United States
Environmental Protection
AEcncv
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA 456/F-99-006R
November 1999
Air,
EPA
TECHNICAL BULLETIN
NITROGEN OXIDES (NOx),
WHY AND HOW
THEY ARE CONTROLLED
T ECHNOLOQY
ENTER
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EPA-456/F-99-006R
November 1999
Nitrogen Oxides (NOx),
Why and How They Are Controlled
Prepared by
Clean Air Technology Center (MD-12)
Information Transfer and Program Integration Division
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
U.S. Environmental Protection Agency
foiJ-Q'i 5, Library (PL-12J)
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DISCLAIMER
This report has been reviewed by the Information Transfer and Program Integration
Division of the Office of Air Quality Planning and Standards, U.S. Environmental Protection
Agency and approved for publication. Approval does not signify that the contents of this report
reflect the views and policies of the U.S. Environmental Protection Agency. Mention of trade
names or commercial products is not intended to constitute endorsement or recommendation for
use. Copies of this report are available form the National Technical Information Service,
U.S. Department of Commerce, 5285 Port Royal Road, Springfield, Virginia 22161, telephone
number (800) 553-6847.
CORRECTION NOTICE
This document, EPA-456/F-99-006a, corrects errors found in the original document,
EPA-456/F-99-006. These corrections are:
Page 8, fourth paragraph: "Destruction or Recovery Efficiency" has been changed to "Destruction
or Removal Efficiency;"
Page 10, Method 2. Reducing Residence Time: This section has been rewritten to correct for an
ambiguity in the original text.
Page 20, Table 4. Added Selective Non-Catalytic Reduction (SNCR) to the table and added
acronyms for other technologies.
Page 29, last paragraph: This paragraph has been rewritten to correct an error in stating the
configuration of a typical cogeneration facility.
PageSO, Internal Combustion Reciprocating Engines: A sentence has been added to the end of this
section to refer the readers to Table 13 for more information;
Page 41, third through seventh paragraphs: These paragraphs were renumbered to correct for a
numbering error (numbers 6 and 7 were used twice).
n
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FORWARD
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emerging and existing air pollution prevention and control technologies, and provides public
access to data and information on their use, effectiveness and cost. In addition, the CATC will
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and others, as resources allow, related to the technical and economic feasibility, operation and
maintenance of these technologies.
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in
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ACKNOWLEDGMENTS
This technical bulletin was made possible through the diligent and persistent efforts of
Lyndon Cox, Senior Environmental Employee with the Clean Air Technology Center (CATC).
Lyndon did an exceptional job identifying information sources, gathering relative data and putting
this bulletin together. The CATC also appreciates the helpful and timely comments and
cooperation of the following peer reviewers:
Jim Eddinger, Combustion Group, Emission Standards Division, Office of Air Quality Planning
and Standards, Office of Air and Radiation, U.S. EPA.
Doug Grano, Ozone Policy and Strategies Group, Air Quality Strategies and Standards Division,
Office of Air Quality Planning and Standards, Office of Air and Radiation, U.S. EPA.
William Vatavuk, Innovative Strategies and Economics Group, Air Quality Strategies and
Standards Division, Office of Air Quality Planning and Standards, Office of Air and Radiation,
U.S. EPA.
Ravi Strivastava, Air Pollution Technology Branch, Air Pollution Prevention and Control
Division, National Risk Management Research Laboratory, Office of Research and Development,
U.S. EPA.
In addition, the CATC thanks the individuals, companies and institutions who supplied
information on nitrogen oxide abatement technology used to prepare this Technical Bulletin.
Contributors are indicated in the REFERENCES section of this bulletin.
IV
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TABLE OF CONTENTS
TOPIC Page
WHY SHOULD WE CONTROL NOx? 1
WHAT IS NITROGEN OXIDE? 2
WHERE DOES NOx COME FROM? 4
HOW DOES NOx AFFECT THE ENVIRONMENT? 5
ARE THERE OTHER NOx RELATED ISSUES? 7
WHAT ABATEMENT AND CONTROL PRINCIPLES APPLY? 8
WHAT ABATEMENT TECHNOLOGIES ARE AVAILABLE? 11
EXTERNAL COMBUSTION 11
EXTERNAL COMBUSTION: POLLUTION PREVENTION METHODS.... 15
LESS EXCESS AIR (LEA) 15
BURNERS OUT OF SERVICE (BOOS) 15
OVER FIRE AIR (OFA) 15
LOWNOx BURNERS (LNB) 15
FLUE GAS RECIRCULATION 15
WATER OR STEAM INJECTION 16
REDUCED AIR PREHEAT 16
FUEL REBURNING 16
COMBUSTION OPTIMIZATION 16
AIR STAGING 16
FUEL STAGING 17
OXYGEN INSTEAD OF AIR FOR COMBUSTION 17
INJECTION OF OXIDANT 17
CATALYTIC COMBUSTION 17
ULTRA-LOW NOx FUELS 17
NON-THERMAL PLASMA 18
EXTERNAL COMBUSTION: ADD-ON CONTROL TECHNOLOGY 18
SELECTIVE CATALYTIC REDUCTION (SCR) 18
SELECTIVE NON-CATALYTIC REDUCTION (SNCR) 18
SORPTION - BOTH ADSORPTION AND ABSORPTION 19
COMBINED TECHNOLOGY APPROACHES 19
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TABLE OF CONTENTS (continued)
TOPIC Page
INTERNAL COMBUSTION 19
INTERNAL COMBUSTION: POLLUTION PREVENTION METHODS .... 20
LOWNOx BURNERS (LNB) 20
STEAM / WATER INJECTION 20
CATALYTIC COMBUSTION 20
AIR-FUEL RATIO AND IGNITION TYPE 21
PRE-STRATIFIED CHARGE (PSC) 21
LEAN BURN 21
INTERNAL COMBUSTION: ADD-ON CONTROL TECHNOLOGY 21
SELECTIVE CATALYTIC REDUCTION 21
NON-SELECTIVE CATALYTIC REDUCTION (NSCR) 22
NON-THERMAL PLASMA REACTORS 22
DO FUELS AND COMBUSTION TYPE AFFECT ABATEMENT? 22
SOLID FUELS 22
LIQUID FUELS 23
SEMI-SOLID FUELS 23
GAS FUEL 24
COMBUSTION SYSTEMS 24
DRY BOTTOM BOILERS - WALLED FIRED, FRONT-FIRED
or OPPOSED-FIRED 25
DRY BOTTOM BOILERS - TANGENTIALLY FIRED 26
WET BOTTOM (SLAG TAP) BOILERS 26
FLUIDIZED BED 27
STOKERS WITH TRAVELING GRATE 28
STOKERS WITH SPREADERS 28
GAS TURBINES 29
INTERNAL COMBUSTION RECIPROCATING ENGINES 30
WHAT DOES NOx ABATEMENT AND CONTROL COST? 30
ARE THESE METHODS SUFFICIENT? 34
CONCLUSIONS 40
REFERENCES 42
VI
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FIGURES
1. NOx Map 6
2. Ozone Map 6
TABLES
1. Nitrogen Oxides 2
2. NOx Control Methods 9
3. External Combustion NOx Limiting technologies 12
4. Internal combustion NOx Limiting Technologies 20
5. Common Combustion Systems 24
6. NOx technologies currently used for dry bottom wall-fired,
front-fired or opposed fired boilers 25
7. NOx technologies currently used for dry bottom tangentially
fired boilers 26
8. NOx technologies currently used for wet bottom (slag tap) boilers 27
9. NOx technologies currently used for fluidized bed combustion 28
10. NOx technologies currently used for stokers with traveling grates .... 29
11. NOx technologies currently used for stokers with spreader grates 30
12. NOx technologies currently used for gas turbines 31
13. NOx technologies currently used for stationary internal
combustion engines 31
14. 1993 Costs of NOx Controls 32
15. 1997 Costs of NOx Controls 33
16. Unit Costs for NOx Control Technologies for Non-Utility
Stationary Sources 35
vii
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Nitrogen Oxides (NOx),
Why and How They Are Controlled
When we try to look only at one thing in Nature,
we find it connected to everything else.
John Muir
"Nitrogen oxides (NOx) are a very interesting and important family of air polluting chemical
"compounds. This bulletin explains why NOx are important air pollutants and how NOx are
-formed and react in the atmosphere. This bulletin also discusses the principles on which all NOx
control and pollution prevention technologies are based; available NOx technologies for various
combustion sources; and performance and cost of NOx technologies..
WHY SHOULD WE CONTROL NOx?
NOx represent a family of seven compounds. Actually, EPA regulates only 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 air pollutant by itself, but also reacts in the atmosphere to form ozone (O3) and acid
rain. It is important to note that the ozone that we want to minimize is tropospheric ozone; that
is, ozone in the ambient air that we breathe. We are not talking about stratospheric ozone in the
upper atmosphere that we cannot breathe. Stratospheric ozone protects us and the troposphere
~ from ionizing radiation coming from the sun.
EPA has established National Ambient Air Quality Standards (NAAQS) for NO2 and tropospheric
"ozone. The NAAQS define levels of air quality that are necessary, with a reasonable margin-of
safety, to protect public health (primary standard) and public welfare (secondary standard) from
any known or anticipated adverse effects of pollution. The primary and secondary standard for
NO2 is 0.053 parts per million (ppm) (100 micrograms per cubic meter), annual arithmetic mean
concentration.
Tropospheric ozone has been and continues to be a significant air pollution problem in the United
States and is the primary constituent of smog. Large portions of the country do not meet the
ozone NAAQS and thereby expose large segments of the population to unhealthy levels of ozone
in the air. NO2 reacts in the presence of air and ultraviolet light (UV) in sunlight to form ozone
and nitric oxide (NO). The NO then reacts with free radicals in the atmosphere, which are also
created by the UV acting on volatile organic compounds (VOC). The free radicals then recycle
"NO to NO2. In this way, each molecule of NO can produce ozone multiple times.40 This will
continue until the VOC are reduced to short chains of carbon compounds that cease to be photo
•reactive (a reaction caused by light). A VOC molecule can usually do this about 5 times.
In addition to the NO2 and Ozone NAAQS concerns, NOx and sulfur oxides (SOx) in the
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atmosphere are captured by moisture to form acid rain. Acid rain, along with cloud and dry
deposition, severely affects certain ecosystems and directly affects some segments of our
economy. All of these facts indicate an obvious need to reduce NOx emissions. However, to
successfully do so, we must understand the generation and control of the NOx family of air
pollutants.
WHAT IS A NITROGEN OXIDE?
Diatomic molecular nitrogen (N2) is a relatively inert gas that makes up about 80% of the air we
breathe. However, the chemical element nitrogen (N), as a single atom, can be reactive and have
ionization levels (referred to as valence states) from plus one to plus five. Thus nitrogen can form
several different oxides. Using the Niels Bohr model of the atom, valence state relates to the
number of electrons which are either deficient (positive valence) or surplus (negative valence) in
the ion when compared with the neutral molecule. The family of NOx compounds and their
properties are listed in Table 1.
Table 1. Nitrogen Oxides (NOx)
Formula
N2O
NO
N202
NA
NO2
NA
NA
Name
nitrous oxide
nitric oxide
dinitrogen dioxide
dinitrogen trioxide
nitrogen dioxide
dinitrogen tetroxide
dinitrogen pentoxide
Nitrogen
Valence
1
2
3
4
5
Properties
colorless gas
water soluble
colorless gas
slightly water soluble
black solid
water soluble, decomposes in water
red-brown gas
very water soluble, decomposes in water
white solid
very water soluble, decomposes in water
Oxygen ions are always at valence minus 2. Depending upon the number of oxygen ions (always
balanced by the valence state of nitrogen), NOx can react to either deplete or enhance ozone
concentrations. The nitrogen ion in these oxides really does a dance in which it has (at different
times) various numbers of oxygen ions as partners. Nitrogen changes its number of partners when
it changes its ionization energy level. This happens whenever NOx: (1) is hit with a photon of
ionizing radiation (UV or a shorter wavelength light); (2) is hit with enough photons that together
transfer enough energy to change its ionization level; (3) is catalyzed; (4) is stimulated sufficiently
by thermal (IR) energy; (5) reacts with a chemically oxidizing or reducing radical (an ionized
fragment of a molecule); or (6) reacts with a chemically oxidizing or reducing ion (an atom with
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unbalanced electrical charge).
When any of these oxides dissolve in water and decompose, they form nitric acid (HNO3) or
nitrous acid (HNO2). Nitric acid forms nitrate salts when it is neutralized. Nitrous acid forms
nitrite salts. Thus, NOx and its derivatives exist and react either as gases in the air, as acids in
droplets of water, or as a salt. These gases, acid gases and salts together contribute to pollution
effects that have been observed and attributed to acid rain.
Nitrous oxide (N2O), NO, and NO2 are the most abundant nitrogen oxides in the air. N2O (also
known as laughing gas) is produced abundantly by biogenic sources such as plants and yeasts. It
is only mildly reactive, and is an analgesic (i.e., unlike an anaesthetic you still feel pain, but you
feel so good that you just don't mind it). N2O is an ozone depleting substance which reacts with
O3 in both the troposphere (i.e., below 10,000 feet above sea level) and in the stratosphere
(50,000 - 150,000 feet). N2O has a long half-life, estimated at from 100 to 150 years.
