First name : Mohsen

Last name : Soleimani Karizmeh

Student Number : 5663775

Topic : NOx reduction by staged

combustion and its advantages and
disadvantages

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1. Introduction:

NOx plays important role in atmospheric chemistry and air pollution. It has
some impacts on environment, atmosphere and human that force the human
to reduce the anthropogenic amount of NOx emission. But also it has some
natural sources that we are not going to do anything with it in this article. In
addition the anthropogenic emission is very significant in compare with
natural sources (like lightening, aviation, biomass burning and .....) and we
have to reduce this amount by some new technologies like staged
combustion as much as we can. Most of NOx from combustion is because of
high temperature and we call this NOx , thermal NOx and we will discuss it
later . So , for reducing this amount we need to reduce the temperature that
also has some other impacts on our system and our efficiency . We can do
the combustion in two stages and for first stage we are in fuel-rich regime
and in second stage after injection of some air to the system we are in the
fuel-lean regime and by this staging technology we also reduce the
temperature and thermal NOx as well.

1.1. NOx definition:

NOx (nitrogen oxide) is refer to the overall amount of all nitrogen oxides that
are: NO, NO2 , N2O ,N2O3 , N2O4,N2O5 . But NOx is generic for mono
nitrogen compounds that are NO and NO2 . These two compounds can
produce only in high temperature environment which the combustion and its
high temperature is a good place for their formation .In fact this high
temperature can be the engine for an endothermic reaction between
nitrogen and oxygen. Also we have to mention that NO will oxidize to NO2
and the amount of NO2 is higher than NO on the surface.

1.2. Health effect:

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NOx can react with NH3 or moisture and produce nitric acid and small
particles. Nitric acid will produce acid rain that impacts the environment, the
fabrics and causes rubbers to crack . Small particles can penetrate into the
sensitive parts on lung and produce respiratory problems. And in some cases
it leads to heart disease and more hospital admissions and death.

In sunny days and in the presence of hydrocarbons, NOx can produce

photochemical smog that is surface ozone, aldehydes and
peroxyacetylnitrate (PAN) that leads to the respiratory symptoms and
reducing the vision.

1.3. The formation of NOx :

NOx can form in three ways by combustion that are: thermal, prompt and
fuel NOx .

Thermal: thermal NO is found mainly in the high-temperature zone and is

a function of temperature and the residence time of nitrogen in this area
and less dependent on the oxygen concentration. It is formed by the
oxidation of molecular nitrogen in combustion air and fuel gases (such as
natural gas) by the extended Zeldovich mechanism that is these three
equations:

Fuel: Fuel NO is formed by the oxidation of nitrogen chemically bound in

fuel. In fact the nitrogen from the coal or oil realises as a radical and produce
NO. It is more in combusting of coal in compare with oil. But, In the

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production of natural gas and liquid petroleum gas, combustible gaseous
nitrogen compounds such as ammonia and amines are removed to a low
level and as a result less fuel NO will produce.

Prompt NO: It observed in fuel-rich flames and at low temperatures and its
formation is independent of combustion temperature. It is formed from
reaction of atmospheric nitrogen, with radicals that are in the fuel (such as C,
CH, and CH2).These reactions can produce nitrogen compounds other than
NOx which they will oxidize to NO later.

1.4. Emission of NOx:

The statistic from EPA showed that most of the NOx emission is from the
vehicles of the road, fossil fuel combustion and industrial processes and also,
most of fossil fuel combustion occurs in the furnaces.

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 Figure1: National Nitrogen Oxides Emission by Source Sector in 2005

2. Staged combustion:

This combustion is using to reduce the emission of NOx from the industrial
combustions that are a large fraction of the total NOx emission. The
mechanism of this combustion for pulverized coal is shown in this picture.

Figure 2: The mechanism of Staged combustion

This kind of combustion has three steps that are: devolatisation , primary
combustion and secondary combustion . Devolatisation takes just 100 ms
and in this step most of the nitrogen coal devolatise and the pyrolysis
products oxidise and produce HCN, NH3, NO and char nitrogen. In the second
step that takes 2-3 seconds the concentrations don’t change significantly
and just some primary coal nitrogen converts to N2. At the third step that
starts with burnout air, NOx can form or even destroyed.

