STEAM GENERATOR

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NOX REDUCTION

Primary Measures for

NOX Reduction

KWS The reproduction, transmission or use of this document or its contents is not permitted without express written authority.
Offenders will be liable for damages. All rights, including rights created by patent grant or registration of a utility model or
design, are reserved. Contents by KWS.
For training only
 STEAM GENERATOR
KWS
Power Tech
Tr aining Cent er
NOX REDUCTION

KWS The reproduction, transmission or use of this document or its contents is not permitted without express written authority.
Offenders will be liable for damages. All rights, including rights created by patent grant or registration of a utility model or
design, are reserved. Contents by KWS.
For training only
 STEAM GENERATOR
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NOX REDUCTION

Contents

1 Primary Measures for NOX Reduction ....................................................3

1.1 Nitrogen oxides ....................................................................................................................3
1.1.1 Nitrogen oxide compounds ..................................................................................................3
1.1.2 Origin of the nitrogen oxide compounds present in the flue gas .........................................3
1.1.3 Nitrogen oxide formation of different fuels and types of firing .............................................9
1.1.4 Examples of the influences of different operating parameters on the formation of nitrogen
oxide ..................................................................................................................................11
1.2 Nitric Oxide Reduction .......................................................................................................17
1.2.1 Nitric oxide reduction measures ........................................................................................17
1.2.2 Limits of nitric oxide reduction measures...........................................................................23
1.2.3 Some notes on low NOx firings .........................................................................................29
1.3 Outcome of low NOx firings ...............................................................................................37
1.4 Problems with the Corrosion of Heating Surfaces with the Nitric Oxide Reduction ..........47
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1 Primary Measures for NOX Reduction

1.1 Nitrogen oxides

1.1.1 Nitrogen oxide compounds

Nitrogen oxide is formed with almost every combustion of fossil fuels with air. They are present as
different chemical compounds. The nitrogen oxides relevant for power plants are the following
nitrogen – oxygen compounds.

formation tempera-
chemical ture
Name Colour Characteristics
formula
°C
nitrous oxide non-poisonous
N2O colourless
(laughing gas) sweet odour

Nitrogen oxide NO > 650 colourless non-poisonous

very poisonous
Nitrogen dioxide NO2 < 650 yellowish-brown
pungent odour

Table 1.1:

1.1.2 Origin of the nitrogen oxide compounds present in the flue gas

In general, two sources of nitrogen can be distinguished: the nitrogen from the fuel (fuel nitrogen)
and the nitrogen from the air (air nitrogen). Both form oxides of nitrogen during combustion through
different mechanisms and at different temperatures: the fuel nitrogen oxides (called fuel NOx) and
the air nitrogen oxides (called thermal NOx). Prompt nitrogen oxide (called prompt NOx) is formed
through a third chemical mechanism.

• The fuel nitrogen oxide (Chemical species: NO)

– Formed in the flame from nitrogen organically bound in the fuel.

– Formation begins at temperatures around 680 °C.

– Increases up to roughly 1 400 °C, then flattens out.

• The thermal nitrogen oxide (Chemical species: NO)

– Formed in the flame from the air nitrogen with oxygen from the combustion air and the
combustion water.

– Formation begins at temperatures above 1 300 °C.

– Increases exponentially with the temperature.

– Increases with the residence time in the flame.

• The prompt nitrogen oxide (Chemical species: NO)

– Formed in the flame.

– Of secondary significance for power plants.

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Type of formation Mechanism of formation Site of formation – influence variables

CN + H2 → HCN + H flame
fuel NOx CN + H2O → HCH + OH
CN + N2 → HCN + N O2 concentration and residence time
excess O2 flame and post reaction zone
O+N → NO + N
N + O2 → NO + O concentration of O atoms
thermal NOX,

excess fuel (O2 dissociation at ϑ > 1 300 °C)

N + OH → NO + H residence time and high temperature

CN + H2 → HCN + H flame
CN + H2O → HCH + OH
prompt NOX
CN + N2 → HCN + N
N+O → NO O2 concentration, O and N radicals and temperature

Table 1.2:

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Figure 1.1: A schematic representation of the NOx formation with coal dust firings

During “normal” combustion, NO forms almost exclusively, because at temperatures > 650 °C and in
the presence of O2, this is the more thermodynamically stable compound. The conversion of NO to
NO2 occurs in the furnace through slow chemical reactions at temperatures of less than approximately
600 °C, because NO2 is the more thermodynamically stable compound at temperatures < 200 °C.

The formation of N2O occurs in fluidised bed combustions (FBC) due to analogous reasons.