Oxidation of N2O by O3 can occur at any temperature and yields both molecular oxygen (O2) and
either NO or two NO molecules joined together as its dimer, dinitrogen dioxide (N2O2). The NO
or N2O2 then oxidizes quickly (in about two hours) to NO2. The NO2 then creates an ozone
molecule out of a molecule of oxygen (O2) when it gets hit by a photon of ionizing radiation from
sunlight. N2O is also a "Greenhouse Gas" which, like carbon dioxide (CO2), absorbs long
wavelength infrared radiation to hold heat radiating from Earth, and thereby contributes to global
warming.
Emissions of NOx from combustion are primarily in the form of NO. According to the Zeldovich
equations, NO is generated to the limit of available oxygen (about 200,000 ppm) in air at
temperatures above 1,300°C (2,370°F). At temperatures below 760°C (1,400°F), NO is either
generated in much lower concentrations or not at all. Combustion NO is generated as a function
of air to fuel ratio and is more pronounced when the mixture is on the fuel-lean side of the
stoichiometric ratio50 (the ratio of chemicals which enter into reaction). The Zeldovich equations
are:
N + O2 - NO + O
N + OH - NO + H
Except for NO from soils, lightning and natural fires, NO is largely anthropogenic (i.e., generated
by human activity). Biogenic sources are generally thought to account for less than 10% of total
NO emissions. NO produces the same failure to absorb oxygen into the blood as carbon
monoxide (CO). However, since NO is only slightly soluble in water, it poses no real threat
except to infants and very sensitive individuals.
NO2 is present in the atmosphere and in acid rain. It produces nitric acid (HNO3) when dissolved
in water. When NO2 reacts with a photon to make O2 become O3, NO2 becomes NO. This NO is
then oxidized within hours to NO2 by radicals from the photo reaction of VOC. Therefore, our
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present ozone concentration is the product of both NOx and VOC pollution.
Dinitrogen trioxide (N2O3) and dinitrogen tetroxide (N2O4) exist in very small concentrations in
flue gas. However, they exist in such low concentrations in the atmosphere that both their
presence and their effect are often ignored. N2O4 is two NO2 molecules joined together (another
dimer) and reacts like NO2; so, the presence of N2O4 may be masked by the more abundant NO2.
Dinitrogen pentoxide (N2O5) is the most highly ionized form of nitrogen oxide. It is generated in
air in a very small concentration, unless it is emitted from a process (such as a nitric acid
production facility) that is specifically designed to generate it. N2O5 is highly reactive, and forms
nitric acid (HNO3) when it decomposes in water.
Some experts feel that NO2 is a good surrogate for NOx because NO is rapidly converted to NO2,
and N2O has such a long life because it is not highly reactive. Others feel that due to their role in
forming ozone, both NO and NO2 should be considered NOx. Still others feel that all nitrogen
oxides (including N2O) need to be regulated. NO and NO2 are certainly the most plentiful forms
of NOx and they are largely (but not exclusively) from anthropogenic sources. N2O is largely
biogenic, and as such is not subject to regulation. For environmental purposes, using the
concentration of NO2 as a surrogate for the concentration of NOx has seemed to suffice, for it is
the precursor for ozone.
WHERE DOES NOx COME FROM?
Automobiles and other mobile sources contribute about half of the NOx that is emitted. Electric
power plant boilers produce about 40% of the NOx emissions from stationary sources.34
Additionally, substantial emissions are also added by such anthropogenic sources as 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.1 These various sources produce differing
amounts of each oxide. The anthropogenic sources are approximately shown as:
Mobile Sources
50%
Electric Power
Plants
20%
Everything Else
30%
This shows a graphic portrayal of the emissions of our two greatest sources of NOx. If we
could reduce the NOx emissions from just these two leading categories; we might be able to live
with the rest. However, don't expect either of these categories to become zero in the foreseeable
future. We cannot expect the car, truck, bus, and airplane to disappear. The zero-emission car is
still on the drawing board and not on the production line. Also, social customs will have to
change before consumption of electricity can be reduced.
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In all combustion there are three opportunities for NOx formation. They are:
1. Thermal NOx - The concentration of "thermal NOx" is controlled by the nitrogen and oxygen
molar concentrations and the temperature of combustion. Combustion at temperatures well
below 1,300°C (2,370°F) forms much smaller concentrations of thermal NOx.
2. 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.
^3. 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 NOx during combustion, just like fuel NOx. The abundance of
prompt NOx is disputed by the various writers of articles and reports - probably because they
each are either considering fuels intrinsically containing very large or very small amounts of
nitrogen, or are considering burners that are intended to either have or not have fuel-rich regions
in the flame.
HOW DOES NOx AFFECT THE ENVIRONMENT?
Because NOx are transparent to most wavelengths of light (although NO2 has a brownish color
and the rare N2O3 is black), they allow the vast majority of photons to pass through and,
therefore, have a lifetime of at least several days. Because NO2 is recycled from NO by the photo
^reaction of VOC to make more ozone, NO2 seems to have an even longer lifetime and is capable
-- of traveling considerable distances before creating ozone.' Weather systems usually travel over the
'earth's surface and allow the atmospheric effects to move downwind for several hundred miles.
This was noted in EPA reports more than twenty years ago. These reports found that each major
-city on the East coast has a plume of ozone that extends more than a hundred miles out to sea
before concentrations drop to 100 parts per billion (ppb). Another report cited the same
phenomenon for St. Louis. Therefore, this problem was not just on the sea coast. Since ozone in
clean air has a lifetime of only a few hours, this phenomenon is admeasure of the effect and the
persistence of both VOC and NOx.
Differences in the distance estimates between the emission of NOx and the generation of ozone
may be related to differences in plume transport (wind) speeds as well as other meteorological and
air quality factors. It is important to note that, under the right conditions, power plant plumes may
travel relatively long distances overnight with little loss of VOC, NO and NO2. These pollutants
can thus be available to participate in photochemical reactions at distant locations on the
"following day.41 Figure 1 shows a map of NOx concentration drawn by the Center for Air
-Pollution Impact and Trend Analysis (CAPITA) at Washington University in St. Louis and
-reported to the Ozone Transport Assessment Group, a national workgroup that addressed the
problem of ground-level ozone (smog) and the long-range transport of air pollution across the
Eastern United States. OTAG was a partnership among the EPA, the Environmental Council of
the States (ECOS) and various industry and environmental groups with the goal of developing a
thoughtful assessment and a consensus agreement for reducing ground-level ozone and the
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pollutants that cause it. The animated version of Figure 1 shows the trajectory of NOx emissions
moving with the weather over an 8 day period.
Figure 2 is a map of ozone concentration that shows the same trajectory over the 8 day period.
The animated version shows concentrations of both NOx and ozone moving with the weather for
several hundred miles.5
NOx Total Emissions & Airmass History
90000
80000
70000
60000
50000
40000
30000
20000
Figure 2 NOx Map
Ozone Concentrations & Airmass History
Figure 3 Ozone Map
Ozone is the primary constituent of smog. Between 1970 and 1990, we in the United States have
tried to control ozone primarily by controlling the emissions of VOC. However, we have had
mixed results, for although some areas reduced their VOC emissions and attained their ozone
goals, others have not. It now appears that the communities that failed to meet their ozone goals
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may not be completely at fault, for they appear to be affected by NOx and VOC emissions in the
air coming to them. To meet the ozone NAAQS, EPA must now regulate emissions of NOx
regionally.
ARE THERE OTHER NOx RELATED ISSUES?
Yes. Nutrient enrichment problems (eutrophication) occur in bodies of water when the
availability of either nitrates or phosphates become too large. As a result, the ratios of nitrogen to
^phosphorus, silicon, and iron and other nutrients are altered. This alteration may induce changes
in phytoplankton, produce noxious or toxic brown or red algal blooms (which are called "red
tides"), or stimulate other plant growth. The algal blooms and plant growth produce a shadow
and cause the death of other plants in the water, which depletes the oxygen content of the water
(hypoxia) when the plants die, sink, and decay. Such eutrophication can make the bottom strata
of water unihabitable for both marine animals (such as fish and shellfish) and aquatic plants. It can
progress to virtually the complete depth of the water. It is estimated that between 12% and 44%
of the nitrogen loading of coastal water bodies comes from the air,^. Inland lakes are also
affected in this way.
.Another dimension of the problem is that high temperature combustion can convert sulfur in fuel
to SO2 and SO3. While SO2 is toxic and forms sulfurous acid when dissolved in water, SO3 is
both toxic and hygroscopic (moisture absorbing) and forms sulfuric acid by combining with
* moisture in the atmosphere. SO2 and SO3 form sulfites and sulfates when their acids are
« neutralized. Both of these acids can form solid particles by reacting with ammonia in air. SO2
z.and SO3 also contribute to pH (acidity) changes in water, which can adversely affect both land
and aquatic life. Therefore, both NOx and SOx from combustion can kill plants and animals.
CAPITA has shown that there are about equal amounts by weight of sulfate/sulfite, nitrate and
organic particles making up 90% of Particulate Matter less than 2.5 microns in aerodynamic
diameter (PM-2.5). This was confirmed by Brigham Young University researchers. The Six
Cities Study, published in the New England Journal of Medicine in 1990, has shown that illness
and premature death are closely correlated with the amount of PM-2.5 in the air. Therefore, there
is epidemiological data indicting nitrogen oxides, sulfur oxides, and/or organic compounds as
PM-2.5 aerosols. There is currently no evidence that separately examines the health effects of
each of these substances. PM-2.5 usually appear as smog, smoke, white overcast, haze, or fog
which does not clear when air warms up. Brown smog is colored by nitrogen dioxide.
Because the nitric acid, sulfurous acid and sulfuric acid react with ammonia in air to form solid
crystals that are much smaller than 2.5 microns and can be nucleation sites for particle growth, we
jieed to be concerned about each of these pollutants. Some research indicates that even insoluble
-particles much smaller than 2.5 microns in size can exhibit severe toxic effects.38 The smallest
particles that have shown toxicity have a diameter of about 3% to 5% of the wavelength of any
color of visible light. Therefore, these particles are too small to even scatter light and cannot even
be detected optically.
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Acid deposition occurs from airborne acidic or acidifying compounds, principally sulfates (SO4'2)
and nitrates (NO3"'), that can be transported over long distances before returning to earth. This
occurs through rain or snow (wet deposition), fog or cloud water (cloud deposition), or transfer
of gases or particles (dry deposition). While severity of damage depends on the sensitivity of the
receptor, acid deposition and NOx "represent a threat to natural resources, ecosystems, visibility,
materials, and public health."(section 401(a)(l) of the Clean Air Act).40
WHAT ABATEMENT AND CONTROL PRINCIPLES APPLY?
NOx abatement and control technology is a relatively complex issue. We shall try to provide a
structure to the spectrum of 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.
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 NOx.3 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. Chapter 9 of the OAQPS Control Cost Manual provides
guidance on the application, sizing, and cost of these scrubbers (referred to as gas absorbers).
Also, Table 16 in this Bulletin presents some information for non-combustion NOx sources.
Other then that, non-combustion NOx sources are not addressed in this Bulletin.
For combustion sources, this Bulletin defines abatement and emission control principles and states
the Destruction or Removal Efficiency (DRE) that each successful technology is capable of
achieving. The effectiveness of pollution prevention measures in reducing NO and NO2
generation also is expressed in terms of relative DRE; i.e., the amount NOx generation is reduced
by using a prevention technology compared to NOx generation when not using that technology.
Then, specific boiler types and combustion systems and applicable NOx technologies for each
system are discussed. Finally, the cost of these technologies is considered.
Many new combustion systems incorporate NOx prevention methods into their design and
generate far less NOx then similar but older systems. As a result, considering DRE (even a
relative DRE) for NOx may be inappropriate. Comparing estimated or actual NOx emissions
from a new, well-designed system to NOx emitted by a similar well-controlled and operated older
system may be the best way of evaluating how effectively a new combustion system minimizes
NOx emissions.
Table 2 lists principles or methods that are used to reduce NOx. Basically there are six principles,
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with the seventh being an intentional combination of some subset of the six.
Table 2. NOx Control Methods 6'7
Abatement or Emission
Control Principle or
Method
1 . Reducing peak temperature
2. Reducing residence time
at peak temperature
3. Chemical reduction of NOx
4. Oxidation of NOx with
subsequent absorption
5. Removal of nitrogen
6. Using a sorbent
7. Combinations of these
Methods
Successful Technologies
Flue Gas Recirculation (FOR)
Natural Gas Reburning
Low NOx Burners (LNB)
Combustion Optimization
Burners Out Of Service (BOOS)
Less Excess Air (LEA)
Inject Water or Steam
Over Fire Air (OF A)
Air Staging
Reduced Air Preheat
Catalytic Combustion
Inject Air
Inject Fuel
Inject Steam
Fuel Reburning (FR)
Low NOx Burners (LNB)
Selective Catalytic Reduction (SCR)
Selective Non-Catalytic Reduction
(SNCR)
Non-Thermal Plasma Reactor .