2.1. Furnace:

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In this experiment we are going to use the combustion chamber with
different wall temperatures (1000 °C, 1100 °C and 1300 °C) to see what the
effect of wall temperature is. The pulverized coal is supplied by the primary
air and it will inject to the chamber from its top. Preheated air will injected to
the chamber by the secondary air that is inducing a recirculation of
combustion products and primary reaction zone that consists combustion air
and fuel. It helps to produce more volume for combustion and less
temperature in contrast with the normal combustion that occurs around the
flame that has more temperature.

2.2. Coal combustion:

We used four different kinds of coal with different amount of nitrogen for
having more experimental decision that are : Lignite coal Lausitz (L) a high
volatile lignite coal , Kleinkopje (K) low volatile bituminous coal, Budryk (B)
medium volatile bituminous coal and Polish Hard Coals (PHC) high volatile
bituminous coal . You can see their composition in below table.

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 Table 1. Fuel K B P L
analyses HC
Carbon (C) [%] 65.30 57.30 80.9 56.70
Hydrogen (H) 3.90 4.00 5.0 5.60
[%] 7.02 3.52 2.94 21.44
Oxygen (O) [%] 1.30 0.77 1.2 0.55
Nitrogen (N) 0.28 0.64 <0.3 0.61
[%]
Sulphur (S) [%]
Fixed Carbon 56.20 43.20 64.2 36.20
[%] 21.60 23.30 29.8 48.70
Volatiles [%] 18.60 26.30 4.0 4.90
Ash [%] 3.60 6.90 2.0 10.20
2.3.
Moisture [%]
The LCV [MJ/kg] 23.94 22.69 32.35 18.97

results:

-At first we can compare the results for staged combustion and unstaged
combustion that both of them have the same wall temperature (in this
experiment). It shows that in unstaged , the more volatile content, the more
NOx emission we have , but in staged combustion it is totally the opposite .

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Figure 3: Relationship between NOx and volatile matter content in coal
(unstaged flameless coal combustion; λtotal=1.16; wall temperature 1300
°C)

Figure4: Relationship between NOx and volatile matter content in coal (air
staging flameless coal combustion; λlocal=0.8, λtotal=1.16; wall temperature
1300 °C)

-In the second experiment we want to compare the change of NOx with
change in air stoichiometry .

For lignite coal , we conducted two different wall temperatures . The

emission has to stay under limit of 200mg/m3 N for this kind of coal that
forced us to reduce the air stoichiometry to 0.95 . For bituminous coals local
air stoichiometry have to be between 0.75 -0.95 . As you can see by
increasing the air stoichiometry , the emission of NOx is going to increase
too . It means that with less air stoichiometry we would have less Fuel NO

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formation , but it increases the formation of HCN and NH3 which can produce
from reaction of NO with hydrocarbons .

Figure 5: Effect of air stoichiometry on NOx emission (air staging flameless

coal combustion; λtotal=1.16)

-In the third experiment we tried to find the influence of staged combustion
on NO emission and also the effect of flame on this fact .
We carried out the experiment both with air and Ar/O2 (79 % of argon and 21
% of oxygen)mixture under air staging conditions. The results show us that
the NO concentration is decreasing with increasing the axial distance that it
means the staged combustion is a good way to reduce the NOx emission .
On the other hand when we are going to use the Ar/O2 mixture and as a
result , the only nitrogen that we have is the nitrogen in the fuel. So the
difference between the air and Ar/O2 mixture in NOx emission can be from
the nitrogen in the air. As we said the formation of thermal NO from air
nitrogen is depend on the temperature. In flameless combustion , the

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recirculating flue gas will decrease the temperature and as a result the
formation of thermal NO reduce significantly .But in compare with flame
combustion the fuel NO is a little higher .

Figure 6 :Fuel-NO portion out of total NO emission (air staging flame Lausitz
coal combustion; λlocal=0.8, λtotal=1.16; wall temperature 1300 °C)

-Now there are some other things that can affect the NOx emission
amount:
By using information from other experiments that used different fuels we
found some other results that we can mention them here .
The secondary injection can be effective on our NO amount . In fact , the
farther secondary injection the lower the formation of NO. It can be
concluded that the products of primary combustion will oxidize and produce
NO when we do the secondary injection .

