Combustion

Numerical Design of Thermal Systems

M. Masoero

Dipartimento Energia

1
 Definition of Com bustion

• Combustion is a process involving exothermic

REDOX reactions with a high activation energy
• FUELS:
– Hydrocarbons (CnHm) of fossil or biological origin
– Phosphor, sulphur, magnesium, boron, aluminum,
ammonia, hydrazine, ….
• OXIDIZERS:
– Oxygen (air)
– Halogens (chloride, fluorine, ….)

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 Flam m ability and I gnition lim its

• For combustion to take place, defined fuel/oxidizer ratio

and temperature conditions are required.
• The autoignition temperature of a substance is the
lowest temperature at which it will spontaneously ignite
in a normal atmosphere without an external source of
ignition, such as a flame or spark. This temperature is
required to supply the activation energy needed for
combustion.
• The flammability temperature is the minimum value at
which a liquid or solid fuel develops enough vapors to
form a flammable gaseous mixture (combustion, in fact,
always occurs in the gas phase)

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 Flam m ability and I gnition lim its

Lower limit Upper limit

Pure Air Pure Fuel

0% 100%

Excess air Incomplete

combustion combustion

Stoichiometric combustion

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 Flam m ability lim its in Air

Fuel
gas
formula
formula ignition
temp. accens. lowerinferiore
Lim. flamm. upper
Lim. flamm.
superiore
temp.°C
(°C) limit
infiammabilità
limit
infiammabilità

METANO CH4 537 5 15

PROPANO C3 H8 504 2,1 9,5
BUTANO C4H10 431 1,5 8,5
ETANO C2 H6 470 2,9 12,5
ETILENE C2 H4 425 2,7 34
PROPILENE C3 H6 460 2 11,7
IDROGENO H2 400 4 75
MONOSSIDO DI CARBONIO CO 605 12,5 74
ACETILENE C2 H2 310 1,5 80,5

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 Com bustion of Hydrocarbons C x H y

General chemical formula of a hydrocarbon (HC)

 y y
C x H y +  x +  ⋅ O 2 ⇒ x ⋅ CO 2 + ⋅ H 2 O
 4 2

• The number of CO2 molecules depends on

the number x of carbon atoms (C).
• The number of H2O molecules depends on
the number y of hydrogen atoms (H)

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 Stoichiom etric m ethane-ox ygen com bustion

• The formula fulfils the law of mass conservation: the total

mass of combustion products is equal to the sum of the
masses of fuel and oxidizer:
16 mol (CH4) + 64 mol (O2) → 44 mol (CO2) + 36 mol (H2O)
• Molecule composition is modified, but individual atoms
are preserved

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 Air com position

AIR: 21% O2
79% N2

To provide 1 m3 of O2
to a combustion process
N2 1/0.21 = 4.76 m3 of air
are needed

O2

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Stoichiom etric com bustion of m ethane in air

air dry fumes

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Com bustion of m ethane in air w ith 30% excess air

air dry fumes

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 M ain characteristics of Fuels

• Chemical composition
• Physical properties (density, viscosity, ….)
• Lower Heating Value (LHV), Hi
• Higher Heating Value (HHV), Hs
• Stoichiometric Air/Fuel ratio (A/F)st, αst
• Theoretical Combustion Temperature (TCT)

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 Properties of som e gaseous hydrocarbons
• Avogadro’s Law:
1 kmol of gas → 22.4 m3 @ 1013 mbar, 273 K
• Methane (CH4)
– 1kmol = 16 kg → ρ (CH4) = 16/22.4 = 0.71 kg/m3
– ρ(CH4)/ ρ(air) = 0.71/1.29 = 0.55
– Hi = 35.88 MJ/m3 lighter than air!
• Propane (C3H8) [psat = 7 bar]
– 1kmol = 44 kg → ρ (C3H8) = 44/22.4 = 1.96 kg/m3
– ρ(C3H8)/ ρ(air) = 1.96/1.29 = 1.52
– Hi = 46.37 MJ/m3 heavier than air!
• Butane (C4H10) [psat = 2 bar]
– 1kmol = 58 kg → ρ (C4H10) = 58/22.4 = 2.59 kg/m3
– ρ(C4H10)/ ρ(air) = 2.59/1.29 = 2.01
– Hi = 46.37 MJ/m3

