Content of Lecture

1. Phenomenology of Combustion
2. Thermodynamic Fundamentals
3. Chemical Reaction Kinetics
4. Ignition and Ignition Limits
5. Laminar Flame Theory
6. Turbulent Combustion
7. Pollutants of Combustion
8. Combustion of Liquid and Solid Fuels
9. Numerical Simulation
10. Measurement Techniques of Combustion Processes
11. Applied Aspects of Turbulent Combustion
12. Technical Burner Systems
13. Internal Combustion Engines

8/1

Content

7. Pollutants of Combustion
7.1 NOX - Formation
• 4 mechanisms of formation
• Strategies for NOX reduction

7.2 UHC- and Soot-Formation

• Unburned hydrocarbons
• Soot formation

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1
 Pollutant-Emission and Impact
Emissions partly dangerous for human being, nature, buildings
(Smog, acid rain, greenhouse effect, ...)

Important Pollutants Impact

• Unburned hydrocarbons (CXHY,UHC) Smog (near ground), toxic
greenhouse gas (stratosphere)
• particles, soot and ash dirt, smog, respirable, carcinogenic
• Carbon monoxide (CO) toxic
• Nitrogen oxides (NOX := NO, NO2) “Summer smog”, toxic
• sulphur oxides (SOX := SO2, SO3) “Winter smog”, acid rain, corrosive,
toxic

Also not wanted are:

• Dioxin and Furan
• Carbon dioxide (CO2)
• Water (H2O)
• Nitrous oxide / laughing gas (N2O)
highly toxic, mutagen
greenhouse gas
cloud formation, greenhouse gas
greenhouse gas, ozone killer
8/3

Pollutant-Emission and Impact

Emissions partly dangerous for human being, nature, buildings
(Smog, acid rain, greenhouse effect, ...)

Important Pollutants Impact

• sulphur oxides (SOX := SO2, SO3) “Winter smog”, acid rain, corrosive,
toxic

8/4

2
 Pollutant-Emission and Impact
Emissions partly dangerous for human being, nature, buildings
(Smog, acid rain, greenhouse effect, ...)

Important Pollutants Impact

• Nitrogen oxides (NOX := NO, NO2) “Summer smog”, toxic

8/5

NOX-Formation

8.1 NOX-Formation
NOX (=NO + NO2) emission can be controlled by primary measures
affecting the firing
(SOX almost not controllable)

4 Mechanisms of Formation
• Thermal NO (Zeldovich) T high
• Prompt NO (Fenimore) T lower
• Fuel NO for coal, (oil)
• via N2O (Wolfrum) p high, lean (Gas turbine)

NO
"Thermal NO"

"Prompt NO"

height above flame

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3
NOX-Formation

Thermal NO (Zeldovich NO)

Main rate determining reaction

O + N2 → NO + N k1 = 1,8 1014 exp(-318kJ/mol/RT)
cm3/mol s
further on
N + O2 → NO + O
N + OH → NO + H
• has very high activation energy (N2-
triple bond) → high temperature (above
1800 K significant)

k1 • slow→ residence time is important,

formed also in exhaust gas

T
8/7

NOX-Formation

Prompt NO (Fenimore 1979)

Oxidation of air-N2 with fuel-radicals (CH, ...)

• complex, e.g.

CH* + N2 → HCN + ... → ... → NO

→ N2

• Radicals necessary: formation only in flame front

• Especially in rich combustion (more CH)
• Starts at about T = 1000 K
• small T-dependence
• Often prompt NO  thermal NO, but it gives lower possible NO-limit
also for Low-NOX-burner

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4
 NOX-Formation

Fuel NO

• From oxidation of nitrogen being bound in the fuel (up to 2% in

waste, coal, oil, negligible in natural gas, gasoline)
• Complex radical mechanism, but can be calculated
• Starts at T = 1000 K

N2
Fuel N .....
O2
NO

• Fuel NO can sometimes be reduced by a fuel-rich step of

combustion, because then reaction path to N2 is preferred.

8/9

NOX-Formation

NO-Formation via N2O

• Typ. Reaction

N2 + O + M → N2O + M → NO

• Three-body-reaction → infrequent, but probability increases strongly

with pressure !
• Therefore important for lean ultra-low NOx gas turbines with 16 - 30 bar

Thermal Equilibrium NO <---> NO2

T > 650°C T < 650°C

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5
NOX-Formation

NO - Reduction in the exhaust (secondary methods)

Selective catalytic reduction (SCR process)
• Catalyst necessary
• NH3 addition (NO + NH2-> N2 and H2O)
• Wide temperature range
• Expensive

Selective non-catalytic reduction (SNCR process, DeNOx

process, Redox process)
• NOX-reduction in gas phase (no catalyst)
• NH3 addition
• Temperature has to be controlled very accurately, around 1300 K
(T < 1200K -> not enough activation Energy
T > 1400K -> NH2 is oxidized to form NO)
• Cheaper
8/11

NOX-Formation

NO - reduction by primary methods (by combustion technology)

Reduction of temperature !!! → reduced thermal NO

• Lean premixed combustion
→ (Tflame lower) Tad
• T reduction due to ceramic rods in flame
• Porous combustion NO
• Staged combustion (later)
• Flue gas recirculation (later)
1 2
l
• Optimization of residence time
• therm. NO formation, if T high, O2 existing (→ hold residence time short)
• fuel NO reduction (fuel rich, with HCN) (→ hold residence time long)

• combustion with pure oxygen (no N2 from air, therefore no NOX)

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6
UHC- and Soot Formation

8.2 UHC- and Soot-Formation

Unburned hydrocarbons (UHC) if

• Incomplete combustion
• residence time (or reactor length) is to short
• incomplete mixing
• temperature to low (especially in mixing region with cold secondary air)
• Flame quench ("Quenching")
• "too" lean mixture (beyond lean extinction limit)
• "too" turbulent (local blow out of flame)
• Interruption of combustion near wall (IC engine)
• heat transfer to wall
• loss of reactive radicals due to surface reactions

8/13

UHC- and Soot Formation

Example: UHC Formation in IC Engines

UHC formation near piston ring

between 2-6 % of fuel mixture are trapped near piston ring, escaping
with exhaust, partly unburned
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7
UHC- and Soot Formation

Soot Formation

• Conglomerate from many C- and H-Atoms (and others), Ratio C:H  8:1

• "Primary particles"
• spherical structure
• diameter 10 - 50 nm
• around 105 C-Atoms
• invisible

• Visible is "agglomeration" of primary particles

• out of 100 to 1000 primary particles
• Extension typically 1 - 100 µm

• Sometimes loose coupled "Aggregates" out of

several agglomerations (Soot flakes)
TEM recording
• Note: Soot filter in trucks reduce maybe only the
size (soot is then invisible, but even more dangerous)

8/15

UHC- and Soot Formation

Soot Formation
if

• rich mixture (much C, few O)

• T between 1100 and 1500°C
• (especially in diffusion flames)

• Mechanism is complex:
• C2 → C6 → C10 → ... → C60 → ... → C10000

Non-premixed flame:
• Soot formation inside of fst
• Soot oxidation further downstream, where
O2 is available.

8/16

8
Summary

NOx - Formation
• 3 mechanism of formation
• Thermal NOx depends strongly on temperature
• T reduction !
• by diverse methods
• e.g. lean combustion
• e.g. staged combustion

UHC- and Soot-Formation

• Unburned hydrocarbons from quench near wall
• Soot: formation in rich flames, radiates

8/17