Air Pollution Control Technologies Compendium

Aiir Pollution
Co
ontrol Te
echnologies
Co
ompendium
Prepared by
Y.M. Fahmy, P. Fornasiero, S. Zinoviev and S. Miertus
INTERNATIONAL CENTRE FOR SCIENCE AND HIGH TECHNOLOGY

Trieste, 2007
UNITED NATIONS INDUSTRIAL DEVELOPMENT ORGANIZATION

Pre
e fa c e
This present Compendium has been developed as part of the programme of the
International Centre for Science and High Technologies of the United Nations Industrial
Development Organization (ICS-UNDIO). UNIDO is a specialized agency of the United Nations
dedicated to promoting sustainable industrial development in developing and transition-
economy countries. It harnesses theforces of government and the private sector to foster
competitive industrial production and international industrial partnership and promote
socially equitable and environmentally friendly industrial development. The International
Centre for Science and High Technology is an institute within the framework of UNIDO,
with headquarters in Trieste, Italy at the AREA Science Park. The Centre’s mandate is the
transfer of know-how and technology in favour of developing countries and is based on
the premise that competitive industrial technological capability cannot be built-up without
adequate scientific knowledge and commitment to a sustainable development approach
based on new and environmentally friendly technologies.
In the programme of the Area of Pure and Applied Chemistry one of the
subprogrammes is dedicated to Catalysis and sustainable Chemistry. The activities with this
subprogramme are focused on specific topics such as catalysis for exploitation renewable
resources, catalysis for environmentally friendly processes and catalytic technologies for
cleaner production.
The rapid implementation of various technologies focused primarily on increasing
the economic efficiency of industry has had an important environmental impact.
Industry, besides of transport - is the largest consumer of natural resources and
one of the main contributors to overall pollution. The industrial sector generates pollutants
such as organic substances, CO2, SOx and NOx emissions, hydrocarbons, volatile organic
compounds (VOC) and persistent organic pollutants (POPs). Is compendium focuses on air
pollution control technologies including catalysis for pollution reduction and prevention both
for stationary and mobile applications.
Stanislav Miertus
Chief of Area
Pure and Applied Chemistry
3
Contents
1 Pollutants and Pollution Sources 9

1.1 Main Sources of Air Pollution 9
1.2 Air Pollution Effects on Human Health 10
1.3 Criteria for Air Pollution Control Technologies Selection 11
1.4 References 12
2 Techniques for Air Pollution Measurements 13

2.1 Sulfur Dioxide 13
2.2 Carbon Monoxide 14
2.3 Nitrogen Oxides 14
2.4 Photochemical Oxidant 14
2.5 Hydrocarbons 14
2.6 Particulate Matter 15
2.7 Environmental Quality Standards 15
2.7.1 National Ambient Air Quality Standards (NAAQS) 16
2.8 References 17
3 NOx Abatement Technologies 19

3.1 NOx Sources 19
3.2 NOx Abatement and Control Strategies 20
3.2.1 Selective Catalytic Reduction of NOx 22
3.2.2 NOx Abatement System in Gas Turbines 25
3.2.3 Internal Combustion Reciprocating Engines 25
3.2.4 Air-fuel Ratio and Ignition Type 26
3.2.5 Influence of Fuel Quality on the Combustion’s Emissions 26
3.2.6 Fluidized Bed Combustion 28
3.2.7 Combined Technology Approaches 28
3.3 Selected Available Technologies and Supplier References 29
3.4 Conclusions 44
3.5 References 45
4 SOx Abatement Technologies 47

4.1 Control of SOx and H2SO4 Emission 48
4.2 Absorption Techniques 49
4.3 Adsorption Technique 51
4.4 Alternative Fuels 52
4.5 Implemented or Commercial Technologies 52
4.6 References 60
5 Volatile Organic Compounds (VOCs) 61

5.1 Introduction 61
5.2 VOC Destruction Technology 61
5.2.1 Thermal Oxidation 61
5.2.2 Catalytic Oxidation 62
5.2.3 Adsorption 64
5.2.4 Condensation, Refrigeration and Cryogenics 66
5
5.2.5 Biological Oxidation 66
5.2.6 General Applicability of VOC Control Systems 67
5.3 Some Commercial Technologies 68
5.3.1 Oxidizer Types 68
5.3.2 Direct Fired Thermal Oxidizers (DFTOS) 69
5.3.3 Recuperative Oxidizers 69
5.3.4 Regenerative Thermal Oxidizers (RTOs) 70
5.4 Example of Commercial Technologies 71
5.5 Examples of Commercial Catalysts 73
5.5.1 Engelhard Catalysts 73
5.5.2 Photocatalytic Self-cleaning Ceramic 73
5.6 References 74
6 POPs and Chlorinated Organic Pollutants 75

6.1 Introduction 75
6.2 Unintentionally produced POPs and air pollution 76
6.3 Formation of dioxins 76
6.4 Chlorinated VOC and Other Halogenated Pollutants 78
6.5 Prevention of PCDD/F formation during incineration 79
6.6 End-of-pipe prevention and removal techniques 80
6.7 Chemical destruction of POPs and chlorinated pollutants in emissions 82
6.8 Treatment of macro streams of POPs and chlorinated pollutants 87
6.9 References 90
7 Technologies for Particulate Emission Control 91

7.1 Introduction 91
7.2 Particulate Formation 92
7.3 Particulate Emissions Control Systems 94
7.3.1 Gravity Settling Chambers 94
7.3.2 Centrifugal Separators 95
7.3.3 Particulate Wet Scrubbers 96
7.3.4 Electrostatic Precipitators 99
7.3.5 Filters 100
7.4 Commercially Available Technologies 101
7.5 References 102
8 Abatement of the Hydrocarbon and CO Emissions from Gas Turbine 103

8.1 Gas Turbines 103
8.2. Catalytic combustion 104
8.3 Catalytic control of Hydrocarbon Emissions from Gas Turbine 105
8.2 Catalytic control of CO Emissions from Gas Turbine 106
8.3 Gas Turbine Aftertreatment Catalyst Deactivation 107
8.4 References 107
9 Ozone Control Strategies 109

9.1 Strategies for Reducing Ground-level Ozone 110
9.2 Ozone Abatement in Jet Aircraft 110
9.3 References 110
10 Air Pollution from Mobile Sources 111

10.1 Automotive Emission Characteristics and Regulations 111
10.2 Catalytic Converter and Three-way Catalysts 113
6
10.2.1 Principle and Operation of TWCs 115
10.3 Next Generation Technology for Emissions Control 119
10.3.1 Hydrocarbon Adsorber Systems 119
10.3.2 Electrically/Chemically Heated Catalyst Systems 120
10.3.3 Close-coupled Catalyst (CCC) 120
10.3.4 New Catalysts 121
10.4 Diesel Engine Emissions 121
10.4.1 Emission Formation in Diesel Engines 122
10.4.2 Diesel Fuel 123
10.4.3 World Diesel Emission Standards 125
10.4.4 Diesel Emission Control Technologies 126
10.4.5 Advanced Diesel Engine Technologies 127
10.4.6 Diesel Oxidation Catalyst 128
10.4.7 Lean NOx Catalyst 128
10.4.8 Selective Catalytic Reduction 129
10.4.9 NOx Adsorbers 130
10.4.10 Diesel Particulate Filters 130
10.5 Diesel Filter Regeneration 131
10.6 Other Control Technologies 133
10.7 Future Trends 133
10.8 References 134
11 Appendices 137
11.1 Web Directory 137
11.2 Glossary 138
7
AIR POLLUTION CONTROL TECHNOLOGIES
1 Pollutants and Pollution Sources
Air pollution is a topic, which, among many others, has been at the forefront of
social concern for the past several years. Most of this concern has been directed toward
the health, distributional, regulatory and technological aspects of prevention or reduction of
pollutants emissions in the atmosphere.
As the population grows, industry expands to make more and increasingly diverse
products and the use of transport increases. Therefore the emissions of some pollutants
is inevitably increasing. High pollution emission have already, on several occasions and in
several places, led to ground level concentrations that were associated with dramatic rises
in mortality and morbidity.
The term air pollution is the presence in the atmosphere of solid particles, liquid
droplets or gaseous compounds, which are not normally, present or which are present in a
concentration substantially greater than normal and harmful to living organisms and to the
environment.
1..1 Main Sources of Air Pollution
Major sources of air pollution are:

 Combustion processes;
 Industry;
 Vehicles;
 Unsanitary disposal of household and municipal wastes;
 Indiscriminate use of insecticides and pesticides in the agriculture;
 Respiration of man and animals.
Common air pollutants and the relative main sources are presented in Table 1.1
Table 1.1: Common air pollutants and their sources

Pollutants Main Sources
Suspended particulate matter (SPM) Automobiles, power plants, boilers, industries requiring
crushing and grinding like cement factory.
Sulfur oxides (SO x) Power plants, boilers, sulfuric acid manufacture, petroleum
refining.
Lead Battery manufacturing, automobiles.
Nitrogen oxides (NO x) Automobiles, power plants, nitric acid manufacturing.
Carbon monoxide (CO) Automobiles.
Hydrogen sulfide (H 2S) Pulp and paper, petroleum refining.
Hydrocarbons (HC) Automobiles, petroleum refining.
Ammonia (NH3) Fertilizer plants.
9
POLLUTANTS AND POLLUTION SOURCES
An excellent summary (1) of the major atmosphere pollutants was published by

US Department of Energy.
NOx emission per year: > 30 mmt (millions of metric tons) globally, 21 mmt in the
USA, 95 % from vehicles and power sources.
Non-CH4 VOCs emission per year: 79 mmt in the USA, 87% from stationary and
mobile engines.
CO emission per year: > 107 mmt globally, 79 mmt in the USA, 80% from mobile
engines.
SO2 emissions per year: > 42 mmt globally, 22 mmt in the USA.
CH4 emissions per year: 160 mmt from natural sources (rice, animals); 370 mmt
from human derived sources (cars, refineries, coal mines, and fills); 27.2 mmt from US
human sources, but only 0.12 mmt of CH 4 from US industry; 500 adsorbed by the Earth.
N2O emissions per year: 11 mmt from natural sources; 3 mmt from human
sources (fertilizer, fuel oil, cars); 10 mmt adsorbed by the Earth.
CO2 emission per year: 160000 mmt generated naturally, worldwide; 8000 mmt
from human derived sources, global; 165000 mmt adsorbed by the Earth, the balance is a
global increase of 3000 mmt per year; 1375 mmt CO2 from energy production in the USA.
In the year 2005, the dramatic dimension of the problem has been confirmed by
the US Department of Energy (2). The evidences clearly indicate that CO 2, CO, VOCs, NOx,
and SO2 represent major air pollutants. Notably, although the amount of released N 2O is
relatively small, there is a growing attention to this pollutant due to its long lifetime in the
atmosphere (over 150 years) (3-6)
1..2 Air Pollution Ef fects on Human Health
Air pollutants can have the following effects on the human health:
 Immediate effects: sudden increase in air pollution has often been associated with
immediate increase in the mortality and morbidity especially due to respiratory
disease.
 Delayed effects: chronic bronchitis, lung cancer, dermatitis due to irritants and
carcinogens in smoke and other pollutants.
Carbon monoxide (CO) is one of the most toxic gases emitted by automobiles. It
interferes with absorption of oxygen by hemoglobin (red blood cells), impairs perception and
thinking, slows reflexes, cause drowsiness, brings or angina and can cause unconsciousness
and death; it affect growth in pregnant women and tissue development of young children.
Nitrogen oxides (NOx) can increase susceptibility to viral infections such as

influenza, bronchitis and pneumonia.
Lead affects circulatory, reproductive, nervous and kidney systems, suspected of

causing hyperactivity and lowered learning ability in children, hazardous even after exposure ends.
10
Sulfur dioxide (SO2), has irritating capacity and have development of bronchial
obstruction. It has also settled down that the lingering exposition increase the risk of
development of sharp and chronic conjunctivitis.
Particles irritates mucous membranes and may initiate a variety of respiratory

diseases, line particles may cause cancer. A strong correlation exists between suspended
particulates and infant mortality in urban areas.
Ozone (O3) Ozone can irritate lung airways and cause inflammation much like a
sunburn. Other symptoms include wheezing, coughing, pain when taking a deep breath, and
breathing difficulties during exercise or outdoor activities. People with respiratory problems
are most vulnerable, but even healthy people that are active outdoors can be affected when
ozone levels are high. Repeated exposure to ozone pollution for several months may cause
permanent lung damage. Anyone who spends time outdoors in the summer is at risk,
particularly children and other people who are active outdoors.
Even at very low levels, ground-level ozone triggers a variety of health problems
including aggravated asthma, reduced lung capacity, and increased susceptibility to
respiratory illnesses like pneumonia and bronchitis.
1..3 Criteria for Air Pollution Contro

ol Te
echnologies Selection
Beside the main human activities (big industrial plants) also the following small
and medium Enterprises contribute to air pollution and shuold be subjected to air pollution
control. (7-20):
1. Agricultural Chemical Applicators 14. Laboratories
2. Asphalt Applicators 15. Lawnmower Repair Shops
3. Asphalt Manufacturers 16. Lumber Mills
4. Auto Body Shops 17. Metal Finishers
5. Bakeries 18. Newspapers
6. Distilleries 19. Pest Control Operators
7. Dry Cleaners 20. Photo Finishing Laboratories
8. Foundries 21. Printing Shops
9. Furniture Manufacturers 22. Refrigerator/Air Conditioning Service
10. Furniture Repairs and Repair
11. Gasoline Service Stations 23. Tar Paving Applicators
12. General Contractors 24. Textile Mills
13. Hospitals 25. Wood Finishers
The number of technology options available for reducing environmental impact are
highest early on in the life cycle and then decrease drastically. In contrast, costs associated
with resolving an environmental problem typically increase exponentially as the process
matures and the scale of equipment gets larger. There are technologies to control generic
classes of air pollutant emissions such as CO, Volate Organic Compounds (VOCs), NO x
or SOx. The specific choice of control technology, in most cases, is driven by the need
to meet regulatory compliance at the lowest cost. The most cost-effective strategy for a
given application, depends on a number of factors, including the nature of the pollutant, its
concentration, the flow rate of the exhaust, and regulation. The decision is based on:
 Capability of treating a variety of wastes with varying constituents with minimal
pretreatment or characterization;
 Secondary waste stream volumes that are significantly smaller than the original
waste stream volumes and which contain no toxic reaction byproducts;
1
1
POLLUTANTS AND POLLUTION SOURCES
 Complete mineralization of organic contaminants;

 Offgas and secondary waste composition;
 Cost and Risk.
1..4 Refere
ences
1. Emissions of greenhouse gases in the United States: 1987-11992, DOE/EIA Report 0573, US Government
printing offices, Washington, DC, October, 1994.
2. http://www.eia.doe.gov/oiaf/1605/ggrpt/summary/index.html
3. Thiemens, M.H.&Trogler, W.C. Science, 1991, 251, 932.
4. Armor J.N., Catal. Today, 38 (1997) 163.
5. http//www.epa.gov
6. Air Pollution Control Engineering, de Nevers N., second Edition, 2000, Mc Graw Hill, New York.
7. Bell M.L., Davis D.L., Gouveia N., Borja-Aburto V.H., Cifuentes L.A., Environmental Research 100 (2006)
431.
8. Chow J.C., Watson J.G., Shah J.J., Kiang C.S., Loh C., Lev-On M., Lents J.M., Molina M.J., Molina L.T.,
Journal of Air & Waste Management Association 54 (2004) 1226.
9. Diem J.E., Ricketts C.E., Dean J.R., Climate Research 30 (2006) 201.
10. Gregg J.W., Jones C.G., Dawson T.E., Nature 424 (2003) 183.
11. Herndon S.C., Jayne J.T., Zahniser M.S., Worsnop D.R., Knighton B., Alwine E., Lamb B.K., Zavala M., Nelson
D.D., McManus J.B., Shorter J.H., Canagaratna M.R., Onasch T.B., Kolb C.E., Faraday Discuss. 130 (2005)
327.
12. Klumpp A., Ansel W., Klumpp G., Calatayud V., Garrec J.P., He S., Penuelas J., Ribas A., Ro-Poulsen H.,
Rasmussen S., Sanz M.J., Vergne P., Environ. Pollut. 139 (2006) 515.
13. Marshall J., Nature 437 (2005) 312.
14. Molina M.J., Molina L.T., Journal of the Air & Waste Management Association 54 (2004) 644.
15. Seigneur C., Aiche Journal 51 (2005) 356.
16. Pataki D.E., Alig R.J., Fung A.S., Golubiewski N.E., Kennedy C.A., McPherson E.G., Nowak D.J., Pouyat R.V.,
Lankao P.R., Global Change Biology 12 (2006) 2092.
17. Kaye J.P., Groffman P.M., Grimm N.B., Baker L.A., Pouyat R.V., Trends in Ecology & Evolution 21 (2006)
192.
18. Mitchell V.G., Diaper C., Water Sci. Technol. 52 (2005) 91.
19. Mitchell V.G., Diaper C., Environmental Modelling & Software 21 (2006) 129.
20. de Gouw J, Warneke C, Mass Spectrometry Reviews 26 (2007) 223.
12
2 Te
echniques for Air Pollution Measure
ements
To monitor air pollution, trace substance must be measured at levels of ppm (part
per million) or ppb (part per billion) using high-sensitive analytical methods. The influence of
coexisting substances. Complicates both qualitative and quantitative determination. Most of
the analytical methods currently performed on gas components are chemical methods where
ambient air passes through an absorbent by bubbling to adsorb the desired component; the
component trapped by the adsorbent is quantitatively determined. In recent years, physical
methods have been developing by which air samples directly introduced into an analysis
unit are quantitatively determined.This chapter will briefly discuss systems most generally
used in continuous analyzers focusing on measurement methods for substances specified
in environmental quality standard relating to air pollution. For each major air pollutant, EPA,
defined a reference method, which is the test method that is considered the standard
against which other methods can be tested. There are equivalent methods, which have been
checked against the reference method and found to give similar results. The equivalent
methods are generally simplier, cheaper and easier to use than the reference methods and
therefore are commonly used by national and regional ambient monitoring agency.
2..1 Sulfur Dioxide
Sulfur dioxide is a pollution generated by combustion of fuels containing sulfur,

including coal and petroleum. At present, environmental concentration of sulfur dioxide in air
tends to decrease by progress of techniques of desulfurization (Prevention).
The so colled West-Gaeke method is the EPA reference method for SO 2 (1-3). It
consist in bubbling a known volume of air trough a solution of sodium tetracloromercurate,
which forms a complex with SO2. After several intermediate reactions, the solution is treated
with pararosaniline to form the intensely colored methyl solfonic acid, whose concentration
is determined in a colorimeter. The EPA’s regulations for locating ambient air monitors are in
40CFR58 App. E. The description of the analytical methods to use for measuring pollutants
in ambient air are in 40CFR50 App. A-H.
Solution conductometry is specified as measurements method concerning
environmental standards. When ambient sample air passes through an absorbent (hydrogen
peroxide solution acidified by sulfuric acid), SO2 contained in the air is absorbed by the
absorbent to form sulfuric acid according to the following reaction formula, resulting in the
elevation of conductivity.
H2O2 + SO2  H2SO4
Based on this change in conductivity, the concentration of SO 2 in the sample air
is continuous determined.
In addition, JIS (Japan International Standard) also specifies the flame photometric
detection (FPD) method, coulometry and ultraviolet fluorometry for continuous analyzers.
1
3
TECHNIQUES FOR AIR POLLUTION MEASUREMENTS
2..2 Carbon Monoxide

Measuring methods specified by environmental standards and by JIS include non-
dispersive infrared absorption (NDIR) method (continuously determined the concentration
of the CO in ambient sample air due to change in the absorption of infrared rays by using a
selective detector) and hydrogen flame ionization detection (FID) method and rated potential
electrolytic method.
2..3 Nitrogen Oxides

Environmental standards are specified for NO2, which is produced by the oxidation
of NO arising in the course of combustion.
The measuring method specified in environmental standards is absorptiometry
using Saltzmann reagent and chemiluminescence method.
Absorptiometry Using Saltzmann

This method allows to continuously measures both the concentration of NO and
NO2 in an ambient sample air by means of absorptiometry using an absorbent (Saltzmann
reagent). The absorbent (a mixed solution of N-1-naphthylethylene diamine dihydrochlorate,
sulfanilic acid and glacial acetic acid) selectively absorbs NO2 contained in the ambient
sample air to produce a purplish red color. The concentration of NO2 in ambient sample air
is determined by measuring this absorption. NO is determined in the same manner after the
introduction of ambient sample air, which has already been analyzed on NO2, into oxidizing
solution (potassium permanganate solution acidified by sulfuric acid) to oxidize NO into NO2.
2..4 Photochemical Oxidant

An oxidant is a generic name of oxidizing substances including ozone and nitrogen
dioxide. Environmental standards define photochemical oxidants as substances releasing
iodine from neutral potassium iodide solution (total oxidant), other than nitrogen dioxide.
There are continuous analyzers for total oxidant based on absorptiometry and coulometry,
and those for ozone based on chemiluminescence and ultraviolet absorption method.
Absorptiometry Using Neutral Potassium Iodide Solution

This is the method of measuring the concentration of the total oxidant in ambient
sample air with the absorbance of iodine, which is released by contacting ambient sample
air with neutral potassium iodide absorbent at a constant ratio of flow.
2..5 Hydrocarbons
The thought that hydrocarbons other than methane (present in general ambient
air around 2 ppm) should be treated as “non-methane hydrocarbons”, namely, pollutants is
currently accepted generally. No environmental standards are established for non-methane
hydrocarbons, and guideline value is given. JIS specifies hydrogen flame ionization detection
(FID) method as continuous analyzer for hydrocarbons in ambient air.
Hydrogen Flame Ionization Detection (FID) Method

This is the method for determining the concentration of hydrocarbons in ambient air
by measuring minute electric current due to ions, which arise on combustion of hydrocarbons
in hydrogen flame, after isolating methane and non-methane hydrocarbons from ambient
sample air by means of gas chromatography.
14
2..6 Partticulate Matter

Atmospheric particulate matter is fine solid matter or liquid matter floating in
atmospheric air. Of the particulate, environmental standards specify particulate having a
diameter lower than 10 m, which is considered to affect health. Particulate arising during
industrial combustion process may have small particle size and high contents of heavy metals.
Measurement of Atmospheric Particulate Matter by the Light Scattering Method

This is the method for determining the weight concentration of atmospheric
particulate matter floating in atmospheric air by measuring the intensity of scattered light
which is known to be proportional to the weight concentration of particulate matter within
the same particulate system on exposing particulate to light.
Measurement of Atmospheric Particulate Matter by -ray Absorption Method

This is the method of determining the atmospheric particulate matter by measuring
the absorption quantity of -ray emitted by low energy -ray source caused by atmospheric
particulate matter collected on the filter.
Chemiluminescence Spectroscopy
Chemiluminescence, like atomic emission spectroscopy (AES), uses quantitative
measurements of the optical emission from excited chemical species to determine analyses
concentration; however, unlike AES, chemiluminescence is usually emission from energized
molecules instead of simply excited atoms. The bands of light determined by this technique
emanate from molecular emissions and are therefore broader and more complex then bands
originating from atomic spectra. Furthermore, chemiluminescence can take place in either
the solution or gas phase, whereas AES is almost strictly as gas phase phenomenon.
2..7 Enviro
onmental Quality Standard
ds
Environmental quality is certainly a worldwide concern. Air pollution knows
no boundaries, and reducing it is of the utmost importance. Countries are established
environmental regulations more and more restrictive. However, a completely unpolluted
environment at no cost to everyone is an impossible dream. The emission standards
philosophy is based on the definition of maximum possible (or practical) degree of emission
control. Notably, the degree for a certain pollutant varies between classes of sources.
Determining the emission standard for each class of pollutants and for each type of emitters,
the pollution emission rate will be the lowest possible, leading to the cleanest possible air.
A different approach is that of Air Quality Standards, based on a zero-damage philosophy. It
is assumed that for each pollutant exist (and can be determined) a threshold below which
no air pollution would occur. Dose response data, time of exposure, sinergic effects, bio-
accumulation are some of many important parameters which are used to prepare Quality
Standards. An example of Environmental Quality Standards is reported in Table 2.1.
1
5
TECHNIQUES FOR AIR POLLUTION MEASUREMENTS
Table 2.1: Environmental quality standards in Japan
Substance SO2 CO Suspended* NO2 Photochemical**`

ppm ppm particulate ppm oxidants
matter ppm
mg/m3
Conditions 0.1/h 20/h 02/h 00.4-0.06/d 0.06/h
0.04/day 10/day 0.1/day
Measuring Solution Non dispersive Piezoelectric Absorptiometry Absorptiometry
methods conductimetry infrared balance method (Saltzman reagent (NGKI)
method (NDIR) Beta-ray solution) Coulometry
-UV fluorescence absorption
method method Chemiluminescence -UV Absorptiometry
method Chemiluminescence
-Light scattering method
method
* Suspended particulated matter shall mean airborn particles of 10 m or less in diameter.

** Photochemicaloxidantsareoxidizingsubstancessuchasozoneandperoxiacetylnitrateproducedbyphotochemical
reactions (only those capable of isolating iodine from neutral potassium iodide, excluding nitrogen dioxide).
2..7.1 National Ambient Air Quality Standard

ds (NAAQS)
The Clean Air Act, which was last amended in 1990, requires EPA to set National
Ambient Air Quality Standards for pollutants considered harmful to public health and the
environment. The Clean Air Act established two types of national air quality standards.
Primary standards set limits to protect public health, including the health of “sensitive”
populations such as asthmatics, children, and the elderly. Secondary standards set limits to
protect public welfare, including protection against decreased visibility, damage to animals,
crops, vegetation, and buildings (3-18).
TheEPAOfficeofAirQualityPlanningandStandards(OAQPS)hassetNationalAmbient Air
Quality Standards for six principal pollutants, which are called “criteria” pollutants. They are
listed in Table 2.2. Units of measure for the standards are parts per million (ppm) by volume,
milligrams per cubic meter of air (mg/m 3), and micrograms per cubic meter of air (µg/m3).
Table 2.2: National ambient air quality standards
POLLUTANT STANDARD VALUE * STANDARD TYPE

Carbon Monoxide (CO)
8-hour Average 9 ppm (10 mg/m3) Primary
1-hour Average 35 ppm (40 mg/m3) Primary
Nitrogen Dioxide (NO 2)
Annual Arithmetic Mean 0.053 ppm (100 µg/m3) Primary & Secondary
Ozone (O3)
1-hour Average 0.12 ppm (235 µg/m3) Primary & Secondary
8-hour Average 0.08 ppm (157 µg/m3) Primary & Secondary
Lead (Pb)
Quarterly Average 1.5 µg/m3 Primary & Secondary
Particulate (PM 10) Particles with diameters of 10 micrometers or less
Annual Arithmetic Mean 50 µg/m3 Primary & Secondary
24-hour Average 150 µg/m3 Primary & Secondary
Particulate (PM 2.5) Particles with diameters of 2.5 micrometers or less
Annual Arithmetic Mean 15 µg/m3 Primary & Secondary
24-hour Average 65 µg/m3 Primary & Secondary
Sulfur Dioxide (SO 2)
Annual Arithmetic Mean 0.030 ppm (80 µg/m3) Primary
24-hour Average 0.14 ppm (365 µg/m 3) Primary
3-hour Average 0.50 ppm (1300 µg/m 3) Secondary
* Parenthetical value is an approximately equivalent concentration.
16
2..8 Refere
ences
1. de Nevers N., Pollution Control Engineering, 2000, Mc Graw Hill, New York.
2. Cooper, H. B. B., Jr. and Rossano A.T. Jr., Source Testing for Air Pollution Control, Environmental Research
and Applications, Inc., Wilton, CT, 1971.
3. http://www.epa.gov/epahome/lawregs.htm and http://www.epa.gov/air/criteria.html
4. Pollution: Causes, Effects and Control, R. M. Harrison Ed., The Royal Society of Chemistry, Cambridge,
1996.
5. Diem J.E., Ricketts C.E., Dean J.R., Climate Research 30 (2006) 201.
6. Pataki D.E., Alig R.J., Fung A.S., Golubiewski N.E., Kennedy C.A., McPherson E.G., Nowak D.J., Pouyat R.V.,
Lankao P.R., Global Change Biology 12 (2006) 2092.
7. Kaye J.P., Groffman P.M., Grimm N.B., Baker L.A., Pouyat R.V., Trends in Ecology & Evolution 21 (2006)
192.
8. Mitchell V.G., Diaper C., Water Science and Technology 52 (2005) 91.
9. Mitchell V.G., Diaper C., Environmental Modelling & Software 21 (2006) 129.
10. Herndon S.C., Jayne J.T., Zahniser M.S., Worsnop D.R., Knighton B., Alwine E., Lamb B.K., Zavala M., Nelson
D.D., McManus J.B., Shorter J.H., Canagaratna M.R., Onasch T.B., Kolb C.E., Faraday Discuss. 130 (2005)
327.
11. M.L.Bell, D.L.Davis, N.Gouveia, V.H.Borja-Aburto, L.A.Cifuentes, Environmental Research 100 (2006) 431.
12. Chow J.C., Watson J.G., Shah J.J., Kiang C.S., Loh C., Lev-On M., Lents J.M., Molina M.J., Molina L.T.,
Journal of the Air & Waste Management Association 54 (2004) 1226.
13. Gregg J.W., Jones C.G., Dawson T.E., Nature 424 (2003) 183.
14. de Gouw J, Warneke C, Mass Spectrometry Reviews 26 (2007) 223.
15. Klumpp A., Ansel W., Klumpp G., Calatayud V., Garrec J.P., He S., Penuelas J., Ribas A., Ro-Poulsen H.,
Rasmussen S., MSanz.J., Vergne P., Environ Pollut. 139 (2006) 515.
16. Marshall J., Nature 437 (2005) 312.
17. Molina M.J., Molina L.T., Journal of the Air & Waste Management Association 54 (2004) 644.
18. Seigneur C., Aiche Journal 51 (2005) 356.
1
7
3 NOx Abatement Te
echnologies
NOx represent a family of seven compounds (Table 3.1). EPA regulates nitrogen
dioxide (NO2) as a surrogate for this family of compounds because it is the most prevalent
form of NOx in the atmosphere that is generated by anthropogenic (human) activities. NO2
is not only an important primary air pollutant, but since it reacts in the atmosphere, it
is also a secondary pollutant. NO2 react with water in the atmosphere to form acid rain.
Furthermore, NO2 can react with air in the presence of ultraviolet light (UV) to form ozone and
nitric oxide (NO). Then, NO can react with free radicals, created by UV irradiation of VOC,
forming PAN (1).
Table 3.1: Nitrogen Oxides (NO x)

Formula Name Properties
N2 O Nitrous oxide Colorless, water soluble
NO Nitric oxide Colorless gas, slightly water soluble

N2 O 2 Dinitrogen dioxide
N2 O 3 Dinitrogen trioxide Black solid, water soluble, decomposes in water
NO2 Nitrogen dioxide Red-brown gas, very water soluble, decomposes in water
N2 O 4 Dinitrogen tetroxide
N2 O 5 Dinitrogen pentoxide White solid, very water soluble, decomposes in water
3..1 NOx Sources

Mobile sources contribute for about 50% of the total NO x emissions. Electric
power plant boilers produce about 40% of the NO x emissions from stationary sources (2).
Additionally, substantial emissions arise from industrial boilers, incinerators, gas turbines,
reciprocating spark ignition and Diesel engines in stationary sources, iron and steel mills,
cement manufacture, glass manufacture, petroleum refineries, and nitric acid manufacture.
Biogenic or natural sources of nitrogen oxides include lightning, forest fires, grass fires,
trees, bushes, grasses, and yeasts.
Nitrogen oxides can be grouped as follows accordingly with their formation
processes during the combustion.
Thermal NOx: The concentration of “thermal NO x” is controlled by the nitrogen

and oxygen molar concentrations and the temperature of combustion. Combustion at
temperatures well below 1300 °C forms relatively low concentrations of thermal NO x.
Fuel NOx: Fuels that contain nitrogen (e.g., coal) create “fuel NOx” that results
from oxidation of the already-ionized nitrogen contained in the fuel.
Prompt NOx: Prompt NOx is formed from molecular nitrogen in the air combining
with fuel in fuel-rich conditions, which exist, to some extent, in all combustion. This nitrogen
then oxidizes along with the fuel and becomes NO x during combustion, just like fuel NOx.
19
NOX ABATEMENT TECHNOLOGIES
3..2 NOx Abatement and Contro

ol Strategies
NOx abatement and control technology is a relatively complex issue. We shall try
to provide a structure of the main NOx pollution prevention and control technologies by first
giving the principles that are used. Then we shall describe the more successful pollution
prevention and emission control technologies and strategies. The Destruction or Removal
Efficiency (DRE) that each successful technology is capable of achieving, is one of the key
parameters for selecting the best available technology. Therefore effectiveness of pollution
control / reduction of NO and NO2 is also expressed in terms of relative DRE; i.e., comparison
of the NOx generated in the presence of a NO x reduction technology and in its absence.
In the case of combustion process, specific boiler types and combustion systems
will be considered along with the specific NO x technologies that can be applied. Notably,
many new combustion systems incorporate NO x prevention methods into their design and
significantly reduce NOx emissions compared to similar but older systems. As a result, the
use of DRE (even a relative DRE) for NOx may be inappropriate. In fact, the comparison
between actual NOx emissions from a new, well-designed system with those emitted by a
similar older system, equipped with the same NOX controlled technology, may be the best
way of evaluating how effectively a new combustion system minimizes NO x emissions.
The selection of the specific NOx abatement technology for a combustion system
should be based on the analysis of the required system modifications. Specifically, technical
and economic fusibility are primary restrictions. Therefore, in the process of identification of
the best applicable pollution prevention and emission control technologies, it must be first
consider the combustion system design.
The major types of combustion systems are shown in Table 3.2
Table 3.2: Common combustion systems (4)

Type of Combustion Unit Fuel
Dry bottom boilers - wall-fired, front-fired or Opposed-fired pulverized coal, gas, or liquid
Dry bottom boilers - tangentially fired pulverized coal, gas, or liquid
Wet bottom (slag tap) boilers - cyclone-type burners pulverized coal, gas, or liquid
Fluidized bed coal
Stokers with traveling grate crushed coal
Stokers with spreader grate crushed coal
Gas turbines gas and liquid
Internal combustion engines gas and liquid
There are two primary control techniques:
1. combustion modifications to suppress the formation of nitrogen oxides,
2. add-on controls (flue gas treatment) to reduce nitrogen oxides to molecular

nitrogen.
Table 3.3 lists principles or methods that are used to reduce NO x;
20
Table 3.3: NOx Control methods - (P) pollution prevention and (A) add-on technology *
Method Technologies Abatement Type

(P and A)
1. Reducing peak temperature Combustion Optimization P
Burners Out Of Service (BOOS) P
Less Excess Air (LEA) P
Inject Water or Steam P
Flue Gas Recirculation (FGR) P
Natural Gas Reburning P
Low NOx Burners (LNB) P
Catalytic Combustion P
Over Fire Air (OFA) P
Air Staging P
Reduced Air Preheat P
2. Reducing residence time Inject Air P
at peak temperature Inject Fuel P
Inject Steam P
3. Chemical reduction of NOx Fuel Reburning (FR) P
Low NOx Burners (LNB) P
Selective Catalytic Reduction (SCR) A
Selective Non-Catalytic Reduction A
(SNCR)
4. Oxidation of NOx with Non-Thermal Plasma Reactor A
Subsequent absorption Inject Oxidant A
5. Removal of nitrogen Oxygen Instead Of Air P
Ultra-Low Nitrogen Fuel P
6. Using a sorbent Sorbent In Combustion Chambers A
Sorbent In Ducts A
7. Combinations of these All Commercial Products P and A
Methods
 Summary of NOx Control Technologies and Their Availability and Extent of Application, EPA 450/3-92-004.
Reducing Temperature (Method 1): This technique is based on the possibility

to carry out the combustion at reduced / lower temperatures. This is achieved by avoiding
the stoichiometric air to fuel ratio (the exact ratio of reactants that are needed for full
combustion). This technique avoids the ideal stoichiometric ratio because this is the ratio
that produces higher temperatures and therefore generates higher concentrations of thermal
NOx. Combustion temperature may be reduced by: (a) using fuel rich mixtures to limit the
amount of oxygen available; (b) using fuel lean mixtures to limit temperature by diluting
energy input; (c) injecting cooled oxygen-depleted flue gas into the combustion air to dilute
energy; (d) injecting cooled flue gas with added fuel; or (e) injecting water or steam. Low-NOx
burners are based partially on these principles.
Reducing Residence Time (Method 2): Reducing residence time at high

combustion temperatures can be done by ignition or injection timing with internal combustion
engines. It can also be done in boilers by restricting the flame to a short region in which the
combustion air becomes flue gas. This is immediately followed by injection of fuel, steam,
more combustion air, or recirculating flue gas. This short residence time at peak temperature
keeps the vast majority of nitrogen from becoming ionized. This bears no relationship to total
residence time of a flue gas in a boiler.
Chemical Reduction of NOx (Method 3): This technique is based on the use of
a reducing agent, which react with NOx leading to N2 formation. Examples include Selective
Catalytic Reduction (SCR), which uses ammonia, Selective Non-Catalytic Reduction (SNCR)
21
that use ammonia or urea, and Fuel Reburning (FR). Non-thermal plasma, in the presence of
a reducing agent, is an emerging and innovative technology.
Oxidation of NOx (Method 4): This technique is based on the possibility to fully
oxidize NOx to favor water to absorb them (i.e., it is based on the greater solubility of NO x at
higher N valence state). This is accomplished either by using a catalyst, injecting hydrogen
peroxide, creating ozone within the air flow, or injecting ozone into the air flow. Notably, non-
thermal plasma, in the absence of a reducing agent, can effectively oxidize NOx. A scrubber
must be added to the process to absorb N 2 O5, avoiding emissions to the atmosphere.
Emissions of nitric acid can be controlled as well. In this case, nitric acid can be neutralized
by basic liquids in the scrubber. Notably, nitric acid can be collected and then sold (also as
a calcium or ammonia salt).
Removal of nitrogen from combustion (Method 5): Reduction of NOx formation

can be achieved by removing nitrogen from the combustion either by: (a) using oxygen instead
of air in the combustion process; or (b) using ultra-low nitrogen content fuel. Notably, the
use of pure oxygen produces a rather intense flame that must be subsequently and suitably
diluted. Using ultra-low-nitrogen content fuels with oxygen can nearly eliminate fuel and
prompt NOx.
Sorption (adsorption and absorption) (Method 6): Treatment of flue gas by

injection of sorbents (such as ammonia, powdered limestone, aluminum oxide, or carbon)
can remove NOx and other pollutants (principally sulfur). There have been successful efforts
to make sorption products a marketable commodity. This kind of treatment has been applied
in the combustion chamber, flue, and baghouse. The use of carbon as adsorbent has not led
to a marketable product, but it is sometimes used to limit NOx emissions in spite of this. The
sorption method is often based ao the use of a dry sorbent, but slurries have been used.
This method uses either adsorption or absorption followed by filtration and/or electrostatic
precipitation to remove the sorbent.
Combinations of these methods (Method 7): Many of these methods can be

combined to achieve a higher NOx reduction efficiency. For example, a fuel-rich cyclone
burner (Method 1) can be followed by fuel reburn (Method 3) and over-fire air (Method 1).
Other control technologies that are intended to primarily reduce concentrations of sulfur also
strongly affect the nitrogen oxide concentration.
Existing NOx abatement technologies for stationary sources can be divided into two
categories, external combustion applications (e.g., boilers, furnaces and process heaters)
and internal combustion applications (e.g., stationary internal combustion engines and
turbines) (5-9). These categories can be further subdivided into pollution prevention (which
reduces NOx generation) and add-on control technologies, which reduces NOx emissions (flue
gas treatment). Each NOx abatement technology has different implementations, development
histories, and, therefore, commercial status. Selection of a suitable technology must occur
after an evaluation of the technical and economic feasibility of each NO x technology to
accurate be implemented on an existing system. The available options may be limited by
inability to adjust the existing combustion system.
3..2.1 Selective Catalytic Reduction of NOx
Selective Catalytic Reduction of NOx represent a key external combustion

application which deserve great attention. The active catalytic component and temperature
ranges may be classified as indicated:
22
Low temperature (175-250 oC): Platinum - based catalysts

