Overview, Types, Sources & Control measures.

1. An Overview of the Nitrogen Oxides

Problem
 Most of the world’s nitrogen is in the atmosphere as an
inert gas.
 In crustal rocks it is the 34th most abundant element
with an abundance of only ≈ 20 ppm.

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 Although nitrogen forms eight different oxides, our
principal air pollution interest is in the two most
common oxides, nitric oxide (NO) and nitrogen
dioxide (NO2).
 In addition, we are beginning to be concerned with
nitrous oxide (N2O). It may be a significant contributor
to global warming and to the possible destruction of
the ozone layer.

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1.1 Comparison with Sulfur Oxides
 Fig. 12.1 (next slide) shows part of how nitrogen moves
in the environment, as a result of human activities.

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COMPARISON/CONTRAST BETWEEN SULFUR AND NITROGEN
OXIDES:

COMPARISONS
1. Both react with oxygen and water in the atmosphere
to form acids which cause acid rain.
2. Both lead to the formation of PM10 (Particulate
Matter 10 micrometers in diameter) in urban areas.
3. Both are released to the atmosphere in large
quantities through combustion processes and are
currently regulated by the EPA (See Table 12.1)
4. Sulfur oxides and nitrogen dioxide are respiratory
irritants when present in large quantities
CONTRASTS

 Sulfur oxides come from sulfur contaminants in fuels. However, most

nitrogen oxides are formed by the reaction of atmospheric nitrogen
with oxygen in high temperature flames. In essence, sulfur oxides
are formed from things that we take from the ground and nitrogen
oxides are formed from things that are in the air.
 The formation of nitrogen oxides in a flame can be controlled by
altering temperature, oxygen content, or time. However, the same
can't be done for sulfur oxides.
 The ultimate product of sulfur oxides removed in control equipment is
CaSO4. CaSO4 is a low-solubility solid that can be placed in landfills.
We don't have as much luck with nitrogen oxides. The final products
of nitrogen oxide cleanup are N2 and O2which will be returned to the
atmosphere.
 Nitrogen Oxides
BASICS
NOx

There are eight known oxides of nitrogen.

Some of these oxides natural, others are man made.
The stability of the N-N triple bond in elemental
nitrogen gas limits the natural production of nitrogen
oxides.
The three main Nitrogen Oxides present in the air are
Nitrous Oxide, Nitric Oxide, and Nitrogen Dioxide.

Formation: N2(g) +O2(g)  2NO(g)

Oxides of Nitrogen
Nitrogen oxide can refer to a binary compounds of
oxygen and nitrogen, or a mixture of such compounds:

 NO, nitric oxide

NOx
 NO2, nitrogen dioxide

 NO3, Nitrate radical

 N2O, nitrous oxide, a greenhouse gas

 N2O3, N2O4, N2O5

 Nitrogen Oxides

PROPERTIES AND BEHAVIOUR

 NO, NO2 and N2O can be isolated at room
temperature.
 N2O3, N2O4, and N2O5 all decompose rapidly at room
temperature.
 Nitrate radical is very reactive.
 N2O is stable and rather unreactive at room
temperature,
 NO and NO2 are quite reactive but nevertheless quite
stable when isolated.
 Nitrogen Oxides
BASICS

N2O NO NO2
Nitrous Oxide Nitric Oxide Nitrogen Oxide
Dinitrogen Oxide Nitrogen Monoxide
Nitrogen
Oxidation
Number
+1 +2 +4
Lewis
Structure :N=N=O: :N=O: :O-N=O
Odd number of electrons Odd number of electrons
Colorless, non-toxic, Toxic, reddish-brown,
Colorless, odorless, non-
Properties non-flammable gas with
flammable, toxic gas
non-flammable gas
slight odor. with strong odor
Decomposition of Majority from natural
nitrogen containing sources, twenty percent Secondary pollutant
Sources compounds in soil and from the oxidation of from nitric oxide
lightning. nitrogen in automobiles.
 NOx are produced during combustion, especially at high
temperature. They are important trace species in Earth's
atmosphere. In the troposphere, during daylight, NO reacts
with partly oxidized organic species (or the peroxy radical) to
form NO2, which is then photolyzed by sunlight to reform NO:

NO + CH3O2 → NO2 + CH3ONO2 + sunlight → NO + O

 The oxygen atom formed in the 2nd rxn then goes on to

form ozone; this series of reactions is the main source
of tropospheric ozone. CH3O2 is just one example of many
partly oxidized organic molecules that can react with NO to
form NO2.
NO + CH3O2 → NO2 + CH3ONO2 + sunlight → NO + O

