Combustion stoichiometry

Fuel and air may be mixed in different amount. If they were burnt in
proportion, no O2 is excess after fully oxidizing fuel.
balance of reactant and product O2

4.78 moles of air

This is called burning with stoichiometric air
Stoichiometric fuel/air Mass of Fuel

Note: 3.78 N2 + O2= 4.78 mole of air Effective mol. Weight of air
3.78 mole 1 mole
 Derivation from stoichiometric combustion
Equivalent ratio As burned

Stoichiometric ratio

Fuel lean ⇒ <1 (D>N) ; Excess air than required for Stoichiometric burning
Fuel Rich ⇒ >1 (D<N); Insufficient air

Under fuel lean, exhaust gas contain unused O2

2
1
Moles of O2 equating
∅ ( 𝑛+
𝑚
4 ) =2 𝑛 +2 𝑎+
𝑚
2
𝟏 𝒎
𝒂=( − 𝟏)( 𝒏+ )
∅ 𝟒
Fuel rich condition → exhaust gas has CO2, HC and other stuff
A typical coal Lignite is burnt with φ =0.95

Exhaust gas composition: Stoichiometric condition

CH0.96 O0.18 N0.016 S0.012 + x (O2 + 3.78 N2) ; x=?

Balance of O atoms → CO2 + 0.48 H2O + 0.016 NO + 0.012 SO2 + 3.78 x N2

0.18 + 2 x = 2 + 0.48 + 0.016 +0.024
⇒ x = 1.17
For φ =0.95 air is measured by 1/φ
Lean 3.78 × 1.17/0.95
CH0.96 O0.18 N0.016 S0.012 + (O2+3.78N2)
→ CO2 + 0.48 H20 + 0.016 NO + 0.012 SO2 +4.66 N2 + 0.06 O2
Thus for each mole of C combusted 6.23 mole of exhaust gas
(1+0.48+4.66+0.012+0.06+0.016)

= 0.05 × 1.24
= 0.06
 Combustion sources
Pollutant Concentration by combustion whether stationary or transportation is a
major source of CO, NOx, SO2. Also HC, precursor O3 and PM2.5.
CO2 and CO: When C containing fuel is burnt, best outcome is CO2 implies
maximum heat release; CO2 is not an air pollutant in regional or local level
Stoichiometry

CO2 reduction can be achieved by increasing energy efficiency and by

increasing renewable source of energy such as solar and wind power
CO: During C fuel combustion → CO → CO2
i) Due to improper mixing of fuel and air
ii) Quenching or with fuel rich ( less O2)
When flame is rapidly cooled CO2 is partitioned between CO and CO2

N2

Fuel rich condition

e.g. CH4 is burnt at =1.05

Exhaust gas =
CO= 0.19 g mole/ mole of
fuel
Stationary source is operated at Modern automobile run at
 SO2: S is minor constituent. Natural gas has H2S. Coal has organic and inorganic S

Control of SO2 emission

Remove S from Capture S during Remove SO2 from the

fuel before burning combustion flue gas

NOx: 90% NO + 10% NO2 NOx

Fuel NOx Thermal NOx Prompt NOx

due to presence in fuel At high T, atomic O radical N2 +CH* radical in
~0.1% N in fuel ( free valency electron) splits fuel rich condition
N2 in transport section → HCN → NO
Fuel NOx formation and control
• N found in form of pyridine (C5NH5) or
pyrrole ( C4NH5) in solid or liquid fuel
• Difficult to remove from fuel compared to S.
Fuel NOx ≠ f(T) in combustion
Radicals +N2 → HCN, N, NH, NH2, NH3,
NO
Derivable but slow Amines (?)

N+N=N2 Slow reaction

Relatively non reactive
Conversion of fixed N → N2 can be speeded up by fuel rich condition in part of
the combustion zone → Staged combustion
 Air Air

Burnout CO; T>1300 °C

Fuel

Φ>1 Φ<1
Air Air

Stage 1 Stage 2

N → N2 Air is added to complete combustion of C and H

Outcome: 20-60% reduction in fuel NOx

 Thermal NOx reduction and control (f(T))
Insignificant for T< 1500 K, High if T>1800 K
Zeldovich mechanism
N2 + ↔ NO + k1= 1.8× 1011 exp (-38370/T) (i)
+ O2 ↔ NO + k1= 1.8× 104 exp (-4680/T) (ii)
+ OH ↔ NO + H k1= 7.1× 107 exp (-450/T) (iii)

This is limited by rate of reaction (i) =f (T) so a small +ΔT =↑ +NOx

To limit thermal NOx, limit flame temperature. So dilute air-fuel mixture with an
inert compound

(1) Air (φ<1) (2) Recycled and cooled exhaust gas from the flue (3) Add
steam or water
 Particulate Matter
Classification of particles generated in combustion
Type Description
Ash Incombustible material in fuel (Metals, Al, Ca,
Fe, Si, Ti, Zn, Mg, K)
Soot Carbonaceous particles formed by pyrolysis
(Combustion in the lack/ absence of O2) due to
incomplete combustion
Char Unburnt, Carbonaceous, non volatile material
in pulverized coal that burns slowly than
volatile
Coke Large (1-50 µm), porous carbonaceous shells
formed from the spray droplets of fuel oil
Acid droplets Originally from S in fuel and produced by a
gas to particle conversion involves H2SO4+H20
in the exhaust