Medium temperature (300-450 oC): Vanadium - based catalysts
High temperature (350-600 oC): Zeolite - based catalysts
A more complete list of catalyst manufactures, general catalyst composition,

catalyst support structures, and temperatures of operation is shown in Table 3.4 and Table
3.5 shows the solution for some problem for SCR.
Table 3.4: SCR NO x catalyst technologies.*
Company Catalyst Description Operating Temperature (oC)
Babcock Hitachi V/Ti/Metal plate 240-415

Camet Precious metal/metal monolith 225-275
Cormetech V/Ti/Extruded monolith 200-450
Engelhard Precious metal/Ceramic monolith 175-320
Engelhard V/Ti/Ceramic monolith 300-440
Engelhard Zeolite/Ceramic monolith 440-590
Hitachi Zosen V/Ti/Extruded monolith 330-420
Hitachi Zosen V/Ti/Wire mesh 330-420
JHI V/Ti/Extruded monolith 200-400
JMI V/Ti/Metal monolith 340-425
HKI V/TI/Extruded monolith 300-400
MIHI V/Ti/Extruded monolith 200-400
Norton Zeolite/Extruded monolith 220-520
Steuler Zeolite/Extruded monolith 300-520
UBE V/Ti/Extruded monolith 250-400
* Ref: R.M. Heck, R.J. Farrauto, Catalytic air pollution control: commercial technologies, van Nostrand Reinhold,
New York, p. 170, 1995.
Table 3.5: Representative problems of SCR and some of the possible solutions.
Problems Solution
Poisoning by SO3 Use of TiO2-V2O5 catalyst

Clogging by dust Use of monolithic honeycomb type
Abrasion by coal dust Hardening the part of gas entrance in catalyst
Catalytic Oxidation SO2 to SO3 by catalyst Decrease of V2O5 loadingand addition WO 3
Leak of ammonia Decrease of NH3/NOx molar ratio
Pollution by aged catalyst Recovery of heavy metal and TiO2 from spent catalyst
The position of the SCR reactor in the process effluent of a thermal power plant
strongly influences the selection of the catalyst composition and its physical structure should
be used. For a high-ash, high-sulphur exhaust, there are three possible positions for the SCR
catalyst.
23
High dust: for high-dust/coal-fired boiler applications, a V2O5/TiO2 or zeolite-

containing extruded catalyst of low cell density operating at 350-400 oC and from 3,000
to 5,000 hr-1 space velocity is preferred. The SCR catalyst is located before any flue gas
particulate or scrubbing operations, so it must have large channels or holes to avoid plugging
and excessive backpressure.
Low dust: The SCR catalyst can be positioned downstream of an electrostatic

precipitator to provide the catalyst with a low-dust environment. Extruded homogenous
honeycombs composed of V 2O5/TiO2, zeolite, or (in some cases) combinations of these
materials are commonly used. A major problem in low-dust system SCR is covered of the
catalyst by very fine dust particles, which have passed the electrostatic filter, thus making it
unavailable for catalytic action.
Tail end location: This location provides the cleanest feed gas to the catalyst
since it has passed through an electrostatic precipitator and a flue gas desulfurizer. Extruded
homogenous zeolites or ceramic or metal substrates washcoated with V2O5/TiO2 or zeolites
can be used.
Trends in NOx control technology

Recently natural gas or other hydrocarbons tent to be used as reducing agent in
stationary SCR rather than NH3 (10). For many new power plants, natural gas is commonly
used as a fuel and is readily available as effective NOx reducing agent. NH3 is more expensive,
requires special handling and storage, and requires a sophisticated metering system to
avoid NH3 slip.
An ideal situation for elimination of NOx from combustion processes is to avoid
producing it initially. An exciting new possibility is the use of catalysts for both liquid and
gaseous fuels in the primary combustion process, replacing conventional burners. In
catalytically supported thermal combustion, a honeycomb-supported catalyst initiates
oxidation of a fuel such as natural gas (11-12). The heat generated at the catalyst surface
brings the bulk gas temperature to a condition where it can burn homogenously. The key
to the process concept is that the initial fuel-air mixture is below the flammability limit,
and thus the adiabatic temperature rise produces a gas below that required for nitrogen
fixation (< 1500 oC) so that almost no NO isx formed (<10 ppm). Furthermore, the oxidation
reactions are so efficient that the unburned hydrocarbon and CO contents of the exhaust are
exceedingly small (<5 ppm). There are substantial materials and process problems to be
solved before this technology can be commercialized. The temperatures that the catalyst and
substrate will experience are considerably higher than any other known catalytic processes.
After the exothermic reaction of the fuel brings about a high-temperature exposure of about
1300 oC, the catalyst must continue to function at inlet temperatures of less than 400 oC
during start-up periods. For fuels like natural gas, where Pd is the most active catalyst, this
is a major problem. The substrate material, be it ceramic or metal, must have excellent
thermal shock resistance so as not degrade or crack during the periodic high-temperature
surge common in power generation. For gas-fired turbine power plants, inlet temperatures
currently do not exceed about 1300-1400 oC, so this could be an ideal solution for future
NOx emission control (13-19).
It is important to make that most NO x exhaust streams contain high levels of
water vapor. Water vapor has been established (20-21) as a known inhibitor in most catalytic
NOx reduction processes. Thus, any study announcing new catalysts for NO x removal must
consider and evaluate the materials performance in wet NOx atmospheres water vapor of
> 10%. Unless there is a worldwide reduction of sulfur levels in fuels, NO x, streams will
usually have ppm levels of some sulfur compound; thus NOx-removal catalysts must also be
tested for their resistance to sulfur (H 2S or SOx).
24
3..2.2 NOx Abatement System in Gas Tu

ur b i ne s
Gas turbines use the Brayton Cycle with a burner to raise temperature of gas
after compression and before expansion through the turbine. Turbines mainly use reducing
peak temperature and reducing residence time (Methods 1 and 2) approaches to limit NO x
emissions. Because addition of particles to air flow entering the turbine would accelerate
erosion of turbine blades, sorbents (Method 6) could only be applied after the expansion in
the turbine. NOx reduction (Method 3) has been used to treat exhaust gases.
Table 3.6: Efficiency of NO x abatement technologies currently used for gas turbines
NOx Abatement Method Technique Efficiency
1.Reduction peak temperature Natural Gas Reburning (NGR) 70-85%

Low NOx Burners (LNB)
Inject Water or Steam
Reduced Air Preheat
Catalytic Combustion
2.Reduction residence time Air Staging of Combustion 70-80%
at peak temperature Inject Steam
3.Chemical reduction of NO x Selective Catalytic Reduction (SCR) 70-90%
Selective Non-Catalytic Reduction (SNCR)
Fuel Reburning (FR)
Low NOx Burners (LNB)
4. Oxidation of NOx with Non-Thermal Plasma Reactor (NTPR) NO-data
Subsequent absorption
5. Removal of nitrogen Ultra-Low Nitrogen Fuel NO-data
6. Use of a sorbent Sorbent in Ducts 60-90%
There has also been some success in reducing NOx concentrations when burning
biomass fuels in a boiler.
Table 3.6 reports the efficiency of the presents NOx abatement technologies used
for gas turbines.
It is worth noting that many turbine operators claim significant improvement of
air pollution control as a consequence of “good combustion practices. They mostly refers to
reduction of particulate emissions (often focusing the attention to the reduction of the visible
fraction of PM). However, the NOx emission data are rarely reported. Cogeneration units use
a gas turbine to generate electricity and provide preheated combustion air for a boiler. Gas
turbine exhaust contains typically 10-15% oxygen and therefore it can be effectively used to
provide combustion air for a low-pressure boiler. This latter system can be used to provide
steam for another turbine, a process heater, a space heater, or a combination of these.
Notably, sorbent particles can be introduced into the exhaust gas turbine flow in order to
control NOx.
3..2.3 Inte
ernal Combustion Reciprocating Engines
Internal combustion engines use air-to-fuel ratio and ignition/injection timing to

control maximum temperature and residence time. This can reduce the concentration of NOx
that is generated by reducing peak temperature (Method 1). Valve timing adjustments can
reduce residence time at peak temperature (Method 2) to control NO x formation. Chemical
reduction of NOx (Method 3) is used in catalytic converters to reduce NO x to N2. Some
stationary engines use both Method 3 and NOx oxidation (Method 4). A non-thermal plasma
25
reactor was developed for treatment of diesel exhaust. A plasma ignition system allows
greater freedom in the air-fuel ratio and the ignition timing of spark ignition engines. See
Table 3.7 for NOx technologies used for stationary internal combustion engines.
Table 3.7: Efficiency of NO x technologies currently used for stationary internal combustion engines
NOx Abatement Method Technique Efficiency
1.Reduction of peak temperature Air/fuel Ratio 20-97%

Timing of Ignition/Type of Ignition
Pre-Stratified Combustion
2.Reducing residence time Valve Timing NO-data
at peak temperature
3.Chemical reduction of NO x Selective Catalytic Reduction (SCR) 80-90%
Non-Selective Catalytic Reduction (NCSR)
80-90%
4. Oxidation of NOx with Non-Thermal Plasma Reactor (NTPR) 80-95%
Subsequent absorption
5. Removal of nitrogen Ultra-Low Nitrogen Fuel NO-data
6. Use of sorbent Sorbent In Exhaust Ducts 60-90%
Adsorber in fixed Bed
3..2.4 Air-fuel Ratio and Ignition Type
For internal combustion reciprocating engines, retardation of injection or spark

ignition, or an air-fuel ratio that departs from stoichiometric conditions will reduce peak
temperature. Lower peak temperature limits the amount of NO x formation. This technique
can achieve up to 50% control efficiency (22-23). When a three-way catalyst is used for
spark ignition engines, exhaust gas must have no more than 0.5% oxygen. This technique
can reach up to 98% efficiency. The use of plasma ignition (an alternating current or AC
system) instead of a direct current (DC) spark ignition system can also allow a greater fuel-
lean departure from the stoichiometric ratio. NOx emissions from internal combustion
engines using plasma ignition have been reported to be reduced by up to 97% (24-26).
Delaying injection of fuel in a compression ignition (diesel) engine can significantly reduce
NOx emissions. The amount of this reduction will depend upon the engine, valuing, and fuel.
However excessive timing retard can cause combustion instability or misfire (27) .
3..2.5 Influ
uence of Fuel Quality on the Combustion’s Emissions
The selection of combustion system strongly depends on the available fuel,

environmental constrain, availability of technical support and financial criteria. As far as
concern with fuel quality, it must be clearly stated that the presence of impurities in a fuel
strongly influence combustion performances and exhaust emissions (SOX, NOx, heavy metals,
VOC…). The concentration of fuel’s impurities depends on the type of sources, purification
process, and supplier. Even “natural gas” (methane) may contain propane, butane, and
carbon monoxide, in various percentage.
Solid Fuels
The combustion of a solid fuel, such as coal, is achieved by first allowing the
gasification of the volatile fraction of the fuel in a primary burner. A flow of air ensure
26
the removal of the volatile fraction from char and its oxidation. The remaining solid needs
further combustion air to burn. This process provides supplementary heat, part of which is
used to volatilize additional fuel. The simple control of combustion temperature would limit
the amount of air which react with the char fraction. Therefore, the volatile fraction must be
oxidized in over-fire-air or a secondary stage of burner with its air control system. The
balance of combustion air must be carefully adjusted taking into consideration the
composition of fuel, the boiler loading, and transient loads. Fast dynamic air adjustments
are recommended.
Pulverized coal can be burned in a similar way to oil. The flame is usually well
defined and, depending on particle size of fuel, char may remain in suspension in flue gas
throughout burning. Normally, the volatile fraction burns in air together with the fine fuel
particles. However, if the particles of the fuel are too coarse, char will continue burning
on its trajectory after leaving the flame. At a certain point the combustion ends. The trade
jargon for this is “ unburned carbon (UBC),” “carbon in the ash (CIA),” or “loss of ignition
(LOI).” These terms refer to carbon in char that does not burn along the trajectory. UBC can
be minimized by grinding particles finer and separate the various fractions of fuel particles
so that larger ones are returned to the roller mill or grinder.
Particles will become fly ash if they are small enough. UBC ranging from 0.5%
to 5% is considered acceptable. Therefore, the dimensions of the solid fuel particle is an
important parameter for the control of air pollution. Great attention must be dedicated to the
control of air to fuel stoichiometry and to the combustion temperature to minimize unburned
carbon in the ash. Notably, biomass represent an important solid fuel. However, in general,
it cannot be pulverized to small particles, but can burn to ash in a short time.
Even if particulate emissions from solid fuel are a serious problem, it exists a
set of technologies to control them (slag tap or ash pit, baghouse, and/or electrostatic
precipitator).
Liquid Fuels
Liquid fuels burn like the volatile fraction of solid fuel provided that the droplets are
small enough. Liquid fuels usually have less nitrogen content than solid fuels. Combustion
of liquids and gases can be controlled much more readily than that of solid fuel. Optimised
combustion of liquids can be performed without residual ash. The fuel-air ratio can be used
to control combustion temperature and therfore to minimize NOx generation. The flame can
be well defined and combustion is essentially completed within the flame.
Semi-solid Fuels
Semi-solid fuels are residuals from refineries. They are not clean burning fuels
like distillates and often are not even liquid at room temperature. Many impurities, typically
found in crude oil, are concentrated in semi-solid residual fuel. These fuels can contain
more nitrogen than coal, but usually contain less sulfur (28). Therefore, semi-solid fuels are
intermediate between coal and oil.
Gas Fuel
Natural gas is desulfurized before it is sent in a pipeline. Therefore, natural gas
has almost no sulfur, essentially no impurities, and no ash. The only thing that varies is heat
content per cubic meter. This variance is caused by natural gas producers supplementing
natural gas with propane, liquefied petroleum gas (butane), carbon monoxide, or other
gaseous fuel. As a result, air to fuel ratio must be carfully cheked to prevent changes in the
stoichiometric ratio.
27
3..2.6 Fluidized Bed Combustion
Fluidized bed combustion occurs in a bed of crushed coal that has air flowing
upward through it to make coal particles behave like a fluid. Boiler pipes can be either
submerged in the bed or exposed to the hot gases after they leave the bed. The fluidized bed
is temperature controlled (Method 1). The bed is also a chemically reducing region in which
available oxygen is consumed by carbon (Method 3) that reduces ionization of nitrogen.
Excess of air is injected (Method 2) over the fluidized bed to complete combustion of CO
and other burnables.In fluidized bed combustion it is possible to cold pulverized limestone
(Method 6) to control NO x emission. Notably, sulfur oxides, eventuallly produced during the
combustion can react with the limestone to form gypsum, a marketable product. Therefore,
gypsum must be separated from the ash. As a result, NO x generation can be essentially
limited to prompt NOx and fuel NOx .
3..2.7 Combined Te
echnology Approaches
The choice of technologies depends upon the type of combustion system, type
of boiler or other energy conversion device, and type of fuel used. Available technologies
will be narrowed by consideration of turndown ratio, stability of combustion, availability or
access to burners, air supply controls, fuel impurities, and cost among other factors. There
are many examples and here are a few of them. Selective catalytic reduction of NO x to
N2 can be followed by selective oxidation of sulfur dioxide to sulfur trioxide. Then sulfuric
acid is formed followed by scrubbing sulfuric acid from the flue gas (29). LNB can be used
in conjunction with SCR or SNCR to achieve a greater overall DRE than any of these can
achieve alone. Water/steam injection can be used with SCR to achieve a DRE greater than
SCR can achieve alone. Fuel reburning and SCR can be used together as well as separately,
to get the maximum NOx reduction (30).
28
3..3 Selected Avvailable Te

echnologies and Supplier Refere
ences
No. 1
Classification of technology: Air Pollution (Prevention Method)
Name of technology/technique: Less excess air (LEA)
Application: All fuels, used for dry bottom wall-fired, front-fired or opposed-fired boilers,
dry bottom tangentially fired boilers, wet bottom (slag tap boilers), fluidized
bed combustion, stokers with traveling grates and stokers with spread
grates.
Description: Reduces oxygen availability: Excess airflow for combustion has been
correlated the with amount of NO x generated. A net excess airflow lower
than 2% can strongly limit NOx content of flue gas. Although there are fuel-
rich and fuel-lean zones in the combustion region, the overall net excess air
is limited when using this approach.
Advantages: Easy modification.
Disadvantages: Low NOx reduction, reduction combustion efficiency.
Ref./Source: www.cleaver-brooks.com/Emissions1.html
No. 2
Name of technology/technique: Burners out of service (BOOS)
Application: All fuels, multiple burners for BOOS, used for dry bottom wall-fired, front-
fired or opposed-fired boilers.
Description: Staged combustion: multiple-burner equipment can have part of an array of
burners with some “burners out of service” (not feeding fuel, but supplying
air or flue gas). This allows the burners around them to supply fuel and
air to air or flue gas flowing from the BOOS. The result is a multi stage
combustion process by stages with temperatures always lower than when
all burners are in service. Therrefore, thermal NOx emission are lower. The
degree of NOx reduction depends upon the spatial relationship betwen the
BOOS and the other burners.
Advantages: Low cost, no capital cost for BOOS.
Disadvantages: Higher air flow for CO
Ref./Source: Methods for Reducing NOx Emissions, C. Latta, Roy F. Weston Inc., Plant
Engineering, September 1998.
No. 3
Name of technology/technique: Over fire air (OFA)
dry bottom tangentially fired boilers, wet bottom (slag tap boilers), fluidized
bed combustion, stokers with traveling grates and stokers with spread
grates.
Description: The OFA completes the combustion. When the primary combustion is
carried out with a fuel-rich mixture. The temperature i keept low by working
under off-stoichiometric combustion. The unburned fuel is fully oxidised in
the OFA.
Advantages: Low operating cost.
Disadvantages: High capital cost.
29
No. 4
Name of technology/technique: Low NOx burner (LNB)
Application: All fuels, used for dry bottom wall-fired, front-fired or opposed-fired boilers
and stokers with spread grates.
Description: A LNB provides a stable flame that has several different zones. For example,
the first zone can be primary combustion. The second zone can be Fuel
Reburning (FR) with fuel added to chemically reduce NOx. The third zone can
be the final combustion in low excess air to limit the temperature. There are
many variations on the LNB design. The LNB has produced up to 80% DRE.
This can be one of the less expensive pollution prevention technologies
with high DRE.
Advantages: Low operating cost, compatible FGR.
Disadvantages: Moderately high capital cost.
Ref./Source: Gas Reburning for High Efficiency NOx Control Boiler Durability Assessment,
B. A. Folsom, T. Sommer, D. Engelhardt, and S. Freedman, 96-RP139.04, Air
& Waste Management Assn. Regulatory Developments in NOx Controls for
Utility Boilers, C. Harrison, 96-RP139.03, Air & Waste Management Assn.
Overview of NOx Emission Control for Utility Boilers, J. E. Staudt, Proceedings
of the American Power Conference, 1993.
Select the Right NOx Control Technology, S. Wood, Chemical Engineering
Progress, January 1994.
No. 5
Name of technology/technique: Flue gas recirculation (FGR)
Application: All fuels, low nitrogen fuel, used for dry bottom wall-fired, front-fired or opposed-
fired boilers, bottom tangentially fired boilers, wet bottom (slag tap) boilers.
Fluidized bed combustion and stokers with traveling grates.
Description: < 30% flue gas recirculated with air, decreasing temperature: decreasing
recirculation of cooled flue gas reduces temperature by diluting the oxygen
content of combustion air and by causing heat to be diluted in a greater
mass of flue gas. Heat in the flue gas can be recovered by a heat exchanger.
This reduction of temperature lowers the NOx concentration. If combustion
temperature is held down to below 760° C, thermal NOx formation can be
negligible.
Advantages: High NOx reduction, potential for low nitrogen fuels.
Disadvantages: Moderately high capital cost. And operating cost, affects heat transfer and
system pressures.
Ref./Source: Fossil Fuel Combustion, A Source Book, W. Bartok and A. Sarofim, Wiley-
Interscience, John Wiley & Sons.
No. 6
Name of technology/technique: Water or steam injection
fired boilers, bottom tangentially fired boilers, wet bottom (slag tap) boilers
and stokers with traveling grates.
Description: Injection of water or steam causes the stoichiometry of the mixture to be
changed and adds steam modifics the reaction stoichiometry and reduces
the working temperature. Both of these actions leads to lower thermal NOx
emissions.
30
Advantages: Moderate capital cost, NOx reduction similar to FGR.

Disadvantages: Efficiency penalty.
No. 7
Name of technology/technique: Reduced air preheat
fired boilers, bottom tangentially fired boilers, wet bottom (slag tap) boilers,
fluidized bed combustion, stokers with traveling grates and stokers with
spread grates
Description: Air is usually preheated to cool the flue gases, reduce the heat losses,
and gain efficiency. However, this can raise the temperature of combustion
favoring NOx formation. By reducing air preheat, the combustion temperature
is lowered and NOx formation is reduced. This can lower efficiency, but can
limit NOx generation.
Advantages: High NOx reduction potential.
Disadvantages: Significant efficiency loss.
No. 8
Name of technology/technique: Fuel reburning (FR)
Application: All fuels, pulverized solid, used for bottom tangentially fired boilers, wet
bottom (slag tap) boilers, fluidized bed combustion, stokers with traveling
grates and stokers with spread grates.
Description: Recirculation of cooled flue gas with added fuel (this can be natural gas,
pulverized coal, or even oil spray) causes heat dilution, similar to that
abserved in the case of FGR, and a reduction of the primary combustion
temperature. When the FR is added in a secondary combustion stage, the
presence of fuel chemically reduces newly generated NO x to molecular
nitrogen. The fuel is only partially consumed in the reduction NO x of and
its burning is completed in a subseguent stage using either combustion
air nozzles or over-fire-air. This technique has been demonstrated to be
effective with residence times from 0.2 seconds to 1.2 seconds and has
achieved up to 76% DRE.
Advantages: Moderate cost, moderate NOx removal.
Disadvantages: Longer residence times.
Ref./Source: Gas Reburning for High Efficiency NOx Control Boiler Durability Assessment,
B. A. Folsom, T. Sommer, D. Engelhardt, and S. Freedman, 96-RP139.04,
Air & Waste Management Assn.
No. 9
Name of technology/technique: Combustion optimization
Application: Gas liquid fuel, used for dry bottom wall-fired, front-fired or opposed-fired
boilers, stokers with traveling grates and stokers with spread grates.
Description: Combustion optimization refers to the active control of combustion. In a
natural gas fired boiler, by decreasing combustion efficiency from 100% to
99%, NOx generation dropped to a much more acceptable level. For coal-fired
boilers a 20% to 60% reduction in NOx has been experienced. These active
combustion control measures seek to find optimum combustion efficiency
and to control combustion (and hence emissions) at that efficiency. Another
approach uses a neural network computer program to find the optimum
31
control point. Still another approach is to use software to optimize inputs

for the defined output. One vendor decreases the amount of air that is
pre-mixed with fuel from the stoichiometric ratio (ratio that produces the
hottest flame) to lengthen the flame at the burner and reduce the rate of
heat release per unit volume. This can work where the boiler tubes are far
enough away from the burner. Carbon monoxide, unburned fuel, and partially
burned fuel that result can then be subsequently oxidized in over-fire-air at
a lower temperature. Combustion must be optimized for the conditions that
are encountered. 50% DRE has been reported.
Advantages: Minimal cost.
Disadvantages: Longer residence times.
Ref./Source: www.marathonmonitors.com
www.ucicl.eng.uci.edu/research/active-control/
GNOCIS - 1999 Update on the Generic NOx Control Intelligent System,
G. Warriner, AJA.Sorge, M. Slatsky, J. Noblett, J. Stallings, EPRI-DOE-EPA
Combined Utility Air Pollution Control Symposium: The MEGA Symposium,
Atlanta, August 1999.
Obtaining Reduced NOx and Improved Efficiency Using Advanced Empirical
Optimization on a Boiler Operated in Load-Following Mode, P. Patterson,
EPRI-DOE-EPA Combined Utility Air Pollution Control Symposium: The MEGA
Symposium, Atlanta, August 1999.
No. 10
Name of technology/technique: Air staging
dry bottom tangentially fired boilers, wet bottom (slag tap) boilers, stokers
with traveling grates and stokers with spread grates.
Description: Combustion air is divided into two streams. The first stream is mixed with
fuel in a ratio that produces a reduced flame. The second stream is injected
downstream of the flame and makes the net ratio slightly rich air in DRE up
to 99% have been reported.
Advantages: Reduce peak combustion temperature.
Disadvantages: Extend combustion to a longer residence time at lower temperature
Ref./Source Maximum Achievable Control Technology for NOx Emissions from Thermal
Oxidation, P.Nutcher and D. Lewandowski, 94-WA74A.03, Air and Waste
Management Association, Annual Meeting, Cincinnati, OH, June 19-24 1994.
No. 11
Name of technology/technique: Fuel staging
dry bottom tangentially fired boilers, wet bottom (slag tap) boilers, stokers
with traveling grates and stokers with spread grates.
Description: This Technologyis is based on the staging of combustion. Fuel is divided
into two streams. The first stream feeds primary combustion that operates
in a reducing fuel to air ratio. The second stream is injected downstream
of primary combustion, causing the net fuel to air ratio to be only slightly
oxidizing. Excess fuel in primary combustion dilutes heat to reduce
temperature. The second stream oxidizes the fuel while reducing the NOx to
N2. This is reported to achieve a 50% DRE.
Advantages: Reduce peak combustion temperature.
32
Disadvantages: Extend combustion to a longer residence time at lower temperature.

Ref./Source: Maximum Achievable Control Technology for NOx Emissions from Thermal
Oxidation, P. Nutcher and D. Lewandowski, 94-WA74A.03, Air and Waste
Management Association, Annual Meeting, Cincinnati, OH, June 19-24, 1994.
No. 12
Name of technology/technique: Oxygen instead of air
Application: All fuels, used for wet bottom (slag tap) boilers.
Description: Use oxygen to oxidize fuel: an example of this is a cyclone burner where the
flame is short and intense. This technique has reduced NOx by up to 20% in
burners using conventional fuel. This technique also is usable with low-NOx
burners to prevent the prompt NOx from being formed.
Advantages: Moderate to high cost, intense combustion.
Disadvantages: Eliminates only prompt NOx, furnace alteration.
Ref./Source: Reducing NOx Emissions, B. Chambers, Glass Industry, May 1993.
Nitrogen Oxides Control Technology Fact Book, Leslie L. Sloss, Noyes Data
Corp., 1992.
No. 13
Name of technology/technique: Inject oxidant
stokers with traveling grates and stokers with spreader grates.
Description: Chemical oxidant injected in flow: The oxidation of nitrogen to its higher
valence states makes NOx soluble in water. Gas absorbers can be effective
used. Many oxidants have been injected into the airflow such as ozone, ion-
ized oxygen, or hydrogen peroxide. Non-thermal plasma generating oxygen
ions within the air flow have been also used. Water, hydrogen peroxide, or
an alkaline fluid can effectively absorb nitric acid.
Advantages: Moderate cost.
Disadvantages: Nitric acid removal.
No. 14
Name of technology/technique: Catalytic combustion
Application: Gas liquid fuels.
Description: Catalytic combustion at occurs lower temperature with respect to the
uncatalysed reach an the resulting reduction in the working temperature
leads to a significant NOx reduction. This technique is not used often
because it is very load sensitive. However, where it is used, catalytic
combustion can achieve less than 1-ppm concentration of NOx in the flue gas.
Advantages: Lowest possible NOx emissions.
Disadvantages: Very high capital cost, high operating cost, catalyst deactivation.
Ref./Source: Low-Emission Gas Turbines Using Catalytic Combustion, S. Vatcha, Energy
Conversion Management, Vol. 38 No. 10-13, pp. 1327-1334.
33
No. 15
Name of technology/technique: Ultra-low nitrogen fuels
Application: All ultra-low nitrogen fuels, dry bottom wall-fired, front-fired or opposed-fired
boilers, dry bottom tangentially fired boilers, wet bottom (slag tap) boilers,
fluidized bed combustion, stokers with traveling grates and stokers with
spreader grates.
Description: Uses low-nitrogen fuel: These fuels can avoid NOx that results from nitrogen
contained in conventional fuels. Up to 70% reduction in NOx emissions
has been reported. Now there are ultra-low-nitrogen liquid fuel oils. These
oils contain 15-20 times less nitrogen than standard fuel oil. This oil is
now commercially available and competitively priced. Ultra-low-nitrogen oil
is most frequently used in Southern California where the air pollution is
particularly a problem. Natural gas can be considered a low-nitrogen fuel.
Coke (the quenched char from coal) can also be an ultra-low-nitrogen fuel
because nitrogen in the volatile fraction of the coal is removed in making
coke.
Advantages: Eliminates fuel NOx, No capital cost.
Disadvantages: Slight rise in operating cost.
Ref./Source: www.cleaver-brooks.com/Emissions1.html
No. 16
Name of technology/technique: Non-thermal plasma reactor (NTPR)
Application: Dry bottom wall-fired, front-fired or opposed-fired boilers, dry bottom
tangentially fired boilers, wet bottom (slag tap) boilers, fluidized bed
combustion, stokers with traveling grates and stokers with spreader grates.
Description: Reducing agent ionized or oxidant created in flow: Using methane and
hexane as reducing agents, non-thermal plasma has been shown to
remove NOx in a laboratory setting with a reactor duct only 2 feet long. A
transient high voltage that created non-thermal plasma ionized the reducing
agents. The ionized reducing agents reacted with NOx and achieved a 94%
DRE. There are indications that an even higher DRE can be achieved. A
successful commercial vendor uses ammonia as a reducing agent to react
with NOx in an electron beam generated plasma. Such a short reactor can
meet available space requirements for virtually any plant. The non-thermal
plasma reactor could also be used without reducing agent to generate
ozone and use that ozone to raise the valence of nitrogen for subsequent
absorption as nitric acid.
Advantages: Moderate cost, easy siting, high NO x removal.
Disadvantages: Fouling possible, ozone emission possible.
No. 17
Classification of technology: Air Pollution (ADD-ON Control)
Name of technology/technique: Selective catalytic reduction (SCR)
combustion, stokers with traveling grates and stokers with spreader grates.
Description: Catalyst located in the air flow, promotes reaction between ammonia and
NOx: SCR uses a catalyst to react injected ammonia to chemically reduce
NOx. It can achieve up to a 94% DRE and is one of the most effective
NOx abatement techniques. However, this technology has a high initial
34
cost. In addition, catalysts have a finite life in flue gas and some ammonia
“slips through” without being reacted. SCR can used precious metal
based catalysts or base metal and zeolite based catalysts. However, the
base metal and zeolite catalysts operate at higher temperatures then the
precious metal catalysts.
Advantages: High NOx removal
Disadvantages: Very high capital cost, high operating cost, catalyst siting, increased
Pressure drop possible water wash required.
Ref./Source: Selective Catalytic Reduction Control of NO x Emissions, SCR Committee of
Institute of Clean Air Companies, November 1997.
No. 18
Name of technology/technique: Selective non-catalytic reduction (SNCR)
combustion, stokers with traveling grates, stokers with spreader grates.
Description: In SNCR ammonia or urea is injected within a boiler or in ducts in a region
where temperature is between 900 oC and 1100 oC. This technology is
based on temperature ionizing the ammonia or urea instead of using a
catalyst or non-thermal plasma. It is necessary to control the working
temperature windows to avoid ammonia slip or high NO x emissions. The
temperature “window” is different for urea and ammonia. Reduction of the
NOx by SNCR can have up to a 70% DRE.
Advantages: Using urea-low capital cost moderate NOx removal, Non-toxic chemical.
Using ammonia: low operating cost, Moderate NO x removal.
Disadvantages: Temperature dependent NO x reduction, moderately high capital cost, area
or ammonia storage, handling, injection system.
Ref./Source: Nitrogen Oxides Control Technology Fact Book, Leslie L. Sloss, Noyes Data
Corp., 1992.
Selective Non-Catalytic Reduction for Controlling NO x Emissions, SNCR
Committee of Institute of Clean Air Companies, October 1997
www.cleaver-brooks.com/Emissions1.html.
No. 19
Name of technology/technique: Sorption-both! adsorption and absorption
combustion, stokers with traveling grates, stokers with spreader grates. 1)
Use sorbents in combustion, 2) duct to baghouse, 3) due to electrostatic
precipitator.
Description: Use a chemical to absorb NO x or an adsorber to hold it: Several methods are
used to inject and remove adsorbent or absorbent. One-method sprays dry
powdered limestone into the flue gas. The limestone then reacts with both
sulfuric acid and nitric acid. There is a spray dryer approach that consist of
spraying slurry of powdered limestone and aqueous ammonia into the flue
gas. The limestone preferentially reacts with the sulfur while the ammonia
preferentially reacts with the NOx. In-duct injection of dry sorbents is another
example of this technique and can reduce pollutants in three stages: (1) in
the combustion chamber, (2) in the flue gas duct leading to the baghouse,
and (3) in the flue gas duct leading to the electrostatic precipitator. The by
35
products formed by sorption are gypsum (calcium sulfate) that could be

sold to make wallboard, and ammonium nitrate that can be sold to make
either explosive or a fertilizer. Sorption is reported to have up to a 60% DRE.
Another version uses carbon injected into the air flow to finish the capture
of NOx. The carbon is captured in either the baghouse or the electrostatic
precipitator (ESP) just like other sorbents. There are many absorbents and
adsorbents available.
Advantages: Can control other pollutants as well as NOx.
Moderate operating cost.
Disadvantages: Cost of handling sorbent, space for the sorbent, storage and handling.
Ref./Source: Nitrogen Oxides Control Technology Fact Book, Leslie L. Sloss, Noyes Data
Corp., 1992.
No. 20
Classification of technology: Air Pollution (Add-on Control)
Name of technology/technique: Selective catalytic reduction
Application: Internal Combustion
Description: As with boilers, SCR can be used to obtain up to a 90% DRE of NO x. When
used with a LNB or steam/water injection, NO x can be reduced to 5-10
ppm. With compression ignition engines, zeolite catalysts achieve a DRE of
90+%, while base-metal catalysts can achieve a 80% to 90% DRE.
Advantages: 90% efficiency can be achieved.
Disadvantages: Operating cost.
Ref./Source: Low-Emission Gas Turbines Using Catalytic Combustion, S. Vatcha, Energy
Conversion Management, Vol. 38 No. 10-13, pp. 1327-1334.
Alternative Control Techniques Document -- NOx Emissions from Stationary
Reciprocating Internal Combustion Engines. EPA-453/R-93-032, July 1993.
No. 21
Name of technology/technique: Steam injection
Application: Reduce the concentration of NOx discharged by gas turbine from
200ppm to 6ppm in accordance with the pollution prevention. Chemical;
Petrochemical.
Description: Steam injection was provided in the combustion chamber of the gas turbine
and the flue gas denigration system was installed in the exhaust gas boiler
as a measure for reducing the amount of NOx discharge that was increasing
in line with the installation of gas turbine equipment.
1. Suppression of NOx generation by injecting steam into the gas turbine.
Fuel/Steam = 1/1 ~ 1/1.2
2. Denigration by the ammonia catalytic reduction method.
Catalyst : 4NO + 4NH3 + O2  4N2 + 6H2O
Catalyst : NO + NO2 + 2NH3  2N2 + 3H2O
Implementing company: Ishihara Sangyo Co., Ltd., Yokkaichi Plant.
No. 22
Classification of technology: Air Pollution (Add – on Control)
Name of technology/technique: Combined techniques
Application:. Reduce NOx, SOx and soot in flue gas discharged from chimney stacks.
Description: Flue gas is passed between multiple electrodes charged with high voltage
where soot particles in the flue gas are collected by charging the particles
36
negatively and attracting them to the positive electrode. The particles adhering
to the electrode are removed mechanically by tapping with a hammer.
1. Denigration (Dry ammonia catalytic reduction method)
4NO + 4NH3 + O2  4N2 + 6H2O
2. Desulphurization (magnesium hydroxide method)
SO2 + Mg (OH)2  MgSO3 + H2O
2MgSO3 + O2  2MgSO4
3. Soot ( Electric precipitator )
Advantages: High Efficiency Denigration (80%) Desulphurization (99%) Soot removed
(96%)
Implementing company: Mitsubishi Chemical Co., Ltd.
No. 23
Name of technology/technique: Removal of exhaust NOx by ammonia catalytic reduction
method (SCR)
Application: Chemicals, petrochemical. As a result of changing the boiler fuel from heavy
oil to petroleum coke, the concentration of NOx in the exhaust gas increased
to the nitrogen content in the fuel. Using the dry ammonia contact reduction
method therefore carried out removal of NOx.
Description: Use a high performance honeycomb type catalyst.
4NO + 4NH3 + O2  4N2 + 6H2O
Advantages: Removal of 85% of NOx generated in the boiler furnace in line with witching
of its fuel.
Implementing company: Tosoh Company, Ltd. Yokkaichi Plant
No. 24
Name of technology/technique: Low NOx combustion technology
Preface: Low NOx combustion technologies include the following technologies.
Low NOx burner (aerodynamically controlled tope and split flame type)
Combustion modification such as air staging and flue gas mixing
IFNR (In-Furnace NOx Reduction) combustion.
Application: Boilers for the utility thermal power plant and Boilers for industrial-owned
thermal power plant.
Description: 1. Low NOx Burner
Low NOx type burners control the strength of the fuel mixing with the
combustion air and realize fuel rich region locally in the process firing fuels.
The split flame type burner is of off-stoichiometric firing type and is only
adopted in firing fuel oils. DF (Dual Flow) type low NOx burner is of an
aerodynamically mixing control type and is used for all fuels.
2. Combustion Modification
The air staging and the flue gas mixing technologies are adopted to reduce
NOx emissions in the combustion modification. On staged firing, a part of
combustion air is branched from the stream to the burner firing system, and
introduced to the furnace through OAP’s (Overfire Air Ports), distributed at
the down stream of the burner region. Consequently, fuel rich firing can be
realized by air staging and NOx formation can be therefore reduced. The
flue gas mixing technology gives the decrease of the flame temperature.
Lowering flame temperature, while fuel-NOx, originated by fuel-bound
nitrogen, is insensitive to flame temperature, significantly reduces thermal-
37
NOx originated by molecular nitrogen in the combustion air. This system

