2012/3/9

Aerosol & Particulate Research Laboratory

1
NOx
Thermal NOx vs Fuel NOx
Strategies for Combustion Modifications
Off stoichiometric combustion, flue gas
recirculation, water injection, gas reburning, low
NOx burner
Flue Gas Treatment
SCR, SNR, Absorption, Adsorption
Reading: Chap 16
2012/3/9 Aerosol & Particulate Research Lab 2
Thermal NOx vs Fuel NOx
Thermal NOx: formed by reaction between N
2
and O
2

in the air; sensitive to temperature
Fast formation rate at high temperature
Fast cooling rate freezes formed NOx
Fuel NOx: formed from combustion of fuels containing
organic nitrogen in the fuel; dependent on local
combustion conditions and nitrogen content in the fuel


NOx Control:
combustion modification --> prevent formation
flue gas treatment --> treat formed NOx
Q: Can absorption, adsorption or incineration be used to
control NOx?
2012/3/9 Aerosol & Particulate Research Lab 3
Strategies for Combustion Modification
Reduce peak
temperatures of the
flame zone
Reduce gas
residence time in
the flame zone
Q: Temperature as a
function of equivalent ratio?
tric Stoichiome
air
fuel
/
air
fuel
: ) ( ratio Equivalent
|
.
|

\
|
|
.
|

\
|
|
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Off-Stoichiometric
Combustion/Staged combustion:
combusting the fuel in two or more
steps. Fuel rich then fuel lean.

Flue gas recirculation: reroute
some of the flue gas back to the
furnace; lower O
2
and allow NOx
to proceed the frozen reactions
Water injection: reduce flame
temperature; energy penalty

Modification of Operating Conditions
Why?
http://en.wikipedia.org/wiki/Staged_combustion_cycle_(rocket)
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Gas reburning: injection of natural gas into the boiler
above the main burner to create a fuel-rich reburn zone;
hydrocarbon radicals react with NOx to reduce NOx to N
2
.
http://www.lanl.gov/projects/cctc/factsheets/eerco/gasreburndemo.html
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Low-NOx burner: inhibit NOx formation by
controlling the mixing of fuel and air; lean excess
air and off-stoichiometric combustion

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Flue Gas Treatment
Selective Catalytic Reduction (SCR)


O H N O NH NO
O H N O NH NO
2 2
catalyst supported O V or TiO
2 3 2
2 2
catalyst supported O V or TiO
2 3
6 3 4 2
6 4 4 4
5 2 2
5 2 2
+ + +
+ + +
Q: Should a SCR reactor be
installed before or after
particle control devices?
Q: Why is it called selective?
Temperature ~ 300 - 400
o
C
http://www.lanl.gov/projects/cctc/
factsheets/scr/selcatreddemo.html
Also good for Hg emission control!!!
2012/3/9 Aerosol & Particulate Research Lab 8
O H NO O NH
O H N O NO NH
2 2 3
2 2 2 3
6 4 5 4
6 4 4 4
+ +
+ + +
Temperature ~ 800 - 1000
o
C
Q: Disadvantages of
SCR and SNR?
Above 1000
o
C
Selective Noncatalytic Reduction (SNR)
2 2 2
3 2
2 2 2 2
3 2
2 2
2
O O H OH HO
HNO NO HO
O H HO O H OH
HNO NO OH
HONO NO OH
OH O H
+ +
+
+ +
+
+

Wet Absorption: generally good for only NO
2

because NO is insoluble. Need to oxidize NO first.

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Dry Sorption
Activated carbon (220 ~ 230
o
C): reduce NOx to N
2
;
oxidize SO
2
to H
2
SO
4
if NH
3
is injected, and carbon is
thermally regenerated to remove concentrated H
2
SO
4
Shell Flue Gas Treating System (~ 400
o
C)










Alkali Metal and Alkali Earth Metal based sorbents:
form metal nitrates (e.g. NaNO
3
, Mg(NO
3
)
2
)
CuO O Cu
O H SO Cu H CuSO
O H N O NH NO
CuSO SO O CuO
+
+ + +
+ + +
+ +
2
2 2 2 4
2 2
catalysts as CuSO or CuO
2 3
4 2 2
5 . 0
2 2
6 4 4 4
5 . 0
4
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Quick Reflection