Inject Oxidant
Oxygen Instead Of Air
Ultra-Low Nitrogen Fuel
Sorbent In Combustion Chambers
Sorbent In Ducts
All Commercial Products
Pollution Prevention
Method (P2) or Add-
on Technology (A)
P2
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Method 1. Reducing Temperature -- Reducing combustion temperature means avoiding the
stoichiometric ratio (the exact ratio of chemicals that enter into reaction). Essentially, this
technique dilutes calories with an excess of fuel, air, flue gas, or steam. Combustion controls use
different forms of this technique and are different for fuels with high and low nitrogen content.
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Control of NOx from combustion of high nitrogen content fuels (e.g., coal) can be understood by
the net stoichiometric ratio. Control of the NOx from combustion of low nitrogen fuels (such as
gas and oil) can be seen as lean versus rich fuel/air ratios. Either way, this technique avoids the
ideal stoichiometric ratio because this is the ratio that produces higher temperatures that generate
higher concentrations of thermal NOx.
Combustion temperature may be reduced by: (1) using fuel rich mixtures to limit the amount of
oxygen available; (2) using fuel lean mixtures to limit temperature by diluting energy input;
(3) injecting cooled oxygen-depleted flue gas into the combustion air to dilute energy;
(4) injecting cooled flue gas with added fuel; or (5) injecting water or steam. Low-NOx burners
are based partially on this principle.8'9-10 The basic technique is to reduce the temperature of
combustion products with an excess of fuel, air, flue gas, or steam. This method keeps the vast
majority of nitrogen from becoming ionized (i.e., getting a non-zero valence).
Method 2. Reducing Residence Time — 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.
Method 3. Chemical Reduction of NOx - This technique provides a chemically reducing (i.e.,
reversal of oxidization) substance to remove oxygen from nitrogen oxides. Examples include
Selective Catalytic Reduction (SCR) which uses ammonia, Selective Non-Catalytic Reduction
(SNCR) which use ammonia or urea, and Fuel Reburning (FR). Non-thermal plasma, an
emerging technology, when used with a reducing agent, chemically reduces NOx. All of these
technologies attempt to chemically reduce the valence level of nitrogen to zero after the valence
has become higher." Some low-NOx burners also are based partially on this principle.
Method 4. Oxidation of NOx - This technique intentionally raises the valence of the nitrogen
ion to allow water to absorb it (i.e., it is based on the greater solubility of NOx at higher valence).
This is accomplished either by using a catalyst, injecting hydrogen peroxide, creating ozone within
the air flow, or injecting ozone into the air flow. Non-thermal plasma, when used without a
reducing agent, can be used to oxidize NOx. A scrubber must be added to the process to absorb
N2O5 emissions to the atmosphere. Any resultant nitric acid can be either neutralized by the
scrubber liquid and then sold (usually as a calcium or ammonia salt), or collected as nitric acid to
sell to customers.12'49
Method 5. Removal of nitrogen from combustion — This is accomplished by removing
nitrogen as a reactant either by: (1) using oxygen instead of air in the combustion process; or
(2) using ultra-low nitrogen content fuel to form less fuel NOx. Eliminating nitrogen by using
oxygen tends to produce a rather intense flame that must be subsequently and suitably diluted.
Although Method 2 can lower the temperature quickly to avoid forming excessive NOx, it cannot
10
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eliminate nitrogen oxides totally if air is the quench medium. Hot flue gas heats the air that is
used to quench it and this heating generates some thermal NOx. This method also includes
reducing the net excess air used in the combustion process because air is 80% nitrogen. Using
ultra-low-nitrogen content fuels with oxygen can nearly eliminate fuel and prompt NOx.13
Method 6. Sorption, both adsorption and absorption — 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 an 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 referred to as using a dry sorbent, but slurries also have been used. This method uses either
adsorption or absorption followed by filtration and/or electrostatic precipitation to remove the
sorbent.
Method 7. Combinations of these methods — Many of these methods can be combined to
achieve a lower NOx concentration than can be achieved alone by any one method. For example,
a fuel-rich cyclone burner (Method 1) can be followed by fuel reburn (Method 3) and over-fire air
(Method 1). This has produced as much as a 70% reduction in NOx.55 Other control
technologies that are intended to primarily reduce concentrations of sulfur also strongly affect the
nitrogen oxide concentration. For example, the SOx-NOx-ROx-Box (SNRB) technology uses a
limestone sorbent in the flue gas from the boiler to absorb sulfur. This is followed by ammonia
injection and SCR using catalyst fibers in the baghouse filter bags. The sulfur is recovered from
the sorbent and the sorbent regenerated by a Claus process. This has demonstrated removal of up
to 90% of the NOx along with 80% of the SOx.39-42 EBARA of Japan reported that an electron
beam reactor with added ammonia removed 80% of the SO2 and 60% of the NOx for a utility
boiler in China.54 FLS Milo and Sons reported at the same symposium that 95% of the SO2 and
70%-90% of the NOx were removed in several demonstrations of their SNAP technology, which
is based upon an aluminum oxide adsorber with Claus regeneration.56
WHAT ABATEMENT TECHNOLOGIES ARE AVAILABLE?
In this report existing NOx abatement technologies are 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). These categories are
further subdivided into pollution prevention (which reduces NOx generation) and add-on control
technologies (which reduces NOx emissions).
EXTERNAL COMBUSTION
For external combustion applicable technologies are shown in Table 3 (based on Table 2 in Select
the Right NOx Control Technology, Stephen Wood, Chemical Engineering Progress, January
1994).
11
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Table 3. External Combustion NOx Limiting Technologies
Technique
Less Excess Air (LEA)
Off Stoichiometric
a. Burners Out of
Service (BOOS)
b. Over Fire Air (OFA)
Low NOx Burner
(LNB)
Flue Gas Recirculation
(FGR)
Water/Steam Injection
Reduced Air Preheat
Selective Catalytic
reduction (SCR)
(add-on technology)
Description
Reduces oxygen
availability
staged combustion
Internal staged
combustion
<30% flue gas
recirculated with air,
decreasing temperature
Reduces flame
temperature
Air not preheated,
reduces flame
temperature
Catalyst located in the
air flow, promotes
reaction between
ammonia and NOx
Advantages
Easy modification
Low cost
No capital cost
for BOOS
Low operating cost
Compatible FGR
High NOx reduction
potential for low
nitrogen fuels
Moderate capital cost
NOx reduction similar
to FGR
High NOx reduction
potential
High NOx removal
Disadvantages
Low NOx reduction
a. Higher air flow for
CO
b. high capital cost
Moderately high
capital cost
Moderately high
capital cost and
operating cost
Affects heat transfer
and system pressures
Efficiency penalty
Fan power higher
Significant efficiency
loss (1% per 40 °F)
Very high capital cost
High operating cost
Catalyst siting
Increased pressure drop
Possible water wash
required
Impacts
High CO
Flame length
Flame stability
Flame length
Fan capacity
Header pressure
Flame length
Fan capacity
Turndown stability
Fan capacity
Furnace pressure
Burner pressure drop
Turndown stability
Flame stability
Efficiency penalty
Fan capacity
Efficiency penalty
Space requirements
Ammonia slip
Hazardous waste
Disposal
Applicability
All fuels
All fuels
Multiple burners for
BOOS
All fuels
All fuels
Low nitrogen fuels
All fuels as
Low nitrogen fuels
All fuels
Low nitrogen fuels
All fuels
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* ' .
Table 3. External Combustion NOx Limiting Technologies
Technique
Selective Non-Catalytic
Reduction (SNCR)
(add-on technology)
a. urea
b. ammonia
Fuel Reburning
Combustion
Optimization
Catalytic Combustion
Non-Thermal Plasma
Inject Oxidant
Oxygen instead of Air
Ultra-Low Nitrogen
Fuel
Description
Inject reagent to react
with NOx
Inject fuel to react with
NOx
Change efficiency of
primary combustion
Catalyst causes
combustion to be at low
• temperature
Reducing agent ionized
or oxidant created in
flow
Chemical oxidant
injected in flow
Uses oxygen to oxidize
fuel
Uses low -nitrogen fuel
Advantages
a. Low capital cost
Moderate NOx removal
Non-toxic chemical
b. Low operating cost
Moderate NOx removal
Moderate cost
Moderate NOx removal
Minimal cost
Lowest possible NOx
Moderate cost
Easy siting
High NOx removal
Moderate cost
Moderate to high cost
Intense combustion
Eliminates fuel NOx
No capital cost
Disadvantages
a. Temperature
dependent
NOx reduction less at
lower loads
b. Moderately high
capital cost
Ammonia storage,
handling, injection
system
Extends residence time
Extends residence time
Very high capital cost
High operating cost
Catalyst siting
Fouling possible
Ozone emission
possible
Nitric acid removal.
Eliminates prompt
NOx
Furnace alteration
Slight rise in operating
cost
Impacts
a. Furnace geometry
Temperature profile
b. Furnace geometry
Temperature profile
Furnace temperature
profile
Furnace temperature
profile
Space requirements
Disposal
Uses electrical power
Add-on
Equipment to handle
oxygen
Minimal change
Applicability
All fuels
All fuels
(pulverized solid)
Gas
Liquid fuels
Gas
Liquid fuels
All fuels
All fuels
All fuels
All ultra-low nitrogen
fuels
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Table 3. External Combustion NOx Limiting Technologies
Technique
Use Sorbents (add-on
technology) in:
a. Combustion
b. Duct to Baghouse
c. Duct to Electrostatic
Precipitator
Air Staging
Fuel Staging
Description
Use a chemical to
absorb NOx or an
adsorber to hold it
Admit air in separated
stages
Admit fuel in separated
stages
Advantages
Can control other
pollutants as well as
NOx
Moderate operating
cost
Reduce peak
combustion
temperature
Reduce peak
combustion
temperature
Disadvantages
Cost of handling
sorbent
Space for the sorbent
storage and handling
Extend combustion to a
longer residence time
at lower temperature
Extend combustion to a
longer residence time
at lower temperature
Impacts
Add-on
Adds ducts and
dampers to control air
Furnace modification
Adds fuel injectors to
other locations
Furnace modification
Applicability
All fuels
All fuels
All fuels
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EXTERNAL COMBUSTION: POLLUTION PREVENTION METHODS
LESS EXCESS AIR (LEA)
Excess air flow for combustion has been correlated to the amount of NOx generated. Limiting
the net excess air flow to under 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.43
BURNERS OUT OF SERVICE (BOOS)
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 combustion by stages
with temperature always lower than when all burners are in service. Thus, thermal NOx is lower.
The degree to which NOx generation is reduced depends upon the spatial relationship of the
BOOS to the other burners.44
OVER FIRE AIR (OFA)
When primary combustion uses a fuel-rich mixture, use of OFA completes the combustion.
Because the mixture is always off-stoichiometric when combustion is occurring, the temperature
is held down. After all other stages of combustion, the remainder of the fuel is oxidized in the
over fire aii. This is usually not a grossly excessive amount of air.
LOW NOx BURNERS (LNB)
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 theme of reducing NOx. The LNB has
produced up to 80% DRE.17'18'32'33 This can be one of the least expensive pollution prevention
technologies with high DRE. LNB have had problems with designs that had flame attaching to
the burners, resulting in a need for maintenance. We believe that these design problems should
now be a thing of the past.
FLUE GAS RECIRCULATION (FGR)
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 that is generated. If combustion temperature is held down to below 1,400°F, the
thermal NOx formation will be negligible.50
15
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WATER OR STEAM INJECTION
Injection of water or steam causes the stoichiometry of the mixture to be changed and adds steam
to dilute calories generated by combustion. Both of these actions cause combustion temperature
to be lower. If temperature is sufficiently reduced, thermal NOx will not be formed in as great a
concentration.
REDUCED AIR PREHEAT
Air is usually preheated to cool the flue gases, reduce the heat losses, and gain efficiency.
However, this can raise the temperature of combustion air to a level where NOx forms more
readily. By reducing air preheat, the combustion temperature is lowered and NOx formation is
suppressed. This can lower efficiency, but can limit NOx generation.
FUEL REBURNING (FR)
Recirculation of cooled flue gas with added fuel (this can be natural gas, pulverized coal, or even
oil spray) causes dilution of calories, similar to FGR, and primary combustion temperature can be
lowered. Also, when added as a secondary combustion stage, the presence of added fuel
chemically reduces newly generated NOx to molecular nitrogen. Added fuel is only partially .
consumed in reducing NOx and burning is completed in a later 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.1?
COMBUSTION OPTIMIZATION
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.14-15 For coal-fired boilers a 20% to 60% reduction in NOx has been
experienced. These active combustion control measures seek to find an 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 control point.16 Still another
approach is to use software to optimize inputs for the defined output.52'53
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.14
AIR STAGING
Combustion air is divided into two streams. The first stream is mixed with fuel in a ratio that
16
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produces a reducing flame. The second stream is injected downstream of the flame and makes the
net ratio slightly excess air compared to the stoichiometric ratio. DRE up to 99% have been
reported.51
FUEL STAGING
This is staging of combustion using fuel instead of the air. 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.51
OXYGEN INSTEAD OF AIR FOR COMBUSTION
An example of this is a cyclone burner where the flame is short and intense. Excess fuel air or
steam, injected just after the combustion chamber per Method 2 is sufficient to rapidly quench the
flue gas to below NOx formation temperature. Combustion can then be completed in over-fire
air. Oxygen can now be separated from air at a low enough cost to make this economical.13 This
technique has reduced NOx by up to 20%23 in burners using conventional fuel. This technique
also is usable with low-NOx burners to prevent the prompt NOx from being formed.