needs a fan for recirculating the flue gas.
3. IFNR (in-furnace NOx reduction)
NOx can be decomposed into molecular nitrogen through the reaction of
CHi + NO-> HCN-> NHi-> N2
in the firing region. Here, CHi denotes the hydrocarbon species yielded in
the process of fuel oxidation. Fuel rich firing will accelerate the reaction
above, because the hydrocarbon species yield more under such conditions.
IFNR technology adopts this concept of NOx decomposition. IFNR comprise
of IAP’s (Interstage Air Pons) and OAP’s (Overfire Air Ports). A part of
combustion air also introduce to the furnace through IAP’s as well as
that through OAP’s. IAP’s play a role accelerating both reactions for fuel
oxidation and NOx decomposition, latter of which means the conversion
from the intermediate nitrogen species (HCN, NHi) to N2.
Performance: The efficiencies of NOx reduction are roughly shown below for each of low
NOx technology.
Low NOx Burner: split flame oil atomizer: 20 - 30% depends on fuel nitrogen content
DF (dual flow) burner: 20 - 50% depends on the type of fuel
Combustion Modification: air staging: 20 - 50% depends on OAP capacity
and the type of fuel
flue gas mixing : 10 - 50%, depends on GM fan capacity and the type of fuel
IFNR: IFNR normally used with other NO x reduction technologies, and
following NOx emissions have been already achieved.
Gas firing: 15 - 20ppm (O2 5% corrected)
Oil firing: 45 - 80ppm (O2 4% corrected) depends on fuel nitrogen content
Coal firing: 100- 200ppm (O2 6% corrected), depends on coal properties
Ref./Source: http://nett21.unep.or.jp/CTT_DATA/Contents4.html
No. 25
Name of technology/technique: Combustion improvement system
Description: Combustion air is mixed with portion of flue gas to slow combustion,
avoiding local rise in temperature and thereby reducing NO x generation.
Part of the fuel is used as reducing agent to reduce NO generated in the
combustion chamber, thereby reducing NO x generation.
Advantages: Established and widely employed technology
Capacity: NOx reduction efficiency: Approx. 20 - 50% by combination of these
methods
Application: Fossil power stations etc. (The Kansai Electric Power Co., Inc.)
Source/Ref : http://nett21.unep.or.jp/CTT_DATA/Contents4.html
No. 26
Name of technology/technique: Low NOx burner for industrial furnace
Description: Principle of Low NO x Burner.
Slow combustion has been adapted as a heating efficiency measure by
suppression of mixing of fuel and air during the initial stage of combustion.
The direction of fuel injection is at an angle to the air stream axis, and the
mixing of fuel and air in the primary combustion zone is limited. Therefore
a local high temperature region cannot develop. Fuel, which is not burned
in this zone gradually, mixes with air not used in the initial stages and
38
thus combustion is completed. It is therefore possible to obtain uniform

combustion. The drop both in the maximum flame temperature and local
oxygen partial pressure effectively suppresses thermal NO x and fuel NOx
and thus the NOx value is drastically reduced.
Advantages: This burner is very simple, modification of the burner refractory quarl is
unnecessary and cost is very low. It is fully compatible with energy saving
and with low NOx emission. It can be easily mounted on existing furnaces.
NOx concentration decreased to a value less than half that obtained using
a conventional burner.
Application: Applied to reheating furnaces, soaking pits, heavy forge furnaces and
melting furnaces.
Implementing company: KOBE STEEL, LTD.
Ref/Source: http://nett21.unep.or.jp/CTT_DATA/Contents4.html
No. 27
Name of technology/technique: 3-Stage low NOx combustion system
Description: High performance, super low NOx system, a combination of “ordinary
combustion type” burner and HITACHI ZOSEN’s patented 3-stage combustion
type low NOx system.
Advantages: 1. In case of 3-stage combustion system, reducing combustion is limited
only to the secondary combustion zone, so that reducing atmosphere space
is very narrow. Furthermore, since measure are taken so that combustion
gas with a strong reducing capability does not directly strike the water wall,
adverse effects from such things as reducing corrosion and slagging on
the heating surfaces inside the furnace due to reducing atmosphere, even
in the case of super low NOx combustion, are extremely small compared
to other NOx reduction systems such as OFA combustion system”, which
expose a large part of the furnace inside to reducing atmosphere.
2. Normal oxidizing combustion is performed in the primary combustion
zone (main combustion zone) where most of the fuel burns and combustion
efficiency is very high. The unburnt part from the secondary fuel in the
secondary combustion zone (reducing combustion zone) is burnt in the
tertiary combustion zone (combustion completion zone). Consequently,
combustion efficiency in a 3-stage type low NOx boiler is as high as in
ordinary boilers without NOx reduction.
3. Due to the features mentioned above, the NO x value in a 3-stage
combustion type low NOx boiler can reach to 100 ppm or less with ordinary
bituminous coal. The NOx value decreases if the combustion gas remains
longer in the secondary combustion zone (reducing combustion zone). The
dimensionless residence time of combustion gas in the reducing zone
based on the “specified time”, the time the combustion gas stays in the
reducing zone of a specified boiler. The heavy line in the figure indicates the
guaranteed NOx value (with standard design) with ordinary bituminous coal.
From this, the dimensionless reducing time will be set at about 1.1 for a
boiler with a guaranteed NOx of 100 ppm. As just explained, this low NO x
combustion system consists of three stages, that is, primary, secondary
and tertiary stage, and the following is an explanation of each stage.
Primary Combustion Zone
In the “normal combustion type” non-low NOx burner, normal oxidizing
combustion with an air ratio of 1.0 or over is performed. The amount of
39
fuel here is 65-75% of total boiler fuel and the flame is raised to a very
high temperature and a high combustion efficiency is obtained because the
minimum combustion air needed for complete combustion is applied and
also flame length is adjusted to be as short as possible. Consequently,
the flame in this zone is a bright “golden color” and good combustion can
be confirmed at a glance. Generation of NOx in the primary combustion
area is not controlled at all and the aim is only to reach 100% combustion
efficiency.
Secondary Combustion Zone
25-35% of the fuel for the boiler is blown in from the secondary fuel port.
This secondary fuel includes air for transport but any other air is strictly
excluded to improve its performance as a denitration agent. The denitration
reaction is as follows:
1. Since the secondary fuel port is located just above the burner, secondary
fuel is heated intensely by the burner flame and hydrogen (H2), hydrocarbon
(CmHn), carbon monoxide (CO), charcoal (C), etc. are formed as very active
reducing components.
2. The atmosphere in the center of the secondary combustion zone has very
high reaction ability because the air ratio is about 0.7-0.8 of the theoretical
air ratio.
3. The atmosphere temperature in the secondary combustion zone is a
very ideal at about 1400 °C so that the chemical reaction of the reducing
components and NOx from the primary combustion zone occurs intensely.
4. The secondary fuel is injected in stripes in the horizontal cross section
of the furnace and there are plenty of secondary fuel ports for complete
mixing of the secondary fuel and the combustion gas from the primary
combustion zone.
5. In the course of the process mentioned above, most of NOx in the
primary combustion gas is instantly reduced to inactive N2 by hydrogen,
hydrocarbon, carbon monoxide, charcoal, etc. which are formed from the
secondary fuel.
6. Since combustion in the secondary combustion zone takes place
with insufficient air, there is almost no new generation of NO x while a
sizable amount of unburnt components remains from the secondary fuel.
Consequently, the longer the gas remains in the secondary combustion
zone, the lower NOx becomes.
Tertiary Combustion zone
30-40% of all the air used for combustion is injected from the OFA port and
the unburnt components from the secondary combustion zone are burnt.
The OFA port is positioned so that it is in the ideal gas temperature zone
from the viewpoint of improved combustion of the unburnt components and
for control of new generation of thermal NOx . OFA is injected in stripes on
the horizontal cross section of the furnace, and there are a number of OFA
ports so the OFA is completely mixed with the combustion gas from the
secondary combustion zone. In the tertiary combustion zone, combustion
efficiency increases in accordance with the increase of the space between
the OFA ports and the furnace exit. However, this increases the size and
weight of the boiler, so the size of this space is determined from the total
cost including facility costs and running cost of the boiler.
Implementing company: HITACHI ZOSEN CORPORATION
40
No. 28
Name of technology/technique: High-temperature combustion catalyst
Application: The technology has not been commercialized, but following applications
are expected. Gas turbine, Boiler, Gas-heater, Byproduct gas combustor,
Off-gas treatment, Deodorizer
Description: In order to reduce NOx emission, integrated combustion techniques such as
lean-burn combustion and water injection have been developed. However,
it is difficult to reduce NOx emission to ultra-low concentration, because
thermal NOx is formed by thermo-chemical reaction between nitrogen and
oxygen in air. The NOx formation reaction strongly depends on temperature,
thermal NOx is extensively produced in high temperature zone over than
1500 deg. °C inside a combustion flame.
Catalyst combustion is one kind of flame-less combustion in which fuel
is oxidized perfectly without high temperature zone and which scarcely
produces thermal NOx .
Catalyst is made of Mn-substituted hexa-aluminate (Sr0.8La0.2MnAl11Ol9-a
Catalyst powder is extruded to a honeycomb shape and sintered at high
temperature. Honeycomb shape with 300cells/inch2 is used for natural gas
combustor. In gas-turbine combustor, three types of catalyst honeycomb are
combined. At the top of the catalyst bed, conventional noble metal catalyst
honeycombs, which have a high reaction activity under low temperature, is
located. Two types of hexa-aluminate honeycombs are used in the middle
and bottom parts. Fuel is mixed with air, heated by pre-burner to around
450 °C, and oxidized smoothly in the catalyst bed in which temperature
rises continuously to around 1200 °C.
It was known that catalyst combustion was effective for low NO x combustion,
but catalyst having high temperature durability over than 1000 °C was
not developed. Mn-hexaaluminate is the only one catalyst which can be
stably used over than 1000 °C. 8000 hours of catalyst life at 1300 °C
is confirmed by atmospheric combustion test, and 1000 hours of stable
operation is also confirmed at high pressure combustion test. When
large diameter honeycomb is used for a large-scale combustor, formation
of cracks on the honeycomb caused by thermal stress is an important
problem. Segmentation system, which is effective in reducing thermal
stress, is developed, and optimum shapes of honeycomb segments are
designed with FEM simulation model.
Efficiency: A test device for the 150kW prototype catalytic combustion turbine was
prepared. In the test, turbine pressure ratio, air flow rate and combustor
inlet air temperature were 8.5, 1.8 kg/s and 350 °C, respectively, and
both combustion efficiency higher than 99% and NO x emissions less than
40 ppm were attained after 215 hours of continuous operation. In addition
no visible cracks was observed in either the catalyst honeycomb or the
catalyst holder after the test.
Implementing company: KOBE STEEL, LTD.
No. 29
Name of technology/technique: The SCR DENOX process-haldortopsoe
Applications: The SCR process can be applied in various applications and is especially
dedicated to high NOx -removal efficiencies.
41
Topsoe has applied its SCR DENO x process to applications such as:
Coal fired Boilers, Oil fired Boilers, Lignite fired Boilers, Pet Coke fired
Boilers, Gas fired Boilers, Diesel Engines, Gas Engines, Gas Turbines,
Waste Incinerators
Description: The SCR technology was developed in Japan in the 1970s and first
implemented at fossil fuel-based power plants in major Japan cities, where
the level of photochemical smog had reached unacceptable levels. Since
then, the technology has gradually spread to the rest of the word where it
has found such wide spread use that it today is the most widely applied
technique for reducing NOx in flue gases and exhaust gases. Selective
catalytic reduction, SCR, is considered the most efficient commercially
proven method of removing nitrogen oxides (NOx ) from off-gases. In the
SCR DeNOx process the nitrogen oxides (NO2 and NO) are reacted with
ammonia (NH3) over a catalyst to form harmless and naturally occurring
nitrogen (N2) and water vapor (H2O):
4 NO + 4 NH3 + O2  4 N2 + 6 H2O
6 NO2 + 8 NH3  7 N2 + 12 H2O
The SCR process basically consists of a catalytic reactor and an ammonia
storage and injection system. The reducing agent can be either liquid,
water-free ammonia under pressure or an aqueous ammonia solution at
atmospheric pressure. A solution of urea can be used as well. In case liquid
ammonia is used, the ammonia is volatilized and subsequently diluted with
air before being injected into the exhaust gas duct.
Chemicals Plants
Each application has its own characteristics and different demands to the
DeNOx catalyst and technology. For example, in the high-dust process for
coal-fired boilers, the SCR reactor is placed immediately after the boiler
and upstream of the electrostatic precipitator. The catalyst is exposed to
heavily dust-laden flue gas and must be resistant to erosion and possible
poisons in the fly ash. The SCR process can, in principle, be applied on any
flue gas containing NOx and oxygen.
Topsoe SCR DENOX Catalysts DNX Series.
Topsoe’s DNX-series of catalysts comprises SCR DENOX catalysts, tailored
to suit a comprehensive range of process requirements.
The DNX catalysts feature: High NO x removal activity, Low pressure drop,
Low SO2 oxidation rate and Excellent durability
DNX catalysts are based on a corrugated, fiber reinforced titanium dioxide
(TiO2) carrier. The carrier is impregnated with the active components:
vanadium pentoxide (V 2O5) and tungsten trioxide (WO 3). The catalyst is
shaped to a monolithic structure with a large number of parallel channels.
Efficiency: The unique catalyst design provides a highly porous structure with a large
surface area and an ensuing large number of active sites. The high and well-
defined porosity is the key to:
- A high NOx removal level with minimum ammonia slip
- A low activity towards SO 2 oxidation, minimizing the risk of fouling
downstream equipment
- A high poison resistance ensuring a long and stable service life
- A substantially lower weight than for conventional plate or extruded
catalysts, allowing a fast response to changes in operation
To ensure optimum performance in any type of operating environment, the
DNX catalysts are available in a wide range of channel sizes and chemical
formulations.
42
Ref./Source: www.haldortopsoe.com
No. 30
Classification of technology: Air Pollution
Name of technology/technique: SNOX process-haldortopsoe
The SNOX process is an innovative process, which removes sulphur and
nitrogen oxides from flue gases, recovers the sulphur oxides as concentrated
sulphuric acid and reduces the nitrogen oxides to free nitrogen. The process
is based on catalytic reactions and does not consume water, absorbents or
chemicals, except for ammonia for the reduction of nitrogen oxides. Further
it does not generate secondary sources of pollution such as wastewater,
slurries, or solids, and it does not release CO2 to the atmosphere. Process
heat and the heat content of the flue gas down to a temperature of 100°C
are recovered and utilized in the boiler to increase steam production.
Contrary to other flue gas cleaning processes the operating costs decrease
with increasing sulphur content in the fuel. Thus, with the SNOx process high-
sulphur fuels can be utilized in an environmentally acceptable and
economically attractive way.
Furthermore, the SNOx process accepts flue gas with high content of SO 3.
Apart from being an efficient and cost effective tool in the abatement of
air pollution, the SNOx process meets future regulations and standards for
solid waste management, water pollution, and resource conservation.
Applications: The process is applicable to flue gases from power stations, industrial and
institutional boilers as well as industrial off-gases containing sulphur and
nitrogen oxides.
Particulates contained in the flue gas are removed in a high efficiently fabric
filter or electrostatic precipitator. The flue gas is heated in a rotary heat
exchanger with flue gas from the SO2 converter. In the catalytic DENOX
reactor the nitrogen oxides in the flue gas are reduced selectively with
ammonia to free nitrogen. In the SO2 converter the sulphur dioxide is
oxidized catalytically to sulphur trioxide, which is recovered in the WSA
condenser as concentrated sulphuric acid. Ambient air preheated in the
WSA condenser is used as combustion air for the boiler.
The SNOx plant is fully automat zed and can be operated from the main
control room of a power plant without requiring additional manpower. There
is no hold-up of liquids or solids and response to variations in boiler load is
very fast. The process is adaptable to new or retrofit installations.
All equipment, apart from the WSA condenser, is made of carbon steel or
low alloy steel. The proprietary WSA condenser is in principle an air-cooled
multi-tube falling-film condenser with tubes of glass whereas other parts
in contact with the acid are lined with acid proof bricks or coated with acid
proof polymers. A SNOX plant has only few moving parts, resulting in low
maintenance costs and high on-stream availability.
95% of the sulphur contained in the flue gas is recovered as concentrated
sulphuric acid of commercial grade.
95% of the nitrogen oxides in the flue gas is reduced to free nitrogen.
Fly ash and trace metals in the flue gas are almost quantitatively
removed.
No waste products or wastewater is produced.
Apart from ammonia, no absorbents or auxiliary chemicals are used in the
process.
43
The heat content of the flue gas is utilized down to 100 °C and, together
with the heat of sulphuric acid formation, it is used for increased air preheat
and steam production.
The ammonia slip and most carbonaceous combustibles in the flue gas are
oxidized completely.
The volume of DENOX catalyst required for the denitrification of the flue
gas is substantially smaller than for an SCR process or an SCR process in
combination with other flue gas desulphurization processes.
The process is fully automated, the plant contains only few moving parts,
and there is no circulation of slurries or solids.
The operating costs decrease with increasing sulphur content in the flue gas.
Ref./Source: www.haldortopsoe.com
3..4 Conclusions
The design of the boiler, internal combustion engine, or gas turbine has a major
effect on the operation. NOx formation tends to increase with an increase in boiler capacity,
because larger boilers tend to have more intense combustion with higher combustion
temperatures and longer residence time for flue gases. The same appears to be true for
engines and turbines.
Different fuels require different combustion, abatement and control techniques.
For example different coals show a great variability in the content of volatile components.
The nitrogen content of fuel is important, as are the content of sulfur, lead, mercury and
other contaminants. Ultra-low nitrogen content fuels have been developed and are already
cost competitive. Thus, we can achieve some control of NOx from the lowered concentration
of nitrogen in the fuel without investing in changed burner design.
Tandem application (or use of hybrid control technology) of NOx control techniques
(first SNCR, then SCR in the duct, and then sorption before the ESP have been used to
achieve an overall reduction of 90+% in NOx and 80% in SOx.
Combustion of natural gas and petroleum distillates can be controlled in the
same way as pulverized coal. The major differences between coal and natural gas or oil
are that these better ones: (I) generally are lower in sulfur and ash; (II) usually are lower in
nitrogen; and (III) probably are lower in lead and mercury. Thus, gas and oil do not deactivate
a catalyst used in Selective Catalytic Reduction (SCR) at the same rate that coal or semi-
solid fuels do. The semi-solid petroleum products can actually have higher levels of sulfur,
nitrogen and other impurities than coal. They do not have as much char or ash as coal, but
have more than the lighter distillates.
Most of the NOx control systems are already available commercially available
notably name of the considered technologies have proved to basses performances and a
general applicably to all combustion system.
Please note that abatement and control of NOx from nitric acid manufacturing and
“pickling”baths differs from abatement and control at combustion sources. Combustion
sources all have NOx in a large flow of flue gas, while nitric acid manufacturing plants and
pickling baths try to contain the NOx. Wet scrubbers (absorbers) can control NOx emissions
from acid plants and pickling, and can use either alkali in water, water alone, or hydrogen
peroxide as the liquid that captures the NO x. The wet scrubber operates by liquid flowing
downward by gravity through a packing medium, opposed by an upward flow of gas. Scrubbers
operate on the interchange of substances between gas and liquid. This requires that the
height of the absorber, type of packing, liquid flow, liquid properties, gas properties, and gas
flow should collectively cause a scrubber to have the desired control efficiency.
44
3..5 Refere
ences
1. Nitrogen Oxides: Impacts on Public Health and the Environment, EPA 452/R-97-002.
2. Selective Catalytic Reduction Control of NOx Emissions, SCR Committee of Institute of Clean Air Companies,
November 1997.
3. Nitrogen Oxides Control Technology Fact Book, Leslie L. Sloss, Noyes Data Corp., 1992.
4. NOx Control Technology Data, EPA 600/2-91-029.
5. Bauer F., Energy Engineering, 91 (1994) 17.
6. Alternate Control Techniques Document - NOx Emissions from Cement, Manufacturing EPA-453/R-94-004.
7. The Economic Feasibility of using Hydrogen Peroxide for the Ehanced Oxidation And Removal of Nitrogen
Oxides from Coal-Fired Power Plant Flue Gases, Hatwood J., Cooper C., AWMA Journal, March 1998.
8. Simultaneous SO2, SO3, and NOx Removal by Commercial Application of the EBA Process, Hirano S., Aoki S.,
Izutsu M, and Yuki Y., EPRI-DOE-EPA Combined Utility Air Pollution Control Symposium: The MEGA Symposium,
9. Update on SNAP Technology for Simultaneous SOx and NOx Removal, Felsvang K., Boscak V., Iversen
S., Anderson P., EPRI-DOE-EPA Combined Utility Air Pollution Control Symposium: The MEGA Symposium,
10. Iwamoto, M. and Hamada, H., Catal. Today, 10 (1991) 57.
11. Heck R.M. and Farrauto R.J., Catalytic air pollution control: commercial technologies, van Nostrand Reinhold,
New York, 1995.
12. Zwinkels, M., Jaras, S., Menon, P., and Griffin, T., Catal. Rev-Sci. Eng. 35(1993) 319.
13. Li, Y. and Armor, J.N., J.Catal., 150 (1994) 376.
14. Li, Y., Battavio, P.J. and Armor, J.N. (1993) J. Catal., 1993, 142, 561.
15. Alternative Control Techniques Document - NOx Emissions from Stationary Reciprocating Internal Combustion
Engines, EPA 453/R-93-032.
Engines. EPA-453/R-93-032, July 1993.
17. Chess K., Yao S., Russell A. and Hsu H., Journal of the Air & Waste Management Association, 45 (1995)
627.
18. Anonimous, Oil & Gas Journal, 92 (1994) 134.
19. Manning M., Pipeline & Gas Journal, 222 (1995) 26.
Engines. EPA-453/R-93-032, July 1993.
21. Bartok, W., and Sarofim, A.F., Fossil Fuel Combustion, John Wiley & Sons, New York, 1991
22. Kuehn S.E., Power Engineering, 98 (1994) 23-27.
23. Advanced Reburning for SIP Call NOx Control, EPRI-DOE-EPA Combined Utility Air Pollution Control Symposium:
The MEGA Symposium, Atlanta, August 1999.
24. States’ Report on Nitrogen Oxides Reduction Technology Options for Application by the Ozone Transport
Assessment Group, OTAG, 1996.
25. Alternative Control Techniques - Nitric Acid and Adipic Acid Manufacturing Plants EPA 450/3-91-026.
45
4 SOx Abatement Te
echnologies
Sulfur oxides include sulfur dioxide (SO 2), sulfur trioxide (SO3)
SO2 is a colorless gas, which is moderately soluble in water and aqueous liquid.
The major source of sulfur dioxide is combustion of fossil fuels for generation of electric
power. It accounts for 85% of the sulfur dioxide. Industrial processes such as nonferrous
metal smelting contributes for about 8% to SO 2 emissions and transportation for about 7
%. Once released to the atmosphere, SO 2 reacts slowly to form H2SO3 and H2SO4, inorganic
sulfate compounds, and organic sulfate compounds. Some of the SO 2 is oxidized to SO3
at high temperature. Sulfur trioxide remains in the vapor state while the combustion gases
are very hot. As the gases cool, most of the sulfur trioxide, which is extremely hygroscopic
reaction with water to form sulfuric acid. Sulfuric acid vapor in moderate concentrations (2
to 8 ppm) is very beneficial to electrostatic precipitators because it adsorb particle surfaces
and creates a moderate resistively. High concentrations of H 2SO4 can be detrimental to
precipitator performances. High sulfuric acid levels can also cause significant corrosion
problems for precipitators, fabric filters, and other control devices. The temperature of flue
gases should be kept well above the dew point for sulfuric acid to prevent condensation on
ductwork surfaces and components in the air pollution control system. Sulfur oxides can
also be released from chemical reactors plants that manufacture batteries and sulfuric acid
plants. The sulfur in the fuel or waste being fired enters the combustion process in a variety
of chemical forms including but not limited to inorganic sulfates, organic sulfur compounds,
and pyrite. A small fraction of the fuel or waste sulfur (usually less than five percent) remains
in the bottom ash leaving the combustion processes. The remaining 95+ percent is converted
to sulfur dioxide, which remains in the gaseous form throughout the combustion system. A
small fraction of the sulfur dioxide generated in the combustion zone is oxidized further to
form sulfur trioxide. The reaction mechanisms that could contribute to the formation of this
pollutant are not entirely known; however, they probably include the following:
 Free radical reaction of SO2 with atomic oxygen in the high temperature zones.
 Catalytic oxidation of SO2 on the surfaces of particles entrained in the gas stream.
 Thermal reactions between SO 2 and other inorganic gases generated during
combustion.
The concentration of sulfur trioxide generated during combustion varies widely

from unit to unit; however, sulfur trioxide concentrations are generally related directly to
the concentration of sulfur in the fuel and the concentration of oxygen in the combustion
zone. The sulfur trioxide concentrations are usually 0.5 to 2 percent of the sulfur dioxide
concentration. Sulfur trioxide quickly converts to sulfuric acid upon cooling in the gas stream
or atmosphere.
47
SOX ABATEMENT TECHNOLOGIES
4..1 Contro
ol of SOx and H2SO4 Emission
Air pollution control systems for SO2 removal are large and sophisticated. Sulfur
dioxide is controlled by three different techniques: absorption, adsorption, and the use
of low-sulfur fuels. The control systems used for SO2 are usually not designed to remove
H2SO4. The sulfuric acid concentrations are usually below the levels where it is economically
feasible or environmentally necessary to install control systems. Table 4.1 shows the list
of desulfurization process and Table 4.2 shows the simplified desulfurization process for
developing countries.
Table 4.1: List of desulfurization processes
Wet Type Desulfurization process Absorbent By-product (treatment)

Limestone (line) gypsum Limestone Gypsum (recovery) and
sludge (disposal)
Indirect limestone (line) gypsum Soda, ammonia and Gypsum (recovery)
process (double alkali process) aluminum sulfate
Valuable by-product recovery Caustic soda, (Recovery) Sodium
processes: soda absorption, magnesium and sulfite,sulfur/sulfuric acid
magnesium absorption process ammonia and ammonia sulfate
Waste solution discharge process: Caustic soda and (Disposal)
soda absorption process and magnesium hydroxide
Sodium sulfate and
magnesium
magnesium
Semi-dry type Spray drier process Slaked lime and hot
water curing
Dry type Lime process: Slaked (Disposal or lard
(adsorption) reclamation) Calcium
Intra-furnace flue blow-in process sulfite and gypsum
Activated charcoal process, activated Activated charcoal Sulfuric acid
charcoal mobilized bred.
Sulfur and liquefied SO2)
Electronic radiation process Ammonium sulfate
Fuel Coal preparation
modification
Coal cleaning
Coal briquette including SOx absorbent
Table 4.2: Simplified desulfurization process for developing countries*
1. Fuel modification
Coal preparation
Coal cleaning
Coal briquette including SO x absorbent
2. Fluidized bed combustion
Circulating fluidized bed combustion (CFBC)
Internally circulating fluidized bed boiler (ICFB)
3. Simplified flue gas desulfurization process

Semi-dry type
Spray dryer type
Simplified limestone-gypsum type.
*Advantages: Cost-effective for both initial and operating; easy to operate; 70-80% of SOx removal efficiency
48
4..2 Absorption Te
echniques
Absorption processes use the solubility of sulfur dioxide in aqueous solutions
to remove it from the gas stream. Once sulfur dioxide has dissolved in solution to form
sulfurous acid (H2SO 3), it reacts with oxidizers to form inorganic sulfites (SO 32-) and sulfates
(SO 42-). This process prevents the dissolved sulfur dioxide from diffusing out of solution and
being re-emitted. The most common type of sulfur dioxide absorber is the limestone-wet
scrubber. (Figure 4.1). Limestone is the alkali most often used to react with the dissolved
sulfur dioxide. Limestone slurry is sprayed into the sulfur dioxide-containing gas stream.
The chemical reactions in the recirculating limestone slurry and reaction products must be
carefully controlled in order to maintain the desired sulfur dioxide removal efficiency and to
prevent operating problems. Wet scrubbers used for sulfur dioxide control usually operate
at liquid pH levels between 5 to 9 to maintain high efficiency removal. Typical removal
efficiencies for sulfur dioxide in wet scrubbers range from 80 to 95%. Limestone gypsum
process is used most commonly for treating a great volume of gas from utility boilers, etc. to
cool flue gas by water spray. A prescrubber can be used to dust remove. Gas is then treated
with limestone slurry in a subrequent scrubber. In this configuration 85% to 95% of SO2 is
removed (reaction 1 and 2). Calcium sulfite generated by reaction is oxidized into gypsum by
air bubbling (reaction 3).
1. CaO + SO2 = CaSO3

2. CaCO3 + SO2 = CaSO3 + CO2
3. CaSO3 + ½ O2 + 2 H2O = CaSO4 2H2O
Gypsum is separated from the solution with a thickener or centrifuge.
Mist
Eliminator
City Water
Recirculation Slurry
Fan
Flue
Gas
Absorber Alkali
Storage
Tank
Limestone Slurry
(Powder)
Pump
Lime or
Recirculation
Purge
Tank
Stream Feeder
eder
Pump Clarifier
Slurry Pump
Mixing
Disposal
Underflow
Solid to
Vacuum Tank
Filter Pump
Pump
Figure 4.1: Scheme of a limestone wet scrubber system (adapted from ref 1)
49
Spray towers scrubbers have the best design for sulfur dioxide removal. They
have a spray mechanism for introducing the slurry into the gas stream. Also, their simple,
open design presents fewer opportunities for the alkaline slurry to plug parts. The residence
time is also adequate for sulfur dioxide to be absorbed into the slurry droplets. Venturis
scrubbers are not a good choice in this situation because the residence time is too short. In
sulfur dioxide removal, there must be adequate contact between the pollutant gas and the
alkaline slurry for at least a minimal length of time. While Venturi scrubbers can be used to
remove both particulate and gaseous pollutants, they are primarily designed to maximize the
collection of particles by creating a large difference in velocity between particles and liquid
droplets in the gas stream. Venturi scrubbers also have large pressure drops, so they are
more expensive to operate than spray towers. Impingement plate scrubbers are not good
candidates in this situation because the alkaline slurry would plug the small holes in the
impingement plates.
The wet scrubber (absorber) vessels do not efficiently remove particulate matter
smaller than approximately 5 micrometers. However, as in the case with low-efficiency
particulate wet scrubbers, the particulate removal efficiency increases rapidly with particle
size above 5 micrometers. Usually, a moderate-to-high efficiency particulate control system is
used upstream from the sulfur dioxide absorber to reduce the particulate matter emissions
in the less than 3 micrometer size range. These upstream collectors also reduce the
quantity of particulate matter that is captured in the absorber. The evaporation of water that
occurs in wet scrubber vessels can keep gas temperatures relatively cold, in the range of
43 to 60 oC. These gas temperatures are well below the typical operating temperatures of
other air pollution control systems used on sources that generate sulfur dioxide emissions.
Another type of absorption system is called a spray atomizer dry scrubber, which belongs to
a group of scrubbers called spray-dryer-type dry scrubbers (Figure 4.2). In this case, alkaline
slurry is sprayed into the hot gas stream at a point upstream from the particulate control
device. As the slurry droplets are evaporating, sulfur dioxide absorbs into the droplet and
reacts with the dissolved and suspended alkaline material. Large spray dryer chambers are
used to ensure that all of the slurry droplets evaporate to dryness prior to going to a high
efficiency particulate control system. The term “dry scrubber” refers to the condition of the
dried particles approaching the particulate control system. Fabric filters or electrostatic
precipitators are often used for high efficiency particulate control. Spray-dryer-type absorption
systems have efficiencies that are similar to those for wet-scrubber-type absorption systems.
These generate a waste stream that is dry and, therefore, easier to handle than the sludge
generated in a wet scrubber. However, the equipment used to atomize the alkaline slurry is
complicated and can require considerably more maintenance than the wet scrubber systems.
Spray-dryer-type absorption systems operate at higher gas temperatures than wet scrubbers
do and are less effective for the removal of other pollutants in the gas stream such as
condensable particulate matter. The choice between a wet-scrubber absorption system and a
spray-dryer absorption system depends primarily on site-specific costs. The options available
for environmentally sound disposal of the waste products are also an important consideration
in selecting the type of system for a specific application. Both types of systems are capable
of providing high efficiency sulfur dioxide removal.
50
Truck Delivery of
Calcium Oxide
Dilution
Water
Atomizer
Lime
Feed Tank
Silo
Silo
Slaking
Water
Lime Slurry
Slaker
Screen Fabric
Grit to Flue Filter
Disposal Gas
from
Boiler
Slurry Induced
Pump Spray Dryer Draft Fan
Calcium Hydroxide Absorber
Slurry Holding Tank Air Pollution
Recycling System
Control System
(optional) Waste Product
Figure 4.2: Spray-dryer-type dry scrubber (adapted from ref 1)
4..3 Adsorption Te
echnique
Sulfur dioxide can be collected by adsorption systems. In this type of control
system, a dry alkaline powder is injected into the gas stream (Figure 4.3). Sulfur dioxide
adsorbs to the surface of the alkaline particles and reacts to form compounds that cannot be
re-emitted to the gas stream. Hydrated lime (calcium hydroxide) is the most commonly used
alkali. However, a variety of alkalis can be used effectively. A dry-injection-type dry scrubber
can be used on smaller systems as opposed to using the larger, more complicated spray-dryer-
type dry scrubber. However, the dry injection system is slightly less efficient, and requires
more alkali per unit of sulfur dioxide (or other acid gas) collected. Accordingly, the waste
disposal requirements and costs are higher for adsorption systems than absorption systems.
Alkali
Storage
Tank
Note: flue gas recycle stream
and heat not shown
Feeder
Blower
Acid
Gas Particulate
Control Device
Induced
Combustion Heat
Draft Fan
Process Exchanger
Recycling System
(optional) Solid Residue
Figure 4.3: A flowchart for a dry-injection-type dry scrubber (adsorber) (adapted from ref 1)
51
4..4 Altern
native Fuels
Other techniques used for limiting the emissions of sulfur dioxide are simply to
switch to fuels that have less sulfur or to convert to synthetic (processed) fuels that have
low sulfur levels. The sulfur dioxide emission rate is directly related to the sulfur levels in
coal, oil, and synthetic fuels. However, not all boilers can use these types of fuels. Each type
of boiler has a number of very specific and important fuel characteristic requirements and
not all low sulfur fuels meet these fuel-burning characteristics.
4..5 Implemented or Commercial Te

echnologies
No. 1
Classification of technology: Air pollution control
Name of technology/technique: Flue gas desulfurization (FGD)
Application: Processing of SOx, NOx and dust discharged from Coal Burning Boilers.
Description: Mitsubishi gas chemical to adapted FGD to reduce discharge of SOx, NOx and
dust. Flue gas desulfurization facilities, exhaust gas denitrizer and exhaust
gas dust collector (bag filter) were installed in line with the installation of
the private coal burning power generating plant.
1. Flue gas desulfurization facilities
SO2 + Mg (OH)2  MgSO3 + H2O
MgSO3 + ½ O2  MgSO4
High desulfurization is realized compared with the lime gypsum method.
Extended periods of continuous operation are possible.
2. Exhaust gas denitrizer.
4NO + 4 NH3 + O2  4N2 + 6H2O
2NO2 + 4 NH3 + O2  3N2 + 6H2O
Dry type ammonia catalytic reduction method was adopted because it show
high level of reliability and safety, reaching some at the time high conversion
efficiency.
(3) Exhaust gas dust collector.
The bag filter system was used since in the case of coal burning boilers, the
electric resistance of fly ash in the exhaust gas is high and can cause the
reverse electric dissociation leading to low dust-collecting efficiency.
Advantages: Rate of removal: SO2 = 90%, NOx = 70%, Dust = 99%.
Implementing company: Mitsubishi Gas Chemical Co., Ltd. Yokkaichi Plant
Ref./Source Sources. www.icett.or.jp/te
No. 2
Name of technology/technique: Activated carbon
Application: Reduction of exhaust SO2.
Description: Reduction of the amount of SO2 discharged, by installing the flue gas
desulfurization equipment in the factory, Nippon steel corporation
installed a dry type flue gas desulfurization equipment with activated
carbon. This system that does not require wastewater processing
and is suitable for processing large quantities of exhaust gas.
This process is based on adsorption/desorption reactions on activated carbon.
(I) Adsorption SO2 + H2O + ½ O2  H2SO4
SO2 is adsorbed on the surface of the activated carbon and is oxidized to
form sulfuric acid.
52
(II) H2SO4 + 1/2 C  SO2 + CO2 + H2O

Desorption of SO2 occurs after heating to provote decomposition SO 2
becomes one of the reagents for ammonium sulfate synthesis.
Advantages: Amount of gas processed 900,000 mN 3/h. Desulfurization efficiency over
95%, Adsorption column 450,000 mN 3/h x 2, Cross flow moving bed
system, space velocity 800 h -1, Desorption column 15 T/H x 1, 350 oC
Indirect heating moving bed type heating equipment COG combustion and
combustion gas recirculating system. Byproducts: sulfuric acid.
Implementing company: Nippon Steel Corporation, Nagoya Works
Ref./Sources: www.icett.or.jp
No. 3
Name of technology/technique: Magnesium hydroxide method wet type flue gas
desulfurization
Application: Coal burning boiler/Reduction of SO x in boiler exhausts gas.
Description: The compact and low-pressure loss magnesium hydroxide method with
high desulfurization and dust removal performance was introduced as the
flue gas desulfurization measures when installing the coal burning thermal
power station.
Mechanism of desulfurization reaction
1. Exhaust gas containing SO 2 comes into contact with the absorption
fluid in the scrubber and, in addition to being humidified and cooled until
saturated, SO2 and dust are removed.
2. Air is blown into the bottom part of the scrubber, where magnesium sulfite
of low solubility is oxidized to the magnesium sulfate of high solubility.
SO2 + Mg(OH)2  MgSO3  MgSO4
3. Waste water from the desulfurization process is discharged after treatment
and sludge separation pH of fluid absorbed; 5.5 - 6.0, counter flow contact
spray type with extremely low-pressure loss suitable for removing dust with
grain diameter of 20~30 microns.
Advantages: 1. DeNOx: (Inlet) 240 - 260 ppm  (Outlet) 20 ppm or below.
2. Dust removal: (Inlet) 30 - 40 mg/Nm3  (Outlet) 10 mg/Nm3 or below
Implementing company: Nippon Steel Corporation yard, Tokai Co-operative Power Company
Inc.
Ref./Sources: www.icett.or.jp
No. 4
Classification of technology: Air Pollution Control
Name of technology/technique: Scrubbers
Application: Paper/Pulp- Dust Removal and Desulfurization using Scrubbers
Description: Scrubbers are used with the objective of treating exhaust gas of a oil - fuel
boiler. The exhausted gasses have been previously treated in an electric
dust-precipitator. the gasses enter the main scrubber unit in a tangential
direction, rising as it creates a swirling motion. At the same time, liquid is
sprayed out radially from the spray nozzles in the center. The net effect is
that the swirling motion of the gas and the radial motion of the droplets
collect dust. The main reaction taking place in the absorption process:
2NaOH + SO2  Na2SO3 + H2O
The side reaction occurs:
Na2SO3 + SO2 + H2O  2 NaHSO3
53
The main specifications for the dust-removal scrubber are as follows:

1. Treated gas: 488,000 m/h, at 150 °C
2. Dust content at loading port: 0.35 g/Nm3
3. Dust content at discharge port: 0.12 g/Nm3
4. General dimensions Body diameter: 6,800 mm, Total height: 50,000 mm
Implementing company: Oji Paper Co., Ltd., Kasugai Plant
Ref./Source: www.icett.or.jp
No. 5
Name of technology/technique: Absorption
Application: Food industry, Reduction of SO2 and Offensive Odors from Process Exhaust
Gas
Description: SO2 emissions could be reduced from 250ppm to below under 15ppm,
dust from 200ppm to below and the problem of bad smell was significantly
minimized. 60ppm. The reaction adopted for SO2 removal was:
SO2 + 2NaOH + NaOCl  Na2SO4 + NaCl + H2O.
Deodorization, desulfurization and reduction of dust are carried out by
passing the exhausted gas through a sequence of a cooling tower, an alkali
washing tower and oxidizing tower.
Implementing company: Shikishima Starch Co., Ltd., Suzuka Factory
Ref/Source: www.icett.or.jp
No. 6
Name of technology/technique: Alkali scrubber (absorption tower)
Application: Chemical; Petrochemical industry/Reduction of SO x and dust in Process
Exhaust Gas
Description: The tecnology has been designed to neutralize SO x and capture dust and
steam vapor which are generated in the dissolving process of titanium ore
with sulfuric acid. The process use large amount of alkaline solution and
sea water for the following reactions:
SO3 + 2NaOH  Na2SO4 + H2O
SO2 + 2NaOH  Na2SO3 + H2O
Na2SO3 + 1/2 O2  Na2SO4
The amounts of discharged steam, SO x and dust were reduced by passing
the exhaust gas through a mist catcher, a cooler and an alkali scrubber. In
the scrubber, large amount of sea water are sprayed from the top of the
column counter-currently to the gas, and NaOH solution is sprayed from
nozzles located in several places at the middle of the column. Drain from
the scrubber is discharged after pH adjustment and passing through a
drain filter system.
Implementing company: Ishihara Sangyo Co., Ltd. Yokkaichi Factory
Ref./Source: www.icett.or.jp
No. 7
Name of technology/technique: Simplified limestone/lime gypsum process
Description: This is the simplified wet-type desulfurization system, realizing reduced
investment cost by simplifying the conventional limestone/lime gypsum
process. Kawasaki open spray tower is adopted for the absorber with high
performance spray nozzles and simple internal structures. Gypsum treatment
54
section is also simplified by using continuous Gypsum Centrifuge.