The nitrogen content of the fuel amounts to roughly:

Gas 0%
Oil 0.1 to 0.5 %
Coal 0.7 to 3.0 %

The nitrogen oxide produced during the combustion of hard coals is distributed roughly as follows:

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Type of formation portion in %

approx. 50 to 70 from the volatiles
fuel NOX
approx. 20 to 30 from the residual coke
thermal NOX approx. 10 to 30
prompt NOX insignificant

Table 1.3:

1.1.3 Nitrogen oxide formation of different fuels and types of firing

• Hard coal firing with liquid slag removal

combustion temperature: approx. 1,550 to 1,750 °C

nitrogen oxide: approx. > 30% thermal
approx. 95% NO
approx. 5% NO2

• Hard coal firing with dry ash removal

combustion temperature: approx. 1,300 to 1,400 °C

nitrogen oxide: approx. 70 to 90 % fuel
approx. 10 to 30 % thermal
approx. 95% NO
approx. 5% NO2

• Brown coal firing

combustion temperature: approx. 1,100 to 1,200 °C

nitrogen oxide approx. 100% fuel
approx. 95% NO
approx. 5% NO2

• Fluidised bed combustion

combustion temperature: approx. 850 °C

nitrogen oxide: approx. 100% fuel
approx. 95% NO
approx. 5% NO2

• Refuse combustion

combustion temperature: approx. 800 to 1,000 °C

nitrogen oxide: approx. 100% fuel
approx. 92% NO
approx. 8 % NO2
• Gas turbines

combustion temperature: approx. 1,000 °C

nitrogen oxide: approx 100 % thermal
Full load approx. 0 to 15% NO2
partial load up to 80 % NO2

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1.1.4 Examples of the influences of different operating parameters on the formation of

nitrogen oxide

The formation of nitrogen oxides for the different fuels varies greatly depending on the present operat-
ing parameters, in each case. A few of these relationships are represented in the following figures.

Figure 1.2: The conversion rate of fuel nitrogen into NOx for different fuels

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Figure 1.3: Conversion of fuel nitrogen in heavy fuel oil into NO2

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Figure 1.4: NOx coversion of nitrogen in the fuel with tangential pulverized coal firing

Figure 1.5: Influence of the excess air on the NOx content

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Figure 1.6: Influence of the combustion air temperature on the NOx formation with natural gas firings

1.2 Nitric Oxide Reduction

1.2.1 Nitric oxide reduction measures

In general, a prevention of the formation of nitric oxide, and a reduction of the nitric oxide emissions
can be achieved through:

• the fuel selection,

• primary measures that are performed during combustion in the furnace, and

• secondary measures that are performed in the discharge of flue gas.

If necessary, several measures can be performed in conjunction in order to achieve the desired result.

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Fuel selection, which can only be performed in exceptional cases is understood to be the choice of
low nitrogen fuels such as gas or fuel oil EL. Furthermore, with all coal firings, the integrated combus-
tion of nitrogen-rich refuse derived fuels such as sewage sludge, animal meal, etc. can also be
stopped.

The primary measures are constructive and operating measures affecting the firing in order to pre-
vent or to reduce the formation of nitric oxides. They include the following:

• the reduction of the maximum flame temperature through

– an optimal fuel treatment through, e.g., a finer pulverising

– the reduction of the combustion air temperature through

a reduction of the air preheating
a reduction of the furnace loading
the injection of water/vapour into the combustion zone

• the reduction of the oxygen supply in the flame through

– air staging, that is, the reduction of the local combustion air factor in the burner region
through
a reduction of the secondary and tertiary air mass flows
a flue gas recirculation to the flame (internal recirculation)

– a reduction of the total combustion air factor through

a flue gas recirculation in the furnace (external recirculation)
- through flue gas from aft of air preheaters
- through flue gas from aft of economisers
the injection of water/vapour into the combustion zone

• shortening the residence time at higher temperatures through an appropriate design

– of the burner

– of the furnace

Furthermore, primary measures are constructive and operating measures affecting the firing in order
to destroy any already formed nitric oxides. Among these is the reduction of NO compounds at higher
temperature without catalysers through

• the fuel staging of the performance fuels,

• the addition of a reducing fuel,

• the addition of a reducing agent means related to NH3 (SNCR)

While performing these measures, it must be observed that they can influence each other. In general,
primary measures are:

• more effective,

• more cost-effective and

• less complex

than the secondary measures. Therefore, they are used preferably, because if a pollutant is not pre-
sent in the flue gas, it does not need to be removed.

