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Lecture 1: Basics of Combustion Engineering

Combustion Stoichiometry
1.1

Introduction

1.2

Definitions

1.3

Combustion stoichiometry for gaseous fuels

1.4

Combustion stoichiometry for liquid and solid fuels

1.5

Combustibles burnout for solid fuels

Examples of industrial combustion systems


Boiler fired with pulverised coal
Pulverised coal flame

Examples of industrial combustion systems


Modern reheating furnace

Examples of industrial combustion systems

Flameless oxidation

1.2

Definitions

Chemical Reactions, Atoms and Molecules in Combustion

1
H 2 + O 2 H 2O
2
Hydrogen and oxygen are
reactants

Water is the product

The atoms are conserved (neither created nor destroyed)


Molecules are not conserved
Atoms relevant in combustion are: C,H,O,N,S,Cl

1.1 Definitions
Compounds of carbon and hydrogen are called hydrocarbons.
HYDROCARBONS

Aliphatic
Alkanes CnH2n+2
Alkenes CnH2n
Alkynes CnH2n-2

Alicyclic
CH2
CH2

CH2

Aromatic
Benzene
Benzene derivatives
Naphtalene

The first ten members of the unbranched-chain alkanes series are:

CH4
C2H6
C3H8
C4H10
C5H12

methane
ethane
propane
butane
pentane

C6H14
C7H16
C8H18
C9H20
C10H22

hexane
heptane
octane
nonane
decane

Table 1.1 Names of aliphatic hydrocarbons


No.of C
atoms

Alkane

Alkene

Alkyne

Alkyl
group

CH4 Methane

CH3- Methyl

C2H6 Ethane

C2H4 Ethene

C2H2 Ethyne

C2H5- Ethyl

C3H8 Propane

C3H10Propene

C3H6 Butyne

C3H7-Propyl

C4H10 Butane

C4H8 Butene

C4H6 Butyne

C4H9-Butyl

C5H12 Pentane

C5H10 Pentene

C5H8 Pentyne C5H11- Pentyl

CnH2n+2

CnH2n

CnH2n-2

CnH2n+1-

Other molecules relevant in combustion are:


Haloalkanes

R-X

CH3Cl (chloromethane)

Alcohols

R-OH

C2H5OH (ethanol)

Amines

R-NH2

CH3NH2 (methylamine)

Aldehyde

R-COH

CH3COH (ethanal)

Ketons

R-CO-R

CH3COCH3 (propanone)

Carboxylic Acid

R-COOH

CH3COOH (ethanoic acid)

Amount of substances, mole and mass fractions


1 mole contains 6.023 x 1023 particles (atoms, molecules)
For a mixture of species:

n (total number of moles) = ni


xi

ni
=
n

M mean = xi M i

Mole (volume) fractions and mass fractions:

num ber of kg of species " i"


wi =
=
total num ber o f kg in the system
ni M i
=
nk M
k

xi M i
=
xk M
k

number of moles of species "i" in 1kg of mixture


xi =
=
total number of moles in 1kg of mixture
wi / M i
=
=
1 / M m ean

wi / M i
wk / M
k

Equation of state for gases and gas mixtures

F ( p, T , c) = 0
or

F ( p, T , ) = 0
The perfect gas equation:

pV = nRT
pM m ean
=
=
RT

or

c =

p
RT

wi
Mi

p
R T

The perfect gas law:

pV = nRT

R = 8,314 J/kmol/K

Under constant pressure and temperature one mole (kmol)


of any ideal gas occupies the same volume.
At normal conditions:
p = 760 Tr (1 Tr=133,322 N/m2)
T = 273.15 K (0 C)
1 kmol of gas = 22.418 mn3
1 mol of gas = 22.418 dmn3

1.2 Combustion Stoichiometry for Gaseous Fuels


Stoichiometric Combustion
Combustion is said to be stoichiometric if fuel and oxidizer
consume each other completely forming only CO2 and H2O

CH4 + 2O2 2H2O + CO2

stoichiometric

CH 4 + 3O 2 2H 2 O + CO 2 + O 2

lean

CH4 + O2 H2O + 0.5CO2 + 0.5CH4

rich

1.3 Combustion Stoichiometry for Gaseous Fuels


Mole fraction of fuel in a stoichiometric mixture

1 kmol fuel + O 2 products (CO 2 + H 2 O)


x fuel ,stoich _in _oxygen

number of moles of fuel


=
=
total number of moles (fuel + oxygen)

1
=
1+
x fuel ,stoich _ in _ air

1
1
=
=
1 + / 0.21 1 + 4.762

For example:

CO + 0.5O2 CO2
xfuel,stoich_in_oxygen = 1/1.5=2/3
xfuel,stoich_in_air = 1/(1+0.5/0.21)=0.2958

C3H8 + 5O2 3CO2 + 4H2O


Xfuel,stoich_in_oxygen = 1/(1+5)=1/6
xfuel,stoich_in_air = 1/(1+5/0.21)=0.0403

Excess air ratio (air equivalence ratio)