INJECTION OF OXIDANT
The oxidation of nitrogen to its higher valence states makes NOx soluble in water. When this is
done a gas absorber can be effective. Oxidants that have been injected into the air flow are ozone,
ionized oxygen, or hydrogen peroxide. Non-thermal plasma generates oxygen ions within the air
flow to achieve this. Other oxidants have to be injected and mixed in the flow. Nitric acid can be
absorbed by water, hydrogen peroxide, or an alkaline fluid. Calcium or ammonia dissolved in the
water can make an alkaline fluid that will react with nitric and sulfuric acids to produce a nitrate
or sulfate salt that can be recovered. Alternatively, using water or hydrogen peroxide to absorb
NOx can provide nitric acid for the commercial market.
CATALYTIC COMBUSTION
Use of a catalyst to cause combustion to occur below NO formation temperatures can provide a
suitable means of limiting temperature. This technique is not used often because it is very load
sensitive. However, where it is used, catalytic combustion can achieve less than a 1 ppm
concentration of NOx in the flue gas.
ULTRA-LOW NITROGEN FUELS
These fuels can avoid NOx that results from nitrogen contained in conventional fuels. The result
can be up to a 70% reduction in NOx emissions.43 Now there are ultra-low-nitrogen liquid fuel
17
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oils. These oils contain 15-20 times less nitrogen than standard No. 2 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.
NON-THERMAL PLASMA
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. The reducing agents were
ionized by a transient high voltage that created a non-thermal plasma. 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.
EXTERNAL COMBUSTION: ADD-ON CONTROL TECHNOLOGY
Add-on controls are applicable to a broad range of sources and fuels. This differs from the
pollution prevention techniques listed above in that the prevention techniques must be adapted to
the circumstances of their use.
SELECTIVE CATALYTIC REDUCTION (SCR)
SCR uses a catalyst to react injected ammonia to chemically reduce NOx. It can achieve up to a
94% DRE34 and is one of the most effective NOx abatement techniques. However, this
technology has a high initial cost. In addition, catalysts have a finite life in flue gas and some
ammonia "slips through" without being reacted. SCR has historically used precious metal
catalysts, but can now also use base-metal and zeolite catalysts. The base-metal and zeolite
catalysts operate at much different temperatures then the precious metal catalysts."
SELECTIVE NON-CATALYTIC REDUCTION (SNCR)
In SNCR ammonia or urea is injected within a boiler or in ducts in a region where temperature is
between 900°C and 1100°C. This technology is based on temperature ionizing the ammonia or
urea instead of using a catalyst or non-thermal plasma. This temperature "window" - which is
reported differently by various authors ~ is important because outside of it either more ammonia
"slips" through or more NOx is generated than is being chemically reduced. The temperature
"window" is different for urea and ammonia. Reduction of the NOx by SNCR can have up to a
70% DRE.23'35-43
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SORPTION - BOTH ADSORPTION AND ABSORPTION
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 also is a spray dryer approach that sprays a 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 products formed by sorption are gypsum (calcium sulfate) that is sold to
make wallboard, and ammonium nitrate that can be sold to make either an explosive or a fertilizer.
Sorption is reported to have up to a 60% DRE.23'31 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 ESP
just like other sorbents. There are many absorbents and adsorbents available.
COMBINED TECHNOLOGY APPROACHES
Very seldom is only one method or principle used alone. The choice 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.
ilr
•*There are many examples and here are a few of them. Selective catalytic reduction of NOx 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.30
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.57
INTERNAL COMBUSTION
Now we turn to internal combustion, which usually occurs at elevated pressures. Again, we
divide the technologies between pollution prevention techniques and add-on technologies. This is
shown in Table 4.
- These techniques can be used in combination. Pollution prevention techniques do not have to be
used separately. Add-on techniques could be used sequentially after a pollution prevention
technique when they do not impose conflicting demands on the process.
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Table 4. Internal Combustion NOx Limiting Technologies
Pollution Prevention
Low-NOx Burners (LNB)
Steam/Water Injection
Catalytic Combustion
Air-Fuel Ratio and Ignition Type
Pre-Stratified Charge
Lean Burn
Add-On Control
Selective Catalytic Reduction (SCR)
Selective Non-Catalytic
Non-Selective Catalytic
Reduction (SNCR)
Reduction (NSCR)
Non-Thermal Plasma
INTERNAL COMBUSTION: POLLUTION PREVENTION METHODS
LOW NOx BURNERS (LNB)
Combining the use of LNB with closely controlled air/fuel ratio and water/steam injection can
yield emissions as low as 10 ppm from gas turbines.46
STEAM/ WATER INJECTION
To reduce combustion temperature, steam or water can be mixed with the air flow. This lowers
combustion temperature to below 1,400°F to limit NOx generation to about 40 ppm.46 This can
cause the concentration of CO and unburned hydrocarbons emitted from a turbine to be increased.
However, these can be burned by either a catalyst bed, afterburner, or another stage of
combustion. This otherwise wasted fuel and heat can also be recovered in co-generation boilers.
CATALYTIC COMBUSTION
A catalyst is used to react fuel with air at a lower temperature than normal combustion at which
generation of significant amounts of NOx does not occur. Emissions under 1 ppm NOx have
been reported.46 However, if this combustion is for a turbine, turbine efficiency may depend
upon achieving a higher temperature. When a catalyst is present, you also need to assure that
NOx will not be formed at the combustion temperature that results.
This technology has a relatively high capital and operation and maintenance cost because there is
both a substantial initial investment and a replacement cost for the catalyst. The need for
replacement and, therefore, replacement cost are usually driven by impurities in the fuel.
However, catalytic combustion generates possibly the lowest level of thermal NOx.
20
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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 will limit the amount of NOx formation. This technique can achieve up to 50%
control efficiency.19'48
When a three-way catalyst is used for spark ignition engines, exhaust gas must have no more than
- 0.5% oxygen. This technique can be up to 98% effective.
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%.20-21'45
Delaying injection of fuel in a compression ignition (diesel) engine can reduce the NOx emissions.
The amount of this reduction will depend upon the engine, valving, and fuel. Excessive timing
retard can cause combustion instability or misfire.48 However, some claims of high effectiveness
are to be found with ostensibly excessive retard.
PRE-STRATIFIED CHARGE (PSC)
: PSC refers to an engine equipped with a pre-combustion chamber that receives a rich enough
air/fuel mixture to ignite dependably. This pre-combustion chamber fires a jet of flame into the
"main combustion chamber (cylinder). The main combustion chamber has a fuel-lean mixture that
needs pre-combustion flame to ignite it reliably. The injected flame also produces a swirl in the
main combustion chamber that acts like stratified charge combustion. This dependably ignites the
lean main cylinder mixture. The PSC can achieve NOx emissions~of 2 grams/horsepower-hour
(g/hp-hr) or 140 ppm.48
LEAN BURN
Natural gas fueled engines that operate with a fuel-lean air/fuel ratio are capable of low NOx
emissions. These can achieve less than 1.0 gram/brake horsepower-hour according to the RACT-
BACT-LAER Clearinghouse (RBLC) (http://www.epa.gov/ttn/catc. then £e]ectRBLC).
INTERNAL COMBUSTION ADD-ON CONTROL TECHNOLOGY
SELECTIVE CATALYTIC REDUCTION (SCR)
*
As with boilers, SCR can be used to obtain up to a 90% DRE of NOx. When used with a LNB or
steam/water injection, NOx can be reduced to 5-10 ppm.46 With compression ignition engines,
zeolite catalysts achieve a DRE of 90+%, while base-metal catalysts can achieve a 80% to 90%
DRE.48
21
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NON-SELECTIVE CATALYTIC REDUCTION (NSCR)
NSCR is the same technique used in automobile applications as a three-way catalytic converter. It
does not require injection of a reducing agent because it uses unburned hydrocarbons as a
reducing agent. The catalyst requires that exhaust have no more than 0.5% oxygen. This
technique uses a fuel rich mixture that, combined with back pressure from exhaust flow through
the catalyst, increases the brake specific fuel consumption of the engine. However, NOx control
of 90% to 98% can be achieved.48
NON-THERMAL PLASMA REACTORS
This approach uses a non-thermal plasma to ionize ammonia, urea, hexane, methane or other
reducing agents injected into a flue gas. Combined with the effect of temperature, non-thermal
plasma ionizes the reducing agent that reacts with nitrogen oxides achieving a 94% DRE. This
decreases the amount of reducing chemicals that "slips" through unreacted.20'44 The use of non-
thermal plasma was developed to ionize pollutants and act as a catalyst to control NOx in diesel
exhaust.36
DO FUELS AND COMBUSTION TYPE AFFECT ABATEMENT?
Yes they do. Here again, we find a spectrum of types, almost enough to make every gas turbine,
internal combustion engine, boiler, or furnace seem unique. The type of fuel can vary with the
vein of the mine from which coal was obtained, the well in the oilfield from which crude oil came,
the refinery for petroleum based fuels, or the supplier of natural gas. Thus the concentration of
impurities will vary between sources, refineries, and suppliers. Even "natural gas" (methane) may
contain some "supplier gas" (propane, butane, and carbon monoxide) which will cause the
composition of "natural gas" to vary.
The type of combustion system (low-NOx burner, over-fire air, tangential firing, wall firing, etc)
also will sometimes limit options. Each type of boiler, each type of fuel, each combustion system,
and each construction of a boiler puts constraints on what is possible. It is not possible to treat
each combination of combustion system and fuel in detail in this Technical Bulletin; however, we
will try to show the picture while painting with broad strokes.
The choice of fuel and combustion system often depends upon: (1) what can or cannot be
adjusted; (2) whether ducts are suitable for sorption; (3) what the effect on boiler maintenance
will be; (4) the temperature profile in the flow: (5) how the combustion system can be modified;
(6) what types of burners can be used; and (7) what can either be added or modified. The list
does not end there, but continues. Let us consider some fuels with these limitations in mind.
SOLID FUELS
In burning a solid fuel (such as coal), combustion control is achieved by first getting the primary
burner to gasify the volatile fraction of a fuel. The volatile fraction is carried away from char by
22
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air flow, oxidized in the air flow, and becomes flue gas. Char needs more combustion air to burn
and provide further heat, part of which is used to volatilize additional fuel. To control
combustion temperature, you traditionally would limit combustion air through the char fraction.
The volatile fraction is oxidized in over-fire-air or a secondary stage of burner and must have its
air separately controlled. The balance of combustion air between these stages must be adjusted
for composition of fuel being used, boiler loading, and transient loads. Because all of these
parameters will vary continually, provisions to make balancing adjustments dynamically are
recommended.
Pulverized coal can be burned similar to oil. The flame is usually well defined and, depending on
particle size, char may remain in suspension in flue gas throughout burning. The volatile fraction
burns in air even as char is burned. If the particles are too coarse, char will continue burning on
its trajectory after leaving the flame, but will stop burning at some point. 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 is minimized by grinding
particles finer and classifying 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, particle size at ignition is important. The major concerns are
to control stoichiometry and combustion temperature to minimize unburned carbon in ash.
Biomass is another solid fuel, but burning biomass char is less of a concern than with coal.
Biomass cannot be pulverized to small particles, but can burn to ash in a short time. As with the
^burning of all char, ash and fly ash are problems, but can be treated with a 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 char from solid fuel because combustion is
less dependent on the history of the past few minutes of demand. Combustion is also completed
essentially without residual ash. The fuel-air ratio can be used to control combustion temperature
and can be adjusted to minimize NOx generation. The flame can be well-defined and combustion
is essentially completed within the flame. Therefore, burning oil or liquid-from-coal or liquid-
from-gas is different from burning coal because there is usually less nitrogen in the fuel, a lack of
char, complete burning within the flame and a lack of ash.
SEMI-SOLID FUELS
Semi-solid fuels are residuals from refineries. They are not clean burning 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.50 Therefore, semi-solid fuels are intermediate between coal and oil.
They often have somewhat less impurities than coal (although they can have more impurities), but
23
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they do produce ash.
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,
liquified petroleum gas (butane), carbon monoxide, or other gaseous fuel. As a result, air to fuel
ratio must be controllable to allow for changes in the stoichiometric ratio.
COMBUSTION SYSTEMS
To take advantage of a specific NOx abatement technology, a combustion system must either
have certain features in place, or needed system modifications must be technically and
economically feasible. Therefore, when identifying applicable pollution prevention and emission
control technologies, we must first consider combustion system design. The major types of
combustion systems are shown in Table 5.23
Table 5. Common Combustion Systems
Type of Combustion Unit
Dry bottom boilers - wall-fired, front-fired or
opposed-fired
Dry bottom boilers - tangentially fired
Wet bottom (slag tap) boilers - cyclone-type
burners
Fluidized bed
Stokers with traveling grate.
Stokers with spreader grate
Gas turbines
Internal combustion engines
Fuel
pulverized coal, gas, or liquid
pulverized coal, gas, or liquid
pulverized coal, gas, or liquid
coal
crushed coal
crushed coal.
gas and liquid
gas and liquid
Each NOx abatement technology has different implementations, development histories, and,
therefore, commercial status. Selection of a technology must occur after an engineering study to
determine technical and economic feasibility of each NOx technology. This includes how each
technology can be implemented and its cost. Options may be limited by inability to adjust
combustion system air flow appropriately, ducts that are at the wrong temperature, or ducts that
24
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are too short to provide adequate mixing. These problems can be solved, but may require too
much modification to make them economical.