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-The next result was that the fuel-NO decreased with increasing wall
temperature. But increasing in wall temperature have some impacts by itself
that we will talk about it later .
-Experiments shows that particle size is important in NO amount and smaller
particles of fuel can produce more NO .However, for the small air ratios for
the particle size, the NO amount is the same. So, we can conclude that the
effect of staged combustion is more effective for small particles of the coal.

Figure 6: Variation of NO emission according to the secondary injection

point , residence time up to secondary injection point hs=60 ms ,

hs=80 ms , 110 ms

-The results for staging intensity(the ratio of secondary to the total

combustion air flow rate ) shows that NO formation decreases with

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increasing the staging intensity and it have really critical influence on our
results .

-The second stage residence time is relatively short and char burnout is very
slow and NOx formation from nitrogen in char is very important in NOx
reduction , therefore the coal is not completely oxidize in this stage and at
the end there would be a large amount of unburned carbon in ash .

Effect of staged combustion on waterwall corrosion in boilers:

Before the implementation of some experiments it was believed that there is
no significant effect of Sulfur content of coal on corrosion rate and the gas
phase H2S produced from the sulphur in coal is responsible for corrosion.
But after some experiments it was vividly clear that , corrosion rate is
increase with increasing in wall temperature .Also the deposited FeS that is
because of partially combusted Fe2S (exist in many coals) can sulfidize the
waterwall tubes and increase the corrosion rate .
In other words , higher wall temperature is a result from staged combustion
that leads more corrosion and by staged combustion we have more
unburned coal that will increase the amount of deposited FeS that can
increase the area of severe corrosion .
By oxygen enhanced combustion , we can reduce the amount of unburned
coal and also deposited FeS and and as a result , the waterwall corrosion will
decrease . Also, Going from unstaged to oxygen-enhanced staged operation,
we will achieve about 70% reduction in NOx emission. Furthermore, with
staged combustion we increase the Loss On Ignition (LOI) that again by
Oxygen enhancing we can compensate this increment.

3. Conclusion:

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From these results we understood that staged combustion can has
advantages and also disadvantages and the most important advantage is
reduction in NOx . But there are some deficiencies in this technology that
costs so much. For example, more corrosion rate, more unburned carbon and
so on. But by use of oxygen enhanced combustion and use it with staged
combustion we can reduce some of deficiencies to an acceptable amount. In
fact, these two technologies can support each other and make the results
more environmental friendly and less costly. However, the deficiencies of
staged combustion are not comparable with its advantage. We have to just
find the destroyed equipments by corrosion from deposited FeS and then
change them . Also , our fuel usage rate is a little more than unstaged
combustion, but we can have less NOx emission that is really more important
than these costs. At first, these costs don’t seem to be a large amount that
can put a lot of pressure on an industry to do it. Also , the impacts of more
pollutants in the atmosphere are very significant and in some cases they are
irreversible for a long time and some of compounds have long lifetime in the
atmosphere ,so they will change our atmosphere significantly .We have to
mention that , these days all of the scientist and countries that do care about
the environment , cost billion dollars for just reducing the air pollutants a tiny
amount and in compare with that cost it seems really reasonable to do the
combustion by means of these technologies .

References:
1. Health and environmental impacts of NOx , US EPA

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2. NOx in the Air: Multiple Effects. Blankenship, Karl. Chesapeake Bay
Journal. http://www.bayjournal.com/article.cfm?article=2179. 2008

3.Reduction of NOx Emissions by Staged Combustion in high intensity Spray Combustors

,Tehsuro Hirai ,Nobuki Nagai ,Junji Takado,1987
4. Effect of Two Stage Combustion On NOx Emissions in Pulverized Coal Combustion, Jae
O.Chae and Yung N.Chun ,1991
5. Staged Low NOx Combustion Systems for Coal fired Boilers and Corrosion, Mark cremer ,
Dave Wang , 2003

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