1. Absorber Tower Section
SO2 + H2O + (1/2)O2  H2SO4
2. Absorber Sump Section
CaCO3 + H2SO4 + H2O  CaSO4 2H2O + CO2 (g)
or
Ca(OH)2 + H2SO4  CaSO4 2H2O
Advantages: Simplified configuration ensures low installation and operation costs more
over, the adopted equipment and the selected absorbents are rather
inexpensive.
CaCO3 or Ca (OH)2 as absorbents.
Process by-products (mixtures of gypsum and ash), can be utilized as
retardants for cement manufacturing.
- DeSOx Performance 70 - 95%
- By-Product Gypsum
- Fuel Coal/Oil
- Sulfur Content 0 - 4wt% in coal
- Gas Volume50 km N/H3
This system has been adopted for simplified flue gas desulfurization
systems in China.
Ref./Source: Kawasaki Heavy Industries Ltd., www.khi.co.jp/index_.html
No. 8
Name of technology/technique: Limestone-gypsum flue gas desulfurization system
Application: Boiler for the utility thermal power plant, boiler for industry-owned thermal
power plant.
This process has been adopted more than any other process in the world.
The reason is the facts. that limestone is a very cheap absorbent and
this process gives high desulfurization efficiency. Moreover, for the gypsum
as by-product has a commercial value since it can be used production of
plasterboard or as a retardant in the manufacture of cement.
Process Description: SO2 gas in the flue gas is absorbed by limestone and is oxidized by
reacting with the air accordingly to the following reaction.
CaCO3 + SO2 + (1/2) O2 + 2H2O  CaSO4 2H2O + CO2
The by-product gypsum is recovered by centrifugation.
Advantages: (I) High efficiencies can be achieved.
Desulfurization efficiency: more than 96%
Dust removal efficiency: more than 90%
COD in wastewater: less than 10 mg/l.
(II) Limestone is less expensive than the other absorbents and gypsum has
a commercial value.
(III) It is necessary to provide the countermeasures against scaling and
build-up of solid in slurry liquid.
(IV) Spray tower is adopted as the Absorber, because its structure is simple
and has no scaling trouble.
Treated gas flow rate: 2,400,000 m 3N/h
Inlet SOx concentration: 900 ppm
Desulfurization efficiency: 96%
Dust removal efficiency: 92%
COD in waste water: 5 mg/l
Ref./Source: Ishikawajima-Harima Heavy Industries Co., Ltd., www.ihi.co.jp.
55
No. 9
Name of technology/technique: Mitsui-ge type flue gas SO2 removal system
Limestone or slaked lime is used as absorbent and gypsum is produced
as the by-product. Mitsui Mining delivered many systems for large-scale
thermal power plants with coal-fired boilers.
Description: In case of coal-fired thermal power plants, the fly ash and the acid gasses
can give undesirable effects on the quality of gypsum produced and can
reduce SO2 removal efficiency. Therefore, treatment method has to be
determined depending on the kind of coal used and the performance of EP.
(a) Soot mixing method. This method has been developed as the most
economical process to enable simultaneous dust and SO2 removal. Using
small amount of Na catalyst, Mitsui Mining’s achieved stable performance
of SO2 removal.
(b) Soot separating method
This method has been developed for various kinds of overseas coals- fired
thermal power plants. Pre-scrubber are installed in this configuration to
remove the impurities in flue gas. Stable performance of SO2 removal and
high quality of gypsum are achieved.
(c) Oxidizing methods
Oxidation inside of the absorber has been developed with patent of G.E.
(U.S.A.), and is able to recover high quality gypsum.
Performance: I) SO2 removal efficiency: More than 95%
II) Dust removal efficiency: Less than 15mg/m3N at outlet (in case of coal
fired (Thermal power plants)
III) Pressure loss: Less than 100 mmH 2O as pressure loss of spray type
absorber
IV) By product: High quality gypsum.
Characteristics: I) This system uses the reliable spray type absorber with high performance.
In this absorber gas pressure loss is very low and the big capacity of gas
treatment with one tower is completely performed. Moreover, this system
has been improved for cutting cost and saving space, boost up fan for SO2
removal being excluded and served with IDF.
II) Against the fluctuations of gas volume, Mitsui Mining’s controlling system
can achieve the constantly stable performance.
III) The by-product of gypsum is of good quality, which can be used, as
material of plaster board and cement.
Ref./Source: MITSUI MINING CO., LTD
No. 10
Name of technology/technique: Hitachi wet limestone-gypsum FGD system
Description: Wet Limestone-Gypsum Flue Gas Desulphurization (FGD) System
removes SO2 (sulphur dioxide) contained in the flue gas in contact
with limestone slurry droplets as an absorbent when the flue gas
containing SO2 passes through the absorber. Limestone slurry absorbs
SO2 then it is oxidized by air at the lower part of absorber to produce
calcium sulphate which is extracted from the absorber as gypsum
slurry and finally dewatered and reused in the form of gypsum powder.
Chemical Reaction: CaCO3 + SO2 + 2H2O + (1/2)O2  CaSO4 . 2H2O + CO2
Advantages: I) SO2 removal efficiency higher than 90% can be achieved.
II) By-product gypsum can be reused as material of cement or wall board.
56
III) Limestone, which is supplied stably, is used as an absorbent.

IV) Single absorber tower, which has integrated function of prescrubbing,
absorption and oxidation, is adopted. Moreover it also removes particulate
in the flue gas with high removal efficiency.
Ref./Source: Babcock-Hitachi K.K.
No. 11
Name of technology/technique: Blue sky 2000 process
Description: This plant absorbs efficiently SO 2 gas in the flue gas of oil or coal burning
boiler, glass melting furnace, kiln, etc. by calcium slurry with a little amount
of HCOOH. Moreover the dust in the flue gas is spontaneously removed.
The purity of gypsum as by-product is high and the gypsum can be sold for
cement and wall-board.
Advantages: 1. SO2 absorption efficiency: over than 95%
2. Dust conc. at absorber outlet: less than 0.03 g/m 3N
3. Stoichiometric ratio of CaCO 3: 1 - 3% excess
4. Gypsum purity: over than 90%
5. Pressure drop in absorber: less than 100 mmH2O
6. Purge liquid amount: less than 1/10 of conventional process
This process has the following characteristics by the addition of HCOOH.
1. High SO2 removal ratio even in a low pH range of 4.2 - 5.2
2. Preclusion of scaling and plugging
3. High stoichiometric utilization of the absorbent
4. Low liquid to gas ratio (L/G) and consequently lower energy consumption
for washing fluid circulation.
5. High SO2 absorption over the boiler load changes
6. Simple process, so small installation area
7. High Cl concentration in washing fluid, so little amount of purge liquor
Principle: The free HCOOH spontaneously dissolves the added calcium carbonate
intensively to form calcium formate, which is highly soluble in water. The
washing fluid then contains calcium formate in dissociated form and
provides a large amount of calcium ions for SO 2 absorption from the flue
gas. Because of this, SO2 absorption ratio is enhanced very much. The
details of each section are as follows.
1. Absorption
The flue gas is contacted with the washing fluid in a cocurrent/countercurrent
two-stage absorber. SO2 is absorbed from the flue gas and reacts to form
bisulfite ions.
SO + H O  HSO - + H+
2 2 3
Formate ions in solution react with the H + formed during SO2 absorption.
H+ + HCOO-  HCOOH
Thus, an intensive SO2 absorption occurs in the pH range 4.2 - 5.2, the pH
range that insures the formation of bisulfate, the only water-soluble form of
calcium and sulfur.
2. Oxidation
At the absorber pH of 4.2 - 5.2, oxidation occurs easily without the need for
an acidifying step. Dissolved oxygen in the washing fluid from boiler excess
air and injected air in the absorber sump react to form sulfate.
2HSO - + O  2H+ + 2SO 2-
3 2 4
Calcium ions present in solution combine to produce gypsum.
Ca2+ + SO42- + 2H2O  CaSO4. 2H2O
57
3. Limestone addition
Limestone slurry is added to the absorber sump to replace the calcium lost
with the gypsum. At the low pH, limestone dissociates to produce a washing
fluid with dissolved calcium several orders of magnitude higher than
conventional process.
CaCO3 + H +  Ca 2+ + OH- + CO (g)
2
Ref./Source: TSUKISHIMA KIKAI CO., LTD.
No. 12
Name of technology/technique: The flue gas treatment system of the municipal solid waste
incineration plant
Application: This device is designed mainly for the treatment of exhaust gas generated
by the incineration of municipal solid waste. However, it can also be used
to process gases produced from various types of furnace.
Description: The exhaust gas generated from the incineration of municipal solid waste
contains harmful substances that cause air pollution, such as dust,
acid gases (SOx, HCl, NOx) and heavy metal particles (Pb, Zn, Cu, etc.).
This device removes wide range of these harmful substances with high
efficiency. The exhaust gas from the municipal solid waste incinerator is
cooled to a temperature of 180 to 200 °C by the gas cooler, and then
enters the mixing chamber located at the inlet of the bag filter. Filtration
agency and hydrated lime transported by air from those silos are injected
into the mixing chamber. When mixed with the exhaust gas, the hydrated
lime reacts with hydrogen chloride and sulphur oxides, forming solid matter,
which is collected by the bag filter.
These chemical reactions are as follows:
2HCl + Ca(OH) 2  CaCl2 + 2H2O
SOx + Ca(OH)2  CaSOx + H2O
The surface of the bag filter is also coated with filtration agency and hydrated
lime, and this coating effectively collects dust and heavy metal particles.
Advantages: 1. The device uses dry-type processing which does not affect the exhaust
gas temperature directly. Therefore, no corrosion or dust adhesion trouble
occurs in the equipment.
2. The filtering effect of the filtration agency and hydrated lime prevents
clogging of the filter cloth, providing stable plant operation without an
increase in the filtering pressure loss.
3. The filtering effect of the filtration agency and hydrated lime removes
dust and microscopic heavy metal particles effectively.
Processing capacity
1. Gas volume: no limitation
2. Gas temperature: 160 to 220 °C
Ref./Source KURIMOTO, LTD.
No. 13
Name of technology/technique: Mitsui-bf dry type desox/denox process/mitsui mining
co., Ltd.
Description: Mitsui Mining successfully develops a dry-process, simultaneous
desulfurization and denitrification technology for commercial use on an
industrial scale. This process is applicable for SOx, NOx, dust and toxic trace
elements removal from boiler, furnace and chemical plant flue gases.
58
Applications: - Coal-fired power station - Industrial boilers - Chemical plant

- Petroleum refineries (such as FCC) - Smelting works - Sintering furnaces
- Incinerators used for trash, refuse, waste oil and sludge
- Glass furnaces - Sulfuric acid plant tail gas
Description: The Mitsui-BF System is a three-part process: adsorption, desorption,
and optional by-product recovery. The system is capable of simultaneous
desulfurization and denitrification. Alternatively, it can perform either DeSOx
or optionally DeNOx functions.
Adsorption: Flue gas passes through a bed of activated coke moving
downwards in the two-stage adsorber at a constant flow rate. The activated
coke consists of carbon, and has a large, porous inner surface area. In the
first stage, sulfur oxides are largely removed from the gas by a process of
adsorption into the activated coke, where oxidation occurs, yielding H 2SO4
(sulfuric acid) maintained on the inner surfaces at a temperature of 100 to
200 °C. After desulfurization in the first stage, the flue gas passes through
the activated coke bed in the second stage. Here, it works as a catalyst in
the decomposition of NO x to nitrogen (N2) and water (H2O) by the injection
of ammonia gas (NH3) into the activated coke bed. This chemical reaction
occurs at a temperature of 100 to 200 °C. The adsorber, with its moving
activated coke bed, also functions as a particulate remover. Following the
adsorption process, the particulate emissions will not exceed 30mg/Nm 3
when inlet particulate concentrations are kept within 500 mg/Nm 3. As the
activated coke becomes loaded with sulfur oxides (SOx), its adsorption
capacity deteriorates. The SOx-saturated activated coke is then conveyed
by bucket elevators to the desorber, and regenerated at a temperature
of 400 to 500°C. Simultaneously, ammonium sulfate ((NH 4)2SO4) in the
activated coke is decomposed to nitrogen (N2), sulfur dioxide (SO 2) and
water. After cooling, the regenerated activated coke passes over a vibrating
screen to eliminate mechanically and/or chemically degraded material, and
is then recycled back to the adsorber. This ensures that only activated
coke meeting design-size parameters will be reused in the adsorber.
Activated coke fines can be returned to the boiler as fuel. This desorption
sequence optionally incorporates statistical process control, to optimize
the adsorption capability for site-specific applications, as the adsorption
capacity of the activated coke deteriorates in the process.
BY-PRODUCT RECOVERY
In the process of regenerating the activated coke in the desorption unit, SO2-
rich gas is released. This SO2-rich gas (20 to 25% volume in SO2
concentration) can be treated to form elemental sulfur (S) or sulfuric acid
(H2SO4) by standard methods.
Production of Elemental Sulfur
SO2-rich gas is reduced to H2S in a reduction column by using a carbonaceous
reduction agent. The reduced gas is partially oxidized to SO2 by air injected
at the upper portion of the reduction column and a mole ratio of H 2S/
SO2 is maintained at 2.0. Finally, the mixture of H 2S and SO2 is converted
to elemental sulfur in a Claus unit. The carbonyl sulfide (COS), which is
generated secondarily in the reduction column, is hydrolyzed in the Claus
unit, and elemental sulfur is obtained.
Production of Sulfuric Acid
After dust and impurities are removed from the SO2-rich gas, the gas is
oxidized in a converter to form SO3. The SO3 is then absorbed in an absorber
to form 98% sulfuric acid.
59
ACTIVATED COKE
Mitsui Mining produces high-quality activated coke maximizing the efficiency
of the Mitsui-BF process.
Advantages: Dry process
SOx removal efficiency higher than 98%, NOx removal efficiency higher than
80%
- Flexibility Simultaneous DeSOx/DeNOx, or DeSOx-only, DeNOx-only
operation
- Low power consumption - Minimum installation space required
- No waste water generated - Gas reheating not required - High quality by-
product
- Ease of operation - Low maintenance requirements
Ref./Source: Mitsui Mining co., Ltd
No. 14
Name of technology/technique: SOx reduction technology atmospheric fluidized bed
combustion boiler system (AFBC: Atmospheric Fluidized Bed Combustion)
Capacity: SOx removal efficiency more than 90%
Application: Coal-fired power station etc.
Description: When fluidization medium (limestone, sand etc.) placed on the distribution
panel (perforated panel) is supplied with air from beneath, the medium
floats in the air current within a specific range of the air speed, just as in a
state of boiling. The layer of floating medium in this state is referred to as a
fluidized bed. When coarsely crushed coal is continuously supplied into the
fluidization medium, which is heated in the air-heating furnace to the ignition
temperature of coal, the coal spontaneously starts burning. The furnace
is turned off at this point, and while the coal keeps burning, coal supply
volume is controlled so that the temperature of the fluidized bed stays at
760 to 860 °C. For recovering heat, the fluidized bed combustion boiler has
heat exchanger tubes in its fluidized bed and convection section. The use
of limestone as fluidization medium enables in-furnace desulfurization. Flue
gas from the fluidized bed combustion boiler includes various unburned
components, which are collected by the mechanical precipitator and burned
in the after-burner furnace (CBC) to improve combustion efficiency.
Advantages: - In-furnace desulfurization/Fluidized bed combustion boiler can remove
SOx in the furnace while burning coal, using limestone as the fluidization
medium.
- Use of various types of coal/Since the fluidized bed combustion boiler
ensures stable combustion at low temperature, as compared to the
pulverized coal fired boiler, various types of coal can be used.
Ref./Source: The Kansai Electric Power Co., Inc.
4..6 Refere
ences
1. Air Pollution Control Engineering, N. de Nevers, second Edition, 2000, Mc Graw Hill, New York.
1996.
60
5 Vo
olatile Organic Compounds (VOCs)
5..1 Introduction
The majority of anthropogenic volatile Organic Compounds (VOCs) released into

the atmosphere are from transportation sources and industrial processes utilizing solvents
such as surface coating (paints), printing (inks), and petrochemical processing. Notably VOC
compounds are not formed in industrial processes, they are lost.
VOCs are organic compounds that can volatilize and participate in photochemical
reactions when the gas stream is released to the ambient air. Almost all of the organic
compounds used as solvents and as chemical feedstock are VOCs. However, a few organic
compounds, such as methane, are not considered to be VOCs.
5..2 VOC Destru

uction Te
echnology
In order to reduce the quantities of VOCs that are lost as fugitive emissions, it is
necessary to redesign the industrial processes, both form a chemical and an engineering
point of view. End-of-pipe technology (thermal incinerators, catalytic incinerators, liquid and
solids adsorbents, condensers, biodegradation….) must be applied when redesign of the
process is inapplicable or insufficient (1).
5..2.1 Thermal Oxidation
Thermal oxidation occurs by heating the polluted air to elevated temperatures

(700 – 1000 °C). Thermal oxidation is a process whereby most of the VOCs are broken down
and recombined with oxygen to produce water vapor and carbon dioxide. In a thermal oxidizer,
the polluted air stream is heated to gas temperatures several hundred degrees Celsius
above the autoignition temperature of the organic compounds that need to be oxidized.
Due to these very high temperatures, thermal oxidizers have refractory-lined combustion
chambers (also called fume incinerators) (see Figure 5.1), which increase their weight and
size considerably. The efficiency of oxidation and the design of most oxidizers is governed by
the residence time (from a fraction of a second to more than two seconds), the combustion
chamber temperature and the amount of turbulence the air stream sees. Thermal oxidizers
usually provide VOC destruction efficiencies that exceed 95% and often exceed 99%. One
of the main limitations of thermal oxidizers is the large amount of fuel required to heat
the gas stream to the temperature necessary for high-efficiency VOC destruction. Termed
regenerative thermal oxidizers (RTOs) use heat exchanger to recover some of the heat of the
waste gas and to return it to the inlet gas stream. Therefore, these units, require less fuel
to maintain the combustion chamber at the necessary temperature.
61
VOLATILE ORGANIC COMPOUNDS (VOCS)
Waste Gas Inlet

100°C
350°C
700-1000°C
300°C
Refractory-Lined
Combustion Chamber Heat Gas
Exchanger
Figure 5.1: Thermal oxidizer with recuperative heat exchanger (adapted from ref 1)
Thermal oxidizers have the broadest applicability of all the VOC control devices.
They can be used for almost any VOC compound. Thermal oxidizers can also be used for gas
streams having VOC concentrations at the very low concentration range of less than 10 ppm
up to the very high concentrations approaching 10,000 ppm.
Safety constraints impose to use thermal oxidizers for gas streams having VOC
concentrations not exceeding approximately 25% of the lower explosive limit (LEL). This
constrain has been introduced to be able to cope with possible short-term concentration
spike that would exceed the LEL. The 25% LEL limit depends on the actual gas constituents
and usually is in the 10,000 to 20,000 ppm range.
Thermal oxidizers handling VOC materials that contain chlorine, fluorine, or

bromine atoms generate HCl, Cl 2, HF, and HBr as additional reaction products during
oxidation. A gaseous absorber is used as part of the air pollution control system to collect
these contaminants prior to gas stream release to the atmosphere.
5..2.2 Catalytic Oxidation
Due to the presence of a catalyst, oxidation reactions can be performed at

substantially lower temperatures (250-550 °C) than thermal oxidizers (700-1000°C).
Common types of catalysts include noble metals (i.e. platinum and palladium) and ceramic
materials. VOC destruction by catalytic oxidizers usually exceeds 95% and often exceeds
99%. Due to the relatively low gas temperatures in the combustion chamber, there is no
need for a refractory lining to protect the oxidizer shell. This minimizes the overall weight of
catalytic oxidizers and provides an option for mounting the units on roofs close to the point
of VOC generation. This placement can reduce the overall cost of the system by limiting the
distance the VOC-laden stream must be transported in ductwork.
Catalytic oxidizers are also applicable to a wide range of VOC-laden streams;
however, they cannot be used on sources that also generate small quantities of catalyst
poisons. Catalyst poisons are compounds that react chemically in an irreversible manner with
the catalyst. Common catalyst poisons include phosphorus, tin, and zinc. Another potential
operating problem associated with catalytic oxidizers is their vulnerability to chemicals
and/or particulate matter that masks or fouls the surface of the catalyst. (Masking is the
62
IR POLLUTION CONTROL TECHNOLOGIES
reversible reaction of a chemical with the catalyst and fouling is the coating of the catalyst
with a deposited material.) If the conditions are potentially severe, catalytic units are not
installed.
Clean Gas
Burner
(normally off)
Gas Inlet
Tubular Heat
Exchanger
Catalyst Bed
Figure 5.2: Scheme of a catalytic oxidation system (adapted from ref 1)
As with thermal oxidizers, catalytic oxidizers should not exceed 25% of the LEL, a
value that is often equivalent to a VOC concentration of 10,000 to 20,000 ppm.
The catalytic incineration method has become most popular because, in many
case, it is more versatile and economic for the low concentrations of organic emissions (i.e.,
<5,000 vppm).
The actual operating temperature and amount of preheat varies, depending on the
organic molecule, space velocity, composition of feed (i.e., contaminants water vapor, and so
forth), and organic concentration. Typical examples of operating temperatures are given in
Table 5.1. One-way of comparing thermal versus catalytic abatement is to look at the energy
required (air preheat temperature) to obtain quantitative removal of a given hydrocarbon. The
operating temperatures shown in Table 5.1 are well below the corresponding temperatures
necessary to initiate thermal (noncatalytic) oxidation. The catalyst initiates reaction at lower
temperatures. This demonstrates the major advantage of catalyzed processed, which is that
they proceed faster than noncatalytic reactions, allowing lower temperatures for the same
amount of conversion. This translates directly into improved economic for fuel use and less
expensive reactor construction materials, since corrosion is greatly reduced. Selection of
the catalytic material for various organic pollutants has been the subject of many studies.
Because metal oxides, precious metals, and combinations are used both for hydrocarbons
and chlorinated hydrocarbons. As a rule, precious metals (especially platinum and/or
palladium dispersed on carriers) are preferred because of their, resistance to deactivation,
and ability to be regenerated.
63
Table 5.1: Operating temperatures for catalytic abatement of organic compounds (1)
Temperature rise Operating Concentration

Name of constituent Chemical formula 1,000 temperature before treatment
ppm (°C) (°C) (ppm)
Styrene C6H6CHCH2 138 250 310
Acetaldehyde CH3CHO 35 350 240
Benzene C6 H 8 103 210 380
Toluene C6H5CH3 123 210 320
M-xylene C6H5(CH3) 143 210 270
Phenol C6H5OH 101 300 380
Formaldehyde HCHO 17 150 410
Acrolein CH2CHCHO 51 180 500
Acetic acid CH2COOH 26 350 590
Butyric acid C3H7COOH 66 20 370
Acetone CH3COCH3 57 350 410
Methyl ethyl keton CH3COC2H3 74 220 380
Methyl isobutyl keton CH3COC4H8 116 250 270
Ethyl acetate CH3 COOC2H5 68 350 350
Butyl acetate CH3COOC4H9 108 350 480
Methyl alcohol CH3OH 21 150 830
Ethyl alcohol C2H5OH 44 350 550
Isopropyl alchol C3H7OH 64 280 230
Butyl alcohol C4H9OH 84 260 330
Carbon monoxide CO 9 150 4,000
Methyl cellosolve HOCH2CH2OCH3 55 300 110
Ethyl cellosolve HOCH2CH2OC2H5 76 300 80
Buty cellosolve HOCH2CH2OC4H9 118 300 50
5..2.3 Adsorption
Adsorption systems beds are generally used when the gas stream contains
one to three volatile organic compounds, and it is economical to recover and reuse these
compounds, or when a large number of organic compounds at low concentration, and it is
necessary to pre-concentrate these organics prior to thermal or catalytic oxidation.
Figure 5.3 shows the diagram of a multi-bed adsorber system used for collection
and recovery of organic solvent compounds. The VOC-laden gas is often cooled prior to
entry into the adsorption system to improve the effectiveness of adsorption. As the gas
stream passes through the bed, the organic compounds adsorb weakly onto the surfaces
of the adsorbent (high surface area activated carbon, zeolite, or organic polymer). When
the adsorbent is approaching saturation with organic vapor, a bed is isolated from the gas
stream and desorbed. Low-pressure steam or hot N2 is often used to remove the weakly
adsorbed organics. The concentrated stream from the desorption cycle is treated to recover
the organic compounds. After desorption, the adsorption bed is returned to service, and
another bed in the system is isolated and desorbed.
64
Steam
Bed 1
P VOC
To Atmosphere
Cooling Water
Particulate
Filter Bed 2
LEL
VOC
Solvent
-laden
Air
A P T Bed 3
VOC
Steam and Desorbed

Solvents Vapors
Figure 5.3: Multi-bed adsorber system for solvent recovery
An adsorption system used for pre-concentration prior to solvent recovery is shown

in Figure 5.4. The gas stream cointaining the VOC passes through a rotary wheel containing
zeolite or carbon-based adsorbents. Approximately 75-90% of the wheel is in adsorption
service while the remaining portion of the adsorbent passes through an area where the
organics are desorbed into a very small, moderately hot gas stream. The concentrated
organic vapors are then transported to a thermal or catalytic oxidizer for destruction. The
preconcentration step substantially reduces the fuel requirements for the thermal or catalytic
oxidizer.
Purified
Fan Echaust Air
Solvent-laden
Exhaust Air Hot Air
(Desorption Air)
Pre-filter Rotary
Wheel Solvent-laden
Desorption Air
(Concentrated)
Figure 5.4: Preconcentrator – type adsorption system (adapted from ref 1)
Adsorption systems are not recommended for gas streams that contain particulate
matter and/or high moisture concentrations because the particulate matter and moisture
compete with the gaseous pollutants for pore space on the adsorbent material.
The adsorption removal efficiency usually exceeds 95% and is often in the 98%
to 99% range for both solvent recovery and preconcentrator type systems. In both types of
units, the removal efficiency increases with reduced gas temperatures.
65
The suitability of an adsorption system for a particular situation should be

considered on a case-by-case basis. However, as a general guideline, adsorption systems
can be used for organic compounds having a molecular weight of more than 50 and less
than approximately 200. In fact, the low molecular weight organics usually do not adsorb
sufficiently. The high molecular weight compounds adsorb so strongly that is it is difficult to
remove these materials from the adsorbent during the desorption cycle. Adsorption systems
can be used for a wide range of VOC concentrations from less than 10 ppm to approximately
10,000 ppm. The upper concentration limit is due to the potential explosion hazards when
the total VOC concentration exceeds 25% of the LEV.
5..2.4 Condensation, Refrigeration and Cr yogenics
Condensation, refrigeration, and cryogenic systems remove organic vapor by

making them condense on cold surfaces. These cold conditions can be created by passing
cold water through an indirect heat exchanger, by spraying cold liquid into an open chamber
with the gas stream, by using a freon-based refrigerant to create very cold coils, or by
injecting cryogenic gases such as liquid nitrogen into the gas stream. The concentration
of VOCs is reduced to the level equivalent to the vapor pressures of the compounds at
the operating temperature. Condensation and refrigeration systems are usually used on
high concentration, low gas flow rate sources. Typical applications include gasoline loading
terminals and chemical reaction vessels.
The removal efficiencies attainable with this approach depend strongly on the outlet
gas temperature. For cold-water-based condensation systems, the outlet gas temperature is
usually in the 4 to 10°C range, and the VOC removal efficiencies are in the 90 to 99% range
depending on the vapor pressures of the specific compounds. For refrigerant and cryogenic
systems, the removal efficiencies can be considerably above 99% due to the extremely low
vapor pressures of essentially all VOC compounds at the very low operating temperatures of
-56°C to less than -130°C.
Condensation, refrigeration, and cryogenic systems are usually used on gas
streams that contain only VOC compounds. High particulate concentrations are rare in the
types of applications that can usually apply this type of VOC control system. However, if
particulate matter is present, it could accumulate on heat exchange surfaces and reduce
heat transfer efficiency.
5..2.5 Biological Oxidation
VOCs can be removed by forcing them to absorb into an aqueous liquid or moist
media inoculated with microorganisms that consume the dissolved and/or adsorbed organic
compounds. The control systems usually consist of an irrigated packed bed that hosts the
microorganisms (biofilters). A presaturator is often placed ahead of the biological system to
increase the gas stream relative humidity to more than 95%. The gas stream temperatures
are maintained at less than approximately 40 °C to avoid harming the organisms and to
prevent excessive moisture loss from the media.
Biological oxidation systems are used primarily for very low concentration VOC-
laden streams. The VOC inlet concentrations are often less than 500 ppm and sometimes
less than 100 ppm. The overall VOC destruction efficiencies are often above 95%.
Biological oxidation systems are used for a wide variety of organic compounds;
however, there are certain materials that are toxic to the organisms. In these cases, an
alternative type of VOC control system is needed.
66
5..2.6 Gen
neral Appliicability of VOC Contro
ol Systems
Limiting the consideration of the VOC’s control systems to gas streams having
total VOC concentrations less than approximately 25% of the LEL, it is possible to arbitrarily
divide the control system applicability into two separate groups: low VOC concentration (less
than 500 ppm) and high VOC concentration. It should be noted that there is no generally
accepted distinction between low and high concentration. The low concentration group can
be further divided into three main categories depending on the number of different VOC
compounds in the gas stream and the value of recovering these compounds for re-use
(Figure 5.5 ).
If there are a large number of separate VOC compounds, it is usually not
economically feasible to recover and reuse the captured organics. In this case, thermal or
catalytic oxidizers are used to oxidize the VOC compounds. Adsorbers can also be used as
independent control systems or as preconcentrators for the oxidizers.
If there are less than or equal to 3 VOC compounds, it is usually possible to use
either adsorbers or biological oxidation systems. However, it is necessary to confirm that
the compounds can be desorbed from regenerative-type adsorbers and that the specific
organics are not toxic to the microorganisms in biological oxidation systems. Both thermal
and catalytic oxidizers can also be used for these types of gas streams.
VOC Sources (< 500 ppm)

ppm)
>3
> 3 VOC
VOC Compounds
Compounds ?3
? 3 VOC
VOC Compounds
Compounds ? 3Compounds
? 3 VOC VOC
Recovery // Reuse
Recovery Reuse Recovery // Reuse
Recovery Reuse Compounds
Recovery / Reuse
Not Feasible
Not Feasible Not Feasible
Not Feasible Recovery / Reuse
Feasible
Feasible
Thermal Oxidizers Adsorbers Adsorbers

Catalytic Oxidizers
Oxidizers Biological Oxidizers
Biological
Adsorbers Thermal
OxidizersOxidizers
Thermal
Catalytic
OxidizersOxidizers
Catalytic
Oxidizers
Figure 5.5: Scheme of general applicability of VOC control systems for low concentration sources
If recovery and reuse are necessary, an adsorber system is generally used as

the control technique. Due to the low VOC concentrations, the cost of organic compound
recovery can be quite high.
The applicability of VOC control systems for high concentration systems also
depends, in part, on the number of separate VOC compounds present in the gas stream and
the economic incentives for recovery and reuse. Thermal oxidizers can be used in all cases
in which recovery and reuse are not desired or economically feasible. Catalytic oxidizers can
be used in these same situations if there are no gas stream components that would poison,
mask, or foul the catalyst. Adsorbers can also be used for this service as long as there are
environmentally acceptable means for disposal of the collected organics.
If recovery and reuse are desired, either adsorbers or condenser/refrigeration
systems can be used. Usually, these systems are limited to gas streams containing at
most three organic compounds due to the costs associated with separating the recovered
material into individual components. However, if the process can reuse a multi-component
organic stream, both adsorbers and condenser or refrigeration systems can be used without
the costs of recovered material purification and reprocessing.
67
ppm)
VOC Sources (> 500 ppm)
>
>33 VOC
VOC Compounds
Compounds ? 3 VOC
? 3Compounds
VOC ? 3 VOC
? 3Compounds
VOC
Recovery
Recovery // Reuse
Reuse Recovery / Reuse
Compounds Recovery / Reuse
Compounds
Not
Not Feasible
Feasible Not Feasible
Recovery / Reuse Feasible
Recovery / Reuse
Not Feasible Feasible
Thermal Oxidizers Adsorbers Adsorbers

Catalytic Oxidizers
Oxidizers Thermal
Thermal Oxidizers
Oxidizers Condensers /
Catalytic Oxidizers
Catalytic Refrigeration
Refrigeration
Oxidizers
Figure 5.6: Schema of general applicability of VOC control systems for high concentration sources
5..3 Some Commercial Te

echnologies
Some of the major suppliers of VOC Catalytic systems are listed below
 Allied Signal
 ARI
 Degussa
 Engelhard Corporation
 Haldoe-topsoe
 Hereaas
 Johnson- Mattey
 Nikki Universal
 Nippon shojubai
 Prototech/united catalyst
 W.R.Grace
5..3.1 Oxidizer Types
The most reliable and acceptable means of destroying VOCs, HAPs, and odors
available today is thermal oxidation. Oxidation, typically, is an energy intensive technology
wherein a polluted air stream is heated to a high temperature setpoint that is predetermined
by the nature of the pollutant. The simplest form of an oxidizer is a direct-fired burner that
elevates the air temperature from incoming levels to combustion levels. Because of the high
cost of heating the process exhaust stream to the required oxidation temperature most thermal
oxidizers incorporate some type of primary heat recovery. Primary heat recovery transfers energy
from the hot clean gas stream exiting the oxidizer into the incoming polluted gas stream. This
reduces the amount of additional energy required to achieve the oxidation temperatures. There
are two widely used methods of recovering this thermal energy, recuperative and regenerative.
Sources: http://www.durrenvironmental.com
68
When a catalyst is used to enhance the operation of a thermal oxidizer, the system
is generally referred to as a catalytic oxidizer.
Oxidizer Selection Criteria:
In order to select which type of oxidizer is most advantageous for a specific

application, the following information must be known:
 Process exhaust flow rate

 Process exhaust stream temperature
 Pollutant concentration levels
 Type of Pollutant
 Particulate Emission levels
 Required pollutant control efficiency
In many cases the most advantageous type of oxidizer can be selected based on
the following general guidelines. In other cases two or more oxidizer types may be practical
and a detailed economic analysis based upon the specific costs of fuel and electricity is
required to determine the best selection.
5..3.2 Dire
ect Fire
ed Ther mal Oxidizers (DFTOS)
The simplest Thermal Oxidizer is a Direct Fired unit (sometimes referred to as

an After-Burner) that employs no heat recovery. In this system a fuel burner (mostly natural
gas fired) raises the temperature of the pollutant-laden air to a predetermined combustion
temperature. In order to achieve the a high level of hydrocarbon destruction, the heated
air is kept at the combustion chamber setpoint for a certain minimum time, called the
residence or dwell time. In addition to temperature and dwell time, turbulence also plays
an important role in making oxygen and hydrocarbon molecules to interact more vigorously.
Since DFTOs employ no heat recovery, they are most often applied to very low volume air
streams, usually with very high concentrations of VOCs, HAPs, and other pollutants. These
oxidizers are characterized by specialized burners to insure mixing of combustion air and low
volume, high concentration inert airstreams, which are often injected directly into the burner
ports or directly in the flame cone via lances. This minimizes the risk of explosion and takes
maximum advantage of the enriched fuel value of high VOC content exhaust streams.
5..3.3 Recuperative Oxidizers
A Recuperative Oxidizer is a Direct Fired unit that employs integral primary

heat recovery. To minimize the energy consumption of the oxidizer, the hot air exiting the
combustion chamber is passed over an air-to-air heat exchanger. The heat recovered is used
to preheat the incoming pollutant laden air. The primary heat exchangers are usually supplied
as either a plate-type or a shell and tube type heat exchanger. These heat exchangers can
be designed for various heat transfer efficiencies, but the nominal maximum is 70%. Thus
by the addition of a heat exchanger, the net heat load on the burner can be reduced by up
to 70% of that required in a DFTO. The addition of the heat exchanger, because it is made of
heat corrosion resistant alloy, substantially increases the cost of the oxidizer system. Also,
the fan for moving the polluted gas through the oxidizer must be more powerful to overcome
the additional pressure drop of the heat exchanger. In most cases, the savings in fuel will
more than offset the additional up-front cost within the first two years of operation, however,
even with 70% heat recovery, recuperative oxidizers can be expensive to operate, especially
69
if the airflow is large and has dilute concentration levels, unless additional secondary heat
recovery can be applied to the customer’s process.
5..3.4 Regenerative Ther mal Oxidizers (RTOs)
A Regenerative Oxidizer is also a Direct Fired oxidizer that employs integral

primary heat recovery. However, the RTO operates is periodic, repetitive cycle rather than
a steady state mode. Instead of conventional heat exchangers, which indirectly transfer
heat from hot side to cold side across the exchanger walls, RTOs use a store and release
mechanism. The nature of a RTOs heat recovery process requires it to have at least two
beds of appropriate heat recovery media. In many applications, the additional step of purging
a bed before reversing the flow through it from inlet to exhaust is necessary to maintain
very high destruction efficiencies. This purge step creates the requirement for an additional
(or odd number) chamber making the RTO more complicated and more expensive than a
recuperative oxidizer. RTO systems can utilize more than two beds (operating in parallel)
in order to be capable of handling larger air volumes. The primary advantage of an RTO is
lower operating costs due to high heat recovery and low fuel consumption. Depending on the
mass of media included in an RTO, heat recoveries of up to 95% are common. Because of
their capability for high heat recovery, RTOs are often operated in an “auto-thermal” or self-
sustaining mode, where the heat content of the VOCs being oxidized is enough to sustain
the combustion chamber temperature at setpoint, requiring no external fuel input.
Industries Served by Oxidizers:
 Automotive  Waste Water Treatment

 Surface Finishing/Coating  Tank Farms
 Semiconductor  Printing & Flexography
 Wood Panel Manufacturing  Wall Paper
 Chemical Manufacturing  Flooring
 Petrochemical  Solid Waste Treatment
 Pharmaceutical  Fiber Manufacturing
 Aerospace  Pulp and Paper
 Glass Manufacturing  Rendering
 Foundry  Corn Milling
 Styrene
Application Selection Chart

Choosing the right equipment for VOC control applications depends primarily on
the exhaust air volume and the average concentration of VOCs. The chart displayed provides
general guidelines for choosing equipment to fit particular applications.
70
Sources: http://www.durrenvironmental.com
5..4 Example of Commercial Te

echnologies

Name of technology/technique: Catalytic incinerator
Applied: Chemical industries, painting, printing, rubber and casting factories
Description: This equipment catches malodorous gases with the platinum catalyst and
decomposes them by oxidation to harmless and odorless carbonic acid
gas and water. Compared with the direct combustion type, this equipment
is capable of treating malodorous gases at lower temperature, running
et lower cost. In case of low malodorous substances concentration, it
is advisable to install Honeycomb Type Deodorization Equipment as pre-
treatment equipment to save energy.
Exhaust gasses are pre-heated in a heat exchanger.
Exhaust gasses are heated to the predesigned temperature by the auxiliary
heater (generally to 300 °C ). Electricity, city gas, LPG, kerosene oil, etc.
can be selected as heat source.
When the polluted gas passes through the catalyst-bed, malodorous
substances contained are decomposed by oxidation. Purified gas is
exhausted after passing through the heat exchanger where heat is
exchanged between purified gas and treating gas. In combination with a
steam heater: In case electricity is used as heat source for the auxiliary
heater, it is advisable to use a steam heater together with it to reduce
electric consumption.
71
Advantages: Low running cost: Compared with the direct combustion system, this
equipment is capable of treating malodorous substance at low temperature.
Fuel costs can be reduced by 1/3.
Low boiling organic solvents and wider ranges of malodorous substances
can be purified.
Installation example of the system
Ref./Source: Daikin Industries, Ltd.
72
5..5 Examples of Commercial Catalysts
5..5.1 E ng e l h a r d C a t a l y st s
Carbon monoxide, VOCs or HAPs control VOCat® PTA.