.DRY BOTTOM BOILERS - WALL-FIRED, FRONT-FIRED or OPPOSED-FIRED
Dry bottom pulverized coal, gas, and liquid fuel wall-fired boilers have used low-NOx burners to
inject fuel and air from lower walls. Front-fired boilers have burners on one wall. Opposed-fired
boilers have burners on front and back walls. These boilers typically use methods that reduce peak
temperature, reduce residence time at peak temperature, or chemically reduce NOx (Methods 1, 2
& 3). These methods are used for large utility boilers in which combustion efficiency is all-
important. NOx oxidation with absorption and removal of nitrogen (Methods 4 and 5) represent
newer technologies that may be applied in the future. Using a sorbent (Method 6) is already in
use for some boilers. See Table 6 for NOx technologies used for dry bottom wall-fired, front-
fired or opposed-fired boilers.
Table 6: NOx technologies currently used for dry bottom
wall-fired, front-fired or opposed-fired boilers.
NOx Abatement Method
1 . Reducing peak temperature
2. Reducing residence time
at peak temperature
3. Chemical reduction of NOx
4. Oxidation of NOx with
subsequent absorption
5. Removal of nitrogen
6. Using a sorbent
Techniques Now Available
Flue Gas Recirculation (FGR)
Natural Gas Reburning (NGR)
Low NOx Burners (LNB)
Combustion Optimization
Burners Out Of Service (BOOS)
Over Fire Air (OF A)
Less Excess Air (LEA)
Inject Water or Steam
Reduced Air Preheat
Air Staging of Combustion
Fuel Staging of Combustion
Inject Steam
Selective Catalytic Reduction (SCR)
Selective Non-Catalytic Reduction (SNCR)
Fuel Reburning (FR)
Low NOx Burners (LNB)
Inject Oxidant
Non-Thermal Plasma Reactor (NTPR)
Ultra-Low Nitrogen Fuel
Sorbent In Combustion Chambers
Sorbent In Ducts
Efficiency
50-70%
50-70%
35-90%
60-80%
No Data
60-90%
25
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DRY BOTTOM BOILERS - TANGENTIALLY FIRED
Dry bottom pulverized coal, gas, or liquid fuel tangentiallv-fired boilers use jets from each corner
of a furnace to inject fuel and combustion air in a swirl. The injected mix of fuel and combustion
air forms a fireball in the center of the boiler. This firing configuration is used in medium sized
utility and large industrial boilers. This combustion technique holds flame temperatures down
(Method 1). In addition, chemical reduction of NOx (Method 3) is frequently used. NOx
oxidation (Method 4) techniques may be used in the future. Sorbents (Method 6) are already
used for some boilers. See Table 7 for NOx technologies used for dry bottom tangentially fired
boilers.
Table 7: NOx technologies currently used for dry bottom tangentially fired boilers.
NOx Abatement Method
1 . Reducing peak temperature
2. Reducing residence time
at peak temperature
3. Chemical reduction of NOx
4. Oxidation of NOx with
subsequent absorption
5. Removal of nitrogen
6. Using a sorbent
Techniques Now Available
Flue Gas Recirculation (FOR)
Natural Gas Reburning (NGR)
Over Fire Air (OF A)
Less Excess Air (LEA)
Inject Water or Steam
Reduced Air Preheat
Air Staging of Combustion
Fuel Staging of Combustion
Inject Steam
Selective Catalytic Reduction (SCR)
Selective Non-Catalytic Reduction (SNCR)
Fuel Reburning (FR)
Non-Thermal Plasma Reactor (NTPR)
Ultra-Low Nitrogen Fuel
Sorbent In Combustion Chambers
Sorbent In Ducts
Efficiency
50-70%
50-70%
35-90%
60-80%
No Data
60-90%
WET BOTTOM (SLAG TAP) BOILERS
Wet bottom (slag tap) boilers use cyclone burners to create an intense flame. The flame is so hot
that it melts ash, which then becomes slag that must be removed via a slag tap. These boilers are
known to have higher NOx generation because combustion temperature is so high. As a result,
this high temperature combustion technique is not widely used because the NOx concentration
necessarily must be greater. Removal of non-fuel nitrogen as a reactant from the combustion
process (Method 5) applies here. Reducing residence time at peak temperature, chemical
26
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reduction of NOx, and NOx oxidation with absorption (Methods 2, 3 & 4) also apply to this
combustion system. In addition, some slag tap boilers may be using sorbents (Method 6). There
are recent reports that reducing peak temperature (Method 1) so that ash just melts has been
used. See Table 8 for NOx technologies used for slag tap boilers.
Table 8: NOx technologies currently used for wet bottom (slag tap) boilers.
NOx Abatement Method
1 . Reducing peak temperature
2. Reducing residence time
at peak temperature
3. Chemical reduction of NOx
4. Oxidation of NOx with
subsequent absorption
5. Removal of nitrogen
6. Using a sorbent
1
Techniques Now Available
Flue Gas Recirculation (FOR)
Natural Gas Reburning (NGR)
Over Fire Air (OF A)
Less Excess Air (LEA)
Inject Water or Steam
Reduced Air Preheat
Air Staging of Combustion
Fuel Staging of Combustion —
Inject Steam
Selective Catalytic Reduction (SCR)
Selective Non-Catalytic Reduction (SNCR)
Fuel Reburning (FR)
Non-Thermal Plasma Reactor (NTPR)
Use Oxygen Instead Of Air
Ultra-Low Nitrogen Fuel
Sorbent In Combustion Chambers
Sorbent In Ducts
Efficiency
30-70%
20-50%
35-90%
60-80%
No Data
60-90%
FLUIDIZED BED
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 also is a chemically reducing region in which available oxygen is consumed
by carbon (Method 3) that reduces ionization of nitrogen. Excess air is injected (Method 2) over
the fluidized bed to complete combustion of CO and other burnables. This allows for the addition
of pulverized limestone (Method 6) to coal in the fluidized bed. Sulfur oxides then react with the
limestone to form gypsum, a marketable product. Gypsum must be separated from the ash. As a
result, NOx generation can be essentially limited to prompt NOx and fuel NOx. See Table 9 for
NOx technologies used for fluidized bed combustion units.
27
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Table 9: NOx techniques currently used for fluidized bed combustion.
NOx Abatement Method
1 . Reducing peak temperature
2. Reducing residence time
at peak temperature
3. Chemical reduction of NOx
4. Oxidation of NOx with
subsequent absorption
5. Removal of nitrogen
6. Using a sorbent
Techniques Now Available
Flue Gas Recirculation (FGR)
Natural Gas Reburning (NGR)
Over Fire Air (OF A)
Less Excess Air (LEA)
Reduced Air Preheat
Inject Steam
Selective Catalytic Reduction (SCR)
Selective Non-Catalytic Reduction(SNCR)
Fuel Reburning (FR)
Non-Thermal Plasma Reactor (NTPR)
Ultra-Low Nitrogen Fuel
Sorbent In Combustion Chambers
Sorbent In Ducts
Efficiency
No Data
No Data
35-90%
60-80%
No Data
60-90%
STOKERS WITH TRAVELING GRATE
Stokers with traveling grate cause the coal to move as it burns. Thus, char combustion is in one
zone while volatiles are liberated and combusted in another zone. These stokers are commonly
used with industrial boilers that are smaller than utility boilers. Reducing peak temperature,
chemical reduction of NOx, and sorbents (Methods 1, 3 & 6) usually are applied. Perhaps NOx
oxidation (Method 4) also will apply in the future. See Table 10 for NOx technologies used for
stokers with traveling grates.
STOKERS WITH SPREADERS
Stokers with spreaders throw coal over the grate in a controlled manner. Coal is crushed, but
particles are typically larger than pulverized coal. Therefore, combustion of volatiles begins while
coal is in flight and combustion of char occurs on the grate. This system is used with somewhat
larger boilers than stokers with traveling grates. It can be used in power plants, but this
combustion system is used mainly for industrial boilers. Like stokers with traveling grates,
reducing peak temperature, chemical reduction of NOx, and sorbents (Methods 1,3, and 6)
usually are applied. Perhaps NOx oxidation (Method 4) also will apply in the future. See Table
11 for NOx technologies used for stokers with Spreader grates.
28
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Table 10: NOx technologies currently used for stokers with traveling grates.
NOx Abatement Method
1 . Reducing peak temperature
2. Reducing residence time
at peak temperature
3. Chemical reduction of NOx
4. Oxidation of NOx with
subsequent absorption
5. Removal of nitrogen
6. Using a sorbent
Technique Now Available
Flue Gas Recirculation (FOR)
Natural Gas Reburning (NGR)
Combustion Optimization
Over Fire Air (OF A)
Less Excess Air (LEA)
Inject Water or Steam
Reduced Air Preheat
Air Staging of Combustion
Fuel Staging of Combustion
Selective Catalytic Reduction (SCR)
Selective Non-Catalytic Reduction (SNCR)
Fuel Reburning (FR)
Inject Oxidant
Non-Thermal Plasma Reactor (NTPR)
Ultra-Low Nitrogen Fuel
Sorbent In Combustion Chambers
Sorbent In Ducts "*
Efficiency
35-50%
50-70%
55-80%
60-80%
No Data
60-90%
GAS TURBINES
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 NOx 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. Many turbine operators claim that they use "good
combustion practices" that do reduce the particles that produce visible emissions (which they
equate with pollution), but say nothing about the NOx emissions which are not visible.
Cogeneration units use a gas turbine to generate electricity and provide preheated combustion air
for a boiler. Gas turbine exhaust is typically 10-15% oxygen and can be used to provide
^combustion air for a low pressure boiler. That boiler can be used to provide steam for another
turbine, a process heater, a space heater, or some combination of these. If a steam turbine is used
_to generate electricity, it may constrain what can be done. Sorbent particles can be introduced to
a flow after it leaves a gas turbine in order to control NOx. There has also been some success in
reducing NOx concentrations when burning biomass fuels in a boiler. See Table 12 for NOx
technologies used for gas turbines.
29
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Table 11: NOx technologies currently used for stokers with spreader grates.
NOx Abatement Method
1 . Reducing peak temperature
2. Reducing residence time
at peak temperature
3. Chemical reduction of NOx
4. Oxidation of NOx with
subsequent absorption
5. Removal of nitrogen
6. Using a sorbent
Technique Now Available
Flue Gas Recirculation (FOR)
Natural Gas Reburning (NCR)
Low NOx Burners (LNB)
Combustion Optimization
Over Fire Air (OF A)
Less Excess Air (LEA)
Inject Water or Steam
Reduced Air Preheat
Air Staging of Combustion
Fuel Staging of Combustion
Inject Steam
Selective Catalytic Reduction (SCR)
Selective Non-Catalytic Reduction
(SNCR)
Fuel Reburning (FR)
Inject Oxidant
Non-Thermal Plasma Reactor (NTPR)
Ultra-Low Nitrogen Fuel
Sorbent In Combustion Chambers
Sorbent In Ducts
Efficiency
50-65%
50-65%
35-80%
60-80%
No Data
60-90%
INTERNAL 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 NOx formation. Chemical reduction of NOx (Method 3)
is used in catalytic converters to reduce NOx to N2. Some stationary engines use both Method 3
and NOx oxidation (Method 4). A non-thermal plasma reactor was developed for treatment of
diesel exhaust, but is not yet marketed to our knowledge. A plasma ignition system allows
greater freedom in the air-fuel ratio and the ignition timing of spark ignition engines. See Table
13 for NOx technologies used for stationary internal combustion engines.
WHAT DOES NOx ABATEMENT AND CONTROL COST?
The cost of NOx abatement and control has been changing rapidly with dramatic reductions in
recent years. Table 14 gives the 1993 cost as given in the Alternative Control Techniques
30
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Table 12: NOx technologies currently used for gas turbines.
NOx Abatement Method
1 . Reducing peak temperature
2. Reducing residence time
at peak temperature
3. Chemical reduction of NOx
4. Oxidation of NOx with
subsequent absorption
5. Removal of nitrogen
6. Using a sorbent
Technique Now Available
Natural Gas Reburning (NGR)
Low NOx Burners (LNB)
Inject Water or Steam
Reduced Air Preheat
Catalytic Combustion
Air Staging of Combustion
Inject Steam
Selective Catalytic Reduction (SCR)
Selective Non-Catalytic Reduction (SNCR)
Fuel Reburning (FR)
Low NOx Burners (LNB)
Non-Thermal Plasma Reactor (NTPR)
Ultra-Low Nitrogen Fuel
Sorbent In Ducts
Efficiency
70-85%
70-80%
70-90%
No Data
No Data
60-90%
Table 13: NOx technologies currently used for stationary internal combustion engines.
