nitrogenoxides nox emissions
DESCRIPTION
NO OxideTRANSCRIPT
Nitrogen Oxides (NOx)
Chapter 12Page 147-168
NOx emissions include:
• Nitric oxide, NO, and Nitrogen dioxide, NO2, are normally categorized as NOx
• Nitrous oxide, N2O, is a green house gas (GHG) and receives special attention
Smog precursors:
• NOx, SO2, particulate matter (PM2.5) and volatile organic compounds (VOC).
smog calphotochemi O VOCs NOozone level Ground
3Sunlight
x
“Developing NOx and SOx Emission Limits” – December 2002, Ontario’s Clean Air Plan for Industry
Broad base of sources with close to 50% from the Electricity sector in 1999
NOx reaction mechanisms:
NO O 21 N
21
22
• highly endothermic with hf = +90.4 kJ/mol
• NO formation favoured by the high temperatures encountered in combustion processes
Zeldovich mechanism (1946):
N NO O N1-
1
k
k
2
O NO O N2-
2
k
k
2
H NO OH N3-k
3k
k+1 = 1.8 108 exp{-38,370/T}k-1 = 3.8 107 exp{-425/T}
k+2 = 1.8 104 T exp{-4680/T}k-2 = 3.8 103 T exp{-20,820/T}
k+3 = 7.1 107 exp{-450/T}k-3 = 1.7 108 exp{-24,560/T}
N NO O N1-
1
k
k
2
k+1 = 1.8 108 exp{-38,370/T}k-1 = 3.8 107 exp{-425/T}
Rate-limiting step in the process
K+1 is highly temperature dependent
Combine Zeldovich mechanism with
H O OH O 24-k
4k
To obtain
]OH[k ]O[k]NO[k
1
]O[k]NO[kk
- ]N[k [O] 2
dtd[NO]
322
1-
22
22-1-
21
]N[ [O]k 2 dt
d[NO]2 1If the initial concentrations of [NO]
and [OH] are low and only the forward reaction rates are significant
Modelling NOx emissions is difficult because of the competition for the [O] species in combustion processes
“Prompt” NO mechanism (1971):
N HCN N CH 2
H NO OH N
O NO O N 2
N CO NO O HCN 2
This scheme occurs at lower temperature, fuel-rich conditions and short residence times
Fuel NOx
Organic, fuel bound nitrogen compounds in solid fuels
C-N bond is much weaker than the N-N bond increasing the likelihood of NOx formation
Example of proposed reaction pathway for fuel-rich hydrocarbon flames
NOx control strategies:
• Reduce peak temperatures• Reduce residence time in
peak temperature zones• Reduce O2 content in
primary flame zone
• Low excess air• Staged combustion• Flue gas recirculation• Reduce air preheat• Reduce firing rates• Water injection
Combustion Modification Modified Operating Conditions
Control strategies:
• Reburning – injection of hydrocarbon fuel downstream of the primary combustion zone to provide a fuel-rich region, converting NO to HCN.
• Post-combustion treatment include selective catalytic reduction (SCR) with ammonia injection, or selective noncatalytic reduction (SNCR) with urea or ammonia-based chemical chemical injection to convert NOx to N2.
SCR process:
4 NO + 4 NH3 + O2 4 N2 + 6 H2O
2 NO2 + 4 NH3 + O2 3 N2 + 6 H2O
SNCR process:
4 NH3 + 6 NO 5 N2 + 6 H2O
CO(NH3)2 + 2 NO ½ O2 2 N2 + CO2 + 2 H2O
Low NOX burners:
Dilute combustion technology
Industrial furnace combustion:• Natural gas is arguably “cleanest” fuel – perhaps not
the cheapest.• Independent injection of fuel and oxidant streams
(“non-premixed”). Industrial furnaces have multi-burner operation.
• Traditional thinking has been that a rapid mixing of fuel and oxidant ensures best operation.
• This approach gives high local temperatures in the flame zone with low HC but high NOx emissions.
• Heat transfer to a load in the furnace (radiatively dominated) must be controlled by adjustment of burners.
• High intensity combustion with rapid mixing of fuel and oxidant• High temperature flame zones with low HC but high NOx• Furnace efficiency increased by preheating the oxidant stream
A conventional burner
Lance Air
FuelGas
Combustion Air
Dilute oxygen combustion:• An extreme case of staged-combustion.• Fuel and oxidant streams supplied as separate
injections to the furnace.• Initial mixing of fuel and oxidant with hot combustion
products within the furnace (fuel-rich/fuel-lean jets).• Lower flame temperature (but same heat release)
and more uniform furnace temperature (good heat transfer).
• Low NOx emissions – “single digit ppm levels”
Strong-jet/Weak-jet Aerodynamics
•Strong jet = oxidant
•Weak jet = fuel
Strong-jet/Weak-jet aerodynamics
CGRI burner
Pilot burner portUV scanner port
Fuel nozzle
Air/oxidant nozzle
• Dilute oxygen combustion operation with staged mixing of fuel and oxidant• No visible flame (“flameless” combustion)• More uniform temperature throughout flame and furnace• Low HC and NOx emissions
Queen’s test facility
Queen’s test facility
2750-362 0 750 1750 54624500 5100
1362z
0
1000
500
3000
3362
y
x
-362
0
B2B1 B3
Water-cooled floor panels
SideView
Plenum Wall
FurnaceExhaust
TopView
CGRI burner in operation at 1100OC
CFD rendering of the fuel flow pattern
CGRI burner performance (1100OC)
Oxygen-enriched combustion:
• Oxidant stream supplied with high concentrations of oxygen.
• Nitrogen “ballast” component in the oxidant stream is reduced – less energy requirements and less NOx reactant.
• Conventional oxy-fuel combustion leads to high efficiency combustion but high temperatures and high NOx levels.
• Higher efficiency combustion leads to lower fuel requirements and corresponding reduction in CO2 emissions.
• Does this work with dilute oxygen combustion???
NOx emissions as a function of oxygen enrichment
2
2
2 2
OO
O O A
m 100
m + m
Firing rate as a function of oxygen-enrichment level required to maintain 1100oC furnace temperature
Is oxygen-enrichment a NOx reduction strategy?
• NOx emissions are reduced at high oxygen-enrichment levels … but …
• Only at quite significant enrichment levels, and• With no air infiltration (a source of N2).
NOx emissions as a function of furnace N2 concentration
Capabilities of oxygen-enriched combustion:
• Dilute oxygen combustion systems can work with oxygen-enriched combustion.
• NOx emissions are comparable to air-oxidant operation and NOx reductions are limited by air infiltration.
• NOx emissions also limited by N2 content of the fuel.• Primary benefit is energy conservation (reduced fuel
consumption) and associated CO2 reduction.
Limitations of oxygen-enrichment:
• This is not a totally new technology !!!• Cost of oxygen – high purity O2 is expensive, lower
purity is more feasible in some situations.• Infrastructure costs – oxygen supply and handling.• Furnace modifications – burners, gas handling, etc.
Final Examination• Tuesday, April 22, 1900h• 3rd Floor Ellis Hall• Open book, open notes• Red or gold calculator
CHEE 481 Tutorial Session• Saturday, April 19, 0900h
• Dupuis Hall 217