 These reactions are rather fast so NO and

NO2 cycle, but the sum of their concentration
([NO] + [NO2]) tends to remain fairly constant.
Because of this the two chemicals as a group;
hence the term NOx.
 In addition to acting as a main precursor
for tropospheric ozone, NOx is also harmful to
human health in its own right.
 Sources
 Natural sources:
 Nitric oxide is produced during thunderstorms due to the
extreme heat of lightning,[4] and is caused by the splitting of
nitrogen molecules. This can result in the production of acid
rain, if nitrous oxide forms compounds with the water
molecules in precipitation, thus creating acid rain.
 Biogenic sources:
 Agricultural fertilization and the use of nitrogen fixing plants
also contribute to atmospheric NOx, by promoting nitrogen
fixation by microorganisms.
 Industrial sources-classified by scientists found in
combustion gases
 thermal NOx
 prompt NOx
 fuel NOx
Thermal NOx
 Thermal Nox forms through high temperature
oxidation of the diatomic nitrogen found in
combustion air. The formation rate is primarily a
function of temperature and the residence time of
nitrogen at that temperature. At high
temperatures, usually above 1600°C, molecular
nitrogen (N2) and oxygen (O2) in the combustion
air disassociate into their atomic states and
participate in a series of reactions.
 Thermal NOx
 The 3 principal reactions (the extended Zeldovich
mechanism):
N2 + O → NO + NN + O2 → NO + ON + OH → NO + H
 All rxns are reversible. Zeldovich was the first to
suggest the importance of the first two reactions.
The last reaction of atomic nitrogen with the
hydroxyl radical, OH, was added by Lavoie,
Heywood & Keck to the mechanism.
 Controlled by reducing flame temperatures in the
furnace, flue gas recirculation (FGR).
Fuel NOx
 The major source of NOx production from
nitrogen-bearing fuels such as certain coals and
oil, is the conversion of fuel bound nitrogen to
NOx during combustion. During combustion, the
nitrogen bound in the fuel is released as a free
radical and ultimately forms free N2, or NO. Fuel
NOx can contribute as much as 50% of total
emissions when combusting oil and as much as
80% when combusting coal.
Fuel NOx
 Although the complete mechanism is not fully
understood, there are two primary paths of formation.
 The first involves the oxidation of volatile nitrogen
species during the initial stages of combustion. During
the release and prior to the oxidation of the volatiles,
nitrogen reacts to form several intermediaries which are
then oxidized into NO.
 If the volatiles evolve into a reducing atmosphere, the
nitrogen evolved can readily be made to form nitrogen
gas, rather than NOx.
Fuel NOx
 The second path involves the combustion of nitrogen
contained in the char matrix during the combustion of
the char portion of the fuels.
 This reaction occurs much more slowly than the volatile
phase. Only around 20% of the char nitrogen is
ultimately emitted as NOx, since much of the NOx that
forms during this process is reduced to nitrogen by the
char, which is nearly pure carbon
 Prompt NOx
 This third source is attributed to the reaction of
atmospheric N2, with radicals such as C, CH, and
CH2 fragments derived from fuel, where this cannot
be explained by either the aforementioned thermal
or fuel processes.
 Occurring in the earliest stage of combustion, this
results in the formation of fixed species of nitrogen
such as NH (nitrogen monohydride), HCN
(hydrogen cyanide), H2CN (dihydrogen cyanide)
and CN- (cyano radical) which can oxidize to NO.
In fuels that contain nitrogen, the incidence of
prompt NOx is minimal.
CONTROL TECHNIQUES FOR
NOx REDUCTION
There are only two ways to reduce NOx
emissions:
 Modifying combustion processes to prevent
NOx formation
 Treating combustion gases after flame to
convert NOx to N2
 For smaller industrial sources, like nitric acid plants,
other control techniques are used, e.g., scrubbing with
solutions of NaOH and KMnO4.
 The strongly oxidizing KMnO4 quickly converts NO to
NO2, allowing it to be captured by the alkaline NaOH.
 This process requires an expensive electrochemical
regeneration of the KMnO4; it is not suitable for large-
scale combustion sources.

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Source: Advanced Air Technologies, Inc.
6.1 Nitrogen Oxide Control by
Combustion Modification
 The formation of thermal NO is
increased by increasing any of the
following three variables:
 peak temperature,
 time at high temperature,
 oxygen content at the high
temperature.
 Two-stage combustion or reburning
is a good way for combustion
modification.
Source: EPA
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 In the first stage, the maximum temperature is
lowered because not all the fuel is burned, and the
maximum temperature is reached when all the oxygen
has been used up, so that there is not enough oxygen
to form NO.
 In the second stage, enough of the heat released in the
first stage has been removed that the maximum
temperature reached-in the presence of excess oxygen-
is low enough that the formation of NO is small.