NOx Abatement Method
1 . Reducing peak temperature
2.Reducing residence time
at peak temperature
3. Chemical reduction of NOx
4. Oxidation of NOx with
subsequent absorption
5. Removal of nitrogen
6. Using a sorbent
Technique Now Available
Air/fuel Ratio
Timing of Ignition/Type of Ignitton
Pre-Stratified Combustion
Valve Timing
Selective Catalytic Reduction (SCR)
Non-Selective Catalytic Reduction (NCSR)
Non-Thermal Plasma Reactor (NTPR)
Ultra-Low Nitrogen Fuel
Sorbent In Exhaust Ducts
Adsorber in fixed Bed
Efficiency
20-97%
No Data
80-90%
80-95%
No Data
60-90%
31
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Table 14.1993 Costs of NOx Controls
Control
Device
LNB
Cost of NOx Controls in 1993 Dollars
Low -Cap.
S/MMBTU
650
LNB + FGR
SNCR
1,600
(1994 ESTIMATE)
SCR
2,400
(1994 ESTIMATE)
High -Cap.
S/MMBTU
8,300
3,300
20,000
Low - Oper.
$/MMBTU
340
680
1,500
High -Oper.
S/MMBTU
1,500
1,200
5,800
Low
$/ton
240
650
N/A
700
1,810
500
High
$/ton
4,300
7,630
N/A
1,300
10,900
2,800
Document NOx Emissions from Industrial/Commercial/Institutional Boilers (EPA 453/R-94-022).
The EPA Region III Low-NOx Control Technology Study in 1994 said that low-NOx burners
had both beneficial effects on operating costs and detrimental effects on the burners, their life
expectancy, and the boilers in which they were installed. Coal quality and some boiler designs
caused NOx to remain high even after low-NOx burners were in place. Capital costs ranged from
$1.91 to $54.24 per kW. Operating costs ranged from $-23,000 (a profit) to $1,113,750 per
year. Thus, no reliable cost estimates could be obtained regarding low-NOx burner operation.
Coal quality, boiler capacity, and burner design were among the variables influencing this cost.
Many plants could not even give an estimate. SNCR cost between $700 and $1,300 per ton of
NOx reduced. SCR cost between $500 and $2,800 per ton of NOx reduced.25 However, cost
per ton of NOx removed for all technologies is apparently becoming smaller.
These costs vary by control technique; type of fuel; grade of fuel; size of boiler, engine or turbine;
type of boiler, or turbine; and other factors. Other costs were also changing with time. Therefore
you need to examine the costs of these NOx control technologies for a specific application and at
a particular time.
These preliminary cost estimates will also be further reduced as operating experience is gained,
competition sharpens, and design iterations eliminate.the high-maintenance or life-shortening
features. Confidence in this view of the future is based upon reports that some users of low-NOx
burners had already seen in 1994 that operating costs could be reduced to make the changeover
yield a net profit. SCR and SNCR costs may also have declined further, since there is now
competition for these technologies.
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This analysis was supported by 1997 cost figures. These are presented in Table 15. This table is
from the Analyzing Electric Power Generation Under the CAAA26. It appears that competition
and improved designs are still driving the costs downward. The Table was presented in that
publication and is presented here for your convenience.
Table 15.1997 Costs of NOx Controls
Analyzing Electric Power Generation Under the CAAA ~ Cost Estimates26
Boiler Type
Control Type
Wall Fired
Wall Fired
Tang-Fired
LNB w/o OFA
LNB w/ OFA
LNB w/ OFA
Tang-Fired LNB w/ SOFA
Tang Fired LNB w/ BOFA
Cell Burners
Cyclone
Wet Bottom
Vert. Fired
Non Plug-In Comb. Ctl.
Coal Reburning
NOx Comb. Ctl.
NOx Comb. Ctl.
SCR -Low NOx Rate
SCR- High NOx Rate
SNCR-Low NOx Rate
SNCR-Cyclone
SNCR-High NOx Rate
Nat. Gas Reburn-Low
Nat.Gas Reburn-High
Capital Cost
$/kW
16.8
22.8
32.3
34.7
46.7
22.8
70.7
9.6
10.8
69.7
71.8
16.6
9.6
19
32.4
32.4
Fixed O & M
$/kW/yr
0.25
0.35
0.49
—0.53
0.71
0.34
1.07
0.14
0.17
6.12
"6.38
0.24
0.14
0.29
0.49
0.49
Variable O& M
mils/kWh
0.05
0.07
0
0
0.02
0.07
0.25
0.05
0.05
0.24
0.4
0.82
1.27
0.88
% Control
67.5
67.5
47.3
52.3
57.3
60
50
50
40
70
80
40
35
35
40
50
Note that in Table 8 the following acronyms are used:.
LNB is low-NOx burner
OFA is closed coupled overfire air
SOFA is separate over fire air
BOFA is both close coupled and over fire air
Comb. Ctl. is combined controls
33
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The Institute of Clean Air Companies also suggests that in 1999 SCR will cost $50 - $80 per kW
for retrofit to units, which relates to $400-$ 1800 per ton of NOx that is destroyed.34 Their cost
estimate for SNCR ranges from $5-$ 15 per kW, which relates to $400-$2000 per ton of NOx that
is destroyed.35 Cost-effectiveness does not correlate with boiler capacity alone - other variables
such as type and quality of fuel, type of boiler, SNCR/SCR design, etc enter into the analysis.
While the "Performance of Selective Catalytic Reduction on Coal-fired Steam Generating Units"
study was for Germany, it cited a recent cost range for SCR from $52 to $77 per kW with retrofit
units tending to have lower costs. Thus, the costs in Germany were very similar to costs in the
U.S.A., except that retrofit costs usually are greater in the United States.
Table 16, Unit Costs for NOx control Technologies for Non-Utility Stationary Sources, is from
the report "Ozone Transport Rulemaking Non-Electricity Generating Unit Cost Analysis." The
report was prepared for EPA by the Pechan-Avanti Group. It indicates efficiencies and cost
estimates for various NOx technologies for the year 2007. This appears to be a conservative
estimate of efficiency and cost. Efficiencies indicated in the table tend to be lower than currently
demonstrated efficiencies. Costs were based on historical information and, therefore, should be
high estimates because NOx technology costs appear to be declining over time. The table was
included here to indicate the relative efficiency and cost of NOx technologies for specific types of
combustion systems.
The Alternative Control Techniques Document NOx Emissions from Stationary Reciprocating
Internal Combustion Engines contains cost algorithms for the pollution prevention techniques and
control technology applied to internal reciprocating engines. Costs for NOx elimination run from
$250/ton to $l,300/ton for engines larger than 1,000 horsepower. For smaller engines the cost
runs from $400/ton to over $3,500/ton.
ARE THESE METHODS SUFFICIENT?
YES, these methods are sufficient to meet the present goal of reducing NOx emissions 2 million
tons below 1980 emissions.47 The goal appears to be set at a level that can be achieved based on
the state of NOx technology in 1996. However, we will have to see whether achieving our
present goal provides the needed relief. A still more stringent set of standards may become
necessary at sometime in the future.
As a high-technology nation and with a large urban and suburban population, we depend on
automobiles, buses, airplanes, railroads, and trucks for transportation. We also depend upon
electric power for computers, lights, air conditioning, and commerce. Therefore, we seem caught
in a dilemma, for, while we depend on transportation, vehicles produce most of our NOx. While
we also consume electric power as part of our market economy, electric power generation also
generates over 40% of our NOx from stationary sources in 1995.34
We also need to generate less NOx without regard to the ionization level of the nitrogen. In
1999, we are currently not capable of doing that. Therefore, we must do the best that we can,
34
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Table 16: Unit Costs for NOr Control Technologies for Non-Utility Stationary Sources
Source Type/Fuel Type
ICI Boilers - CoalAVall
ICI Boilers - CoalAVall
ICI Boilers - CoalAVall
ICI Boilers - Coal/FBC
ICI Boilers - Coal/Stoker
ICI Boilers - Coal/Cyclone
ICI Boilers - Coal/Cyclone
ICI Boilers - Coal/Cyclone
ICI Boilers - Coal/Cyclone
ICI Boilers - Residual Oil
ICI Boilers - Residual Oil
ICI Boilers - Residual Oil
ICI Boilers - Residual Oil
ICI Boilers - Distillate Oil
ICI Boilers - Distillate Oil
ICI Boilers - Distillate Oil
ICI Boilers - Distillate Oil
ICI Boilers - Natural Gas
ICI Boilers - Natural Gas
ICI Boilers - Natural Gas
ICI Boilers - Natural Gas
ICI Boilers - Natural Gas
ICI Boilers - Wood/Bark/Stoker
ICI Boilers - Wood/Bark/FBC
ICI Boilers - MSW/Stoker
ICI Boilers - Process Gas
ICI Boilers - Process Gas
ICI Boilers - Process Gas
ICI Boilers - Process Gas
ICI Boilers - Coke
ICI Boilers - Coke
ICI Boilers - Coke
ICI Boilers - LPG
ICI Boilers - LPG
ICI Boilers - LPG
ICI Boilers - LPG
ICI Boilers - Bagasse
ICI Boilers - Liquid Waste
ICI Boilers - Liquid Waste
ICI Boilers - Liquid Waste
ICI Boilers - Liquid Waste
Internal Combustion Engines - Oil
Control Technology
SNCR
LNB
SCR
SNCR - Urea
SNCR
SNCR
Coal Reburn
NGR
SCR
LNB
SNCR
LNB + FOR
SCR
LNB
SNCR
LNB + FGR
SCR
LNB
SNCR
LNB + FGR
OT + WI
SCR
SNCR - Urea
SNCR - Ammonia
SNCR - Urea
LNB
LNB + FGR
OT + WI
SCR
SNCR
LNB
SCR
LNB
SNCR
LNB + FGR
SCR
SNCR - Urea
LNB
SNCR
LNB + FGR
SCR
IR
Percent
Reduction (%)
40
50
70
75
40
35
50
55
80
50
50
60
80
50
50
60
80
50
50
60
65
80
55
55
55
50
60
65
80
40
50
70
50
50
60
80
55
50
50
60
80
25
Ozone Season
Cost Effectiveness ($1990/ton)
Small* Large*
1,870
3,490
2,910
1,220
1,810
1,480
3,730
3,730
1,840
940
5,600
2,670
3,460
2,810
10,080
5,960
6,480
1,950
8,400
6,110
1,620
5,190
2,090
1,660
2,610
1,950
6,110
1,620
4,990
1,870
3,490
2,910
2,810
10,000
5,960
6,240
2,090
940
5,560
2,670
3,320
1,840
1,380
2,600
2,450
910
1,350
1,110
710
710
1,560
1,020
1,950
920
1,840
4,950
3,520
1,810
3,460
1,560
2,930
1,420
760
2,770
1,430
1,210
1,830
1,560
1,420
760
2,570
1,380
2,600
2,450
4,950
3,440
1,810
3,220
1,430
1,020
1,910
920
1,710
1,160
35
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Source Type/Fuel Type
Internal Combustion Engines - Oil
Internal Combustion Engines - Gas
Internal Combustion Engines - Gas
Internal Combustion Engines - Gas
Internal Combustion Engines - Gas
Internal Combustion Engines - Gas
Internal Combustion Engines - Gas
1C Engines - Gas, Diesel, LPG
1C Engines - Gas, Diesel, LPG
Gas Turbines - Oil
Gas Turbines - Oil
Gas Turbines - Natural Gas
Gas Turbines - Natural Gas
Gas Turbines - Natural Gas
Gas Turbines - Natural Gas
Gas Turbines - Natural Gas
Gas Turbines - Natural Gas
Gas Turbines - Jet Fuel
Gas Turbines - Jet Fuel
Process Heaters - Distillate Oil
Process Heaters - Distillate Oil
Process Heaters - Distillate Oil
Process Heaters - Distillate Oil
Process Heaters - Distillate Oil
Process Heaters - Distillate Oil
Process Heaters - Distillate Oil
Process Heaters - Residual Oil
Process Heaters - Residual Oil
Process Heaters - Residual Oil
Process Heaters - Residual Oil
Process Heaters - Residual Oil
Process Heaters - Residual Oil
Process Heaters - Residual Oil
Process Heaters - Natural Gas
Process Heaters - Natural Gas
Process Heaters - Natural Gas
Process Heaters - Natural Gas
Process Heaters - Natural Gas
Process Heaters - Natural Gas
Process Heaters - Natural Gas
Process Heaters - Process Gas
Process Heaters - Process Gas
Process Heaters - Process Gas
Process Heaters - Process Gas
Process Heaters - Process Gas
Process Heaters - Process Gas
Process Heaters - Process Gas
Percent
Control Technology Reduction (%)
SCR
IR
AF RATIO
AF + IR
L-E (Medium Speed)
L-E (Low Speed)
SCR
IR
SCR
Water Injection
SCR + Water Injection
Water Injection