This noble metals based catalyst family is designed to abate pollutants generated
during the process of purification of terephthalic acid, a key raw material to produce
polyethylenterephthalate (PET). The volatile organic compound (VOC) most difficult to abate during
this process is methyl bromide. These catalysts were specifically, but not exclusively, designed.
VOCat® 350 HC and 360 PFC.

These noble metals based two catalysts were specifically designed to selectively
abate both chlorinated and fluorinated VOCs (including dioxins and furans) producing the
relevant halogenated acids, easy to be scrubbed during a further step. Amount of generated
chlorine and fluorine, very nasty to be eliminated, is produced at lowest possible level.
VOCat® 310 ST S and ST H

These noble metals based, two catalysts provide effective VOC abatement in an
environment rich in sulfur.
VOCat® RCO
This is a noble metal-based catalyst family, designed to either retrofit or build
up new regenerative oxidizers. It is useful to treat very large exhaust flows with a VOC
total amount of more than 1 g/Nm 3. Those catalysts substantially lower operating costs of
regenerative oxidizers with a quick payback period (often less than 1 year).
Zeolite rotor concentrators

This product family is aimed to optimize economics of either thermal or catalytic
oxidizers (also regenerative ones). It is economically convenient to treat exhaust flows
larger than 20–30,000 Nm3/h and with a VOC total amount of less than 1–2 g/Nm3. These
concentrators safely and effectively adsorb and desorb VOC in such a way that 85–95% of
the original flow rate can directly proceed to the stack, whereas a much lower flow rate, rich
of VOCs, is sent to the oxidizer. The latter can, therefore, work with much lower operative
costs. The payback period is very quick. Special hydrophobic zeolites are coated onto a
fiber–ceramic honeycomb. The same technology–but with non-rotating panels–is used in VOC
abatement for food service.
5..5.2 Photocatalytic Self-cleaning Ceramic
The self-cleaning ceramic can degrade contaminants (e.g., oil) on the surface,
deodorize some harmful gases, and kill bacteria or virus. It can be used for indoor or outdoor
fitment for kitchen, toilet, natatorium, operating rooms, and so on.
Solid superacid photocatalyst with high efficiency

The solid superacid photocatalyst possesses higher photocatalytic activity and
higher efficiency for destroying organic contaminants at room temperature. It can be applied
to the areas including environmental protection, reclamation of noble metal, preservation of
fruits and so on.
73
Multi-functional photocatalytic air cleaner

The air cleaner has multi-functions such as destroying volatile organic compounds
(e.g., trichloroethylene, benzene, formaldehyde, etc.), killing bacteria, deodorization, and
dedusting. It is favorable for reducing air pollution in home vehicles, hotel, offices, meeting
rooms, and so on.
Source: http://www.nerc-cfc.com/production.html
5..6 Refere
ences
1. Air Pollution Control Engineering, de Nevers N., second Edition, 2000, Mc Graw Hill, New York.
2. www.epin.ncsu.edu
3. Buscom.com
4. www.engelhard.com
74
6 POPs and Chlorinated Or ganic Pollutants

6..1 Introduction
Persistent organic pollutants (POPs) are the group chemical substances of
natural or anthropogenic origin, which are extremely toxic and very stable. These compounds
resist photolytic, chemical and biological degradation. They are also characterized by low
water solubility and high lipid solubility, resulting in bioaccumulation in fatty tissues of living
organisms thereby posing a risk of adverse effects to human health and the environment.
POPs are transported in the environment in low concentrations by fresh and marine waters
and can transfer long distances in the atmosphere, resulting in widespread distribution
across the globe. Thus, both humans and environmental organisms are exposed to POPs
around the world, in many cases for extended period of time. Over the past several years,
the risks posed by POPs have become of increased concern in many countries.
One of the first dioxin public awareness raising events may be considered the
accident at a chemical plant in Seveso, Italy on the 10th July 1976, when a toxic cloud
containing 2,3,7,8-tetrachloro-dibenzo-p-dioxin, the most toxic POP and one of the most
toxic man-made substances was released in the atmosphere. During the eighties the public
concern on POP emissions grew, focusing mainly on waste incinerators, which are the main
source of dioxins, but also on industrial organochlorine processes.
In the late eighties and in the nineties many local and international organizations
began considering the POPs problem with more attention. In May 1995, the UNEP Governing
Council adopted the Decision concerning Persistent Organic Pollutants. This process led in
2001 to the signature by the representatives of 92 countries of the Stockholm Convention
on POPs, which included a list of 12 substances. The Stockholm Convention is now signed
by over 150 countries and represents the main driving force in the international fight against
POPs. The detailed information on the state of the art on POPs and Stockholm convention
can be found on the websites of UNEP www.chem.unep.ch/pops and at www.pops.int.
The 12 POPs recognized by the Stockholm Convention on POPs as requiring the

most urgent action are shortly described in this section. Some POP chemicals have been
produced intentionally on the industrial scale to be used mainly in agriculture and electrical
equipment. These are nine pesticides, namely chlordane, dieldrin, heptachlor, toxaphene,
aldrin, endrin, DDT, mirex, hexachlorobenzene (HCB), and PCBs which are the group of
substances known for their wide use as transformer and condenser heat exchange oils,
insulation liquids, plasticizers, lubricants, etc. Polychlorinated dibenzo-para-dioxins (PCDD)
and polychlorinated dibenzofurans (PCDF) are other 2 POPs which group of substances on
the list of POPs are the infamously known dioxins and furans, more precisely a group of 17
toxic congeners belonging to the classes of. These latter have been produced unintentionally,
normally as by products of combustion processes and in some other sources, including
chlorine industries. The threat by the PCDD/F to humans and the Environment is recognized
as of major importance due to their extreme toxicity and very high persistence. It is mainly
dioxins and furans that raise a special concern related to air contamination, as these
75
POPS AND CHLORINATED ORGANIC POLLUTANTS
substances, once occurred in the gaseous emissions of industrial plants then can transfer
atmospherically over very long distances. Along with dioxins and furans also PCBs and HCB
can be formed as byproducts in some processes and are also designated by the Convention
as the so-called unintentionally produced (UP) POPs.
The provision is made in the Convention on POPs that all existing stockpiles of
intentionally produced industrial POPs (pesticides and PCBs) have to be destroyed and their
production be stopped. Regarding the UP POPs the Convention requires that their production
be minimized and eliminated where possible. With this aim two basic approaches can be
applied, namely prevention and end-of-pipe practices. This chapter will review some technical
aspects on these practices related in particular to the presence of POPs in air emissions.
It is known that many other chlorinated and halogenated substances also manifest
high or POP-like or toxicity. The 12 POPs by the Stockholm Convention are also comprised in
the list of 16 chemicals subject to the Geneva Convention on Long-Range Transboundary Air
Pollution (LRTAP). In addition to the 12 POPs, many other halogenated organic compounds
are on the list of persistent toxic substances (PTS), ozone depleting substances (ODS),
hazardous air pollutants, etc.
The technical approaches described here as applicable to the efficient destruction

of POPs, which are all chlorinated compounds, can be considered also useful for removal of
other chlorinated/halogenated pollutants, in addition to what have been already presented
in the previous chapter on VOC.
6..2 Unintentionally produ

uced POPs and air pollution
Speaking about the air contamination by POPs and other chlorinated compounds
the dioxin problem is by no doubt to be considered as priority. The issue of dioxin pollution
owes attention mainly to waste incinerators, which have always been the main source of
global dioxin contamination. Dioxins and furans present in the air and dust also constitute
the second major way of dioxin intake after food.
The Stockholm Convention outlines a number of processes and devices recognized

as the PCDD/F sources, namely: waste incinerators (municipal, medicinal, hazardous waste,
and sewage sludge), some processes of pulp and paper, metallurgical, and organochlorine
industries, cement production, fossil-fuel-fired combustors, and forest fires, etc. The
Convention also requires that measures be taken regarding these sources so that the levels
of UP POPs are reduced or eliminated, by using best available techniques (BAT) and best
environmental practices (BEP). This means that the existing processes should be managed
in the proper way or modified or replaced so that PCDD/F formation is prevented by design
or that proper post-treatment is applied in order to remove these contaminants from the
emissions. Being the dioxin and furan compounds the more thermodynamically stable of
the class, it can be guaranteed that given the proper practice of emission control to remove
PCDD/F the other UP POPs present (HCB, PCB) and other chlorinated organics will be also
efficiently removed.
6..3 Form
mation of dioxins
There are a total of 17 individual compounds from the class of dioxins and furans
(congeners) which are considered as dioxins and furans on the list of POPs. As it was
mentioned, the 2,3,7,8-TCDD congener (see Fig. 6.1) is the most toxic from all the 17 and
76
its toxicity equivalent factor (TEF) was assigned one. The rule which defines the toxicity of a
dioxin / furan congener is exactly the presence of the four chlorine atoms at all of positions
2,3,7,8 of the structure. If at least one chlorine at these positions is missing the congener
is not toxic; if additional chlorines (up to eight possible) are present at other positions of
the rings, such congeners are normally less toxic (TEF less than 1). Therefore the measure
of dioxin contamination is usually presented in toxic equivalents (TEQ), i.e. the sum of
concentrations of all 17 congeners (they usually occur together) where for each conger its
component concentration is multiplied by its respective TEF. The TEQ value is often used in
regulatory limits, and for air contamination levels the PCDD/F usually range in the order of
nanograms per cubic meter TEQ.
Dioxins Furans
Figure 6.1. Toxic PCDD/PCDF congeners are shown which are characterized by the presence of chlorine atoms
at positions 2,3,7,8 (lateral) and chlorine or hydrogen atoms at positions 1,4,6,9 (in brackets)
Chlorinated dioxins and furans are the most toxic products of incomplete
combustion. The formation mechanisms for these compounds have not been yet completely
elucidated. It is believed that there are at least three possible types of formation mechanisms.
In principle, the dioxins are formed in any high temperature process given the presence of
organic matter, oxygen and chlorine. The first mechanism is the so-called ìpass-throughî
mechanism whereby the dioxins originally present in the combusted material are released
and exit unaltered. In the second mechanism, PCDD/F are formed from the precursors,
which are the chlorinated aromatic compounds possessing the appropriate structure to yield,
after structural rearrangement at elevated temperature, the structural skeleton of PCDD/F.
Typical precursors are chlorophenols and PCBs. Dioxins and furans can also be formed in
incinerators via the ìde-novoî synthesis, which is a catalytic process that takes place on the
surface of fly ash in the presence of organic matter, oxygen, chlorine and a transition metal,
e.g. copper. PCDD/F formed by either of these mechanisms or their combination, normally
are adsorbed on the fly ash particles.
Usually the formation of dioxins from precursors occurs at cooling of the flue
gases. PCDD/F formation appears to be more favored over the temperature range from 240
to 540°C. At temperatures well above 540°C PCDD/F are readily oxidized. However, even
though high temperatures are involved in most incinerators, boilers and other combustion
devices and PCDD/F are initially destroyed, the chlorinated precursors, which originated in
the fuel and/or waste can volatilize and move with the gas stream through the combustion
process until they reach the temperature range favorable for dioxin and furan formation (240
to 540°C).
There are several basic principles and approaches that should be applied to
reduce dioxin and furan emissions in combustion processes:
77
Primary control or prevention techniques

• Optimum burnout: temperatures >850°C, residence time >2 seconds, good turbulence
• Quenching (rapid drop to low temperature)
• Addition of inhibitors
End-of-pipe or removal methods

• Dust separation (electrostatic precipitators, fabric filters)
• Adsorption on carbon (flow injection, fixed bed etc.)
• Catalytic oxidation
The plot in Fig. 6.2 gives a comparison of efficiencies of different approaches

to reduce dioxins in the emission gases, from good combustion practices (prevention) to
the end-of-pipe approaches, such as particulate filtration (electrostatic precipitators, fabric
filters), adsorption on carbon, and catalytic oxidation approaches.
Figure 6.2. Efficiency comparison of different post-treatment systems for PCDD/F removal in combustion plants.
6..4 Chlorinated VOC and Other Halogenated Pollutants

Combustion processes, which give rise to dioxins and UP POPs, can also produce
a number of other chlorinated or halogenated hazards, especially when chlorinated waste is
incinerated. Some hazardous chlorinated organics can be found in the emissions as the by-
products of combustion and industrial processes or as undestroyed chemicals from waste
disposal operations. Chlorinated chemicals from the VOC list include chlorides of methyl, vinyl,
ethyl, di- and trichloroethanes, chloroform, trichloroethylene, mono- and dichlorobenzenes.
Chlorinated PTS chemicals (see www.chem.unep.ch/pts) include polybrominated biphenyls
(PBB) and diphenylethers, chlorinated naphthalenes and paraffins, pentachlorophenol (PCP),
lindane, etc. Tens of chlorofluorocarbons (CFCs) and other substances from the class of
halogenated C1-C3 hydrocarbons belong to the class of ODS (http://www.epa.gov/ozone/
78
ods.html). There are many halogenated compounds on the EPA list of 188 hazardous air
pollutants (http://www.epa.gov/ttn/atw/188polls.html).
The standard techniques for elimination of VOC and particulate in flue gases
(see chapters 5 and 7) are usually suitable to get rid of the halogenated pollutants, as
well. However, in the case the chlorinated and halogenated VOC are chemically destroyed,
an additional problem connected with the formation of the halogen hydride arises. In some
cases this just can be solved by connecting a caustic scrubber right after the treatment
step. In other cases, this can result in harm produced to the system, e.g. catalyst poisoning,
corrosion, etc. In addition, some halogenated chemicals are more stable and resistant to
chemical treatment than normal VOC, which may require prolonged residence time of more
severe conditions. In some processes special treatment, e.g. special catalysts, may be
applied for chlorinated VOC removal which is different then for other VOC. On the contrary,
if the emission control systems are designed to remove dioxins and POP, as a rule, the
chlorinated VOC at the same concentrations can also be easily removed.
6..5 Preventtion of PCDD/F form

mation during incineration
The best way to control dioxin and furan emissions is preventing their formation
by reducing or eliminating chlorine in the fuel and waste material being burned, e.g. in the
case of municipal solid waste incinerators (MSWI) which contribute most of the PCDD/F air
emissions. It can be argued whether it is at all worthwhile to incinerate municipal waste, the
topic that has become an issue at the centre of attention of ecologists, industries, NGOs,
governmental and international organizations. Even if a MSWI is provided with a system to
capture dioxin emissions, one of its byproducts is the fly ash. Fly ash contains very high
dioxin levels and therefore has to be treated as a hazardous waste. Some ecologists and
defenders of the classical MSW management say that there is no reason, neither economical
nor ecological, to landfill a ton of a highly toxic fly ash instead of landfilling three tons of
low toxic MSW. Unfortunately, the dioxin problem has been recognized in its dimension
after a number of MSWI plants were already in operation. A strong public campaign against
construction of new MSWI now exists worldwide. In developed countries substantial funds
have been raised to modify these processes or to close them, but still many old incinerators
remain in operation.
Should the chlorine containing materials be incinerated this must be carried out
in the proper manner, in strict conformance with the technical requirements defined by the
existing regulations. Since the dioxin formation is favored at cooling of the combustion
gases, containing incomplete combustion products and chlorine atoms, as was previously
mentioned, it is important to provide sufficient oxygen and temperature so that that, before
the effluents are cooled, the organic matter is exhaustively defragmented and oxidized
in order to suppress the ìpass-throughî and ìprecursorî routes of PCDD/F formation. The
standard rules require that the incinerators be designed so that the combustion gases
reside for at least 2 seconds in the zone of the furnace heated over 850°C and in the
presence of at least 6% of oxygen.
Rapid quenching of combustion gases from temperatures of over 600°C to below

100°C is another practice which helps to reduce the formation of dioxins via ìde novoî and
ìprecursorî mechanism. This way the temperature range of dioxin formation is passed very
quickly, so only small quantities of dioxins are formed because their formation involves
heterogeneous mass transfer processes that are relatively slow.
79
The particular attention should be paid to the best techniques and practices applied
to the incineration of the hazardous and other POP waste, e.g. PCB and stockpiled chlorinated
pesticides, since in this case the burnt material is the pure dioxin precursor and the risks of
dioxins emissions are particularly high as their formation is intrinsically inevitable. Although
this chapter is mainly dedicated to the techniques of reducing of UP POPs in emissions by
the end-of-pipe approach, which presumes that these dangerous compounds have been
formed, it has to be underlined that as in the case of MSW disposal practices, the alternative
techniques of hazardous chlorinated waste treatment should be given priority where possible.
A number of such modern techniques have been appearing recently and gaining popularity,
also thanks to the support of environmental and international organizations. These emerging
technologies are based on the processes other than incineration and high temperature
oxidative treatment (e.g. reduction based processes and low temperature oxidation), so that
the formation of PCDD/F is excluded by the nature of chemical process. UNIDO has been
promoting the introduction of non-combustion techniques through demonstration projects
with the support of GEF and of local governments in several countries. A number of such
newly emerged non-combustion technologies are in commercial operation in Japan, Australia,
Europe, Canada and USA and pilot and demonstration activities exist around the world. ICS-
UNIDO has recently published a review of non-combustion technologies for destruction of
stockpiled POPs (1).
In addition, incineration of hazardous waste can be conducted in a more efficient

manner by alterative design of the plant or combination with other physical treatment.
Several techniques aim at homogenization of waste material in order to perform combustion in
a homogeneous (non-flame) manner and thereby exclude low temperature zones in the
combustion chamber and reduce the amount of partial combustion products. For example
better mixing of solid waste in the combustion chamber can be achieved by using fluidized
bed incineration, and better heat temperature distribution throughout the reactor zone is
achieved in the Isotherm power waste recovery process. A number of dense phase oxidation
processes exist that also guaranty a homogeneous and flameless oxidation in the media,
such as supercritical / subcritical water oxidation, wet air oxidation, and molten salt/metal/
slug oxidation processes. Other technologies achieve better oxidation efficiency by using
more severe plasma treatment (a number of plasma arc oxidation and pyrolysis technologies
exist) or by combining combustion with other treatment, such as infrared (IR), ultraviolet
(UV), microwave (MW) irradiation. These assist mass transfer processes and defragment
bigger organic molecules and simplify their oxidation.
6..6 End-of-pipe prevention and re

emoval techniques
The prevention practices described above rarely allow reaching the required 0.1
ng-TEQ/m3 in the air emissions of incinerators. In addition to these, the end-of-pipe practices
(additional modules) should be also applied in the processes based on combustion or high
temperature oxidation of chlorinated substances. These modules are designed to capture,
destroy, or prevent formation of dioxins in the post-combustion zone. This can be done
by a number of approaches, usually by their combination. Most diffused modules include
scrubbers, filtration with activated carbon, particulate capture systems (described in the
following chapter), post-combustion chambers and afterburners, including catalytic oxidation
systems. Some modern techniques for treatment of POPs in gaseous emissions use plasma
or reductive environment. In this section we will briefly describe the post-combustion modules
which are installed in incinerators (Fig. 6.3) and in other potential POP production sources.
80
Figure 6.3. Organizational diagram of the rotary kiln type hazardous waste incineration plant. Reproduced from (2).
To widen the spectrum of approaches and methods that can be to destroy POPs
and chlorinated VOC in the gaseous phase it is useful also to consider here the post-
treatment systems employed in desorption processes, such as various technologies for
soil remediation or for treatment of other highly contaminated matrices (PCB equipment,
sludges, etc.) which are based on the evaporation of the contaminant as the first step. As
an example the soil remediation system based on vapor extraction could be considered, as
presented in Fig. 6.4. Unlike incinerators, where the end-of-pipe systems are designed to
treat micro amounts of pollutants (mainly PCDD/F), the post-treatment systems in desorption
technologies usually have to address high concentrations of pollutants in the air or vapor
steam (mainly original undestroyed contaminants which, in case if a chlorinated compound
is desorbed thermally, would also contain some amount of PCDD/F).
Treatment of gaseous effluents arising from the thermal desorption of polluted
soils as well as treatment of some gaseous streams from chemical industries containing
halogenated VOC is usually the same as applied for other VOC (post-combustion, catalytic
oxidation, adsorption, etc.) (3). However, in the case of treatment of halogenated VOC vapors
by oxidative techniques, post-treatment in caustic scrubber would be required in order to
remove hydrochloric acid. In addition, if catalytic oxidation is applied to treat halogenated VOC,
other catalyst formulations maybe used, especially for more resistant and more concentrated
pollutants, as the oxidation catalysts based on platinum or chromium or magnesium
oxides would be easily poisoned by acidic environment created by oxidation products.
Figure 6.4. Typical soil vapor extraction system. Reproduced from (4).
81
The techniques and practices listed below in this and the following sections are
applicable not only for POP destruction but also for a majority of VOC and organic pollutants.
However, we have focused in a specific manner on the methodologies which are promising
for destruction of polychlorinated pollutants and which are not listed in chapter 5, including
some emerging ones. Before going to the techniques used to destroy POP and halogenated
pollutants in effluent gases (sections 6.6 and 6.7) letís consider some basic methods that
are used either i) to intensify the main combustion step (post- or secondary combustion, in
addition to the previously mentioned IR, UV, and MW intensification methods in incineration),
ii) to remove other hazards, e.g. chlorine and hydrochloric acid from combustion gases
(scrubbers; can be also considered as preventive to PCDD/F formation), or iii) to remove
contaminants physically without destruction (adsorption).
Secondary combustion chambers or afterburners are used in incinerators and

are placed immediately after the furnace and are designed to destroy any undestroyed
chlorinated waste if such is treated and to destroy the PCDD/F and incomplete combustion
products formed during the first step. To guarantee high temperature and efficient oxidation,
the post combustion chambers or afterburners are fuelled with methane or other auxiliary
combustible and are equipped with air inflow system. Additional liquid waste can be also
added directly in the secondary combustion chamber.
Scrubbers are essential in any process where chlorinated waste undergo thermal
high temperature treatment. Scrubbers remove hydrochloric acid or other halogen hydride
and free chlorine from the combustion gases by reaction with alkali solution. Concentrated
NaOH or KOH, CaOH solutions in water are usually used. This treatment is applied after the
gases exit from the furnace or the secondary combustion chamber. The alkaline solution is
introduced as a counter flow shower or the gases pass bubble through a vessel containing
the solution. Several scrubbers can be placed consecutively and can be followed with the
washing by pure water in a similar way. First scrubbers can be also designed in the way to
provide excellent heat exchange and rapid quenching of the combustion gases which helps
to order to reduce the dioxin formation rate. Scrubbing of incineration off-gases per se
cannot efficiently destroy halogenated chemicals; however, it eliminates hydrochloric acid
and chlorine gases formed during incineration, therefore also reducing the probability of new
POP formation in the post combustion zone.
Adsorption of PCDD/F from off-gases is one of the most efficient treatment

methods to remove these compounds. Such systems may have different design but are all
based on the same principle of adsorption of dioxins on carbon, activated carbon, or coke.
Other adsorbents can also be sometimes used, such as zeolites and synthetic polymers.
Adsorption of the flat aromatic dioxin and furan molecules on carbon surface is very strong
and allows a very efficient capture of these substances from the gaseous state as well as
of other chlorinated aromatics. Filtering post-treatment systems are usually installed as the
end modules of the process. Dioxins are not destroyed and remain in the adsorbed state,
so the used filters have to be periodically replaced and treated as the hazardous waste, e.g.
in the similar manner as the fly ash.
6..7 Chemical destru

uction of POPs and chlorinated pollutants in
em
missions
Modern incinerators and thermal desorption units can be also equipped with the
catalytic oxidation systems or other type of post-oxidative treatment aimed to destroy any
residual waste or newly formed dioxins coming after incineration or to destroy the pollutants
82
coming from soil remediation by thermal desorption. Post-oxidation systems can be also
installed in other processes that yield gaseous emissions containing chlorinated organics
and POPs, such as organochlorine chemical production processes and non-combustion
hazardous waste destruction technologies.
Catalytic oxidation or catalytic post-combustion systems (Fig. 6.5) are usually

installed in incinerators as the final step before the emissions go in the atmosphere. These
systems are designed to treat small amounts of chlorinated chemicals, such as PCDD/F in
the gaseous phase. In the case of bigger amounts of the treated pollutant in the emission,
like in the case of chlorinated VOC treatment the catalytic oxidation module can be followed
by scrubber and washing systems in order to remove hydrochloric acid.
Catalytic oxidizers and carbon filters are the essential components that allow
effective reduction of the dioxin levels in production sources to the acceptable/req uired
values. Unlike filters, the catalysts do not accumulate the pollutant and do not raise the
issue of their disposal. The activated carbon filters should be more frequently replaced
than catalysts. This increases the cost of operating incinerators, however even very stable
catalysts require periodical replacement as these can be poisoned/deactivated by a number
of substances that present in the emissions. Because of this, the catalysts may contribute
more than the other post-treatment process modules to the overall maintenance and
consumables costs of the plant. Many new catalysts and processes capable of treating
streams containing chlorinated hydrocarbons have been commercialized in the last years.
Figure 6.5. Basic arrangement of the catalytic oxidation module. Reproduced from (5).
Particulate filtration and catalytic oxidation processes can be also coupled by

introducing the catalyst in the membrane filter (catalytic filtration), as in the Gore process
using TiO2/V2O5/WO3 catalyst and the polytetrafluoroethylene fiber (see Fig. 6.6) (6). This
process has been successfully demonstrated/used in numerous combustion facilities,
including waste incinerators, pyrometallurgical plants, cement kilns burning hazardous
waste, etc.
83
Figure 6.6. Remediaô Dioxin/Furan Catalytic Filter System. Reproduced from www.gore.com/remedia.
In general, most post-treatment catalytic systems employ catalysts based on

TiO2 also using supported V 2O5 and WO3. These catalysts also allow reduction of NOx and
ammonia in the gas emissions. Operation temperatures can range from 160°C to 350°C,
and different designs of the catalytic reactors are available. Noble metal catalysts can also
be used. For example, the treatment of off-gases from the production of vinyl chloride is
based on bimetallic Pt and Pd on -alumina catalysts. An activated alumina specially treated
to resist chlorine anions is used to decompose the aromatic hydrocarbon solvents and some
of the chlorinated hydrocarbons. (7)
Other post-treatment techniques based on oxidation applicable for moderate

amounts of POPs and halogenated VOCs treatment in emissions include UV oxidation,
biofiltration and non-thermal plasma.
Photolytic (UV) oxidation technologies use UV light to ionize the organic molecules,
by breaking molecular bonds and creating free radicals. UV or near UV light can be used (150-
350 nm) which is sufficient to destroy VOC and chlorinated VOC. The free radicals formed
from oxygen and pollutant molecules then recombine and yield harmless oxidation products,
such as carbon dioxide, water, and hydrogen chloride, in the case of chlorinated pollutants.
Similar photo-catalytic technologies use UV light in the presence of titanium dioxide (TiO 2) as
a catalyst. The catalytic UV oxidation techniques allow carrying out the reactions at moderate
or ambient temperatures.
Figure 6.7. Flow diagram of the PTI photolytic destruction process. Reproduced from US-EPA (8).
84
A photolytic destruction system developed by Process Technologies, Inc. (PTI),

feeds off-gas from an SVE system to a sorption chamber containing a fluidized bed of adsorbent
material (Fig. 6.7). The adsorption unit concentrates the contaminants from the air stream
and is connected to a desorption column where the contaminants are realized and the more
concentrated stream is then fed into the photolytic reactor. Short wavelength UV light (185-
254 nm) is used, which efficiently destroys halogenated hydrocarbons. A proprietary reagent
is used (mainly calcium hydroxide), which reacts with the degradation products coming from
the photolytic destruction step, forming solid and stable products. The technology was
tested in various programmes by U.S. Navy and in the Superfund Innovative Technology
Evaluation (SITE) Demonstration Program. Compounds treated in the system included
several halogenated VOCs, such as 1,2-DCE, TCE, PCE, as well non-halogenated VOCs (3).
Adsorption-Integrated-Reaction (AIR) Process by KSE, Inc. is an example of

photocatalytic technology which was demonstrated in full scale applications in groundwater
strippers and soil vapor extraction processes at several air force bases and in the SITE
Emerging Technology Program in 1995 (US) (3). In the photocatalytic processes, free
radicals are formed when the influent stream contacts the catalyst (TiO2), which is activated
by the UV light energy, but also in the gaseous phase by absorption of the UV light directly
(photolytic pathway). The radicals then recombine to form water vapor, carbon dioxide, and,
if chlorinated VOCs are treated, halogenated acids. More novel photocatalytic systems use
coating glass fibers with TiO2 and filling of the reaction vessel with UV-lit fibers. Another
approach is a solar-powered system in which the UV light from the sun activates the TiO2.
DREs for photo-catalytic oxidation systems normally exceed 99% for chlorinated VOC, such
as TCE, DCE, vinyl chloride, etc.
Biofiltration processes can be used for treatment of remediation off-gas streams.

The gas is passed through a bed of biologically active filter (Fig. 6.8). The organic content is
adsorbed on the filter and degraded to carbon dioxide and water. Various media (organic or
synthetic) can be used for these systems.
Figure 6.8. Basic arrangement of the biofiltration process. Reproduced from (5).
85
Until recently, biofilters were not designed to treat chlorinated compounds.

However, recent demonstrations have suggested that they can be used to remove these
compounds, as well. The technique has been successfully applied to chlorinated VOCs such
as PCE and TCE. While highly aerobic conditions achieve good removal of light to moderately
halogenated organics, heavily halogenated species would require anaerobic or co-metabolic
conditions (added methane, propane, or aromatics). However, only limited data exist on
the use of biofiltration for chlorinated pollutants. The method does not yet operates on the
commercial scale for treatment of POP and chlorinated VOC.
Non-thermal plasma (see also chapter 3) is a relatively new technology which

involves the destruction of organic compounds by ionization in the gas stream at temperatures
from 30°C to 120°C and at atmospheric pressure. This method is particularly useful when
treating pollutants at concentrations in the range of ppm. Specific plasma technologies
include silent discharge plasma, gas-phase corona reactor, tunable hybrid plasma, and low-
pressure surface wave plasma. The principle of non-thermal plasma treatment is basically
the same as in the case of UV oxidation. Electrons generated in the electrical discharge
then ionize the molecules of pollutants and oxygen in the gaseous phase producing radicals
and ions, which then recombine yielding oxidation products. Recently, a number of hybrid
non-thermal plasma techniques appeared, where plasma processing is combined with other
methods such as wet processing, the use of adsorbents, and catalysis. For example, a
photocatalyst (TiO2) can be introduced in order to intensify ionization of molecules. Wet
processing during plasma treatment can be efficient in incinerators, especially for POP
destruction, in order to remove dust and hydrochloric acid.
Figure 6.9. Basic scheme of the non-thermal plasma set-up for treatment of pollutants in gaseous emissions.
Reproduced from (4).
The principle components of a typical non-thermal plasma system (Fig. 6.9) are
the reactor vessel and, if chlorinated compounds are treated, an acid scrubber. The reactor
cell is connected to the power supply and control system for corona production. In a gas-
phase corona reactor, contaminated influent gas is forced through a reaction chamber, where
it is ionized by plasma. The reaction produces carbon dioxide and water, and in the case of
halogenated hydrocarbons, halogen hydride.
86
6..8 Tre
eatment of macro stre
eams of POPs and chlorinated pollutants
In this group we will consider several destruction technologies which have been
designed to process wastes containing POP as well as other hazardous chemicals, e.g. military
waste and VOC. A detailed review of these and other non-combustion technologies suitable to
process POP wastes was recently produced by ICS-UNIDO (1). Some of these technologies can
treat pollutants in the gaseous phase, e.g. originally in the gaseous state, vaporised, or as
aerosols. As a rule, such treatment is justified to treat more concentrated pollutant streams
than the previously described techniques for destruction of residual or micro amounts of POP
in the emissions. Therefore, these methods can be suitable to treat chlorinated pollutants
coming after thermal desorption processes used in remediation activities or from the industrial
processes that produce gaseous streams of concentrated chlorinated pollutants, or other
concentrated organic matter containing such. It is assumed that these technologies, originally
designed to be stand alone, can be in principle coupled to the emission sources of different
types and therefore can be also considered as POP pollution control methods.
There are not too many non-combustion chemical technologies that have been
specifically designed to treat concentrated chlorinated chemicals in effluents. The three non-
combustion POP destruction processes that can treat gaseous streams directly are Gas-Phase
Chemical Reduction (GPCR) and PLASCON, an ìin flightî plasma arc system. Plasma arc
processes are sometimes assimilated to incinerators, but there are several substantial
differences that concern the nature of processes, design, and efficiency. As for the two
above, CerOx process can also be considered theoretically applicable to gaseous emissions. In
practice, none of these processes have been applied as an additional air pollution control
module as these were designed for macro concentrated waste disposal. Some other
processes, such as MCD (Mechanochemical Decomposition) by EDL in Australia and BCD
(Base Catalysed Decomposition) by BCD Int. can also treat vaporised pollutants coming after
desorption processes, however the treatment in these processes takes place in the dense
phase, i.e. after condensation of the pollutants, therefore, such technologies can not be
considered directly applicable to gaseous effluents.
GPCR technology provided by Canadian Hallett Environmental was designed for

treatment of stockpiled POPs by reduction of the chlorinated molecules in the gaseous phase
with hydrogen. The technology operates at temperatures of 875°C and low (atmospheric)
pressures. Emissions include mainly hydrogen chloride, methane and other low molecular
weight hydrocarbons.
CxHyClxOz + H2 --> CH4 + H2O + HCl (thermal)
The process (see Fig. 6.10) can treat basically all types of chlorinated waste in
different forms, namely bulk organic solids and liquids, high-strength PCB oils and mixed
solid materials, aqueous waste, contaminated soils and sediments.
Since the GPCR process is based on the gas-phase reaction it is provided with a
gas fed module, so POPs and other chlorinated organics present in the gaseous state can
be treated directly in the continuous manner. This makes this technology a possible option
to couple to a facility which produces POP emissions. However, the costs of this technology
setup and operation may be considered too elevated to be applied for destruction of micro
amounts of pollutants in the gaseous phase. This technology shows excellent destruction
efficiencies but can be suitable only for the oxygen free gaseous streams containing high
concentration of chlorinated pollutants.
87
Figure 6.10. Organizational diagram of the GPCR process. Reproduced from (9).
PLASCON, now marketed by DoloMatrix Int. Ltd., is an argon plasma arc process
and is designed to process CFC and organic liquids, such as PCBs. PLASCON is an “in flight”
plasma process which operates in the gaseous phase in the continuous regime (Fig. 6.11).
The waste mixes directly with the argon plasma column. Argon is used as the plasma gas
since it is inert and does not react with the torch components. The waste is fed directly into
the plasma torch within the current of argon, where it is rapidly heated (one millisecond) up
to 12.000°C and then passes into the flight tube where its pyrolysis occurs in nearly 20 ms
at temperature of about 3000°C.
Figure 6.11. Basic scheme of the PLASCON plasma torch system. Reproduced from the vendor website (www.
srlplasma.com.au) and (10).
88
In the beginning of the flight tube oxygen is also added (limited amount) to ensure
that any carbon formed during pyrolysis is then converted to carbon monoxide. The high
temperature generated by plasma causes compounds to dissociate into their elemental ions
and atoms. Recombination occurs in a cooler area of the reaction chamber, followed by rapid
(2 ms) alkaline quenching from 1500°C to less than 100°C. Such rapid quenching prevents
the formation of dioxins and furans. The PLASCON process is applicable to the gaseous
streams and was successfully applied for destruction of CFC in Australia. In principle, it can
be applied as an add-on module to the processes that yield gaseous emissions containing
high concentrations of POPs and chlorinated VOC. The process is highly efficient, easy in
operation and compact, however maybe costly for low concentrated pollutants due to high
electricity and argon consumption.
CerOx, developed by CerOx Corporation, USA, is a mediated electrochemical

oxidation process able to destroy hazardous organic waste derived from industrial processes
and laboratory wastes, such as biogenic wastes, toxic chemicals, pesticides, herbicides,
PCBs, dilute organics in water, etc. by converting them into CO 2 and water.
The organic molecule to be destroyed is being put in contact with the aqueous
solution of Ce4+ species, which is a strong oxidizing agent. Ce4+ then vigorously reacts with
the organics oxidizing it to CO2 and water and being itself reduced to Ce . After
3+
the cerium
anion is reduced to Ce 3+ by taking an electron from an organic compound, it is brought to
the electrochemical cell where it is reoxidized back to Ce4+. The latter is again introduced in
the reaction vessel thereby closing the process cycle. The two consecutive process modules
treat organics in water and in the gas phase respectively (see Fig. 6.12). The second reactor
module is designed to treat VOC and partial oxidation products in the emissions arising from
the first step. It uses a counter current flow of Ce 4+ allowing the Ce4+ to oxidize organics.
Figure 6.12. Gas-phase CerOx treatment. Reproduced from the vendor website (www.cerox.com).
89
The gas phase reactor can process small amounts of VOCs and can be sized to
handle large quantities of compounds that transform into gas phase at lower than 95°C. In
this connection, its application to treat chlorinated chemicals in emissions can be considered
a possible option.
6..9 Refere
ences
1. S. Zinoviev, P. Fornasiero, A. Lodolo, S. Miertus, Non-combustion technologies for POP destruction. Review
and Evaluation, ICS-UNIDO Publications, 2007 (in press).
2. H.-U. Hartenstein, Performance of commonly used combustion technologies for POPs destruction, in STAP/
GEF Technical Workshop on Emerging Innovative Technologies for the Destruction and Decontamination of
Obsolete POPs, Washington, 1-3 October 2003.
3. Off Gas Treatment Technologies for Soil Vapor Extraction Systems: State of the Practice, U.S. EPA, March
2006, EPA-542-R-05-028.
4. Guide for Conducting Treatability Studies Under CERCLA, Soil Vapor Extraction, U.S. EPA, September 1991,
EPA/540/2-91/019A.
5. FRTR Remediation Technologies Screening Matrix, available at www.frtr.gov.
6. M. Plinke, R.L. Sassa, W.P. Mortimer Jr., G.A. Brinckman, US 5620669, 1997.
7. Alternative technologies for the Destruction of Chemical agents and Munitions. National Research Council,
Washington D.C.: National Academy of Sciences, 1993.
8. Technology Profiles Eleventh Edition. Volumes 1-3, U.S. EPA, September 2003, EPA 540/R-03/501.
9. GPCR presentation at South American regional workshop on the environmentally sound destruction of POPs
and the decontamination of POP containing waste in the framework of Basel and Stockholm conventions,
San Pablo, Brazil, 7-10 December 2004, available at crsbasilea.inti.gov.ar/evento11.htm.
10. T. Bridle, Scheduled Waste Management: The Australian Experience, in POPs Workshop on Emerging
Innovative Technologies for the Destruction and Decontamination of Obsolete POPs, 1st-3rd October 2003.
90
7 Te
echnologies for Partticulate Emission Contro
ol
7..1 Introduction
The present chapter provides technologies available for particulate emission
control for stationary applications: the use of gravity settling chambers, centrifugal
separators, particulate wet scrubbers, electrostatic precipitators and fabric filters will b e
briefly discussed (1,2).
Definitions
Particulate matter (PM) is a major class of air pollution. Black smoke, or soot,
is the most visible emission, but other, less visible pollutants are emitted. Combustion
and non-combustion industrial processes, mining and construction activities, vehicles and
incinerators are examples of potential sources of particulate. Beside these antropogenic
emissions, natural sources (volcanos, forest fires, wind storm, and so forth) are present,
enhancing the negative impact on a global scale. An enormous number of parameters influence
the particulate formation/ageing process, which leads to particulate matter in large variety
of shapes and sizes, and therefore of physical and chemical properties. The concept of
“aerodynamic diameter” has been developed to describe, in a simple and universal way, how
a particle behaves in air. The aerodynamic diameter is the diameter of a spherical particle
having a density of 1 gm/cm 3 that has the same inertial properties (i.e. terminal settling
velocity) in the gas as the particle of interest. The range of particle sizes of concern for air
emission evaluation is quite broad. The Environmental Protection Agency (EPA) (http://www.
epa.gov) has defined four terms for categorizing particles of different sizes (Table 7.1).
Table 7.1: Environmental protection agency terminology for particle size
EPA Description Particle size