( xair / x fuel )
( xair / x fuel ) stoich

Fuel equivalence ratio

( wair / w fuel )
( wair / w fuel ) stoich
1
=

>1

Stoichiometric combustion

<1
=1

Lean combustion

>1

<1

Rich combustion

Minimum oxygen requirement for a mixture of gaseous fuels


Fuel composition

Chemical reactions

H 2 + 0.5O 2 H 2 O
CO + 0.5O 2 CO 2

Molar fractions of
species are known
xH2, xCO, xCH4,
xO2, xCnHm

CH 4 + 2O 2 CO 2 + 2 H 2 O
C n H m + (n + m/4)O 2 nCO 2 + m/2H 2 O

Minimum oxygen requirement is then uniquely determined

lO2,min = 0.5x H+ 0.5xCO+2xCH4+ (n + m/4)xC H


2

lO2,min is in kmol O2/kmol fuel

x O2

Minimum air requirement for a mixture of gaseous fuels

l air,min =

l O2 ,min
0.21

= 4.7619 l O2 ,min

The excess air ratio

amount of dry air supplied per kmol of fuel


lair
=
=
minimum dry air requirement per kmol of fuel lair,min

Amount of combustion products


Fuel composition

Chemical reactions

Composition and amount (per a unit of fuel) of combustion


products are uniquely determined for a given excess air ratio
Fuel
Combustion products
CO2
H2O
N2
O2
component
H2
1
1
CO
1
2
CH4
CnHm
n
m/2
O2
1
N2
-

Vwet = x H 2+ x CO + 3x CH+ (n + m / 2)x C n H m+ x N 2 +0.79l


4

+ ( 1)l air,min

air,min

Vdry = xCO + x CH 4 + nx C H +
n m

x N 2 +0.79lair,min + ( 1) lair ,min

Composition of combustion products


Fuel composition

Chemical reactions

Composition and amount (per a unit of fuel) of combustion


products are uniquely determined for a given excess air ratio
Fuel
Combustion products
CO2
H2O
N2
O2
component
H2
1
1
CO
1
2
CH4
CnHm
n
m/2
O2
1
N2
-

Vwet = x H 2+ x CO + 3x CH+ (n + m / 2)x C n H m+ x N 2 +0.79l


4

+ ( 1)l air,min

air,min

Vdry = xCO + x CH 4 + nx C H +
n m

x N 2 +0.79lair,min

+ ( 1) lair ,min

1.3 Combustion stoichiometry for liquid and solid fuels


For solid and liquid fuels the fuel composition is usually expresses
in mass fraction (percentage)
The following applies:
c+h+s+o+n+moisture+ash =1
Coal Fettnuss mvb
4%
Carbon
82%

1%

h
n
o
H2O

c dry =

3%
1%
4%

ash 4%

c dry_ash_ free =

Coal Analysis as fired (as received)

c as_ received
1 moisture
c as_ received

1 moisture ash

Minimum oxygen and air requirements for a solid fuel


Fuel composition
Mass fractions of species are
known: c,h,s,o,n,
moisture,ash

Chemical reactions

C + O 2 CO 2

H 2 + 0.5O 2 H 2 O
S + O 2 SO 2

Minimum oxygen and air requirements are then uniquely determined

l O2 ,min

c
1 h
s
o
=
+ +

12
2 2
32 32

in kmol O2/kg of fuel

l a ir, m in =

l O 2 , m in
0 .2 1

in kmol air/kg of fuel

Amount of combustion products


Fuel composition
c,h,s,o,n,
moisture,ash

Chemical reactions

C + O 2 CO 2

H 2 + 0.5O 2 H 2 O
S + O 2 SO 2

Composition and amount (per unit of fuel) of combustion


products are uniquely determined for a given excess air ratio

Vwet =

c
h moisture
s
n
+ 0.79l air,min + ( 1)lO2 ,min
+
+
+
+
12 2
18
3 2 28

c
Vdry = 12

s
n + 0.79l
+ ( 1)lO2 ,min
+
+
air,min
3 2 28

Oxygen (%,vol,dry) content in combustion products as a function


of excess air ratio
6

Dutch Natural Gas


C2H6
O2 % vol, dry

CH4

coal Fettnuss

0
1.0

1.1

1.2

Excess air ratio

1.3

1.4

Carbon dioxide concentration (%,vol,dry) as a function of


excess air ratio
20
18

coal Fettnuss

16

C2H6

CO2 % vol, dry

14
12
10

CH4

8
6

Dutch Natural Gas

4
2
0
1.0

1.1

1.2

Excess air ratio

1.3

1.4

1.4 Combustibles burnout for solid fuels


Total combustibles = 1 - ash
Solid fuel
Combustion air

Combustion products

FURNACE

Unburned solids

Co+Ash0=1

C1+Ash1=1

mo (kg/s)

m1 (kg/s)

Question: What fraction of combustibles has been burned ?

Solid fuel

Combustion products

FURNACE
Combustion air
Co+Ash0=1

Unburned solids

mo (kg/s)

C1+Ash1=1

m1 (kg/s)

Mass balance of combustibles:


moCo = m1C1 + bmoCo
Mass balance of ash (ash is assumed to be an inert):
m0Ash0 = m1Ash1

C 1 A sh0
b = 1
C 0 A s h1

A sh0
1
A s h1
=
1 A sh0

Burnout of combustibles
100.00

Ash0=4%

99.75

Combustibles burnout in %

99.50

Ash0=8%

99.25
99.00

Ash0=12%

98.75
98.50

Ash0=16%

98.25
98.00

Ash0=20%

97.75
97.50

Ash0=30%

97.25
97.00
0

Carbon in ash in %

10