Steam Injection
LNB
SCR + LNB
SCR + Steam Injection
SCR + Water Injection
Water Injection
SCR + Water Injection
LNB
LNB + FOR
SNCR
ULNB
SCR
LNB + SNCR
LNB + SCR
LNB + FOR
LNB
SNCR
ULNB
LNB + SNCR
SCR
LNB + SCR
LNB
LNB + FOR
SNCR
ULNB
SCR
LNB + SNCR
LNB + SCR
LNB
LNB + FGR
SNCR
ULNB
SCR
LNB + SNCR
LNB + SCR
80
20
20
30
87
87
90
25
80
68
90
76
80
84
94
95
95
68
90
45
48
60
74
75
78
92
34
37
60
73
75
75
91
50
55
60
75
75
80
88
50
55
60
75
75
80
88
Ozone Season
Cost Effectiveness (S1990/ton)
Small* Large*
4,690
2,430
3,730
3,430
890
4,000
5,547
1,840
4,690
3,080
4,240
3,590
2,490
1,170
4,850
3,750
5,040
3,080
4,240
8,290
10,130
6,210
5,110
18,970
7,160
18,770
8,330
6,010
3,730
3,080
4,730
10,560
11,170
5,250
7,610
5,560
3,580
24,840
6,960
23,880
5,250
7,610
5,560
3,580
24,840
6,960
23,880
1,850
1,320
900
1,080
N/A
1,500
1,075
1,160
1,850
1,540
1,860
1,750
1,190
240
1,140
1,570
2,060
1,540
1,860
2,320
4,000
3,230
1,450
12,520
3,630
10,910
3,290
1,690
2,050
860
2,510
7,170
6,550
4,290
5,890
3,740
2,870
16,760
5,080
16,500
4,290
5.890
3,740
2,870
16,760
5.080
16.500
36
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Source Type/Fuel Type
Process Heaters - LPG
Process Heaters - LPG
Process Heaters - LPG
Process Heaters - LPG
Process Heaters - LPG
Process Heaters - LPG
Process Heaters - LPG
Process Heaters - Other Fuel
- Process Heaters - Other Fuel
Process Heaters - Other Fuel
Process Heaters - Other Fuel
Process Heaters - Other Fuel
Process Heaters - Other Fuel
Process Heaters - Other Fuel
Adipic Acid Manufacturing
Adipic Acid Manufacturing
Nitric Acid Manufacturing
Nitric Acid Manufacturing
Nitric Acid Manufacturing
Glass Manufacturing - Container
Glass Manufacturing - Container
Glass Manufacturing - Container
Glass Manufacturing - Container
Glass Manufacturing - Container
; Glass Manufacturing - Container
Glass Manufacturing - Flat
Glass Manufacturing - Flat
Glass Manufacturing - Flat
Glass Manufacturing - Flat
Glass Manufacturing - Flat
Glass Manufacturing - Pressed
Glass Manufacturing - Pressed
Glass Manufacturing - Pressed
Glass Manufacturing - Pressed
Glass Manufacturing - Pressed
Glass Manufacturing - Pressed
Cement Manufacturing - Dry
Cement Manufacturing - Dry
Cement Manufacturing - Dry
Cement Manufacturing - Dry
Cement Manufacturing - Dry
Cement Manufacturing - Wet
Cement Manufacturing - Wet
- Cement Manufacturing - Wet
Iron & Steel Mills - Reheating
Iron & Steel Mills - Reheating
Iron & Steel Mills - Reheating
Percent
Control Technology Reduction (%)
LNB
LNB + FOR
SNCR
ULNB
•SCR
LNB + SNCR
LNB + SCR
LNB + FGR
LNB
SNCR
ULNB
LNB + SNCR
SCR
LNB + SCR
Thermal Reduction
Extended Absorption
Extended Absorption
SCR
SNCR
Electric Boost
Gullet Preheat
LNB
SNCR
SCR
OXY-Firing -t-
Electric Boost
LNB
SNCR
SCR
OXY-Firing
Electric Boost
Cutlet Preheat
LNB
SNCR
SCR
OXY-Firing
Mid-Kiln Firing
LNB
SNCR - Urea Based
SNCR - NH3 Based
SCR
Mid-Kiln Firing
LNB
SCR
LEA
LNB
LNB + FGR
45
48
60
74
75
78
92
34
37
60
73
75
75
91
81
86
95 ~
97
98
10
25
40
40
75
85
10
40
40
75
85
10
, 25—
40
40
75
85
30
30
50
50
80
30
30
80
13
66
77
Ozone Season
Cost Effectiveness (S1990/ton)
Small* Large*
8,290
10,130
6,210
5,110
18,970
7,160
18,770
8,330
6,010
3,730
3,080
4,730
10,560
11,170
1,000
210
840
1,010
940
17,050
2,240
4,040
3,320
4,550
10,960
5,540
1,660
1,380
1,490
4,530
20,910
1,930
3,570
3,080
5,170
9,310
1,110
1,340
1,280
1,490
6,850
1,010
1,260
5,840
3,160
720
900
2,320
4,000
3,230
1,450
12,520
3,630
10,910
3,290
1,690
2,050
860
2,510
7,170
6,550
1,000
210
840
1,010
940
17,050
2,240
4,040
3,320
4,550
10,960
5,540
1,660
1,380
1,490
4,530
20,910
1,930
3,570
3,080
5,170
9,310
1,110
1,340
1,280
1,490
6,850
1,010
1,260
5,840
3,160
720
900
37
-------
Source Type/Fuel Type
Iron & Steel Mills - Annealing
Iron & Steel Mills - Annealing
Iron & Steel Mills - Annealing
Iron & Steel Mills - Annealing
Iron & Steel Mills - Annealing
Iron & Steel Mills - Annealing
Iron & Steel Mills - Galvanizing
Iron & Steel Mills - Galvanizing
Municipal Waste Combustors
Medical Waste Incinerators
Space Heaters - Distillate Oil
Space Heaters - Distillate Oil
Space Heaters - Distillate Oil
Space Heaters - Distillate Oil
Space Heaters - Natural Gas
Space Heaters - Natural Gas
Space Heaters - Natural Gas
Space Heaters - Natural Gas
Space Heaters - Natural Gas
Ammonia - NG-Fired Reformers
Ammonia - NG-Fired Reformers
Ammonia - NG-Fired Reformers
Ammonia - NG-Fired Reformers
Ammonia - NG-Fired Reformers
Ammonia - Oil-Fired Reformers
Ammonia - Oil-Fired Reformers
Ammonia - Oil-Fired Reformers
Ammonia - Oil-Fired Reformers
Lime Kilns
Lime Kilns
Lime Kilns
Lime Kilns
Lime Kilns
Comm /Inst Incinerators
Indust Incinerators
Sulfate Pulping - Recovery Furnaces
Sulfate Pulping - Recovery Furnaces
Sulfate Pulping - Recovery Furnaces
Sulfate Pulping - Recovery Furnaces
Sulfate Pulping - Recovery Furnaces
Ammonia Prod, Feedstock Desulfunzation
Plastics Prod-Specific, (ABS) Resin
Starch Mfg, Combined Operations
Control Technology
LNB
LNB + FOR
SNCR
LNB + SNCR
SCR
LNB + SCR
LNB
LNB + FOR
SNCR
SNCR
LNB
SNCR
LNB + FOR
SCR
LNB
SNCR
LNB + FGR
OT + WI
SCR
LNB
SNCR
LNB + FGR
OT + WI
SCR
LNB
SNCR
LNB + FGR
SCR
Mid-Kiln Firing
LNB
SNCR - Urea Based
SNCR - NH3 Based
SCR
SNCR
SNCR
LNB
SNCR
LNB + FGR
OT + WI
SCR
LNB + FGR
LNB + FGR
LNB + FGR
Percent
Reduction (%)
50
60
60
80
85
90
50
60
45
45
50
50
60
80
50
50
60
65
80
50
50
60
65
80
50
50
60
80
30
30
50
50
80
45
45
50
50
60
65
80
60
55
55
Ozone Season
Cost Effectiveness ($1990/ton)
Small* Large*
1,350
1,790
3,130
3,460
8,490
9,070
1,170
1,370
2,140
8,570
2,810
10,000
5,960
6,240
1,950
8,330
6,110
1,620
4,990
1,950
8,330
6,110
1,620
4,990
940
5,560
2,670
3,320
1,110
1,340
1,280
1,490
6,850
2,140
2,140
1,950
8,330
6,110
1,620
•4,990
6,110
7,610
7,610
1,350
1,790
3,130
3,460
8,490
9,070
1,170
1,370
2,140
8,570
4,950
3,440
1,810
3,220
1,560
2,860
1,420
760
2,570
1,560
2,860
1,420
760
2,570
1,020
1,910
920
,710
,110
,340
,280
,490
6,850
2.140
2,140
1,560
2,860
1,420
760
2,570
1,420
5,890
5.890
38
-------
Source Type/Fuel Type
By-Product Coke Mfg; Oven Underfmng
Pri Cop Smel; Reverb Smelt Fum
Iron Prod, Blast Furn; Blast Htg Stoves
Steel Prod, Soaking Pits
Fuel Fired Equip, Process Htrs, Pro Gas
Sec Alum Prod; Smelting Furn/Reverb
Steel Foundries, Heat Treating Furn
Fuel Fired Equip, Furnaces, Natural Gas
Asphaltic Cone; Rotary Dryer, Conv Plant
Ceramic Clay Mfg, Drying
Coal Cleamng-Thrml Dryer; Fluidized Bed
Fbrglass Mfg; Txtle-Type Fbr, Recup Fum
Sand/Gravel, Dryer
Fluid Cat Cracking Units, Cracking Unit
Conv Coating of Prod; Acid Cleaning Bath
Natural Gas Prod, Compressors
In-Process; Bituminous Coal; Cement Kiln
In-Process, Bituminous Coal; Lime Kiln
In-Process Fuel Use.Bituminous Coal; Gen
In-Process Fuel Use, Residual Oil; Gen
In-Process Fuel Use, Natural Gas, Gen
In-Proc,Process Gas.Coke Oven/Blast Furn
In-Process, Process Gas; Coke Oven Gas
Surf Coat Oper.Coating Oven Htr;Nat Gas
Solid Waste Disp,Gov, Other Incm;Sludge
Control Technology
SNCR
LNB + FOR
LNB + FOR
LNB + FOR
LNB + FOR
LNB
LNB
LNB
LNB
LNB
LNB
LNB
LNB + FGR
LNB + FGR
LNB
SCR
SNCR - urea based
SNCR - urea based
SNCR
LNB
LNB
LNB + FGR
LNB
LNB
SNCR
Percent
Reduction (%)
60
60
77
60
55
50
50
50
50
50
50
40
55
55
50
20
50
50
40 ~
37
50
55
50
50
45
Ozone Season
Cost Effectiveness ($1990/ton)
Small* Large*
3,130
1,790
900
1,790
7,610
1,350
1,350
1,350
5,250
5,250
3,490
4,040
7,610
7,610
5,250
5,547
1,280
1,280
1,420
6,010
5,250
7,610
5,250
5,250
2,140
3,130
1,790
900
1,790
5,890
1,350
1,350
1,350
4,290
4,290
2,600
4,040
5,890
5,890
4,290
1,075
1,280
1,280
1,060
1,690
4,290
5,890
4,290
4,290
2,140
NOTE 'Small source cost per ton values are used to estimate control costs for all sources with 1995 NO, emissions below 1 ton per day If the
ozone season daily 1995 baseline NO, value is 1 ton or more, the cost per ton value for large sources is used
N/A = not applicable. The population of medium speed gas-fired 1C engines are all considered small
39
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and hope that we can endure while looking for the discovery and cost-reduction of the "better
technology" that is capable of meeting the goal of sustainability. The reference literature
suggests that the leading edge of pollution prevention and control technology in 1999 is capable
of about 94%-99% control of NOx or 1 ppm-5 ppm of NOx.27-28
As we all know, the leading edge technology always costs more because engineering has not yet
shifted from feasibility to cost-reduction, and competition in the technology is not fully developed.
Therefore, we can expect technology to be more affordable with time and to also improve its
capability. We should expect to see the goal change with time as the technology advances, and as
the achievable goal becomes both more stringent and more economically feasible. At one time,
the capabilities that we now have seemed beyond imagining, and the costs seemed prohibitive.
We live in an interesting time when the NOx pollution prevention, abatement, and control
technology is becoming more capable and more affordable.
CONCLUSIONS
1. Different fuels require different combustion, abatement and control techniques. Different coals
have a varying content of volatile ingredients. 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
designs.29
2. 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 of engines and turbines.
3. Staging of the combustion is implicit in several pollution prevention techniques. 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 which is referred to as "polishing") have been
used to achieve an overall reduction of 90+% in NOx and 80% in SOx, even without using low-
NOx burners to lower NOx generation.
4. Combustion of natural gas and petroleum distillates can be controlled in much the same way as
pulverized coal. The major differences between coal and natural gas or oil are that gas and oil:
(1) generally are lower in sulfur and ash; (2) usually are lower in nitrogen; and (3) 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.
5. 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.
40
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6. We should expect the declining cost trend of control technology to continue as operating
experience is gained, firing techniques are adapted to fuels, design flaws are corrected, and
new designs appear. We should expect to see costs become less as they are driven down by
competition between suppliers of successful technologies.
7. NOx control technology appears capable of more than just meeting EPA's present goal and this
should provide emission credits that can be traded to those firms that choose to continue emitting
poorly controlled emissions. The sale of these credits by those that over-corrected for the present
goal should further offset any net costs in adopting these control technologies.
8. Commercially available NOx control systems are already available. The availability of these
technologies was part of the basis of the recent NOx SIP Call and Title IV regulations.
9. There has been an economic incentive to make combustion more efficient and to innovate ways
to control nitrogen oxides. However, the amount of time and money that must be invested for a
full-scale test of a strategy is significant. Acceptance requires that a technology be tried and
succeed before a larger scale test is even contemplated. This delays acceptance of improved
techniques.