Supercoarse  > 10 m
Coarse  m<  < 10 m
Fine  m<  < 2.5 m
Ultrafine < 0.1 m
Using this division of particulates according to their size, the EPA has identified
various categories of particulate emission for the purposes of defining emission control: (I)
Total Suspended Particulate Matter (TSPM); (II) PM10; (III) PM2.5; (IV) particles less than 1
micrometer; and (V) condensable particulate matter. As outlined below, these categories are
based on the environmental impact of each.
Total Suspended Particulate Matter includes a broad range of particle sizes from
0.1 m to about 30 m in diameter, ie, fine, coarse, and supercoarse particles.
PM10 is defined as particulate matter with a diameter of 10 m collected with
50% efficiency by a PM10 sampling collection device. However, for convenience, the term
PM10 is often used to include all particles having an aerodynamic diameter of less than or
equal to 10 m. PM10 is regulated as a specific type of "pollutant" because particles in this
size range can penetrate into the lower respiratory tract.
91
TECHNOLOGIES FOR PARTICULATE EMISSION CONTROL
Analogously, PM2.5 is particulate matter with a diameter of 2.5 m collected

with 50% efficiency by a PM2.5 sampling collection device. The EPA has chosen 2.5
m as the partition between fine and coarse particulate matter. Relative to coarse and
supercoarse particles, PM2.5 particles settle quite slowly in the atmosphere and are of
particular concern from the point of view of human health due to their potentially long
airborne retention time and the inability of the human respiratory system to defend itself
against particles of this size.
Particles less than 1 micrometer in diameter is relatively hard to collect and
therefore they can represent a significant fraction of the particulate emissions from some
types of industrial sources. Particles in the range of 0.2 to 0.5 m are common in many
types of combustion, waste incineration and metallurgical sources. Particulate can be much
smaller than 0.1 m. These sub-micrometer particles are composed of 20 to 50 molecules
clustered together in a stable form. Particles with diameter between 0.01 and 0.1 m tend
to agglomerate rapidly to yield particles in a range greater than 0.1 m.
Condensable particulate matter originates from condensing gases or vapors.
7..2 Partticulate Form

mation
In general, the mechanism of particle formation determines the size and
composition of emitted particles. Not surprisingly, any such formation mechanism is in turn
strictly connected to the source of particle emission. In the following paragraphs, the main
sources of particulate emisions are summarised.
Physical attrition/mechanical dispersion occurs when two surfaces rub together
and generates primarily moderate-to-large sized particles (5 m < diameter <1000 m). The
composition and density of particulates thus formed are identical to those of the parent
materials. Mining or construction activities are typical examples of processes where physical
attrition is a relevant source of PM formation of this type. Figure 7.1 shows the grinding
of a metal rod on a grinding wheel, which yields small particles that break off from both
surfaces. In general, any part in movement contributes to particulate emission.
Housing
Grinding
Whell
To Fan
Parent
Material
Particles
and Air
Air Handling
Hood Duct
Figure 7.1: Particulate generated by physical attrition during the operation of a grinding wheel (adapted from ref 1)
Combustion process: When a fuel is injected into a hot combustion chamber,

most of the organic compounds in the fuel are rapidly vaporized and oxidized in the gas
stream. The fuel is quickly reduced to ash (incombustible material) and slow burning char
(organic compounds) only. Eventually, most of the char will also burn leaving primarily
the incombustible matter. Ash and char particles are primarily in the 1 to 100 µm range.
This mechanism for particle formation can be termed combustion particle burnout. The
combustion process of a fuel is rather complex and it is out of the scope of this brief
92
survey to analyze the mechanism of soot formation in detail. However, it is important to

underline that condensation to clusters of polycyclic aromatic hydrocarbons present in the
fuel, due to Van der Wall forces, and successive coagulation, can lead to primary soot
particles. Soot is produced even in the combustion of methane (Figure 7.2). In fact, during
the oxidation, a small portion of methane can decompose into methyl radicals which, under
fuel rich conditions, form small molecules and reactive radicals of various sizes. Addition of
hydrocarbon radicals to those species allows the growing of the radicalic hydrocarbons, which
then can chemically condense to form chainlike aggregates (primary particles). The particles
may be more or less liquid and they may contain small aromatic moieties, interconnected by
flexible hydrocarbon chains (3,4).
Formation of PAH
CH4 aromatic rings (Polycycle Aromatic
Hydrocarbons)
Methane fuel
Desorption
Pyrolise Chemical
condensation
Pyrens
Reactive small
molecules and radicals
Graphitisation
• CH3 HCCH
Methylradical Acetylene
Corones
Desorption
• C3H3 • C6H5
Propargylradical Phenylradical
Ovalenes
Figure 7.2: Simplified schema of particulate formation hypothesis of radicals during methane combustion
During heating of the particles in the flame, their chainlike, aliphatic structure
is increasingly converted into aromatic rings and compounds, as a consequence of the
extraordinary aromatic stability. Subsequently, the polyaromatic compounds may detach
from the particles when they lay at the surface and all chemical bonds are saturated. As
heating continues the particles form increasingly larger arrays of aromatic rings, becoming
more and more graphitic and therefore denser. The particles tend to coagulate and pick up
small radicals and acetylene for surface growth.
Homogeneous and heterogeneous nucleation occurs when the gas temperature

decreases below the dew point and vapor phase materials condense to a particulate form
(Figure 7.3). Homogeneous nuclei are composed of only one vapor phase compound, whereas
heterogeneous nucleation is the condensation of material on the surfaces of existing
particles, resulting in particulates composed of more than one compound. The vapor phase
material which can nucleate in exhausted air can be grouped in two main categories: (I)
organic compounds and (II) inorganic metals and metal compounds like mercury, lead, lead
oxide, cadmium, cadmium oxide, cadmium chloride, and arsenic trioxide. Homogeneous and
heterogeneous nucleation generally create particles that are very small, often between 0.1
and 1.0 m.
93
Figure 7.3: Municipal waste incinerator: homogeneous and heterogeneous nucleation of particulate (adapted
from ref 1)
Droplet evaporation is caused by air pollution control systems that use recycled
water from wet scrubbers (vide infra) to cool the gas streams. The recycled water, containing
solid materials, is injected into the hot gas streams. The evaporation of the small water
droplets leads to release of the suspended and dissolved solids as small particles in the
size range 0.1 to 20 m.
7..3 Partticulate Emissions Contro

ol Systems
Particulate emissions control systems apply forces to the particles in order to

remove them from the gas stream. Depending on particle size, the collection mechanism
can be based for instance on the effect of inertia, of Brownian diffusion, of gravity or of
electrostatic attraction. The main particulate control techniques can be divided into the
following five categories.
7..3.1 Gravity Settling Chambers
A gravity settler (Figure 7.4) is a long chamber through which the polluted gas is
forced to pass slowly, allowing time for particles to settle by gravity to the bottom. These
devices are used only for large particles (diameter greater than 75 m). In fact, the very low
terminal settling velocities of most particles encountered in the field of air pollution limit the
usefulness of gravity settling chambers. The cross section area (WH) is much larger than
that of the duct approaching it, so that the linear gas velocity inside the chamber is lower
94
that in the inlet duct, thereby favoring settling of particulate. These devices must be cleaned
manually at regular intervals, but their design and construction are simple. Through the last
three decades, the stringent control requirements adopted have resulted in a sharp decline
in the use of this type of collector. However, these devices still have some use in treating
very dirty gases from metallurgical industries.
Gas Flow
OUT
W
H Outlet Baffles
L
Gas Flow
IN
Inlet Baffles
Figure 7.4: Gravity settling chambers (adapted from ref 1)
7..3.2 Centrifugal Separators
Centrifugal separators are mechanical collectors that use centrifugal force to

drive the particle to the collection surface. In general, the gas stream is forced to spin in a
cyclonic manner (Figure 7.5). The mass of the particles causes them to move toward the
cyclone body wall and then settle into the hopper of the cyclone. The cleaned gas turns
and exits the cyclone. There are two main types of mechanical collectors: (I) large-diameter
cyclones, and (II) small-diameter multi-cyclones.
Large-diameter cyclones are usually 30-180 cm in diameter. They have a high
efficiency for particles of diameter higher then 20 m, require low capital cost and they
can operate at relatively high temperature. The fact that there are no moving parts reduce
significantly their maintenance cost.
Cleaned Gas
Gas Outlet Tube
Inlet
Cyclone body
Dirty Gas
Conical Section
Dust
Figure 7.5: Large-diameter cyclones (adapted from ref 1)
95
In order to increase the spinning of the gas stream, small-diameter multi-cyclone

tubes have been developed (Figure 7.6). Vanes located on the inlet of each of the tubes
create an efficient spinning movement of the gas stream. These type of cyclones usually
have diameters of 8-30 cm. Due to the limited gas handling capacity of each tube, large
numbers of tubes are mounted in parallel in a single collector. Small-diameter multi-cyclones
are utilised to collect considerably smaller particles than large-diameter cyclones. In normal
application, the separation efficiency of small-diameter multi-cyclones is sharply decreased
when particle diameter decreases below 5 m; and these systems cannot be used for very
large diameter material (above 30-50 m), as large particles may plug the spinner vanes in
the multi-cyclone tubes. However, it should be noted that specially designed cyclones with a
different geometry with respect to that shown in Figure 7.5 have been developed to provide
high-efficiency particulate matter collection down to a particle size of 1 m (5-8).
The presence of sticky and/or wet particulate matter in the gas stream is an
important considereation in multi-cyclone systems. In fact, sticky and/or wet particulate
matter can accumulate on the cyclone body wall or the inlet spinner vanes of conventional
multi-cyclone collectors, reducing the performances of the system.
A strategy sometimes used with centrifugal separators is to use cyclones as a pre-
collector of large-diameter embers generated in some combustion systems. Removal of
embers is necessary to protect high-efficiency particulate control systems located downstream
from the mechanical collectors.
Traeted Gas
Outlet Tube
Dirty Gas
Inlet
Spinner
Vane
Collecting
Tube
Fly Ash
Particle
Figure 7.6: Small-diameter multi-cyclone (adapted from ref 1)
7..3.3 Partticulate We
et Scru
ubbers
The term scrubber was originally used to describe a device for collecting fine
particles on liquid drops. Nowadays, this term has a more general meaning. In fact, even
devices using a liquid to control sulfur dioxide emission, are called scrubbers.
The basic idea of scrubber is to make a liquid drop and the particle touch each
other, so that the particle will adhere to the drop. Therefore it is necessary to properly
introduce a large number of liquid drops (normally water) into the gas stream. The mixture
of the gas and liquid containing the particulate can easily separated in a cheap cyclone, as
depicted in Figure 7.7. Finally, the liquid can be separated from the solid, and recycled.
96
Scrubber Cyclone
Dirty gas Mixed gas Clean g as
gas-liquid gas-liquid
and liquid
contactor separator
Dirty liquid
Clean liquid liquid-solid

separator
Liquid recirculating pump
Collected solid
Figure 7.7: Schematic composition of a scrubber installation (adapted from ref 1)
Contact of the water drops with the gas to be cleaned may be achieved in a number
of ways. In cross-flow scrubbers (Figure 7.8), multiple spray nozzles are located on the roof
of the scrubber and dispense uniformly the liquid over the horizontally incoming gas. The
liquid is collected at the bottom of the device. Efficiency improves with decreasing drop size
and increasing height of the scrubber. However care must be taken to ensure that the drops
size is not too small, as this may result in a too slow vertical velocity. If this is slower than
the horizontal gas velocity, the drops can pass out with the gas and they will therefore not
be collected in the scrubber. This may represent a serious limitation for certain applications.
Liquid in
Gas in Gas out
Liquid out
Figure 7.8: Scheme of a cross-flow scrubber (adapted from ref 1)
In counter-flow scrubbers (Figure 7.9) the spray nozzles, are located in the roof
of the scrubber. The liquid falls by gravity. The gas stream enter from the bottom of the
scrubber and flows upwards. In this configuration a potential drawback is blowing the drops
out through top of the scrubber (ie, in the wrong direction).
Gas out Liquid in
Gas in Liquid out
Figure 7.9: Scheme of a counter-flow scrubber (adapted from ref 1)
97
In co-flow scrubbers (Figure 7.10), both the gas and the liquid enter at the left
and exit at right. However, the liquid enters at right angle to the gas flow. The gas velocity is
partially reduced by the liquid injection.
Gas in Gas out
Liquid out
Liquid in
Figure 7.10: Scheme of a co-flow scrubber (adapted from ref 1)
All three of these general methods have been incorporated into the many types
particulate wet scrubbers are used in industrial processes: Venturis, impingement and sieve
plates, spray towers, mechanically aided, condensation growth, packed beds, ejector, mobile
bed, caternary grid, froth tower, oriented fiber pad, wetted mist eliminators. As this list is
quite extensive, for brevity only selected samples will be discussed here.
A typical co-flow Venturi scrubber is shown in Figure 7.11 (9). Particulate matter,
which accelerates as it enters the throat, is driven into the slow moving, large water
droplets that are introduced near the high velocity point at the inlet of the Venturi throat.
The adjustable dampers in the unit illustrated are used to adjust the open cross-sectional
area and thereby affect the speed of the particles entrained in the inlet gas stream. Venturi
scrubbers include the following different design types: (i) fixed throat, (ii) adjustable throat,
(iii) collision (opposed-adjustable), (iv) single rod decks, and (v) multiple rod decks.
Gas Inlet
Spray
Header
Liquid
Inlet Throat
Movable
Throat
Dumper
Gas Outlet
Outlet
Figure 7.11: Co-flow venturi scrubber (adapted from ref 1)
Figure 7.12 shows an impingement plate scrubber. These scrubbers usually have
one to three horizontal plates, each of which has a large number of small holes. The gas
stream accelerating through the holes vapourises water droplets in the water layer above the
plate. Particles impact with these water droplets.
98
Clean Gas
Mist Eliminator
Liquid Inlet
Plate
Downcomer
Dirty Gas
Figure 7.12: Impingement plate scrubber (adapted from ref 1)
Figure 7.13 report a typical spray tower scrubber. This is the simplest type of
particulate wet scrubber in commercial service. Sets of spray nozzles located near the top
of the scrubber vessel generate water droplets that impact with particles in the gas stream
as the gas stream moves upwards.
Clean Gas
Liquid Sprays
Dirty Gas
Figure 7.13: Spray tower scrubber (adapted from ref 1)
7..3.4 Electrostatic Pre

ecipitators
The basic idea an electrostatic precipitator is to give the particles an electrical

charges and then to put them in an electrostatic filed that drive them to the collecting wall.
Figure 7.14 shows a simplified scheme of an electrostatic precipitator with two plates. In
this configuration, the dirty gas passes between the plates, which are electrically grounded.
Between the plates are rows of wires, held at a typical voltage of 40000 volts. The combination
of charged wires and grounded plates produces at the same time the free electrons to
charge the particles and the field to drive them to the plates. On the plate the particle
loses its charge, adheres to other preadsorbed particles forming a “cake”. This solid cake
is removed by rapping the plates at regular intervals with a mechanical or electromagnetic
rapper that strikes a blow on the edge of the plate. The composition of the particulate matter
is very important because it influences the electrical conductivity within the dust layers on
the collection plate (10-12).
There are three main styles of electrostatic precipitators: (i) negatively charged
dry precipitators, (ii) negatively charged wetted-wall precipitators, and (iii) positively charged
two-stage precipitators.
99
The negatively charged dry precipitators are the type most frequently used on
large applications such as coal-fired boilers, cement kilns, and kraft pulp mills. They are also
widely used in air conditioning systems for buildings . In this case, charging and collecting
are carried out in separate parts of the electrostatic precipitator, giving the name of two
stage precipitators. Wetted-wall precipitators (sometimes called wet precipitators) are often
used to collect mist and/or solid material that is moderately sticky. The positively charged
two-stage precipitators are used only for the removal of mists.
Electrostatic precipitators can have very high efficiencies due to the strong
electrical forces applied to the small particles. These types of collectors can be used when
the gas stream is not explosive and does not contain entrained droplets or other sticky
material.
High-voltage Wires for

2H Upper
Corona Discharge L
Wire
Dust-collection Support
Plates
Corona Discharge
along the Length Clean Gas
of a Wire
Dirty Gas h
Lower
Wire
Collected Dust
Support
on Plates
Ground Duct Removed from

Plates to Hoppers
Figure 7.14: Scheme of an electrostatic precipitator with two plates and four wires (adapted from ref 1)
7..3.5 Filters
Filters divide the gas flow into smaller parts where they can collect the particles.
In general two categories of filter are used in air pollution control: surface filters and depth
filters. Construction of filters with holes as small as many of the particle to collect is very
difficult. Therefore, in general, the sizes of the holes of industrial filters are significantly
bigger than the particle diameter. Nevertheless, they act as efficient surface filters (Figure
7.15a), as, when fine particles are caught on the side of a hole, they tend to bridge over the
hole, reducing its dimensions. The cake of collected material becomes the “effective” filter,
while the “original” filter act as a support. The growing cake have average pore size smaller
than the diameter of the incoming particles. The particulate is collected on the front surface
of the cake. For that reason this is called a surface filter.
Depth filters (Figure 7.15b) are the other important class of filter used in air
pollution control. They collect particles throughout the entire filter body. Each layer has
the same filtration efficiency, however mass deposition decrease logarithmically from inflow
to outflow. The separation efficiency depends on pore size of the filter (or the particulate
diameter), on the depth of the filter, and on the gas velocity (13-14).
100
Filtered exhaust Filtered exhaust
Figure 7.15 a: Wall flow filter, surface filtration Figure 7.15 b: Depth filter, depth filtration
(adapted from ref 1) (adapted from ref 1)
7..4 Commercially Avvailable Te

echnologies
No.1
Type of Industry:Chemical; Petrochemical
Subject: Reduction of Smoke Dust in Boiler Exhaust Gas
Purpose: To keep the concentration of the smoke dust discharged from coal boilers
under 0.03 g/Nm3 in accordance with the regulation of the local prefecture.
Principle: The temperature of the exhaust gas is around 150°C.The bag filter chamber
is divided into 6 chambers with 450 filter cloths suspended in each chamber
for a total of 2,700 pcs. Clogging of the filter cloth is effectively prevented:
the dust adhered to the external surface of the filter cloth can be dropped
into a hopper by means of periodical pulses of cleaning air jets from a
rotating manifold mounted on the cell plate. The interval of these pulses
can be arranged to keep the pressure difference on the filter cloth at about
100 mmAq.
Effect and Achievement: Operation is carried out with a bag filter outlet dust concentration of
0.025 g/Nm3 as compared with the inlet dust of 4 ~ 17g/Nm3.
The system can operate below 0.010g/Nm3 if there is no leakage in the
cell plate packing. Although the bag filter will be bypassed when the boiler
fuel is changed from coal to heavy oil, the regulation value of dust can be
attained with desulfurization equipment installed downstream.
Future: Although the physical properties tests are conducted with samples for
diagnosis of deterioration of the filter cloth, there is no appropriate guide on
damage or deterioration, so there is a tendency towards over maintenance
to avoid damage of the filter cloth during operation.
Implementing company: Japan Synthetic Rubber Co., Ltd. Yokkaichi Plant
No. 2
Type of Industry:Petroleum refining
Subject: Reduction of Dust Discharged from Catalyst Regenerator
Purpose: To reduce the dust in the exhaust gas discharged from the catalyst
regenerator unit of the fluidized catalytic cracker from 0.30 g/Nm3 to 0.03
g/Nm3.
Details: Normally, the dust concentration is high in the exhaust gas discharged from
the catalyst regenerator unit, since it contains scattered catalysts. The
electric precipitator was therefore installed to collect the dust and to clean
the exhaust gas.
Principle: The basic structure of the electric precipitator consists of 1) electric
discharging poles, 2) dust collecting poles to collect the dust charged by
corona current, ) striking devices to release the dust adhering to the pole
10
1
plates, 4) discharge device to process the dust collected and ) shielding of

the dust collecting unit and high voltage insulating mechanism. The dust
particles in the discharge gas are charged by corona discharge from the
discharging pole and are attracted to the dust collecting pole by Coulomb
force. The dust that has collected and grown on the dust collecting pole is
separated from the pole by the impact of the striker and is removed after
falling down by the gravity.
Future: It is necessary to adapt the optimum processing conditions to the maximise
exhaust gas purification, and in particular it must be 1) increase the corona
discharge by maintaining a high load voltage, 2) maintain adequate gas
temperature - higher than the dew point but not too high (normally 230-
300°C ), 3) adjust strike time and 4) refrain from storing excessive dust in
the hopper of the electric dust collector.
Implementing company: Showa Yokkaichi Sekiyu Co., Ltd. Yokkaichi Refinery.
7..5 Refere
ences
1. Air Pollution Control Engineering, N. de Nevers, second Edition, 2000, Mc Graw Hill, New York.
1996.
3. Gruenberger TM, Moghiman M, Bowen PJ, Syred N, Combustion Science and Technology, 2002, 174 (5-6):
67-86.
4. Barone AC, D’Alessio A, D’Anna A, Combustion and Flame, 2003, 132 (1-2): 181-187.
5. Cooke MJ, Ford NJ, Pragnell RJ, Journal of the Institute of Energy, 1991, 64 (461): 239-246.
6. Easom BH, Burlatsky SF, Altman RF, Chang R, Pollution Engineering, 1999, (7): 40-42.
7. Jaworek A, Balachandran W, Krupa A, Kulon J, Lackowski M, Environmental Science and Technology,40 (20):
6197-6207 OCT 15 2006
8. Lehner M, Hoffmann A, Chemical Engineering & Technology, 2004, 27 (7): 722-728.
9. Ananthanarayanan NV, Viswanathan S, Industrial & Engineering Chemistry Research, 1999, 38 (12): 4889-
4900
10. Kim SH, Lee KW, Journal of Electrostatics, 1999, 48 (1): 3-25.
11. Zukeran A, Looy PC, Chakrabarti A, Berezin AA, Jayaram S, Cross JD, Ito T, Chang JS, IEEE Transactions on
Industry Apllications, 1999, 35 (5): 1184-1191.
12. Prasad NVPRD, Lakshminarayana T, Narasimham JRK, Verman TM, Raju CSRK, IEEE Transactions on Industry
Apllications, 1999, 35 (3): 561-567
13. Jung SC, Park JS, Yoon WS, Iternational Journal of Automotive Technology 8 (2): 165-177 APR 2007
14. Yamamoto K, Ochi F, Journal of the Energy Institute, 2006, 79 (4): 195-199
102
8 Abatement of the Hydrocarbon and CO Emissions from

Ga
as Tu
urbine
This short Chapter is specifically dedicated to the abatement of pollutant gasses
from gas turbines, due to the importance of this application. Notably that NO X reduction is
also discussed in Chapter 3.2.2, while the reduction of the emission of volatile organic
compounds is discussed in Chapter 5 and the control of NOx, hydrocarbon and CO emission
from vehicles is discussed in Chapter 10.
8..1 Gas Turrbines
Combustion turbines that burn fuel to generate heat are widely used for the co-
generation of electricity and steam.(1) Gas turbines have usually a coaxial centrifugal air
compressor. The preheated and compressed air at 200 - 500 °C meets the fuel stream
in the combustion chamber. The exhausted gas have a temperature up to 1600-2000 °C,
which is too high for the turbine. Therefore, part of the air is by-passed to cool the combus-
tion gas before it goes to the turbine. Notably that nitrogen oxides are formed during the
combustion process, trough the various mechanisms previously discussed in Chapter 3. We
need to recall that the formation of thermal-NOx is significant at temperatures above approxi-
mately 1500 °C while prompt NOx is only significant at close to stoichiometric conditions in
flame combustors. Finally, the NOx formed as a reaction intermediate, is significant at low
temperatures in and is unstable at higher temperatures. The combustion of fuel containing N
bound species most likely involves the thermal decomposition of the bound nitrogen species
upstream of the combustion zone. Therefore, significant amounts of low molecular weight
molecules, such as NH3, NH2, NH, HCN, CN., can be fed to the gas turbine and partially
remain in the exhaust.
The existing methods for NOx control in gas turbines includes prevention strategies
to control the combustion and end–off pipe measures to clean up the exhaust gas. Primary
measures include, beside catalytic combustion, water or steam injection, lean-premixed
combustion and staged combustion. In this respect it mast be notice that since the 1980s,
a common practice in operation of these gas turbines has been to use water or steam
injection to lower the combustion flame temperature to reduce the NOx emissions. However,
the quenching of the flame results in increased CO and hydrocarbon (HC) emissions. In fact,
the use of water or steam injection typically can reduce the NOx emissions from 150 vppm to
about 40 vppm, with a concurrent increase in CO emissions from 10 vppm to as high as 400
vppm and an increase in hydrocarbon emissions. Furthermore, a water purification stage is
need and water injection can lead to corrosion problem and / or can alter the combustion.
However, water injection is still a viable technology, and in some case is used in combination
with new burner developments and end-off pipe technology.
Lean-premixed combustion has been introduced lately and gives low emission
levels, typically around 25 ppm thermal-NOx. The drawback of this approach is that a
complicated and expensive control systems must added.
10
3
ABATEMENT OF THE HYDROCARBON AND CO EMISSIONS FROM GAS TURBINE
Staged combustors operate first under fuel-rich conditions followed by a quick

quench to fuel-lean. This system offers great potentiality and high efficiency for fuels with
large amount of bound nitrogen species, which can be effectively reduced in the fuel rich
stage. Notably, however that the emissions of other pollutants than fuel-NOx are usually
higher than for other prevention alternatives.
The catalytic combustion (2) is the most promising and challenging strategy for
ultra-low emission gas turbines. It has been shown that it should be the lowest-cost and
preferred technology for applications that require emission levels below 5 ppm (3). This
application will be discussed in more detail in the following 8.2.
The most important end-off pipe technology which can be applied to gas turbine
is the effective selective catalytic reduction (SCR). The major drawbacks of SCR are the high
capital and operating costs, the large bulky catalytic reactor, the need of NOx/NH3 analytical
equipment as well as an ammonia or urea storage and distribution system The selective
non-catalytic reduction (SNCR) is far less effective in NOx reduction even though it is much
cheaper and easy to control.
In any case a critical design features showed to be the design of the postcatalyst
stage with homogeneous combustion to reach low HC and CO emissions.
8..2. Catalytic combustion

The catalytic combustor (2) is basically a lean-premixed combustor, in which the
combustion is stabilized by a catalyst. Here, the combustion can be ultra-lean, since the
catalyst can operate below the limits of homogeneous flammability. Therefore, the thermal-
NOx emission can be very low. Notably that the presence of a catalyst lowers significantly
the temperature of the combustion chamber and of the exhausted gasses (900-1300 °C),
which can go directly to the gas turbine without need for a by-pass of cooling air, as shown
in Figure 8.1.
Fig. 8.1 Schematic representation of a catalytic combustor and a flame combustor in an open-cycle gas turbine.
Typically, the inlet air temperature to the combustor is raised to approximately

200 °C for a low
pressure turbine and to 400 °C for a high pressure turbine at full load. Notably that
at idle and partial load conditions, the gas turbines do not reach the same inlet temperature.
Therefore, a suitable catalyst must be able to ignite the fuel already at significantly low –
ignition temperature. Alternatively to the design and use of highly active catalyst, pilot flames
104
can be used to heat the gas to the catalyst ignition temperature. However, this requires a
careful designed, to control the amounts of thermal-NOx (4).
The main factors which influence the maximum outlet temperature of the combustor
are the amount of cooling air, homogeneity or pattern factor of the fuel-air mixture temperature
losses in the transition duct between combustor and turbine, turbine inlet temperatures and
adiabatic temperature rise on combustion of the fuel. Finally, it must be noted that gas
turbines are designed for a specific turbine inlet temperature, which is not the same as
the combustor outlet temperature. For example, if the gas turbine is designed for an inlet
temperature of 1250 °C, approximately 100 °C could be lost in cooling air and temperature
losses in the transition duct. Further, a 5% inhomogeneity in the air-to-fuel mixing could give
a temperature deviation of ≈ ± 50°C in adiabatic temperature rise. Therefore, the catalyst
must be designed to work at 1400 °C and not at 1250 °C.
Combustor can be made without any large change in the gas turbine design.
8..3 Catalytic contro

ol of Hydrocarbon Emissions from Gas Tu
urbine
While NOx emissions from gas turbine have been the subject of many regulations,
only recently abatement of HC, CO and SO x have been considered. Notably that air quality
regulations have for long time not even considered methane emissions. This is because
methane is non toxic and is largely considered unreactive with regards to the atmospheric
processes that cause photochemical air pollution. Thus, hydrocarbon reduction efficiency
usually concerns the destruction of nonmethane hydrocarbons (NMHC). To meet these
requirements, new catalysts has been developed for simultaneous CO and HC removal (5-
7).The catalytic oxidation activity of these catalysts, strongly depends on the type of
hydrocarbon. For example, unsaturated or substituted hydrocarbons such as alkenes (e.g.,
propylene), aromatics (e.g., toluene), and aldehydes (e.g., formaldehyde) are much easier
to oxidize (i.e., require lower temperature) than saturated paraffins such as propane. Among
saturated compounds, those with lower carbon numbers are more difficult to convert than
those with higher carbons numbers (e.g., propane is much more difficult to convert than
hexane).
Hydrocarbons in the exhaust of combustion turbines are composed of “combustion-
derived” and “fuel-derived” products. Fuel-derived hydrocarbons are uncombusted
hydrocarbons from the fuel that reached the turbine exhaust, whereas combustion-derived
hydrocarbons are compounds that have undergone a partial chemical change in the turbine
combustor that falls short of complete conversion to carbon dioxide and water. Depending
on the fuel source, the exhaust HC species and composition can vary greatly. It has been
reported that, for aircraft turbine engines operating with jet A fuel, combustion-derived
ethylene, acyetlene, propylene, and formaldehyde accounted for a major portion (22 to 43
percent) of the nonmethane hydrocarbons (8). Fuel-derived, C7-C9 hydrocarbons represent
a large portion of the remaining NMHC in the exhaust. On the other hand, the NMHC in
the exhaust of natural gas fired turbines are usually reported to consist of fuel-derived
ethane and propane, with trace levels of combustion-derived formaldehyde, benzene, and
other substances. The requirements of a catalytic NMHC emissions abatement system can
vary widely as a result of these distinctly different NMHC compositions for turbines using
different fuels.
Except for C2-C5 paraffins (i.e., ethane, propane, butane, and pentane), the
conversion rates of NMHC compounds are controlled by the rate of gas mass transfer to the
catalyst surface when operating at temperatures greater than 250 °C. These reactive, often
combustion-derived, hydrocarbons include alkenes, alkynes, aromatics, C+6 paraffins, and
partially oxygenated hydrocarbons. This conversion efficiency will depend primarily on their gas
10
5
ABATEMENT OF THE HYDROCARBON AND CO EMISSIONS FROM GAS TURBINE
phase diffusivities and, as in CO oxidation, on the geometric surface area of the honeycomb
catalyst. The conversion rates of reactive hydrocarbons will always increase with increasing
catalyst cell density, because the geometric surface area for reaction increasing.
However, the absolute conversion level for each species will depend on its diffusion
rate in the exhaust gas. In general, larger, heavier molecules (like C8 and C9 molecules) will
diffuse more slowly than smaller, lighter molecules such as ethylene.
The primary hydrocarbon types found in the exhaust of a natural gas fired
combustion turbine are light paraffins, and these are among the less reactive molecules
for oxidation. Methane, ethane, propane, butane, and (to a lesser extent) pentane) require
special catalysts, higher temperatures, or both before they can be destroyed using practical
volumes of catalyst in a combustion turbine exhaust.
8..2 Catalytic contro

ol of CO Emissions from Gas Tu
urbine
The catalyst used for the abatement of CO emissions from gas turbine can range
from 0.05 to 0.5 percent Pt catalyst dispersed on -Al2O3 on a ceramic honeycomb with 100
to 400 cpsi. Since this reaction is basically bulk mass transfer controlled above 150 °C,
increasing the linear velocity, the reactor volume, and the number of cpsi of the honeycomb
can increase the catalyst efficiency. However, this is at the penalty of increased pressure
drop. Increasing the space velocity diminishes the maximum conversion obtainable. The
oxidation catalyst can be located anywhere downstream in the gas turbine exhaust as
long as the temperature is above 100 °C (preferably above 250 °C) to minimize catalyst
requirements (e.g., volume).
These catalytic systems are assembled in modules (e.g., 2*2 feet) and fabricated
into walls of catalyst. Typical catalytic depths range from 3 to 6 inches. These catalyst walls
have been fabricated up to 30 feet wide. Depending on the installation, space velocities
range from 100, 000 to 300, 000 hr -1 and cell geometries from 100 to 400 cpsi. Pressure
drops of 1 to 10 inches of water are typical. Either ceramic or metallic substrates can be
utilized (9).
CO abatement systems for fuels containing sulphur require special catalyst
formulation and process conditions that minimize the SO 2 to SO3 reaction and reduce the
poisoning effect of both SO 2 and SO3 on the catalyst. Notably that SO2 strongly chemisorbs
onto the Pt sites at temperatures below about 300 °C, resulting in inhibition of the CO
oxidation reaction. Above 300-350 °C, the SO2 is converted to SO3, which can react
with the -Al2O3 washcoat to form Al2(SO4)3. This lead to deactivation by pore blockage.
Therefore catalyst must be designed in such a way that scavenger additives protect the
active phase from SOx adsorption, limits the reaction between SO3 and the washcoat and
includes additives that suppress the activity of Pt toward SO3 production at the reaction
conditions.
Supported noble metal catalysts and in particular supported gold nanoparticles
on transition metal oxides show interesting performances (10). Commercial Engelhard
Technology Camet® CO Oxidation catalyst (11) has interesting performances for such type
of applications. This catalyst, noble metal-based, coated onto a open cross flow channel
(“herringbone” or “skew” type) corrugated metal foil, wound into monolithic structure, is
a good available solution to abate CO from gas turbines exhausts. It can be combined to
the SCR catalyst below for complete exhaust abatement service and provides the lowest
possible pressure drop with very high surface area. It is washable and non-hazardous when
spent. The same technology can be used in several other VOC abatement processes (10).
106
8..3 Gas Turrbine Afterttreatment Catalyst Deactivation
There are three primary sources of catalyst poisons and contaminants in the
exhausts of co-generation combustion turbines: fuel contaminants, boiler leaks, and turbine
lubricants. Of the three, sulphur oxides from liquid fuels are the most common. Poisoning
from boiler feed additives and turbine lubricants can be much more severe.
At temperatures below about 300 °C, SO2 chemisorbs on to the active metal sites
and inhibits the oxidation of both CO and HC (12). It is for this reason that most processes
operate above 300 °C . Notably that SO3 formed from the oxidation of SO2, can react with
alumina leading to formation of Al 2(SO4)3, which further deactivates the catalyst. Catalysts
are therefore formulated to minimize SO3 production. New washcoats have been developed
that adequately disperse the active catalytic
metals but are unreactive towards SO 3.
Catalyst contamination from sources such as turbine lubricant and boiler feed
water additives (e.g., Zn, P, Ca) is usually much more sever than deactivation by sulphur
compounds in the turbine exhaust. This is because these materials irreversibly mask the
catalyst surface. Therefore, catalyst regeneration remains the best option for maintaining
good conversion in the dirtiest environments. Commercial experience led to the development
of catalyst regeneration procedures that can restore most of the original catalyst activity,
however this requires shat down of the process.
8..4 Refere
ences
1. Walsh P. and Fletcher P., Gas Turbine Performance, Second Edition, Blackwell Publishing House, 2004.
2. Magnus Johansson E. et al. in Catalytic Combustion for Gas Turbine Applications, Chapter 6, Catalysis,
Volume 14, The Royal Society of Chemistry, 1999.
3. Dalla Betta R.A., Catal. Today, 47 (1997) 369-375.
4. Sadamori H., Catal. Today, 47 (1999) 325-338.
5. Speronello, B., Chen, J., and Heck, R. 1992. A Family of Verstile Catalyst Technologies for NOx and CO
Removal in CO-Generation. 92-109.06, 85th Annual Awma Meeting, June 21-26, 1992, Kansas City, Mo.
6. Chen, J., Speronello, B., and Heck, R. 1993. Catalytic Control of Unburned Hydrocarbon Emissions in
Combustion Gas Turbine Exhaust. 93-mp 7.03, 8th Annual AWMA Meeting, june, 1993, Denver, Co.
7. Pereira, C., Gulian, F., Czarnecki, L., Rieck, J. 1990. Dual Function Catalyst for Clean Gas Application. 90-
105.6, 83rd Annual AWMA Meeting, June 24-29, 1990, Pittsburgh, pa.
8. Spicer, C., Holdren, M., and Smith, D. 1990. Chemical Composition of Exhaust from Aircraft Engines. Gas
Turbine and Aeroengine Congress and Exposition, June 11-14, 1990, Brussels, Belgium.
9. Pereira, C., Plumblee, K., and Evans, M. 1988. Camet Metal Monolith Catalyst System for Cogen Applications.
2nd International Symposium on Turbomachinery. Combined Cycle Technologies and Cogeneration. IGTI-Vol 3.
Ed. G. Serovy and T. Fransson, Book No. 1002705.
10. Centi G., Ciambelli P., Perathoner S., Russo P., Cat. Today, 75 (2002) 31-15.
11. http:\\www.engelhard.com/etg
12. Heck R.M. and Farrauto R.J., Catalytic Air Pollution Control, Wiley-Interscience; 2 edition, New York (2002).
10
7
9 Ozone Contro
ol Strategies
Ozone, the triatomic form of oxygen (O3) is a gaseous atmospheric constituent. In

the troposphere, it is created both naturally and by photochemical reactions involving volatile
organic compounds resulting from human activities (photochemical smog). Ozone is a strong
photochemical oxidant and therefore, in relatively high concentrations, it can be dangerous
and harmful for human health and can damage the ecosystem, the agricultural activities and
reduce the life of many materials (for instance it can increase the rate of oxidation of plastic
materials). (1-2)
Notably that there is a general great interest towards understanding of the ozone
reaction in the atmosphere and therefore to its control and regulations. In fact it has been
established that chlorine and bromine containing compounds, such as chlorofluorocarbons
(CFCs), halons, a broad range of industrial chemicals used as propellants, refrigerants,
fire retardants, solvents, process agents, foaming agents and fumigants, can attach the
tropospheric ozone layer allowing ultraviolet-B radiation to reach the ground, which could
raise the incidence of skin cancer, cataracts, and other adverse effects on the human
immune. In this respect, a series of international agreements on the reduction and eventual
elimination of production and use of ozone depleting substances have been put in place.
The well known Montreal Protocol became effective in 1989. Currently, more then 160
countries participate in the Protocol. Efforts are dedicated to the recovery of the ozone layer
in about 50 years. In the United States, the U.S. Environmental Protection Agency (EPA)
continues to establish regulations to phase out these chemicals. The Clean Air Act requires
warning labels on all products containing CFCs or similar substances, prohibits nonessential
ozone depleting products, and prohibits the release of refrigerants used in car and home air
conditioning units.
Furthermore, in view of the harmful effects of photochemical pollution in the
lower levels of the atmosphere, the European Council adopted in 1992 Directive 92/72/EEC
on ozone air pollution (the Ozone Directive). The Directive came into force in March 1994. It
established procedures for harmonized monitoring of ozone concentrations, for exchange of
information, for communication with and alerting of the population regarding ozone and to
optimise the action needed to reduce ozone formation.
More delicate problem are related those related to the abatement of ozone
concentration in the urban atmosphere. In fact, motor vehicle exhaust and industrial emissions,
gasoline vapours, and chemical solvents are the major sources of ozone precursors. Strong
sunlight and hot weather cause ground-level ozone to form in harmful concentrations in the
air. Many polluted urban areas tend to have high levels of “bad” ozone, but even relatively
clean areas can suffer of similar problems due to the effects of winds, which can carry VOCs
and NOx emissions hundreds of miles away from their original sources. Ozone concentrations
can significantly vary from year to year, accordingly with weather conditions (number of hot /
sunny days or periods of air stagnation). Therefore long-term ozone concentration predictions
are extremely difficult. The Clean Air Act Amendments of 1990 require EPA, states, and cities
to implement programs to further reduce emissions of ozone precursors from sources such
as cars, fuels, industrial facilities, power plants, and consumer/commercial products. Power
plants have partially reduced emissions, cleaner cars and fuels have been developed, gas
109
OZONE CONTROL STRATEGIES
stations are increasingly using special nozzles at the pumps to recapture gasoline vapours,
and vehicle inspection programs are being improved to reduce emissions.
9..1 Strategies for Reducing Ground-level Ozone