The effectiveness of the primary measures is often greater at full load than at partial load, and except
for brown coal firings usually not sufficient to ensure adherence to the limits required by regulations.
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Therefore, it is the goal of the primary measures to attain as much nitric oxide reduction as possible,
and to undertake secondary measures only for the portion of the nitric oxide reduction that is neces-
sary for safe compliance with the limit values at all load conditions.

The different measures affecting the firing can summarised as follows:

Reduction of the calorific value (moisture)

Reduction of the effective combus-
Sub-stoichiometric combustion
tion temperature
Decrease of the air preheating
Increase of the thermal output (flame cooling)
Cooling through inert gases (flue gas recirculation)

Reduction of the O2 content (flue gas recirculation)

Decrease of the available oxygen Reduction of the air ratio in the burner
Staged combustion in the burner (low NOx burner)
Air staging in the furnace (over-fire air)
Staged fuel addition (fuel staging)

shorter residence time in the re- Constructive design of the burner

gions of high temperature Shorter flame

Influence of the degassing condi- Modify pulverising (fine conversion)

tions Extension of the flame

Delayed mixture of the fuel and air Change of relative speeds between primary and secondary air

Change of secondary air spin

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1.2.2 Limits of nitric oxide reduction measures

The nitric oxide reduction measures are limited by the boundary conditions that must be observed for
the firing. These are:

• processing of a broad spectrum of fuels,

• maintaining the controllability of the firing

• the complete combustion of the fuel with low content of CO and unburned material.

• the operating safety in the form of a stable ignition over the entire working range of the firing

• the operational efficiency of the firing and the steam generator through avoiding erosion, cor-
rosion, and slagging

The table shows some of the possibly occurring risks from the reduction of NOx.

Side effects of the

Effect Consequences Risks
NOx reduction measure
Falling below the ignition tem-
ignition difficul- flame blow off
perature operational safety is reduced
ties emergency shut-off
O2 in the primary air too low
reducing atmosphere service life is reduced
corrosion tube burst
near the walls disruption of operation
furnace temperature fuel losses
too low CO content in- ash usability
degraded burn- creases
exceeding CO limit values
excess air too low out unburnt material in
the ash increases shift of the heat transfer to the
contact heating surfaces slag-
Burnout path too short
ging can increase

Table 1.4:

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It should be noted, in particular, that for nearly all nitric oxide reduction measures the CO content in
the glue gas increases with falling NOx content.

Figure 1.7: Values for NOX and CO depending on the excess air, boiler load: 620 t/h, fuel: HSC-R

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Figure 1.8: CO depending on NOX, boiler load: 620 t/h, fuel: HSC-R

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1.2.3 Some notes on low NOx firings

Reducing the combustion air ratio through air staging

• Reduce the excess air at the individual burner through control engineering measures.
Air staging at the burner as first air – second air – third air, or primary, secondary and tertiary
air with, e.g., λ = 0.7 to 1.0 to 1.2

• Keeping the excess air in the burner region of the furnace low, and increasing it at the furnace
end through overfire air (OFA) or burnout air.

The limits of these measures are:

• the CO formation in the evaporator area, and with that, the falling combustion efficiency (1 %
CO ⇒ 4 % loss of efficiency), and the increasing corrosion of the heating surfaces (H2 + S =
H2S)

• the extension of the combustion path with afterburning in the convective part with a heat shift
from evaporator into the convection heating surface and possibly, exceeding of the ash soften-
ing point and a consequent increase of the fouling of the heating surfaces.

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Figure 1.9: Furnace – air staging

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Reduction of available oxygen through flue gas recirculation

“Cold” flue gas is drawn off, either before or after the air preheaters, and fed back

• into the furnace,

• to the burner area,

• into the primary air

As a consequence of this, the portion of oxygen in the combustion area is reduced and thereby the
temperatures decrease in the flame and in the entire furnace.

The limits of these measures are:

• the CO formation in the evaporator area, and with that, the falling combustion efficiency
(1 % CO ⇒ 4 % loss of efficiency), and the increasing corrosion of the heating surfaces
(H2 + S = H2S)

• the extension of the combustion path with an afterburning in the convection part with a heat
shift from the evaporator into the convection part, and possibly, exceeding of the ash softening
point and a consequent increase of the fouling of the heating surfaces.

• the larger volume flow of flue gas with the consequence of an improved heat exchange due to
higher α values, and with this, a shift of the start of vaporisation (and the end of vaporisation
with forced circulation steam generators) with the consequence of possible evaporator instabil-
ity. An increased erosion due to higher flue gas speeds.

