as Ce2 (SO4)3. On going to fuel-rich

conditions, this species decomposes, releasing SO2,

which is converted into H2S over the noble metal. It has

been found that adsorption of SO2, and hence the storage

capabilities of a Pt–Rh/CeO2–Al2O3 catalyst, are reduced

in the presence of phosphorus. The preferential formation

of a Ce–P–O species (possibly CePO4) inhibiting

formation of the Ce–S–O species (Ce2 (SO4)3) has been

proposed.

Refer back to the CO/M values listed in the final column of Table 2.

How would you explain the variation in these CO/M values with increasing

ageing temperature?

The decrease in the value of CO/M observed as the ageing

temperature increases indicates that the free metal surface area of the

catalyst is decreasing with increasing temperature. This is likely to be due to

sintering of the noble-metal particles, and/or the support.

122
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123
1. Hodges, Laurent, Environmental Pollution, Second Edition, Holt,

Rinehart and Winston, New York, 1977.

2. Myers, P.S., ’Automobile Emissions. A study in environmental

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124
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125
14. Gandhi, H.S., Piken, A.G., Shelat, M, and Delosh, R.G., ‘Evaluation

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126