Strategies for reducing ground-level ozone include are base on prevention and
in particular on the reduction of NOx and VOC emissions from power plants and industrial
combustion sources, on the introduction of low-emission cars and trucks, and on the use of
“cleaner” fuels. (3) All this aspect are discussed separately in the other book chapters.
9..2 Ozone Abatement in Jet Airccraft
Great effort (3-5) has been devoted to the development of ozone abatement
technology suitable for application in Jet Aircraft. Adsorption and thermal and catalytic
decompositions have been investigated so far. The amount of adsorbent (e.g., carbon)
required for such applications would weight too much for practical use. High fuel penalty
limits the use of thermal processes which require high temperatures. Catalytic decomposition
occurs at much lower temperature and is more acceptable. Therefore, the majority of the
aircrafts equipped for ozone abatement, use a catalyst to decompose ozone. (2)
Both precious and base metals were explored for this application. It must be
noticed that, due to the ozone high oxidation capability, it has been observed a rapid
deactivation of many catalytic materials after a short exposure. This caused considerable
problems in early testing because many materials looked good on bench tests but failed in
the aircraft after a relatively short time. (4). The most effective catalytic material is about 1
percent Pd on gama alumina supported on a high cell density ceramic or metallic monolith.
9..3 Refere
ences
1. Pollution: Causes, Effects and Control, Harrison R. M. Ed., The Royal Society of Chemistry, Cambridge,
1996.
2. Heck R.M. and Farrauto R.J., Catalytic Air Pollution Control, Wiley-Interscience; 2 edition, New York (2002).
3. Couach O., Kirchner F., Jimenez R., Balin I., Perego S., van den Bergh H., Atmospheric Environment, 38
(2004) 1425–1436.
4. Heck R., Farrauto R., and Lee H., Cat.Today, 13 (1992) 43-85.
5. Galligan M.P. and Dettling J.C., United States Patent 5620672, 1997.
110
10 Air Polluttion from Mobile Sources

Air pollution generated from mobile sources is a problem of general interest. In
the last sixty-years the world vehicle fleet has increased from about 40 million vehicles to
over 700 million; this figure is estimated to increase up to 920 million by the year 2010 (1).
The environmental concern originated by mobile sources is due to the fact that the majority
of engines employ combustion of fuels derived from crude oil as a source of energy. Burning
of hydrocarbon ideally leads to formation of water and carbon dioxide, however, due to non-
perfect combustion control and high temperatures reached in the combustion chamber,
the exhaust contains significant amounts of pollutants which need to be transformed into
harmless compounds. This chapter is mainly focussed on the catalytic aspects of pollution
abatement, even though the reader should consider that technological solutions such a
electrically heated catalysts, reformulation of the fuel, etc., may heavily affect the converter
performances (2).
10
0.1 Automotive Emission Characteristics and Regulations
Engine exhausts consist of a complex mixture, the composition depending on
a variety of factors such as: type of engine, driving conditions, vehicle speed, etc. The
exhaust contains principally three types of pollutants, unburned or partially burned
hydrocarbons (HC), carbon monoxide (CO) and nitrogen oxides (NOx), mostly NO (see Table
10.1) (3-8). In general, the emissions strongly depend on air-to-fuel (A/F) ratio, as exemplified
in Figure 10.1.
Rich Lean
0.68 0.95 1.22 1.50 l
Pollutant emisions (a.u.)
NO Engine power
HC
CO
10 14 18 22
Air : Fuel ratio, by weight
Figure 10.1: The effect of air-to-fuel ratio (w/w) on engine emissions (after ref. (8))
Tuning of the engine to rich feed gives the highest power output, which, however,
occurs at expenses of high fuel consumption. Under lean-conditions lower combustion
temperatures lead to lower NOx emissions, however, at very high A/F engine misfire occurs,
111
AIR POLLUTION FROM MOBILE SOURCES
leading again to high HC emissions. Under any A/F conditions catalytic abatement of
pollutants is needed to comply with the legislation limits. Only at stoichiometric conditions
appropriate amounts of reducing and oxidising agents are present in the exhaust to carry
out simultaneously the catalytic reactions of NO x reduction and CO and hydrocarbon
oxidation.
Table 10.1: Exhaust emission of vehicles. (from ref 4)
Exhaust
Diesel engine Four stroke spark Four-stroke lean-burn Two-stroke spark-
components and
ignited-engine spark- ignited engine ignited engine
conditions a
NOx 350 - 1000 ppm 100 - 4000 ppm  1200 ppm 100-200 ppm
HC 50 - 330 ppmC 500 - 5000 ppmC  1300 ppmC 20000 - 30000 ppmC
CO 300 - 1200 ppm 0.1 - 6 %  1300 ppm 1-3%
O2 10-15 % 0.2-2 % 4 - 12 % 0.2 - 2 %
H2 O 1.4-7 % 10-12 % 12 % 10 - 12 %
CO2 7% 10-13.5 % 11 % 10 - 13 %
SOx 10 - 100 ppm b 15 - 60 ppm 20 ppm  20 ppm
PM 65 mg/m3
Temperatures rt - 650 °C rt - 1100 °C c rt - 850 °C rt - 1000 °C
 (A/F) e
 1.8 (26)  1 (14.7)  1.16 (17)  1 (14.7) d
is
N2remainder. b For comparison: diesel fuels with 500 ppm of sulphur produce
a
about 20 ppm of SO2. c Close coupled catalyst. d Part of the fuel is employed for scavenging
of the exhaust, which does not allow to define a precise definition of the A/F. e  defined as
ratio of actual A/F to stoichiometric A/F,    at stoichiometry (A/F = 14.7) .
In the past, exhaust emission standards (limits) have been set in most industrialised
countries for passenger cars, light-duty trucks and heavy-duty trucks (gasoline and diesel
engines). For the gasoline engines, nowadays, the requirements are to reduce emissions
by about or even more than 95% in comparison to typical amount of pollutants emitted by
late-sixties automobiles with uncontrolled emissions. As an example, under the European
limits the uncontrolled CO emissions in the late sixties were around 60 g of CO km -1, which
should drop, according to an EU proposal, down 1.0 g km-1 by year 2005. This is equivalent
to a 98% reduction of the CO emissions. Similarly, a very restrictive situation is foreseen for
HC emissions. Both lowering of the limits down to 0.10 g km -1 and the inclusion of the cold
start in the vehicle test are important targets which need to be fulfilled.
The Environmental Protection Agency (EPA) established a federal Test Procedure
(FTP) simulating the average driving conditions in the U.S in which CO, HC, and NO x would
be measured. The FTP cycle was conducted on an engine dynamometer and included
measurements from the automobile during three conditions: (i) cold start, after the engine
was idle for eight hours, (ii) hot start, and (iii) a combination of urban and highway, driving
conditions. Separate bags would collect the emissions from all three modes, and a weighing
factor was applied for calculating the total emissions.
112
The need to control engine emissions according to Clean Act Air, recent
amendments have set up more stringent requirements for automotive emissions (2). The
catalysts will be required to last 100,000 miles for new automobiles after 1996. Furthermore,
the amendments (contingent on tier 2 standards to be set by environmental protection
agency) reduce nonmethane hydrocarbon (NMHC) emissions to a maximum of 0.125 g/mile
by 2004 (down from 0.41 g/mile in 1991), carbon monoxide to 1.7 g/mile (down from 3.4
g in 1991), and nitrogen oxides to 0.2 g/mile (down from 1.0 g).
Engine manufactures have explored a wide variety of technologies to meet the
requirements of the Clean Air Act. Catalysis has proven to be the most effective passive system.
The major worldwide suppliers of automotive catalysts are Engelhard, Johnson Matthey,
Degussa, and Allied Signal. As the automobile engine has become more sophisticated,
the control devices and combustion modifications have proven to be very compatible with
catalyst technology, to the point where today engineering design incorporates the emission
control unit and strategy for each vehicle.
10
0.2 Catalytic Conver ter and Thre
ee-way Catalysts
Emission control catalysts eliminate dangerous engine pollutants from a wide
range of fuels, including gasoline, diesel, natural gas, and alternate fuels. Catalysts
transform pollutants into harmless gases within a catalytic converter before releasing
them into the environment. Historically, four generations of de-pollution catalysts/
converters can be distinguished. The first generation converter typically contained a simple
oxidation catalyst based on Pd/Pt supported on Al2O3. An additional air supply system was
introduced to promote the oxidation. This arrangement was sufficient to meet the initial
standards. NOx control was generally achieved by using an Exhaust Gas Recirculation
system. By recirculating part of the exhaust gases back into the combustion chamber, the
combustion temperature was lowered, resulting in reduced NOx emissions. More stringent
exhaust emissions standards, including tighter NOx control, had been set in the USA by 1977-
1981, which led to an implementation of the control of the exhaust emissions by developing
the so-called dual-way catalyst (second generation) and, subsequently, three- way catalyst
(TWC, third and fourth generation). The former converter usually consisted of a primary
bed containing a Rh/Pt-based catalyst for NOx removal, followed by a secondary bed
containing an oxidation catalyst equipped with an additional air supply to promote the
oxidation reactions. By tuning the engine to run close to stoichiometric conditions, reduction of
NOx to N2 could be achieved in the first bed and CO/HC oxidation to CO2 and H2O was carried
out in the second bed. However, such devices could not withstand the progressively tightening
demand for exhaust control in the USA in the early 80’s, mainly due to the imperfect A/F
control resulting from the use of carburettors. Further, NO x can be easily reduced to NH3
under rich conditions, which can then be back converted over the oxidation catalyst,
making NOx removal inefficient. The advent of oxygen sensors (the so-called  sensor) based
on zirconia type ceramics, led to the development of the modern TWC arrangement. The name
is derived from the ability to simultaneously remove all of the three categories of pollutants,
i.e. NOx, CO and HC, which are present in the exhausts. Of these, NO x removal/reduction is
obviously most efficient under net reducing conditions, in a deficiency of O2. In contrast, both
CO and HC are best converted under net oxidising conditions, in excess oxygen. However, if
one could maintain the A/F ratio close the stoichiometry, then in principle all the three
pollutants could be converted simultaneously. This is illustrated in Figure 10.2. In driving
conditions, A/F is kept close to the stoichiometric point by a fuel injection device regulated
by an electronic feedback system, which uses a signal from the  sensor.
113
Fig. 10.2: Effect of A/F ratio on the conversion efficiency of three-way catalysts. (adapted from ref 4)
To obtain an efficient control of the A/F ratio the amount of air is measured and
the fuel injection is controlled by a computerised system which uses oxygen sensors ()
located at the inlet of the catalytic converter. The signal from the  sensor is used as a
feed-back for the control loop. A second additional  sensor is mounted at the outlet of the
catalytic converter (Fig. 10.3) .
Figure 10.3: A picture of a modern TWC/engine/oxygen sensor () control loop for the engine exhaust control
(Courtesy of Mr. R. Crevatin, University of Trieste)
114
This configuration constitutes the basis of the so called engine on-board diagnostics
(EOBD). By comparing the oxygen concentration before and after the catalyst, A/F fluctuations
are detected. Extensive fluctuations of A/F at the outlet signal system failure. This EOBD
arrangement implicitly assumes that only a narrow A/F window at stoichiometric point is
the fingerprint of an effective TWC type of system. The location of the catalytic converter is
another critical point which determines the conversion efficiency. TWCs typically feature a
so-called light-off type conversion vs. temperature behaviour. This curves is characterised by
conversion which steadily increases from 0 to 100 % conversion, the temperature of 50 % of
conversion being indicated as the light-off temperatures. TWCs are characterised by a light-
off temperature around 250-350°C (Fig. 10.4) (4). This means that an under-floor catalyst
is heated above the light-off temperature within 90-120 s. Differently, when the catalyst is
closely coupled to the engine (CCC close-coupled catalyst) the heating time typically drops
down to 10-20 s. This dramatically affects vehicle emissions immediately after the start
up of the engine. The ULEV (Californian ultra low emissions vehicle) limit (0.064 g of HC
emitted/km) is typically surpassed within 40 s after the engine start-up (9). This requires
for an almost instantaneous heating up of the converter to achieve the required >95-98%
conversion. As a consequence of this location of the catalyst, temperatures up to 1100°C
are easily met by a CCC.
100
CO
Conversion / %
HC
50
NO
0
200 300 400 500
Temperature / °C
Figure 10.4: Light off type catalyst (adapted from ref 4)
It must be realised that the latest US and European legislation (EURO phase V
and US TIER II) limit for automotive emissions require application of the CCCs and EOBD
technologies on the vehicles in order to meet the emissions standards. A high durability i s
also an important requirement for the present and future TWCs, for example a durability up
to 130.000 miles of the catalyst will be demanded by US tier II regulations in 2004. It should
be considered that if a significant part of the vehicles fails the periodical exhaust emission
controls, converter replacement becomes mandatory for a vehicle manufacturer. Accordingly,
an extremely efficient and robust catalyst is required for future vehicle applications.
10
0 .2 . 1 Principle and Operation of TWCs
A typical design of a modern three-way catalytic converter is reported in Figure 10.5.

Basically it is a stainless steel container which incorporates a honeycomb monolith made of
cordierite (2MgO·2Al2O3·5SiO2) or metal (3, 4). The choice and geometrical characteristics
of the honeycomb monolith play a key role in determining the efficiency of the converter. In
115
fact, high conversion must be achieved in the converter and therefore the catalyst works
under conditions where severe mass and heat transfer limitations apply. Typically, both
metal and ceramic monoliths are employed nowadays. The major advantage of the metallic
substrate is that the wall thickness is limited by the steel rolling mill’s capabilities, not
strength. In a typical automotive 400 cell/inch2 application, the frontal flow area in a ceramic
monolith is 69% open (31% closed), while the metallic version has 91% open area. This is
due to the higher wall thickness of ceramic monoliths (0.007 inch (0.178mm)) compared to
metallic ones (0.002 inch (0.050mm)). However, even in this field there has been a strong
improvement of the technology, cell densities as high as 900 cell/inch 2 or even higher are
now commonly available on the market for both types of monoliths. Traditionally, cordierite
monoliths have been employed quite extensively, primarily due to their lower production cost.
However, a major advantage of the metal monoliths resides in their high thermal conductivity
and low heat capacity which allow very fast heating of the CCCs during the phase-in of the
engine, minimising the light-off time.
Figure 10.5: Diagram of a typical car converter (1) monolith and (2) metallic honeycomb (adapted from ref 4)
The monolith is mounted in the container with a resilient matting material to

ensure vibration resistance (10,11). The active catalysts is supported (washcoated) onto
the monolith by dipping it into a slurry containing the catalyst precursors. The excess of the
deposited material (washcoat) is then blown out with hot air and the honeycomb is calcined
to obtained the finished catalyst. This is clearly a very simplified and schematic description
of the washcoating process as multiple layer technology, or multiple catalyst-bed converters
are also employed (10,12). The exact method of deposition and catalyst composition are
therefore highly proprietary and specific for every washcoating company. For example, the
metallic honeycombs are non-porous, which makes adhesion of the washcoat difficult.
Accordingly a FeCrAl based alloy is employed, which contains up to 5 wt% of aluminium; after
an appropriate pre-treatment this element then acts as an anchoring centre for adhesion of
the washcoat.
However, there are some common components, which represent the state-of-art
of the washcoating composition:
 alumina, which is employed as a high surface area support;

 CeO2-ZrO2 mixed oxides, principally added as oxygen storage promoters;
 Noble metals (NM= Rh, Pt and Pd) as active phases;
 Barium and/or lanthana oxides as stabilisers of alumina surface area.
116
Al2O3 The choice of Al2O3 as carrier is dictated by the necessity of increasing the
surface area of the honeycomb monolith which is typically below 2-4 m2 l-1, where the volume
is that of the honeycomb (13). This does not allow achievement of high NM dispersion.
Alumina is chosen due to its high surface area and relatively good thermal stability under
the hydrothermal conditions of the exhausts. In most of the studies -Al2O3 is employed due
to its high surface area with respect to other transitional aluminas (14), however, also other
high temperature aluminas such as - and -Al2O3 can be employed for high temperature
applications such as in the CCCs because of their higher thermal stability compared to -
Al2O3. Since temperatures above 1000°C can be met in the TWCs, stabilisation of transition
aluminas is necessary to prevent their transformation to -Al2O3, which typically features
surface areas below 10 m2 g-1. A number of stabilising agents have been reported in the
literature, lanthanum, barium, strontium, cerium and, more recently, zirconium oxides or
salts being the most investigated (15-22). These additives are impregnated onto -Al2O3 or,
sometimes, sol-gel techniques are employed to improve the stability of the surface area.
CeO2-ZrO2 mixed oxides The beneficial effects of CeO2 containing formulations of

the TWC performances has long been recognised (23). Many different promotional effects
have been attributed to this component such as the ability to:
 promote the noble metal dispersion;

 increase the thermal stability of the Al2O3 support;
 promote the water gas shift (WGS) and steam reforming reactions;
 favour catalytic activity at the interfacial metal-support sites;
 promote CO removal trough oxidation employing a lattice oxygen;
 store and release oxygen under respectively lean and rich conditions.
For a detailed discussion of these roles and their relative importance we refer the
reader to earlier literature (4,24,25).
Among the different roles of CeO2 in TWCs, the OSC is certainly the most important
one, at least from the technological point of view. This is due to the fact that unambiguous
relationships between the TWC activity and OSC performances have been established (26).
Starting from 1995, CeO2-ZrO2 mixed oxides have gradually replaced pure CeO 2 as OSC
materials in the TWCs (27), even though some low purity CeO2 materials may be employed
for less demanding TWC technologies (28). The principal reason for the introduction of CeO2-
ZrO2 mixed oxides in place of CeO2 is due to their higher thermal stability (27,29-32).
A remarkably property of the CeO2-ZrO2 mixed oxides compared to the CeO 2 is

their ability to easily remove bulk oxygen species under moderate temperature even in highly
sintered samples (33). This was associated with the ability of ZrO 2 to modify the oxygen
sublattice in the CeO2-ZrO2 mixed oxides, generating defective structures and highly mobile
oxygen atoms in the lattice which can be released even at moderate temperatures (34,35).
Noble metals Obviously NMs represent the key component of the TWC, as the
catalytic activity occurs at the noble metal centre. However, we purposely discuss the
aspects related to the NM at this point, since its interaction with the various components of
the washcoat critically affects the activity of the supported NM.
In principle, the first aspect to be considered is the choice of the NM and its
loading in the washcoat. Rh, Pd an Pt have long been employed in the TWCs and there is a
general agreement about the specificity of Rh to promote NO dissociation, thus enhancing
the NO removal (24,36-38), even if alternative mechanistic pathways for NO reduction have,
117
also, been proposed (39-41). Pt and Pd are considered as metal of choice to promote the
oxidation reaction, even though Rh also has a good oxidation activity. In particular, except
some initial use in 1975-76, Pd has extensively been added to TWC formulations starting from
mid 90s due to its ability to promote HC oxidation (9,10). In fact, better A/F control (42) and
modification of the support provided high NOx conversion, comparable to the traditional Rh/Pt
catalyst (43). The increase of the use of Pd in the TWC technology adversely affected Pd
market price, which is now comparable to that of Pt. In fact, there is a large demand for Pd
due to the fact that a straightforward way to increase the efficiency of the TWCs at low
temperatures, is that of increasing the NM loading, and particularly that of Pd, which for long
was the cheapest NM among the three ones employed (Figure 10.6).
PGM Prices Demand for PGM

in Autocatalysts
10
2000 Million
oz 9
$ 8
per oz
1500 7
5
1000
4
500
2
0 0
1997 1999 2001 2003 1987 1992 1997 2002
Rh Pt Pd
Figure 10.6: Evolution of the cost and demand of noble metals
On the other hand, use of high NM loading may favour sintering at high temperatures,
leading to deactivation of the TWCs, in addition to the fact that cost-effective TWCs are
required by the market. In summary, the choice and loading of the NM is a compromise
between the required efficiency of the converter and the market price of the NM; ideally a
car maker would prefer to have at the disposal a choice of TWCs with different NMs, which
would allow the best choice to be made according to price fluctuations of the NMs.
Generally speaking, sintering of NM, leading to decrease of the number of active

sites, is a major pathway for the deactivation of the TWCs. In addition to sintering, poisoning of
the catalyst may contribute to deactivation of the TWCs. The latter phenomenon is essentially
related to the mileage travelled, quality of the fuel and the engine lubricating oil (13). However,
there is a number of other phenomena which can contribute to deactivation of the TWCs:
I) sintering of the OSC promoter leading to loss of OSC and, possibly, to encapsulation of
the NM (44); II) sintering of Al2O3 and, more important, deactivation of Rh due to migration
of Rh3+ into the alumina lattice (13). The comprehension of the relative importance of the
different deactivation phenomena is difficult due to the variety of the reaction conditions,
118
TWC preparation methods, etc. For example, when NM were supported on CeO2-ZrO2 mixed
oxides and aged at high temperatures under redox conditions, encapsulation of Pd and Rh
within the pores of the support occurred, while it did not occur for Pt (45).
Albeit it received relatively scarce consideration (46), the issue of sulphur poisoning
of TWC needs some consideration. As above discussion inclusion of CeO2-based promoters
into the washcoat considerably enhances the conversion efficiency of the TWCs. On the
other hand, both CeO2 and ZrO2 are known to easily adsorb SO x species: sulphated ZrO2 is a
well known solid acid catalyst (47). Investigation of reduced and oxidized CeO2 revealed that
SO2 is adsorbed under various forms, both surface and bulk-type of sulphates being formed
(48,49) and may even modify the microstrucutre of the CeO 2-based oxide (50). Curiously,
under oxidizing conditions bulk sulphates decomposed by 600°C whereas surface sulphates
persisted up to 700°C (48). Use of reducing conditions favours elimination of sulphates as
H2S which can be easily detected as rotten-egg odour (51), particularly in the presence of
noble metal (52). The OSC of CeO 2 is detrimentally affected by the presence of SO2, while
addition of ZrO2 to CeO2 increases the resistance of CeO 2 to sulphur poisoning, albeit more
sulphur is adsorbed at the surface (46). This may be associated with the generally higher
OSC efficiency of the CeO2-ZrO2 mixed oxide compared to CeO2 and the possibility that ZrO2
acts as sulphur scavenger. Ni containing oxide are sometimes added to the washcoat in the
USA as sulphur scavengers while their use in Europe is prohibited.
10
0.3 Next Generation Te
echnology for Emissions Contro
ol
As above discussed, TWCs represent a quite mature, highly effective technology

for pollution abatement which, however, brings some inherent limitations which need further
improvement and development. These aspects are essentially related to: I) low activity at low
temperatures (start-up of the engine) and II) use of stoichiometric A/F. As for the first aspect
is concerned, it should be noticed that roughly 50-80 % of HC emissions during the test
procedures are emitted before the TWC reaches the light-off temperature. When, in the last
years, the emissions limits have been pushed down, it appeared clearly that minimization
of warm-up HC emissions was a major problem in the automotive pollution abatement. This
issue has been therefore addressed by introduction of the CCCs onto the market. This
required development of TWCs featuring thermal stabilities well above 1000°C.
In reality, the issue of the start-up emissions can be addressed by different

approaches.
10
0 .3 . 1 Hyd
drocarbon Adsorber Systems
A first possibility is that of collecting the HC emitted during the warm-up of the
converter in a HC trap, typically composed of hydrophobic zeolite. In an optimal trap, HC are
trapped at low temperatures and as the temperature is increased above 250-300°C trapped
HC are released and converted on the TWCs (Fig. 10.7). A suitable trap must also feature
very high thermal stability under hydrothermal conditions, which often is not the case for
zeolite type of systems. We recall that temperatures as high as 850-900°C may be reached
in the under-floor catalysts.
119
• Cold start Hydrocarbon adsorber (HC –adsorber)
HC -
Catalyst HC retained by adsorber
adsorber
• Warmed-up
HC - HC released from adsorber and

Catalyst converted by catalyst
adsorber
Figure 10.7: Scheme of hydrocarbon adsorber systems
10
0 .3 . 2 Electrically/Chemically Heated Catalyst Systems
While Hydrocarbon Adsorber Systems are still under investigation, alternative
approaches have been indicated. It must be recognised that to minimize the emissions,
the catalysts must be heated-up in a minimum time. This can be achieved, for example, by
electrically (Fig. 10.8) or combustion/chemically heated catalyst. In the latter case hydrogen
and oxygen, or CO-rich feed is flowed over the catalysts (53). Oxidation of both CO and H 2
is an easy reaction and occurs at the lowest temperatures over the TWCs (54) leading to
rapid heating of the catalyst. However storage of H 2 on the vehicle or use of rich A/F which
generates high CO and H2 emissions brings complexity to the de-pollution system. HC are in
fact emitted at rich A/F which requires for additional HC trap.
Elettrically heated catalyst (EHC)

Main Quick heat-up of the converter
EHC
Catalyst
Figure 10.8: Scheme of electrically heated catalyst systems
The substrate, onto which the catalyst is deposited, is generally made from metal
so that, when an electric current is passed, it will heat up quickly. This brings the catalyst to
its full operating temperature in a few seconds.
10
0 .3 . 3 Close-coupled Catalyst (CCC)
Useof complex technology clearly pushes-up the costswhile the simplesttechnology
is desirable. Accordingly there has been a strong effort aimed at improving thermal stability
of the washcoat (29). With availability of thermally stable washcoats, application of a start-up
converter, i.e. converter that is closely coupled to the exhaust manifold (Fig. 10.9), became
feasible. This converter allows extremely rapid heating of the catalyst, leading to enhanced
conversions during the warm-up of the engine. Metallic converter can be easily shaped into
the exhaust manifold and result very convenient for such an application also due to their
low thermal capacity. In general, the composition of the close-coupled catalyst is related to
that of the typical TWC in that NM metals and particularly Pd are employed to promote HC
conversion. The OSC promoter may be omitted from these formulations since it promotes
CO conversion, leading to local overheating because of this highly exothermic reaction. On
the other hand, for the purpose of the OBD II technology, there is necessity to monitor the
OSC efficiency since the start-up of the engine. Accordingly ZrO2-rich doped CeO2 promoters
that may feature very high thermal stabilities (29,55), are often added to this catalyst.
120
Start-up converters (close-coupled converters)
Start-up Main
Engine
converter catalyst
Heat up quicker
New thermostable washcoats
Figure 10.9: Scheme of close-coupled catalyst
10
0 .3 . 4 New Catalysts
An alternative approach is that of developing new catalysts showing high conversion

efficiency at low, nearly ambient, temperature (53). A large part of these investigation has
been triggered by the observation by Haruta and co-workers that gold catalysts are able
to efficiently oxidize CO even at subambient temperature provided that nanodispersed Au
particles are prepared on the support (56). Thus, light-off temperatures in the conversion of
the exhausts as low as 100°C could be achieved by depositing small Au particles on reducible
oxides such as CeO 2 and TiO2 (57). However, the durability of gold catalysts under harsh
conditions is still an issue, significant deactivation of cobalt oxide promoted Au catalysts
was observed already after 157 h of reaction at 500°C under simulated exhaust (58). There
is in fact a flourishing activity in the field of low temperatures catalysts (59-61), other noble
metals, in addition to Au, being effective in low temperature oxidation reactions, provided that
appropriate synthesis methodology is employed (59). To our knowledge, however, due to the
nano-dispersed nature of these catalysts, the issue of thermal stability, even at moderately
high temperatures has not been solved as yet. Supported metal nano-particles are, in fact,
quite mobile on the surface, even at ambient temperature in the case of gold, which makes
prevention of sintering phenomena difficult. We believe that thermal stabilisation of nano-
dispersed metals may represent a new breakthrough point in the development of these
environmental catalysts.
10
0.4 Diesel Engine Emissions
The diesel engine, invented in the late 19th century by Dr. Rudolf Diesel, is the
most energy efficient power plant among all type of internal combustion engines known today.
This high efficiency translates to good fuel economy and low greenhouse gas emissions.
Other diesel features that have not been matched by competing energy conversion machines
include durability, reliability, and fuel safety. The downsides of diesels include noise, low
specific power output, NOx and PM emissions, and high cost (61).
The diesel engine is a compression-ignition internal combustion heat engine,

which can be operated, in both the four- and two-stroke cycle. The combustion process can
be theoretically modeled by applying thermodynamic laws of mass and energy conservation
to the processes in the engine cylinder. Basic design and performance parameters in
diesel engines include compression ratio, swept volume, clearance volume, a number of
scavenging characteristics in two-stroke engines, power output, indicated power, mechanical
efficiency, indicated mean effective pressure, brake mean effective pressure, specific fuel
consumption, and more.
121
Driving behind a diesel bus or truck, whether on a highway or in the city, often is
an unpleasant experience because of its emissions. The black smoke, or soot, is the most
visible emission, but other, less visible pollutants are also present. The emissions from a
diesel engine are composed of three phases: solids, liquids, and gases. The combined solids
and liquids are called particulates, or total particulate matter (TPM), and are composed of
dry carbon (soot), inorganic oxides (primarily as sulfates), and liquids. When diesel fuel
is burned, a portion of the sulphur is oxidized to sulphate, which, upon reaction with the
moisture in the exhaust, becomes H 2SO4. The liquid are a combination of unburned diesel
fuel and lubricating oils, called the soluble organic fractions (SOF) or volatile organic fractions
(VOF), which from discrete erosols and/or are adsorbed within the dry carbon particles)
(62). Gaseous hydrocarbons, carbon monoxide, nitrogen oxides, and sulfur dioxide are the
constituents of the third phase.
In diesel engines, fuel is injected into the engine cylinder near the end of the
compression stroke. During a phase known as ignition delay, the fuel spray atomizes into
small droplets, vaporizes, and mixes with air. As the piston continues to move closer
to top dead center, the mixture temperature reaches the fuel’s ignition point, causing
instantaneous ignition of some pre-mixed quantity of fuel and air. The balance of fuel that
had not participated in premixed combustion is consumed in the rate-controlled combustion
phase, also known as diffusion combustion.
10
0 .4 . 1 Emission Form
mation in Diesel Engines
Emissions formed during burning of the heterogeneous diesel air/fuel mixture

depend on the conditions during combustion, during the expansion stroke, and especially
prior to the exhaust valve opening. NO x emissions are formed manly during the premixed
burning. PM, on the other hand, is generated in diesels primarily during the diffusion flame.
The visible smoke emission can be classified into black smoke, also known as hot or solid
smoke, and white smoke also referred to as liquid smoke or fog.
Diesel particulate matter (DPM) is the most complex of diesel emissions.
Diesel particulates, as defined by most emission standards, are sampled from diluted
and cooled exhaust gases. This definition includes both solids, as well as liquid material,
which condenses during the dilution process. The basic fractions of DPM are elemental
carbon; heavy hydrocarbons derived from the fuel and lubricating oil, and hydrated sulfuric
acid derived from the fuel sulfur. DPM contains a large portion of the polynuclear aromatic
hydrocarbons (PAH) found in diesel exhaust. Diesel particulates include small nuclei mode
particles of diameters below 0.04 µm and their agglomerates of diameters up to 1µm.
The flame temperature, due to the high activation energy of the pyrolysis
processes, is one of the key factors that influence soot formation. Soot formation occurs
in flames above 1000 and 1300 °C. Soot is eventually emitted when burnout ceases at
temperatures below 1000 °C. Depletion in local oxygen concentration strongly enhance soot
production. Soot particle formation is also effected by the overall oxygen concentration,
although this may be an indirect effect of the different flame temperatures associated with
different oxygen concentrations. The high pressure used in some diesel can also promote
soot formation. Improved atomisation caused by higher pressure lead to lower penetration
of the droplets into the combustion chamber. Thus, the high concentration of fuel in the high
temperature, low oxygen region establishes the conditions for soot formation. The presence
of chemical impurities or additives of the fuel may affect particulate emissions. Halogens
cause an increase of hydrocarbon radicals by scavenging H atoms. In addition, sulfur
compounds present in the fuel are oxidized to SO2 during the combustion. A small fraction
122
of SO2 can be oxidized to SO 3 if the exhaust temperature exceed 450 °C. The presence
of catalyst favors this oxidation process. Consequently, sulfuric acid and sulfate ions are
formed. Fuel sulfate and calcium of the lubrication oil may react to form gypsum, which may
strongly deactivate the particulate filter and/or hinder its regeneration. On the other hand,
emulsification with water may deplete soot formation. Metals such as nickel or manganese
charge the soot particles electrostatically and reduce agglomeration. The smaller particles
thus formed burn more easily. The characteristics of the fuel sach as viscosity, volatility,
thermal stability, aromatic content and C/H ratio also affect soot occurrence. Hydrocarbons
show the following smoking tendency:
aromatics > alkanes > alkenes > alkynes
Older type of diesel engine had relatively low injection pressure and operated
at low excess of air. Due to inefficient fuel injectors, a significant fraction of the fuel was
stacked to the walls of the combustion chamber as large fuel drops. This resulted in big
flakes of soot. Modern diesel engine works with redesigned fuel and air injectors and a large
excess of air. Therefore, an extremely efficient mixing of air and fuel is guaranteed, resulting
in nearly complete combustion and lower soot emissions.
10
0 .4 . 2 Die
esel Fuel
Diesel fuel is a mixture of hydrocarbons obtained by distillation of crude oil. The

important properties, which are used to characterize diesel fuel, include cetane number (or
cetane index), fuel volatility, density, viscosity, cold behavior, and sulfur content.
Fuel Properties and Emissions

There is a clear correlation between some fuel properties and regulated
diesel emissions. Drawing general conclusions is, however, difficult due to such factors
as intercorelation of different fuel properties, different engine technologies, or engine
test cycles. In heavy-duty engines increasing the cetane number lowers HC, CO, and NO x
emissions, while reducing fuel density lowers NO x and PM but increases HC and CO. Light-
duty engines show different fuel sensitivity than the heavy-duty engines. Sulfur increases
PM in both classes of engines. Sulfur is also known to interfere with several diesel emission
control strategies.
Synthetic Diesel Fuel

Synthetic diesel fuels can be made from carbon containing feedstocks, such as
natural gas or coal, in a process developed by Fischer and Tropsch in the 1920’s. That
process has been further developed by oil companies and is considered a viable option
of natural gas utilization. Synthetic diesel fuels are characterized by excellent properties,
such as very high cetane number and no sulfur content. They can be used in existing
diesel engines without modifications or mixed with petrodiesel. Several studies found
significant reductions in all regulated diesel emissions, including NOx and PM, when using
synthetic fuel.
Biodiesel
Vegetable oil was used as a diesel fuel as early as 1900, when Rudolf Diesel
demonstrated that a diesel engine could run on peanut oil. However, its use as a fuel
attracted little attention except in times of crisis such as during World War II and the energy
shortages of the 1970s. Increasing environmental concerns, expensive overproduction in
123
European agriculture and changes in government policies have resulted in expanded testing
and usage of biodiesel. The name “biodiesel” was introduced in the United States in 1992
by the National SoyDiesel Development Board (now the National Biodiesel Board), which
has pioneered the commercialization of biodiesel in the U.S. Biodiesel is defined as the
mono alkyl esters of long chain fatty acids derived from renewable lipid sources. Biodiesel
is typically produced through the reaction of a vegetable oil or animal fat with methanol in
the presence of a catalyst to yield glycerin and biodiesel (chemically called methyl esters).
Biodiesel has been registered with the US Environmental Protection Agency as a pure fuel
or as a fuel additive and is a legal fuel for commerce. The compression-ignition engine has
certain advantages over spark-ignition engines and role of biodiesel is to contribute to the
longevity and cleanliness of diesel engines.
The use of biodiesel as alternative fuel present the following significant
advantages:
1. Biodiesel can be made from domestically produced, renewable materials.
2. Biodiesel is the only alternative fuel that runs in any conventional, unmodified diesel
engine. It can be stored anywhere that petroleum diesel fuel is stored.
3. Biodiesel can be used alone or mixed in any ratio with petroleum diesel fuel. The most
common blend is a mix of 20% biodiesel with 80% petroleum diesel, or “B20.”
4. The life cycle production and use of biodiesel produces approximately 80% less
carbon dioxide emissions. This is very important in view of the control of the green-
house effect.
5. Combustion of biodiesel provides over a significant reduction in total unburned
hydrocarbons and an almost complete elimination of sulphur dioxide. Biodiesel
further provides significant reductions in particulates and carbon monoxide than
petroleum diesel fuel. However, biodiesel provides a slight increase or decrease in
nitrogen oxides depending on engine family and testing procedures.
6. Biodiesel is 11% oxygen by weight and contains no sulphur. The use of biodiesel
can extend the life of diesel engines because it is more lubricating than petroleum
diesel fuel, while fuel consumption, auto ignition, power output, and engine torque
are relatively unaffected by biodiesel.
Biodiesel is safe to handle and transport because it is as biodegradable non

toxic, and has a high flashpoint of about 150 °C compared to petroleum diesel fuel, which
has a flash point of 50 °C.
Auto ignition, fuel consumption, power output, and engine torque are relatively
unaffected by biodiesel. So basically, the engine just runs like normal (except for the
smell).
Biodiesel can contribute to reduce dependence on petroleum, creating domestic
manufacturing jobs.
Biodiesel is a proven fuel with over 30 million successful US road miles, and over
20 years of use in Europe.
Use of biodiesel in combination with the existing technologies for pollution

abatement (EGR, catalysts, filters, etc.) further enhance the benefits to the environmental.
It should be underline that there are also some disadvantages of Biodiesel.