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 Properties of liquid fuels
Fuel oils
• Hi ≈ 40 MJ/kg
• Mass fraction of carbon ≈ 86%
• Mass fraction of sulphur
– < 0.2% (light fuel oil)
– 0.3-3% (heavy fuel oil)
• Viscosity of heavy oils > 9•10-6 m2/s @50°C (>12°E)
• Spray formation in oil burners → oil viscosity < 2°E
(achieved at ≈110°C)

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 Properties of solid fuels

Coal
• Hi ≈ 30 MJ/kg
• Mass fraction of carbon ≈ 86-92%
• Mass fraction of sulphur should be < 1%
• Moisture content: 2-3%
• Ashes: 5-10%
Wood
• Hi ≈ 17 MJ/kg (dry)
• Mass fractions: C ≈ 50%; O ≈ 40%; H ≈ 6%
• Mass fraction of sulphur should be < 1%
• Moisture content: 15-50%

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 Heating Value – Dry Fuels

• Simplified formulas for dry fuels

 O  MJ 
H s = 0.338 C + 1.42 H −  + 0.104 S  
 8  kg 
• C, H, O, S = mass fraction of carbon, hydrogen,..

H i = H s − 0.09 ⋅ r ⋅ H
• r = vaporisation enthalpy of water = 2.5 MJ/kg
• Reference values:
– p = 1013 mbar
– T = 25°C (liquid / solid fuels); T = 15°C (gaseous fuels)

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 Energy content of M oist Fuels

• Energy content of moist fuels:

H i (100 − U )
H=
100 − 0.025 ⋅U
Where:
Hi = LHV of the dry fuel
U = moisture content of the fuel (as it is)
M moist − M dry
U= 100
M moist

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 Stoichiom etric Air/ Fuel R atio

 y
 1 + 0 . 25 (32 + 3.773 ⋅ 28.16 ) Standard composition (dry air)
(A F)st =  x
y • O2: 21% (volume); 23.2% (mass)
12.011 + 1.008 • N2: 79% (volume); 76.8% (mass)
x

• Benzene
• Gasoline, Diesel
• Methane

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 Stoichiom etric Air/ Fuel R atio

• Alternatively, for a fuel of known mass

composition, the air mass required for complete
oxidation of 1 kg of fuel is:

32  C H S O
M air ,st =  + + − 
23.2  12.011 4 ⋅1.008 32.065 32 

• where C, H, O, S are mass fractions

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 Air I ndex and Ex cess Air

• Actual combustion processes often involve air

quantities different from stoichiometric.
• Air Index (used in I.C. engines):

λ=
(A F) λ < 1 fuel rich mixture
λ = 1 stoichiometric mixture
(A F)st λ>1 fuel lean mixture
• Excess air (used in steady flow systems)
M air − M air , st Va V fumes (CO 2 )st
Eair = ⋅100 (%) λ = = =
M air , st Va , st V fumes , st (CO 2 )
21%
Eair = (λ − 1) ⋅ 100 (% ) λ= measured
21% − (O 2 ) value

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 Theoretical com bustion (flam e) tem perature

• Steady flow (constant pressure) process

(adiabatic, no dissociation)
1 H i, p
TCT p = T0 +
c p [1 + (A/F)]
• Constant volume process
1 H i ,v
TCTv = T0 +
cv [1 + (A/F)]
• The maximum temperature value is achieved when
(A/F) = (A/F)st
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 P ollutant form ation in com bustion

Primary pollutants
• Unburnt hydrocarbons HC
• Nitrogen oxydes NOx
• Sulphur oxydes SOx
• Carbon particulate matter PM (e.g. PM10 → d ≤10 μm)
• Flying ashes
Secondary pollutants
• “acid rain”
• photochemical smog

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