Reduction of the furnace temperature

The heat output in the furnace can be increased through an enlargement of the furnace. This results in
a drop in the furnace temperature.

• The outer heat transfer surfaces can be enlarged.

– The volume increases with the third power a x b x c ⇒ a3.

– However, the wall surface area only increases with the square, or second power,
a x b ⇒ a2,

• The inner heat transfer surface can be enlarged through intermediate walls in the furnace or
heat absorbing tubes.

The limits of these measures are:

• the constructive and financial expenditure for a furnace conversion.

• the control of the steam temperatures becomes problematic because the evaporator, as a ra-
diant heating surface, absorbs a lot of heat in the case of a partial load.

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Fine conversion

A mass flow of fuel produced through fine grinding is burned in the furnace with a lack or air. The very
fine grinding (R0.09 < 12 %) of the fuel occurs through bowl mills with rotary screens – sometimes with
variable rotary speed – or gravity mills. The small grain that is created has a low mass per particle, a
small volume, and a large specific surface. It heats quickly, ignites rapidly, and has a high combustion
temperature. The consequence of this is a high NOx formation. At the same time, there is the forma-
tion of CO and hydrocarbon radicals that break down the NOx that is being generated. In the process,
the NOx content is reduced compared with the customary fuel grain spectrum.

An addition of overfire air occurs in the burnout zone. Thereby, the previously formed CO is burned
and a lower NOx post formation occurs. The overall balance of NOx being formed and broken down
shows that the NOx content of these types of firings is lower.

Figure 1.10: Effect of fine pulverisation

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1.3 Outcome of low NOx firings

Figure 1.11: The reduction of nitric oxides through reducing the primary air ratio
1

0.9

0.8

0.7

0.6
NOx Abatement

0.5

0.4

0.3

0.2

0.1

0
0 6 12 18 24 30 36
over fire air [%]

light oil
heavy oil
natural gas

Figure 1.12: The reduction of nitric oxides through increasing the overfire air

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Figure 1.13: The reduction of nitric oxides through increasing the flue gas recirculation

Figure 1.14: Effectiveness of retrofitting measures for NOx reduction

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Figure 1.15: Low NOx brown coal dust firing – reduction rates of individual measures

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Figure 1.16: Older brown coal dust firing before and after the conversion

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Figure 1.17: Combustion chamber of the Lippendorf brown coal fired steam generator with triple air
staging

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1.4 Problems with the Corrosion of Heating Surfaces with the Nitric Oxide Reduction

With a tangential firing for hard coal with jet burners, the burners are arranged in the corners of
the furnace, and directed in an imaginary burner circle. The staging of the material flows, upper air,
primary air/pulverised coal, intermediate air and lower air, that participate in the combustion, can be
recognised.

Figure 1.18: Tangential firing for hard coals with jet burners without upper air nozzles

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Due to the spatial distance of the fuel nozzles and air nozzles, a delayed mixture of fuel and combus-
tion air is attained, and the flame is elongated. The longer flame radiates more heat, whereby the
flame temperature is reduced. This type of combustion characteristic leads to a comparatively lower
production of NOx. Here, it must be assured that the flames do not contact any heating surface walls,
because otherwise the combustion process is disrupted which leads to increased CO production and
an increased slagging in the heating surface area.
With the air staging and fuel staging of this type of firing, deoxidising acting flue gases can form
near the walls. An indicator for the occurrence of these gases is the presence of CO, and at the same
time, a low oxygen content in the flue gas. This results in the so-called “CO corrosion”, but the corro-
sion is actually caused by H2S.

As countermeasures, additional “upper air nozzles 2” are installed. The air supplied by these nozzles
is guided into the wall area, and is therefore is called “wall air”. A part of the wall air remains over the
total height of the furnace near the walls, and forms an oxidising atmosphere there.

The following figures show these measures for the hard coal fired block in Bexbach, Germany that is
equipped with jet burners of a tangential firing.

Figure 1.19: Furnace sketch Bexbach

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Figure 1.20: Burner secondary air and overfire air system after reconstruction

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Figure 1.21: Distribution of CO and oxygen in the wall areas

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It can be seen that the CO content is very low and the oxygen content is so high such that a corrosion
is safely prevented.

In the following Figure 1.22 and Figure 1.23 it can be seen that with the new operating mode the NOx
concentrations are significantly lower before the catalyst than with the previous operating mode. At the
same time, however, the content of uncombusted material has not increased.

Figure 1.22: NOx concentration values upstream of catalyst

Figure 1.23: Content of combustibles in fly ash

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