The major one is its high production costs. The production of subsidized biofuels can be
partially justified if a high premium is put on the environmental cost of the alternatives.
One additional concern is the environmental impacts of increased fertilizer and pesticide
usage to increase oilseed production for use in manufacturing biodiesel. Finally, biodiesel
124
has a higher viscosity than conventional diesel and therefore becomes less useful at lower
temperatures. This limits its use in Canada, the northern U.S. and much of Europe. In these
areas, biodiesel is marketed as an additive in a five to ten percent blend with conventional
diesel fuel.diesel engines.
Dimethyl Ether
Dimethyl ether (DME) can be made from a variety of fossil feedstock including
natural gas and coal as well as from renewable feedstock and waste. When used as a
diesel fuel, DME offers NOx and PM emission benefits. Emissions of CO and HC which may
increase with DME can be easily controlled by an oxidation catalyst. Energy efficiency of DME
is lower than that of diesel but higher than that of methanol/gasoline engines.
10
0 .4 . 3 Wo
orld Diesel Emission Standard
ds
Diesel emission are clearly more complex than those of gasoline engine and
hence, their catalytic treatment is more complicated and requires new technology.
The popularity of diesel engines is derived primarily from their fuel efficiency
relative to the gasoline spark-ignited engine. Diesel operate very lean of stoichiometric,
with air-to-fuel ratios greater than about 22. They have good fuel economy, producing less
CO2. It is not uncommon for a diesel engine to have a life of 1 million miles, or about
10 times that of the gasoline engine. The diesel fuel and air mixture is highly composed,
raising the gas temperature to the point of combustion. Its lean nature results in a cooler
combustion with less gaseous NOx, CO, and HC emissions than its gasoline counterpart.
The design of the combustion process, however, results in high particulate emission levels.
In the past few years, engine manufactures have made great progress in redesigning the
engine (fuel injectors, timing, and so on) to minimize particulate emissions (63). The units
of measurement for particulates are grams per brake horsepower generated in an hour, or
g/bhp-h. For example, in 1986, particulate emissions from a typical diesel truck engine were
0.6/bhp-h. By 1990, manufacturers had redesigned the engine to reduce the particulates
to 0.25 g/bhp-h. In the U.S, emissions are measured over a standardized Federal Test
Procedure (FTP), The FTP simulates U.S. truck driving conditions. The Clean Air Amendment
of 1990 requires that by 1994 particulate emission be reduced to 0.1 g/bhp-h for truks and
no grater than 0.07 g/bhp-h for buses. This is where catalytic aftertreatment can be used
effectively to bring engines into compliance with the standards (64).
Diesel emission control is being addressed worldwide. In the U.S., Europe, and
Japan, essentially all trucks and buses operate with diesel-fueled engines. In Europe, the
favorable price of diesel fuel relative to gasoline has resulted in a large number of diesel
fueled passenger cars. Trucks are used to ship goods; buses to transport groups of people
(usually within urban areas), and passenger cars are utilized for individual or small groups in
both urban and rural locations. Consequently, the allowable emissions standards differ for
each application. Furthermore, the terrain in the U.S., Japan, and Europe differ sufficiently
that the test conditions must reflect local driving habits. Each vehicle must specific emission
standards as measured in standardized driving cycles that reflect the duty cycle anticipated
for the particular engine. Table 10.2 summarizes current and proposed emission standards
worldwide. In Europe, passenger cars must meet standards reflecting both urban (ECE)
conditions and high-speed extra urban driving (EUDC). For European heavy-duty truck
applications, a 13-mode steady-state test with various loads/torques and speed is utilized.
This test puts emphasis on the high-temperature performance of the catalyst, reflecting high
load conditions. At such high temperatures, minimum generation of sulphate by catalytic
oxidation of gaseous SO2 becomes the most demanding requirement.
125
Table 10.2: Worldwide diesel emission standards
Country/year (vehicle) HC CO NOx Particulate HC + NOx

U.S/1991 (truck) 1.3 15.5 5.0 0.1
U.S/1994(truck) 1.3 15.5 5.0 0.1, 0.07 Bus
U.S/1998 (truck) 1.3 15.5 4.0 0.1
Calif./1998 (truck) 0.025 HCHO 0.05(ULEV) 2.5(ULEV)
Europe/1995(truck) 1.1 4.0 7.0 0.15
Europe/1996(car) 1.0 0.10(DI) 0.9(DI)
Europe/1999(car) 0.5 0.04 0.5
Japan/1998 (car) 0.4 0.08
U.S. truck: HD FTP Transient Cycle, g/bhp-h. Euro truck: R-49 13 Mode. Euro car:
Cycle A, g/km. DI=Dir. Inj. Japan car: 10 Mode, g/km.
10
0 .4 . 4 Die
esel Emission Contro
ol Te
echnologiies
This chapter discusses the general classification of emission control options

available for diesel engines today. Since nitrogen oxides and particulate emissions are usually
the biggest concern, a brief overview of NOx and PM control strategies is presented.
Engine Design for Low Emissions

Changes in diesel engine design introduced over the period from the late 1980’s
to early 2000’s contributed to some 10-fold decrease in emissions without relying on
exhaust gas aftertreatment. The most important of these engine technologies are advanced
fuel injection systems, air intake improvements, combustion chamber modifications, and
electronic engine control. Additionally, exhaust gas recirculation (EGR) was introduced on
both light- and heavy-duty diesel engines to control NOx emissions.
Engine Design for NOx Control

NOx emissions from heavy-duty engines had to be reduced by about 70% to meet
emission standards of the 1990’s. Major technologies, which were employed, included
injection timing retard and intake air-cooling. Implementing high injection pressures prevented
the negative effect of timing retard on fuel economy.
Engine Design for PM Control

PM emissions from heavy-duty engines were reduced by over 90% to meet emission
standards of the 1990’s. Major PM reductions were realized through improvements in air
management, combustion, oil consumption control, and fuel injection.
Exhaust Gas Recirculation

Exhaust gas recirculation (EGR) is an effective strategy to control NOx emissions
from diesel engines. The EGR reduces NOx through lowering the oxygen concentration in
the combustion chamber, as well as through heat absorption. Several configurations have
been proposed, including high- and low-pressure loop EGR, as well as hybrid systems. NOx
emissions may be further reduced by cooled EGR, in which recirculated exhaust gas is
cooled in EGR cooler using jacket water.
EGR effectively reduces NOx emissions while increasing PM emissions and fuel
126
consumption. EGR control systems, utilizing open or closed loop control layouts, have to
provide precise EGR rates and proper A/F ratios in order to achieve their NOx reduction
targets while minimizing PM and fuel economy penalty. Even more precise A/F ratio control
is possible with variable geometry turbochargers and electrically driven chargers. EGR,
especially in uncooled configuration, in conjunction with high engine loads and aged lube
oils may also cause premature engine wear.
Water in Diesel Combustion

Addition of water to the diesel process decreases combustion temperatures and
lowers NOx emissions. The most common methods of introducing water are direct injection
into the cylinder, a process commercialized in certain marine and stationary diesel engines,
and water-in-fuel emulsions. Emulsified fuels, due to increased mixing in the diesel diffusion
flame, can be also effective in simultaneous reduction of PM and NOx emissions.
Ceramic In-Cylinder Coatings
Zirconia based ceramic combustion chamber coatings originally developed for
adiabatic or low heat rejection engines have been shown to reduce diesel emissions.
Reported results indicate that in-cylinder zirconia coatings are capable of reducing the
carbonaceous fraction of diesel particulates without increasing NOx or other regulated
emissions. Reductions in total PM emissions may be achieved by combining zirconia coatings
with diesel oxidation catalysts. In-cylinder coatings are most effective in reducing emissions
from older technology engines of relatively low thermal efficiency.
10
0 .4 . 5 Advanced Diesel Engine Te
echnologies
Emission challenges faced by the diesel engine require substantial reductions of

NOx and PM emissions over the period of 2005-2010, to be achieved by a combination of
engine, fuel, and exhaust aftertreatment technologies. The emerging engine technologies
include optimization of the fuel injection, combustion, and air induction systems, new engine
accessories and subsystem technologies, as well as entirely new combustion techniques
such as the HCCI engine.
Advanced Technologies: Fuel Injection & Combustion

Diesel fuel injection systems for meeting future emission standards require very
flexible rate shaping capacity and capability for pilot- and post-injections with controllable
parameters. Combustion systems for future engines, designed using computerized tools,
provide optimized swirl conditions for efficient air/fuel mixture preparation .
Advanced Technologies: Air Induction

Emerging air induction technology options for meeting future emission standards
include improved air charging strategies, through the use of electric superchargers, charge
air cooling, optimized intake manifolds and intake ports, and variable valve actuation.
Controls for Modern Diesel Engines

The control system of a diesel engine is responsible for maintaining performance
at its optimum while at the same time keeping the engine from exceeding certain emission
limits. The control system performs this function using three groups of components: sensors,
processor, and actuators. Basic control system configurations are the open and the closed
loop systems. A variation of the open loop system utilizing lookup tables, referred to as
scheduled control, was common in diesel engines. Future control systems include model-
based controls and neural networks.
127
10
0 .4 . 6 Diesel Oxidation Catalyst
Diesel oxidation catalysts promote chemical oxidation of CO and HC as well as

the SOF portion of diesel particulates. They also oxidize sulfur dioxide, which is present in
diesel exhaust from the combustion of sulfur containing fuels. The oxidation of SO 2 leads
to the generation of sulfate particulates and may significantly increase total particulate
emissions despite the decrease of the SOF fraction. Modern diesel oxidation catalysts are
designed to be selective, i.e., to obtain a compromise between sufficiently high HC and SOF
activity and acceptably low SO 2 activity.
Commercial Diesel Oxidation Catalysts

The catalysts currently used in the U.S. trucks and European passenger cars are
monolithic honeycomb structures of cordierite with 200-400 cpsi. The catalyzed washcoat
is deposited onto the walls of each channel at a loading of about 2 g/in3 and is typically no
more than about 40-80 microns in the thickest locations (corners or fillets) on the monolith.
The literature reports a Degussa catalyst composed of combinations of Pt 920-60 g/ft3), 3-
10 percent V2O5, and balance TiO2, primarily for use in European passenger car applications
(65-66). Johnson-Matthey is believed to be using a variation of Pt and vanadia for selected
applications (73). The first generation Engelhard catalyst is composed of about 50 percent
catalytically active base metal oxide in combination with an equal amount of alumina with
small amounts of Pt (0.5-2) g/ft3) for truck, bus, and selected passenger car applications in
the U.S. and Europe (67). A joint venture between Nippon Shokubai and Degussa is promoting
the use of a combination of Pd (40 g/ft3 ) supported on zirconia with various promoter
oxides such as the rare earths for trucks (68). All of these technologies are in the early
stages of commercialization, so precise details of the catalyst formulations are not available.
As general rule, the catalyst volume equals the displacement volume of the
engine. Therefore, a 6.0 liter medium-duty truk engine has about 6.0 liters of catalyst. The
catalyst is contained in a steel can, with a mounting material made of a ceramic wrapped
around its outside diameter to ensure mechanical integrity and resistance to vibration (69).
Space velocity vary between about 20,000 and 250,000/hr, depending on the duty cycle
of the vehicle. Catalyst diameters are 7-*10 inches (17.78-25.40 cm), with lengths of 5-7
inches (12.7-17.18 cm) for trucks. They are smaller for passenger car applications.
Deactivation of Diesel Catalyst

The causes for the deactivation of diesel catalysts are thermal degradation and
poisoning by lubrication oil additives, as well as by sulfur. Phosphorus is the most common
oil-derived catalyst poison. Sulfur can be found uniformly distributed over the catalyst length
and the washcoat depth, while phosphorus is selectively adsorbed at the catalyst inlet and
in a thin, outer washcoat layer.
10
0 .4 . 7 Lean NOx Catalyyst
Twogroupsofcatalystsystemsareknownforthereductionof NOxwithhydrocarbons:
a copper substituted zeolite ZSM5 catalyst, which is active at high temperatures, and a
platinum/alumina catalyst, exhibiting low temperature activity. Both catalysts have narrow
operating temperature windows, resulting in only a limited NOx reduction efficiency, and
exhibit other problems. Some lean NO x catalysts have been commercialized, primarily to
provide small deNOx functionality in diesel oxidation catalysts. (4)
128
10
0 .4 . 8 Selective Catalytic Reduction
Due to the limited success of hydrocarbons as efficient reducing agent under lean
conditions, the use of urea as an alternative reducing agent for NOx from heavy duty diesel
vehicles has received attention. Selective catalytic reduction of NOx with NH3 in presence of
excess of O2 is a well implemented technology for NOx abatement from stationary sources
(70). Typically vanadia supported on TiO2, with different promoters (WO3 and MoO3) are
employed in monolith type of catalysts. A sketch of an arrangement for the urea based NO x
abatement technology is shown in Figure 10.10. Typically the urea solution is vaporised and
injected into a pre-heated zone where hydrolysis occurs according to the reaction :
H 2 N  CO  NH 2  H 2O  CO2  2NH 3
Ammonia then reacts with NO and NO2 on the reduction catalyst via the following
reactions:
4NO  4NH 3  O2  4N 2  6H 2O
6NO2  8NH 3  7N 2 12H 2O
This approach has proved to be quite successful and high NOx (up to 80%) could be
achieved on Heavy Duty (HD) diesel engines under driving conditions, even after reasonably
high mileages (200.000-300.000 km), the activity decreased to about 75-80% of the initial
value after over 500.000 km (71,72).
Figure 10.10: A typical arrangement for abatement of NOx from a heavy futy diesel engine using urea as reducing
agent (from ref 4)
A major problem of such system is that an extreme care must be exercised to

develop a suitable urea injection strategy that avoids overloading of the system leading to
ammonia slip (73). Typically ammonia slip should not exceed 10 ppm. While the efficiency
of urea-SCR technology is recognised (74) temperatures, the design of compact converter
systems that require higher conversion efficiency and last but not least the issue of
generalised urea distribution when fuelling the vehicle.
Given the efficiency of such systems, the application of the urea-SCR technology
to Light-duty (LD) diesel engines vehicles was also investigated (75): while appreciable NOx
can be achieved, it must be recognised that typically a ratio of engine displacement-to-
129
catalyst volume of 1:3 is typically employed for the urea-SCR systems that may represent
a serious problem in compact LD vehicles. Clearly an important improvement of the
catalytic performances is needed before such systems can be effectively considered for LD
application.
10
0 .4 . 9 NOx Adsorbers
NOx adsorbers (traps) are the newest control technology being developed for partial
lean burn gasoline engines and for diesel engines (4). The adsorbers, which are incorporated
into the catalyst washcoat, chemically bind nitrogen oxides during lean engine operation.
After the adsorber capacity is saturated, the system is regenerated, and released NOx is
catalytically reduced, during a period of rich engine operation (Figure 10.11) . Typically a
Pt/BaO/Al2O3 catalyst is used to store NOx under oxidising conditions as adsorbed “nitrate”
species, which are then released and reduced on a traditional TWC by temporarily running
the engine under rich conditions.
Figure 10.11: Principle of operation of a NOx adsorber: NOx are stored under oxidizing conditions (1) and then
reduced on a TWC when the A/F is temporarily switched to rich conditions
10
0.4.10 Diesel Partticulate Filters
Diesel particulate traps capture particle emissions through a combination of

surface-type and deep-bed filtration mechanisms, such as diffusional deposition, inertial
deposition, or flow-line interception. Collected particulates are removed from the filter,
continuously or periodically, through thermal regeneration. Diesel filters are very effective
in controlling the solid part of PM emission, but maybe ineffective in controlling non-solid
particulate fractions. Filters have been commercialized for selected retrofit applications and
are on the verge of commercialization for highway light- and heavy-duty diesel engines.
Diesel filter materials should be characterized by high filtration efficiencies, high
maximum operating temperatures, low thermal expansion, resistance to thermal stress,
and chemical resistance to metal oxides (ash) present in diesel particulates. A number
of materials have been under development, including ceramic wall-flow monoliths, ceramic
fibers, or sintered metals.
Wall-Flow Monoliths
Wall-flow monoliths became the most popular diesel filter design. They are derived
from flow-through catalyst supports where channel ends are alternatively plugged to force the
gas flow through porous walls acting as filters. Wall flow monoliths are made of specialized
ceramic materials such as cordierite and silicon carbide. A number of mechanical and
thermal properties have been defined to characterize and compare different monoliths.
Filters of different sizes have been developed and are available as standard products.
130
Ceramic Fibers and Cartridges

Filter cartridges for filtering of diesel particulates can be assembled from high-
temperature ceramic fibers. Fiber filters capture particulates through depth filtration
mechanisms. A number of cartridge designs have been developed, some of them incorporating
electric heaters for regeneration.
Diesel filter systems are designed by combining filter materials with regeneration
methods. The biggest challenge in the system design is to ensure adequate regeneration
and durability. Filters must not be exposed to excessive thermal stress during regeneration
to avoid filter media failure. Based on the principle of regeneration, filter systems are
classified into passive and active. Considering low exhaust temperatures in many diesel
applications, both light- and heavy-duty, most future filter systems are likely to include some
active strategies to support regeneration.
Catalyzed Diesel Filters

Most catalyzed diesel filters utilize monolithic wall-flow substrates coated with
a catalyst. The catalyst lowers the soot combustion temperature, allowing the filter to self-
regenerate during periods of high exhaust gas temperature. A number of diesel filter catalysts
have been developed, including both noble and base metal formulations. Catalyzed ceramic
traps exhibit very good DPM filtration efficiencies, but are characterized by relatively high
exhaust gas pressure drop.
Traps with Fuel Additives

Fuel additives, also called fuel soluble catalysts, can be used in passive diesel
trap systems to lower the soot combustion temperature and to facilitate filter regeneration.
The most popular additives include iron, cerium, copper, and platinum. Many laboratory
experiments and field tests have been conducted to evaluate the regeneration of various
diesel filter media, e.g. the Nextel fibers, using additives. Cerium additive was utilized in a
commercial trap system for diesel cars designed by Peugeot.
10
0.5 Diesel Filter Regeneration
The regeneration of diesel filters is characterized by a dynamic equilibrium between

the soot being captured and the soot being oxidized in the filter. Soot oxidation rates depend
on the filter temperature, soot load in the filter, and a number of other factors. Continuously
regenerating filters operate at a balance temperature, which can be determined through a
laboratory measurement. To facilitate filter regeneration on diesel engines in real operation
the exhaust gas temperature has to be increased or the soot ignition temperature has to be
lowered using a catalyst.
Electrically Regenerated Filters

Electric regeneration of diesel filters can be performed in on-board and various off-
board configurations. On-board regeneration by means of an electric heater connected to the
vehicle power source puts a significant additional load on the vehicle electrical system. Partial
flow layouts or regeneration with hot air are more energy efficient. Filter systems have been
also developed which must be connected to external power source or are removed from the
vehicle for off-board regeneration.
131
Traps with Fuel Burners

Diesel fuel burners can be used to increase the exhaust gas temperature upstream
of a trap in order to facilitate filter regeneration. Fuel burner filters can be divided into single
point systems and full flow systems. The full flow systems can be regenerated during regular
vehicle operation but require complex control strategies to ensure a thermally balanced
regeneration.
Filters rigeneration can be achieved thermally, by burning the soot deposits on
the filter, using for example a dual filter systems such as depicted in Figure 10.12. However,
such systems may be adopted only in the trucks where space requirements are less
stringent compared to passenger cars. In addition there are problems arising from the high
temperatures achieved during the regeneration step when the deposited soot is burned off.
In fact, local overheating can easily occur leading to sintering with consequent permanent
plugging of the filter.
Regeneration period
(1) Burner on
(2)
Working period
Burner off
Figure 2 10.12: Principle of filter operation (1) and filter re-generation (2) for a soot removal system, using fuel
powered burners. (adapted from ref 4)
Microwave Regenerated Filters

Diesel soot, due to its microwave absorption properties, can be heated by
microwave irradiation for regeneration of diesel particulate filters. This method, when used
with filter substrate materials that are transparent to microwaves, allows for selective heating
of the particulates. In case the filter material does adsorb microwave power, microwave
irradiation can be used to heat both the soot and the filter.
Figure 10.13: The working principle of the continuously regenerating particulate trap
132
Continuously regenerating particulate trap

The CRT is a trade name for a two-stage catalytic, passive filter configuration
(Figure 10.13). The CRT system utilizes a ceramic wall-flow filter to trap particulates. The
trapped particulate matter is continuously oxidized by nitrogen dioxide generated in an
oxidation catalyst, which is placed upstream of the filter. The CRT requires ultra low sulfur
fuel and a certain minimum NOx/PM ratio for proper operation.
10
0.6 Other Contro
ol Te
echnologies
Non-thermal plasma technologies are being developed to reduce NO x emissions

from gasoline and diesel exhaust. Since oxidation reactions dominate during plasma
discharges in lean exhaust, the plasma alone is ineffective in reducing NOx. Combined plasma-
catalyst systems, however, have been shown to enhance the catalyst selectivity and NOx
removal efficiency. Non-thermal plasma reactors can be also designed as diesel particulate
matter reducing devices. Plasma technologies still require a significant improvement in their
consumption of electrical energy and in other areas.
10
0.7 Future Tre
ends
Catalysts to enhance low temperature particulate removal to avoid channel plugging

under extended idle operation. Improved light-off activity for hydrocarbons with minimum use
of expensive precious metals will continue to be important for future HC+NO x standards.
More active, selective, and durable catalysts will have to be developed to be compatible
with improved exhaust system designs. Close coupling (i.e., manifold, mounting) of the
catalyst to be the combustion chamber, hydrocarbon trapping, electrically heated monoliths,
particulate traps, and so on all are under consideration by diesel engine manufactures to
further improve the quality of the diesel exhaust.
Natural gas fueled lean-burn engines are growing in popularity for service vehicles
such as buses, delivery trucks, and so on where refueling is handled daily at a central
location (76). Popularity of natural gas fueled vehicles is derived primarily from their clean
burning characteristics relative to diesel (77). Selected vehicles are currently equipped with
Pt-and Pd-containing catalysts to reduce non-methane hydrocarbons and carbon monoxide,
and nitric oxides for stoichiometric engines (78). Methane has been excluded from the
standards in the U.S because of its uncreative disposition towards photochemical smog
generation reactions. In the future, its reduction may become mandated because methane
is a strong “greenhouse” gas. Current catalysts are not sufficiently active to reduce the
methane component of the emissions, so this remains a challenge for improved catalytic
technology. The catalytic reduction of NO x from lean-burn engines may prove to be an even
greater challenge since natural gas not proven to be highly effective as a reductant in real
exhausts. The performance of the most promising zeolite-based catalysts thus far developed
is strongly hindered by the water present in the exhaust (79). One of the most important
technologies that will affect the design of diesel engine exhaust treatment systems in the
near future is NOx reduction. The lean operation of the diesel engine gives rise to high fuel
efficiency, which, in turn, decreases CO 2 emissions that contribute to the “greenhouse”
effect. This advantage, however, may be offset by the inability of existing catalysts to reduce
NOx to N2 in the high O2 content environment. Consequently, there is a strong driving force to
be developing a four-way catalytic system that is capable of reducing NOx to N2 and oxidizing
TPM, HC, and CO to CO 2 and H2O.
133
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11 Appendices
11
1.1 We
eb Dire
ector y
The web is getting a more and more important tool for fast and efficient collection
of information on any topic, including scientific and technological aspects. Nevertheless,
the huge and increasingly amount of information can generate a confusion and inadequate
selection of the priorities. Furthermore, the problem of absence of peer review process for
most of the sources, can lead to superficial and sometimes wrong interpretations. We offer
here a few suggestion on web site, which, in our opinion, can provide useful information
regarding the topic of Air Pollution.
The web site of the U.S. Environmental Protection Agency (http://www.epa.

gov/) has a detailed and rich information on any topics related to the protection of the
environment.
The web site of the European Union offers many information on environment
(http://europa.eu/pol/env/index_en.htm) and specifically also on air pollution (http://
europa.eu/scadplus/leg/en/s15004.htm).
The web site of the World Bank (http://www.worldbank.org/) offers interesting

documents on environmental protection strategies, including financial aspects.
The web site of the Organisation for Economic Co-operation and Development
(OECD) (http://www.oecd.org) is also useful to collect information on environment at http://
www.oecd.org/topic/0,2686,en_2649_37465_1_1_1_1_37465,00.html.
The Department of the Environment and Water Resources of the Australian

Government provides useful information on recent development in air pollution control at
http://www.environment.gov.au/atmosphere/publications/index.html
The International Center for Environmental Technology Transfer has an useful web
site at http://www.icett.or.jp
The web site www.world.org address general problems of environmental pollution.
The web site www. cleanair.org provides information on air pollution worldwide..
137
APPENDICES
11
1.2 Glossar y
Absorption
The transfer of molecules from the bulk of the gas to a liquid surface, followed by diffusion of
these molecules to the bulk of the liquid.
ACFM The acronym for actual cubic feet per minute, which is the actual gas flow rate expressed in the
American Engineering system of units. ACFM is a measure of the volume of gas that passes a
given point during a one-minute period.
Acid Gas Scrubbing System
A wet scrubbing system capable of achieving high acid gas removal efficiency by introducing water,
caustic, or hydrated lime into the gas stream.
Adsorbs The adhesion of a substance to the surface of a solid or liquid.
Adsorption
The process whereby vapor phase compounds in the gas stream pass through a bed or layer of
highly porous material (adsorbent). The vapor phase compounds diffuse to the surface of the
adsorbent and are retained due to weak attractive forces.
Aerosols
The suspension of solid or liquid particles in the atmosphere.
Air Preheater
Indirect heat exchanger designed to transfer heat from combustion gas to the air stream added
to the combustion zone.
Air Toxics (or Hazardous Air Pollutants)
Pollutants that are known to cause or suspected of causing cancer or other serious health effects,
such as developmental effects or birth defects.
Attainment Area
An area that meets the air quality standard for a criteria pollutant (under NAAQS).
Autoignition Temperature
The minimum temperature at which a substance ignites without application of a flame or spark.
Baghouse
This term is often used interchangeably with the term “filtration systems.” However, it is applicable
only to pulse jet, cartridge, reverse air, and shaker-type filtration systems. The term “baghouse”
does not have any clear meaning for HEPA filtration systems.
Bag Blinding
Conditions where the particles (dust) become embedded in the fabric filter over time and are not
removed by the bag cleaning process.
Barometric Pressure
The total pressure exerted by the atmosphere. This term is synonymous with “atmospheric pressure.”
Bottom Ash
Incombustible matter resulting from combustion that does not leave as fly ash.
Burners Out Of Service (BOOS)
An off-stoichiometric combustion modification for control of NOx performed by operating alternate
burners in the combustion zone as either fuel rich, air rich, or air only.
Carbon Bed Adsorber

An air pollution control system that is used to collect and concentrate organic compounds on an
activated carbon adsorbent.
Catalytic Oxidizer
An air pollution control device that uses a catalyst to accelerate the oxidation reaction at lower
temperatures than possible in gas phase thermal oxidation.
Cascade Impactor
A sampling device used to determine the particle size distribution. Particles are separated and
deposited on a series of stages that correspond to different aerodynamic diameters.
Catalyst
A substance, usually present in small amounts compared to the reactants, that speeds up the
chemical reaction rate without being consumed in the process.
138
Clarifier
Vessel where particulate matter of higher density than the surrounding liquid is separated and
removed from the liquid by gravitational settling.
Collection Efficiency
A ratio of pollutants entering a control device versus pollutants leaving the device expressed as
a percent.
Combustion
The production of heat and light energy through a chemical process, usually oxidation. Products
of complete combustion include water and carbon dioxide; while, incomplete combustion can
yield partially oxidized organic compounds and carbon monoxide. Factors that promote complete
combustion include the proper fuel-air ratio, temperature range, and adequate amount of time for
the fuel and its by-products to complete the combustion reactions.
Combustion Particle Burnout
Particulate matter formed and released by the combustion of fossil fuels
Condensable Particulate Matter
Particulate matter, contained almost entirely within the PM2.5 classification that forms from condensing
gases or vapors. It forms by chemical reactions as well as by physical phenomena.
Condenser
A simple, relatively inexpensive device that normally uses water or air to cool and condense a
vapor stream.
Cyclone (Large Diameter)
A type of mechanical collector, usually ranging in size from one to six feet in diameter, that uses
a spinning movement of the gas stream to collect particles ranging in size from one-sixteenth to
more than 6 inches in diameter.
Cyclonic Separator
A mechanical collector that uses centrifugal force to drive particles to the wall of the device.
Desorption
The process of using low-pressure steam or hot nitrogen gas to remove compounds from an
adsorbent bed.
Dew Point
The temperature at which the partial pressure of a substance (in vapor form) equals the equilibrium
vapor pressure of the substance. At this temperature, a vapor begins to condense at a constant
pressure.
DRE The acronym for destruction and removal efficiency
Dry Scrubber
An air pollution control device used to remove an acid gas pollutant from a gas stream. The
pollutant is collected on or in a solid or liquid material, which is injected into the gas stream. A dry
scrubber produces a dry product that must be collected downstream from this control device.
Dust A mixture in air of irregular shaped mineral particulates in the size range from 1 to 200 m formed
by crushing, chipping, grinding or like operations or by natural disintegration of rock and soil.
Electrostatic Precipitator
A type of air pollution control system that uses high voltage fields to electrically charge and collect
particulate matter. The charged particles approach an electrically grounded collection plate and
accumulate as a dust layer, which is partially removed by mechanical rapping (hammers) on aroutine basis.
Emission Sampling Train
Equipment usually consisting of (1) a sampling nozzle and probe, (2) filter and impingers for
collection of gaseous and/or particulate components, (3) flow meter and flow regulation devices,
and (4) a vacuum pump for collecting a representative sample of a gas stream.
EPA The acronym for environmental protection agency.
ESP The acronym for electrostatic precipitator.
Evaporative Cooling Tower
Equipment used to reduce the temperature of a gas stream. Fine droplets, injected into a vessel,
are evaporated as they absorb heat from the gas stream.
139
APPENDICES
Fabric Filter
A filtration device using one or more filter bags, sheets, or panels to remove particles from a gas
stream.
Fan Drive
The way in which the motor shaft is linked to the fan wheel to transmit power and control speed.
Fine Particles
EPA classification of particles having aerodynamic diameters greater than 0.1 micrometer and
less than or equal to 2.5 micrometers.
Flue Gas Desulfurization (FSD)
The process by which sulfur is removed from combustion exhaust gas.
Fly Ash
Uncombusted particulate matter in the combustion gases resulting from the burning of coal and
other material.
FPD The acronym for flame photometric detection
Fuel NOx
Nitrogen oxides generated from the fuel or waste during combustion.
Fugitive Emissions
Emissions that escape from industrial processes and equipment.
Heavy Duty (HD) diesel engines

Diesel vehicles with an engine displacement greater than 8 litres and power outputs of greater
than 150 kW. HD engines are found in heavy road transport, industrial and marine applications.
Medium duty engines fill the gap in the middle and are found in medium size trucks, buses and
light industrial equipment.
Hood A shaped inlet designed to capture contaminated air and conduct it into the exhaust duct
system.
Hood Capture Velocity
The air velocity at any point in front of the hood or at the hood opening necessary to overcome
opposing air currents and to capture the contaminated air at that point by pulling it into the
hood.
Hood Static Pressure
The static pressure in the duct immediately downstream from the hood.
Hopper A device for temporarily storing dust collected by an air pollution control device. Hoppers funnel
solids into the solids handling system. There are two main types used on filtration systems:
pyramidal and trough-type.
JIS The acronym for Japan International Standard.
Light-duty (LD) Diesel

Diesel vehicles with an engine displacement of less than 4 litres and power output of up to 100
kW, and are characterised by relatively high engine speeds. LD engines would normally be found
in passenger vehicle and light commercial vehicle applications.
Low NOx Burner
An off-stoichiometric combustion modification for control of NOx where the mixing of fuel and air
is controlled in a pattern that keeps the flame temperature low and dissipates the heat quickly.
Lower Explosive Limit
The lowest concentration at which a gas or vapor is flammable or explosive at ambient
conditions.
Lowest Achievable Emission Rate (LAER)
This represents the most stringent control technology achieved in practice regardless of co st.
LAER is used to determine emission limits for the NSR program.
140
Maximum Achievable Control Technology (MACT)

EPA standards mandated by the 1990 CAA for the control of toxic emissions from various
industries.
Minimum Transport Velocity
The minimum gas velocity that must be maintained to keep the contaminant from settling out of
the gas flow stream and building up deposits in the ductwork.
Mist Eliminator
A component that passively removes most of the water droplets from a gas stream.
NAAQS National Ambient Air Quality Standards
Overfire Air
An off-stoichiometric combustion modification for control of NOx where the lower burners operate
under fuel rich conditions and air injection nozzles located above these burners complete the
combustion process.
Packed Bed Wet Scrubber

A common type of gas absorber in which scrubbing liquid is dispersed over packed columns
containing packing material. This design provides a large surface area for gas-liquid contact.
Photochemical Reaction
A chemical change triggered by the radiant energy of the sun or other light source.
PM2.5 EPA defines PM2.5 as particulate matter with a diameter of 2.5 micrometers collected with 50%
efficiency by a PM2.5 sampling collection device. However, for convenience in this reference
material, the term PM 2.5 includes all particles having an aerodynamic diameter of less than or
equal to 2.5 micrometers.
PM10 The U.S. EPA defines PM 10 as particulate matter with a diameter of 10 micrometers collected with
50% efficiency by a PM10 sampling collection device. However, for convenience in this reference
material, the term PM 10 includes all particles having an aerodynamic diameter of less than or
equal to 10 micrometers.
Potential-to-Emit
The total emissions that a facility would release by operating at maximum load for 24 hours per
day and 365 days per year.
PCB polychlorinated biphenyl.
POP persistent organic pollutant.
ppb part per billion.
ppm part per million.
ppm(V/V))
The part per million concentrations that is determined by comparing the volume of one constituent
with the total volume of the substance. Gas concentrations are always expressed in a ppm(v/v)
format as opposed to the format often used for liquids. Throughout APTI courses, the term ppm
when applied to gases means ppm(v/v).
ppm (W/W)
The part per million concentrations that is determined by comparing the mass of one constituent
with the total mass of the sample. Liquid concentrations are often expressed in a ppm (w/w)
format as opposed to the ppm(v/v) format used for gases. Throughout APTI courses, the term ppm
when applied to liquids means ppm(w/w). Note that the abbreviation “w/w” is used despite the
fact that the ppm concentration is based on a ratio of masses.
Pulse Jet Fabric Filter
A type of filtration system that uses a short duration pulse of compressed air injected on the
“clean side” of the filter media to routinely clean the filter media. Pulse jets are one of the most
common types of filtration systems. They are sometimes termed reverse jets (not to be confused
with reverse air filtration systems).
Pulverizer
A device used to reduce a substance to a powder form usually by grinding.
141
APPENDICES
Scrubbing Liquid
A liquid used to remove particulate or gaseous pollutants by absorption or chemical reaction
through contact with the gas stream.
of the treatment time (residence time). Space velocity has units of 1/seconds or 1/minutes.
SCWO for supercritical water oxidation.
Smoke A mixture in air of very fine particles formed by combustion or other chemical processes in the
some range from 0.01-1 m. The particles may be irregular in shape if formed of solid material or
they may be spherical if formed by condensation.
Spray-Dryer-Type Dry Scrubber
An air pollution control device for removing acid gases where an alkaline slurry is introduced into
the gas stream and the pollutants absorb into the droplets and react. The droplets dry in the gas
stream leaving particulate matter, which is collected by a downstream particulate control device.
Terminal Settling Velocity

The velocity of a falling particle when the gravitational force downward is balanced by the air
resistance (or drag) force upward.
Thermal NOx
Nitrogen oxides generated from atmospheric nitrogen during combustion.
Particulate Matter
Particulate matter of all sizes is regulated as total filterable particulate matter. This category of air
pollutants was the first one that was subject to air pollution control regulations.
Turbidity
The degree of clearness of a liquid or the lack of visual clarity of a liquid. It is defined by the
measure of light scattering due to the presence of particles suspended in the liquid. Turbidity is
similar to opacity for particles suspended in the gas phase.
Ultrafine Particles
EPA classification of particles having aerodynamic diameters less than or equal to 0.1
micrometer.
Venturi Scrubber
A type of wet scrubber that is usually highly efficient but requires a large amount of energy to
operate. (Wet scrubbers are air pollution control devices.) In venturi scrubbers, a scrubbing liquid
is introduced into the gas stream, which then passes through a contracted area of the scrubber at
a high velocity creating a high dispersion of fine droplets. These fine droplets capture the gaseous
and particulate pollutants.
VOC Volatile organic conpounds.
Wet Scrubber
A vessel used for removing pollutants from a gas stream by means of a liquid spray, liquid jet, or
liquid layer.
142

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Aiir Pollution

INTERNATIONAL CENTRE FOR SCIENCE AND HIGH TECHNOLOGY

UNITED NATIONS INDUSTRIAL DEVELOPMENT ORGANIZATION

1 Pollutants and Pollution Sources 9

2 Techniques for Air Pollution Measurements 13

3 NOx Abatement Technologies 19

4 SOx Abatement Technologies 47

5 Volatile Organic Compounds (VOCs) 61

6 POPs and Chlorinated Organic Pollutants 75

7 Technologies for Particulate Emission Control 91

8 Abatement of the Hydrocarbon and CO Emissions from Gas Turbine 103

9 Ozone Control Strategies 109

10 Air Pollution from Mobile Sources 111

1 Pollutants and Pollution Sources

1..1 Main Sources of Air Pollution

Major sources of air pollution are:

Table 1.1: Common air pollutants and their sources

An excellent summary (1) of the major atmosphere pollutants was published by

1..2 Air Pollution Ef fects on Human Health

Nitrogen oxides (NOx) can increase susceptibility to viral infections such as

Lead affects circulatory, reproductive, nervous and kidney systems, suspected of

Particles irritates mucous membranes and may initiate a variety of respiratory

1..3 Criteria for Air Pollution Contro

 Complete mineralization of organic contaminants;

2..1 Sulfur Dioxide

Sulfur dioxide is a pollution generated by combustion of fuels containing sulfur,

2..2 Carbon Monoxide

2..3 Nitrogen Oxides

Absorptiometry Using Saltzmann

2..4 Photochemical Oxidant

Absorptiometry Using Neutral Potassium Iodide Solution

Hydrogen Flame Ionization Detection (FID) Method

2..6 Partticulate Matter

Measurement of Atmospheric Particulate Matter by the Light Scattering Method

Measurement of Atmospheric Particulate Matter by -ray Absorption Method

Table 2.1: Environmental quality standards in Japan

Substance SO2 CO Suspended* NO2 Photochemical**`

* Suspended particulated matter shall mean airborn particles of 10 m or less in diameter.

2..7.1 National Ambient Air Quality Standard

Table 2.2: National ambient air quality standards

POLLUTANT STANDARD VALUE * STANDARD TYPE

Table 3.1: Nitrogen Oxides (NO x)

NO Nitric oxide Colorless gas, slightly water soluble

N2 O 3 Dinitrogen trioxide Black solid, water soluble, decomposes in water

N2 O 5 Dinitrogen pentoxide White solid, very water soluble, decomposes in water

3..1 NOx Sources

Thermal NOx: The concentration of “thermal NO x” is controlled by the nitrogen

3..2 NOx Abatement and Contro

Table 3.2: Common combustion systems (4)

Dry bottom boilers - tangentially fired pulverized coal, gas, or liquid

Fluidized bed coal

Stokers with traveling grate crushed coal

Stokers with spreader grate crushed coal

Gas turbines gas and liquid

Internal combustion engines gas and liquid

There are two primary control techniques:

1. combustion modifications to suppress the formation of nitrogen oxides,

2. add-on controls (flue gas treatment) to reduce nitrogen oxides to molecular

Table 3.3 lists principles or methods that are used to reduce NO x;

Method Technologies Abatement Type

Reducing Temperature (Method 1): This technique is based on the possibility

Reducing Residence Time (Method 2): Reducing residence time at high

Removal of nitrogen from combustion (Method 5): Reduction of NOx formation