10. There seems to be no control technology which is clearly superior for all combustion systems,
boilers, engines, or fuels. Lacking a clear winner, one must select fuels and control technology
either from among those already proven, or from a growing number of new and promising ideas.
11. The end of the search for control technologies is not yet in sight, and the search must
continue. Past research must of necessity give ambivalent answers, because there are so many
conflicting factors. However, at under $150 per ton of NOx prevented and with up to 80%
control efficiency, the low-NOx burner, where applicable, appears to be among the least
expensive emission control technologies. SCR is more expensive, but can obtain up to 94%
control efficiency. SNCR can be adopted without the initial cost of catalyst, although it is
somewhat less effective. LNB, SCR and SNCR are all viable technologies across a wide
spectrum of applications.
12. Research and development will have to continue to seek more effective answers and try to
balance them against cost and efficiency. The cost will decrease as technology advances,
operating experience is gained, competition becomes sharper, design flaws are corrected, and
better designs become available. Reliability can only be gained with time. Cost will be reduced
with time and experience. We also must expect that the level of pollution prevention and control
technology effectiveness will improve with time.
41
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REFERENCES:
1. Nitrogen Oxides
www.ccinet.ab.ca/casa/nitrogen.htm
2. Pollution Engineering Magazine Online
www.manufacturing.net...eng/archives/1995/poll0401.95/04adp3fl).htm
3. Alternative Control Techniques - Nitric Acid and Adipic Acid Manufacturing Plants
EPA 450/3-91-026
4. Bay Journal, July/August 1996
www.gmu.edu/bios/Bay/journal/96-08/ozone.htm
5. A Graphical Explanation of a regional Ozone Episode
capita.wustl.edu/otag/reports/03epi95/03epi95.html
6. XONON
www.catalytica-inc.com/cs/nox_control.html
7. Summary of NOx Control Technologies and Their Availability and Extent of Application,
EPA 450/3-92-004
8. Sourcebook: NOx Control Teschnology Data, EPA 600/2-91-029
9. Fully Engineered Approach to Acid Rain Control, F. Bauer, Energy Engineering, Vol. 91,
No.4, 1994
10. Alternate Control Techniques Document - NOx Emissions from Cement Manufacturing
EPA-453/R-94-004
11. Put a Lid on NOx Emissions, J. Czarnecki, C. Pereira, M. Uberoi, K. Zak, Pollution
Engineering, November 1994
12. Combined Corona/Catalyst Process for Low-Temperature NOx Control
es.epa.gov/ncerqa_abstracts/sbir/other/air/helfritch.html
13. Reducing NOx Emissions, B. Chambers, Glass Industry, May 1993
14. Marathon Monitors
www.marathonmonitors.com/glassnox.htm
42
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15. Active Control of a Natural Gas-Fired Burner
ucicl.eng.uci.edu/research/active-control/
16. NICE3: More Electricity, Fewer Emissions from Coal-Fired Boilers
es.epa.gov/program/p2dept/energy/nice3/nice3-2.html
17. 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.
18. Regulatory Developments in NOx Controls for Utility Boilers, C. Harrison, 96-RP139.03,
Air & Waste Management Assn.
19. Alternative Control Techniques Document — NOx Emissions from Stationary Reciprocating
Internal Combustion Engines, EPA 453/R-93-032
20. Plasma versus Thermal Effects in Flue Gas NOx Reduction Using Ammonia Radical
Injection, K. Chess, S. Yao, A. Russell and H. Hsu, Journal of the Air & Waste Management
Association, August, 1995, p.627
r21. CNG Installing NOx-reduction System in Compressor Stations, Oil & Gas Journal, Sept. 26,
1994
22. NOx Control Technology Requirements Under the United States 1990 Clean Air Act
Amendments Compare to Those in Selected Pacific Rim Countries, C. A. Miller, R. Hall, R.
Stern, EPA 600/A-94-259
23. Nitrogen Oxides Control Technology Fact Book, Leslie L. Sloss, Noyes Data Corp., 1992
24. Alternate Control Techniques Document ~ NOx Emissions from Industrial/Commercial/
Institutional (ICI) Boilers, EPA 453/R-94-022
25. EPA Region 3 Low-NOx Control Technology Study, K. Bruce, C. Castaldi, J. Cook, D.
Lachapelle, Acurex Environmental Corporation, Acurex Report FR-97-116
26. Analyzing Electric Power Generating Under the CAAA, Office of Air and Radiation, 1998
27. SNRB Catalytic Baghouse Laboratory Pilot Testing, G. Akudlac, G. Farthing, T. Szymanski,
R. Corbett, Environmental Progress, Vol.11, No. 1, 1992
28. Cement Kiln NOx Control, A. McQueen, S. Bortz, M. Hatch, and R. Leonard, IEEE
Transactions on Industry Applications, Vol. 31, No. 1 January/February 1995
29. States' Report on Nitrogen Oxides Reduction Technology Options fpr Application by the
Ozone Transport Assessment Group, OTAG, 1996
43
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30. Retrofit control technology reducing NOx emissions, S. Kuehn, Power Engineering,
February, 1994
31. Advanced emissions control brings coal back to New Jersey, Power. 1994
32. Overview of NOx Emission Control for Utility Boilers, J. E. Staudt, Proceedings of the
American Power Conference, 1993
33. Select the Right NOx Control Technology, S. Wood, Chemical Engineering Progress,
January 1994
34. Selective Catalytic Reduction Control of NOx Emissions, SCR Committee of Institute of
Clean Air Companies, November 1997
35. Selective Non-Catalytic Reduction for Controlling NOx Emissions, SNCR Committee of
Institute of Clean Air Companies, October 1997
36. Emission Control Potential for Heavy-Duty Diesel Engines, QMS Fact Sheet, EPA 420-F-95-
009b, June 1996, www.epa.gov/omswww/noxfact2.htm
37. Effects of Biogenic Emission Uncertainties on Regional Photochemical Modeling of Control
Strategies, S. Roselle, Atmospheric Sciences Modeling Division, Air Resources Laboratory,
National Oceanic and Atmospheric Administration, Atmospheric Environment, Vol. 28, No. 10,
pp 1757-1772, 1994, Elsevier Science Ltd.
38. Relationships Between Respiratory Disease and Exposure to Air Pollution, G. Oberdorster,
R. Gelein, C. Johnston, P. Mercer, N. Corson, and J. Finkelstein, International Life Sciences
Institute, Washington DC, 1998, pp 216-229
39. The Sox-NOx-Rox Box Flue Gas Cleanup Demonstration Project
www.fe.doe. gov/coal_power/fs_snrb.html
40. Nitrogen Oxides: Impacts on Public Health and the Environment, EPA 452/R-97-002
41. Final Report, Volume II: Summary and Integration of Results, OTAG Air Quality Analysis
Workgroup, D. Guinnup and B. Collom
42. Combined SO2/NOx
www.worldbank.org/html/fpd/.../EA/mitigatn/thermair/aqsocbsn.htm
43. Cleaver-Brooks, Emissions
www.cleaver-brooks.com/Emissionsl.html
44
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44. Methods for Reducing NOx Emissions, C. Latta, Roy F. Weston Inc., Plant Engineering,
September 1998
45. Plasma Ignition System Reduces NOx Emissions, M. Manning, Pipeline & Gas Journal,
October 1995, pp. 26-30
46. Low-Emission Gas Turbines Using Catalytic Combustion, S. Vatcha, Energy Conversion
Management, Vol. 38 No. 10-13, pp. 1327-1334
47. Factsheet: Phasel of the NOx Reduction Program
nsdi. epa. go v/acidrain/nox/noxfs .html
48. Alternative Control Techniques Document — NOx Emissions from Stationary Reciprocating
Internal Combustion Engines. EPA-453/R-93-032, July 1993
49. The Economic Feasibility of using Hydrogen Peroxide for the Ehanced Oxidation and
Removal of Nitrogen Oxides from Coal-Fired Power Plant Flue Gases, J. Hatwood, C. Cooper,
AWMA Journal, March 1998
50. Fossil Fuel Combustion, A Source Book, W. Bartok and A. Sarofim, Wiley-Interscience,
John Wiley & Sons
51. 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
52. 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
53. 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
54. Simultaneous SO2, SO3, and NOx Removal by Commercial Application of the EBA Process,
S. Hirano, S. Aoki, M Izutsu, and Y. Yuki, EPRI-DOE-EPA Combined Utility Air Pollution
Control Symposium: The MEGA Symposium, Atlanta, August 1999
55. The State of the Art in Cyclone Boiler NOx Reduction, D. O'Connor, R. Himes, T,
Facchiano, EPRI-DOE-EPA Combined Utility Air Pollution Control Symposium: The MEGA
. Symposium, Atlanta, August 1999
45
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56. Update on SNAP Technology for Simultaneous SOx and NOx Removal, K. Felsvang, V.
Boscak, S. Iversen, P. Anderson, EPRI-DOE-EPA Combined Utility Air Pollution Control
Symposium: The MEGA Symposium, Atlanta, August 1999
57. Advanced Reburning for SIP Call NOx Control, EPRI-DOE-EPA Combined Utility Air
Pollution Control Symposium: The MEGA Symposium, Atlanta, August 1999
The Following are General Background References, which .were used for general information.
They were used in multiple places. The facts presented were also used to develop a consistent
picture of NOx generation and abatement technology in the face of many conflicting claims and
pieces of data. They also were used to understand and reconcile the conflicts in data from
different combustion devices.:
Performance of Selective Catalytic Reduction on Coal-fired Steam Generating Units, U.S. EPA.,
Acid Rain Division, 1997
Alternate Control Techniques Document - NOx Emissions from Iron and Steel Mills
EPA-453/R-94-065
Nitrogen Chemistry and NOx Control in a Fluid Catalytic Cracking Regenerator, X. Zhao, A.
Peters, G. Weatherbee, Industrial Engineering Chemical Research, Vol.36, No. 11, 1997,
American Chemical Society
Control of Combustion-Generated Nitrogen Oxide Emission: Technology Driven by Regulation,
C. T. Bowman, Twenty-fourth Symposium (International) oc Combustion/ The Combustion
Institute, 1992, pp. 859-878
Advanced Biomass Reburning for High Efficiency NOx Control
es.epa.gov/ncerqa_abstracts/sbir/other/air/seeker.html
The Regional Transport of Ozone
www.epa.gov/ttn/otag/about_l.html
OTAG Analysis with PPM
www.epa.gov/capi/otagmain.html
About OTAG
envpro.ncsc.org/OT AGDC/about_otag.html
Air Quality Analysis Working Group
capita.wustl.edu/otag
Clean Air Technology News, Institute of Clean Air Companies, Summer 1998 and Winter 1998
46
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Post Combustion Control of Oxides of Nitrogen Emissions from a 900 TPD Processed Refuse
Fuel Boiler, J. Zakaria, L. Wolfenden, J. Me Conlogue, G. Pierce, The 1994 National Waste
Processing Conference, ASME, 1994
Cost Estimates for Selected Applications of NOx Control Technologies on Stationary
Combustion Boilers (Draft Report), The Cadmus Group, Inc. and Bechtel Power Corporation for
U.S.EPA, March 1996.
Ozone Transport Rulemaking Bob-Electric Generating Unit Cost Analysis, Prepared by Pechan-
Avanti Group for U.S. EPA (Contract Nos. 68D40102 & 68D98052), Setember 17, 1998.
47
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TECHNICAL REPORT DATA
(Please read Instructions on reverse before completing)
1. REPORT NO 2.
EPA-456/F-99-006R
4. TITLE AND SUBTITLE
Nitrogen Oxides (NOJ Why and How They Are Controlled
7. AUTHOR(S)
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Clean Air Technology Center (MD-12)
Information Transfer and Program Integration Division
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Research Triangle Park, NC 27711
15. SUPPLEMENTARY NOTES
For more information, call the CATC Information
at www.epa.gov/ttn/catc
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
November 1999
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO
11. CONTRACT/GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERED
Final
14 SPONSORING AGENCY CODE
Line at (919) 541-0800 or access the CATC Web page
16. ABSTRACT
The purpose of this document is to educate people about nitrogen oxides, how they are formed, the danger
that they represent, and how emissions can be controlled. This knowledge is needed to make an informed
choice of the control technology that is to be used.
17 KEY WORDS AND DOCUMENT ANALYSIS
a DESCRIPTORS
nitrous oxide, nitric oxide, nitrogen dioxide,
dinitrogen pentoxide, nitrous acid, nitric acid,
ozone, volatile organic compounds, VOC,
generation, pollution prevention, control
technology, control technologies, emission
control, acid rain, combustion, boilers, gas
turbines, internal combustion engines, cost of
emission controls, air pollution
18. DISTRIBUTION STATEMENT
Release Unlimited, Available from the OAQPS
TTN Web Page and NTIS
b. IDENTIFIERS/OPEN ENDED TERMS c. COSATI Field/Group
air pollution control technology,
combustion, pollution prevention,
nitrogen oxides, boilers, internal
combustion engines, diesel engines
19. SECURITY CLASS (Report) 21 NO OF PAGES
Unclassified
20. SECURITY CLASS (Page) 22 PRICE
Unclassified
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION IS OBSOLETE
48
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