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 The advantage of this approach is that it is cheap.
 The disadvantages are that it requires a larger fire box
for the same combustion rate and that it is difficult to
get complete burning of the fuel in the second stage.
 Fig. 12.9 (next slide) shows an alternative approach to
designing a low-NOX burner.

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 In normal operation the incoming gas is thoroughly mixed
with air and recycled combustion products (Flue Gas
Recirculation, FGR), with about 15% excess air.
 This thorough mixing, together with excess air, prevents
there ever being any fuel-rich part of the flame, in which
prompt NO can form.
 Fig. 12.10 (next slide) show some test results for this burner,
burning natural gas with 15% excess air and varing degrees
of air preheat and FGR.

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 Experimental results for Low-NOx burner
 The dilution with recycled flue gas simply lowers the
temperature at every part of the flame.
 As the figure shows, it is possible to reduce the NOX to
10 ppm if one is willing to bear the extra cost of
pumping 20 to 40% of the flue gas back into the
burner.
 However, compared to other methods of achieving 10
ppm–i.e., catalytic treatment of the flue gas-the cost of
FGR is very reasonable.

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 This burner is a moderately low-NOX burner when it is
burning fuel oil.
 Ultra-low NOX levels are not achieved since most fuel
oils contain bound nitrogen that is oxidized in the
flames to NOX.
 Also, because there will be a fuel-rich region at the
surface of evaporating oil droplets, there will be
prompt NO formation.

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6.2 Nitrogen Oxide Control by Postflame
Treatment
 Most post flame treatment processes add a reducing
agent to the combustion gas stream to take oxygen
away from NO.
 Almost any gaseous reducing agent can be used, e.g.,
CO, CH4, other HCs, NH3, various derivatives of NH3.

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 In modern auto engines the reaction is
platinum rhodium catalyst
2 NO  2 CO   N2  2CO2

A three-way catalytic converter has three simultaneous tasks:

• Reduction of nitrogen oxides to nitrogen and oxygen:

2NOx → xO2 + N2
• Oxidation of carbon monoxide to carbon dioxide:
2CO + O2 → 2CO2
• Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water:
CxH2x+2 + [(3x+1)/2]O2 → xCO2 + (x+1)H2O

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 For power plants and other large furnaces a variety of
reducing agents are used, of which the most popular is
ammonia.
 The desired reaction is:
6 NO + 4 NH3 → 5 N2 + 6 H2O (12)
 However, there is always some oxygen present, which can lead
to reactions like:
4 NO + 4 NH3 + O2 → 4 N2 + 6 H2O (13)

is which one ammonia molecule is required for each molecule

of NO.

 The NO2 is reduced by:

2 NO2 + 4 NH3 + O2 → 3 N2 + 6 H2O (14)
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 Reactions (12) – (14) can be carried out over a variety of
catalysts, of which zeolites and supported TiO2 are the
most popular, at about 700oF (370oC), or simply in the gas
stream in the part of the furnace where the temperature is
between 1600o and 1800oF (870o – 980oC).
 Below 1600oF the reaction rate is too slow. Above 1800oF the
dominant reaction becomes
NH3 + O2 → NO + 3/2 H2O
which increases rather than decreases the NO content of
the gas.

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 The catalytic processes are called selective Catalytic
Reduction, or SCR.
 The high-temperature ones, without catalysts, are
called Selective Noncatalytic Reduction, SNCR.
 There are experimental processes under development
that adsorb both SO2 and NO onto an activated carbon
adsorbent.
 They are then stripped off one at a time and treated,
making S and N2 the final products.

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Selective Non-Catalytic Reduction
 In SNCR systems, the ammonia
(NH3) or urea is injected into a very
hot gas zone where thermal
reactions leading to the chemical
reduction of nitrogen oxides can
occur.
 These reactions are completed
within the boiler, and no waste
products are generated. However, if
the ammonia or urea is injected into
an area that is too cold, the
reduction efficiency of nitrogen
oxides is low, and some of the
reducing gas (NH3) can be emitted
to the atmosphere. SCNR systems
are capable of reducing nitrogen
oxides from 20 to 60%. Source: EPA
Selective Catalytic Reduction
 In SCR, beds containing
ammonia or urea reduce nitrogen
oxides to molecular nitrogen and
water.
 The catalysts are usually
composed of tungsten and
vanadium deposited through a
substrate that is extruded into a
honeycomb arrangement.
 The gas stream passes through
the channels in the honeycomb.
There are usually two or three
separate catalyst beds in series.
 NOx reduction efficiencies
ranging from 75 to 90% . A conventional SCR system is shown in Figure 7. SCR
systems are now being used for numerous gas turbines
and a growing number of coal- and oil-fired boilers.
SUMMARY
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