Lecture-2: Basics of Combustion Engineering

Mass and Energy Balance

Contents of this lecture
2.1 General Formulation of Mass and Energy Balance
2.2 The First Law of Thermodynamics
2.3 Example of Mass Balance of a Furnace
2.4 Energy Released in Chemical Reactions
2.5 Example of Energy Balance of a Furnace
2.6 Temperature of Adiabatic Combustion
2.7 Furnace Exit Temperature
1

2.1 General Formulation of Mass and Energy Balance

First identify a control volume

m
in , E
in

m
o u t , E
o u t
m
g , E
g

stored , E
stored
m
control volume

Then, specify a time basis

Balance at an instant
Balance over a time interval
2

Mass Balance at an Instant

m
in

m
out
m
g
m
stored
control volume

=0

m
in + m
g m
out = m
stored
m
in m
out

d ( m)

dt

d ( m)
=
dt

We balance rates in kg/s

3

Energy Balance at an Instant

E
in

E
o u t
E

E
stored
control volume

d (E )








Ein + E g E out = E st
dt
We balance rates in J/s
4

Mass and Energy Balance over

a Time Interval t = t 2 t1
t2

m

t1

t2

in

dt m
out
t1

t2

d (m)
dt =
dt = m
dt
t1

min mout = m We balance amounts in kg

t2

t2

t2

t2

d ( E)






t Ein dt + t E g dt t Eout dt = t dt dt = E
1
1
1
1

Ein + E g E out = E
We balance amounts in J
5

Mass and Energy Balance

under Steady-State Conditions

m
in = m
out
E
in + E
g = E
out

2.2 The First Law of Thermodynamics

The first law of thermodynamic is

the overall energy balance that is
extended into all possible forms
of energy.

Systems Considered

control volume

control volume

control volume

An Open System with E
g = 0

Energy Balances

control volume

over a time interval

Ein = E out + E
at an instant
d (E)




E in E out =
dt

dEin = dEout + dE
9

An Open System with E
g = 0

Control volume
E in

E out

Ein = E out + E
10

The First Law of Thermodynamics

An Isolated System

E in = 0
so

and

E out = 0

E = 0

the sum of all energies is constant

in an isolated system
A system operated in a steady-state
E
in = E
out

it is not possible to construct

a perpetuum mobile of the first kind
11

2.2.1 System Energy

2

w2

control volume

1
w1

Center of gravity

z2

control volume

z1

Center of gravity

Reference level (height)

z=0

2
w2
E =U + m
+I
+ m g z
2
2
m
I
2
2
E = U 2 U 1 + ( w2 w1 ) + ( 22 12 ) + m g ( z 2 z1 )
2
2
12

Internal Energy
U = m u (T , p ) = m u (T , v) = m u ( p, v )

dU = d (m u ) = m du + u dm

Specific internal energy (J/kg)

u
u
du =
dT +
dv
T v
v T

p
du = cv dT + (T
p) dv
T v
13

It is not possible to calculate

an absolute value of internal energy
T ,v

u (T , v) = u 0 +

du

T0 ,v0

Instead specifying uo,

the reference enthalpy (h0) is specified
u 0 = h0 p 0 v0
v0 = v(T0 , p 0 )

Equation of state
14

Specific Internal Energy of an Ideal Gas

R T
v=
Mp
R T0
R
u 0 = 0 p0
= T0
M p0
M
p
T
T

R
=
vM
T

R
u (T ) = u 0 + cv (T ) dT = T0 + cv (T ) dT
M
T0
T0
15

The Change of Internal Energy

Ein = E out + E

m
I
2
2
E = U 2 U1 + (w2 w1 ) + (22 12 ) + m g ( z 2 z1 )
2
2
E

R
u (T ) = u 0 + cv (T ) dT = T0 + cv (T ) dT
M
T0
T0

can be calculated

How to calculate

Ein Eout

?
16

Energy Entering and Leaving the System

Ein = Eout + E

Ein Eout

(a) Energy of a stream of fluid

(b) Mechanical work
(c) Heat
(d) Electrical energy

17

Energy of a stream of fluid

Explain why enthalpy is the stream energy

i = u + pv

H = mh

Is enthalpy a state variable ? If so, why?

h
dh =
T

h
dT +
dp
p T
p

18

Energy of a stream of fluid

h
dh =
T

h
dh =
T

h
dT +
dp
p T
p

dT + v T

dp

=0 for an ideal gas

T

h(T ) = h0 + c p (T ) dT
T0

h0=0 for T0=198.15 K

p0=1 bar
19

Mechanical Work
Work is done when an object
is moved against an opposing force
Work is not energy.
Work is means of transmitting energy.
Convention:

control volume

L >0

control volume

L<0
20

Mechanical Work

dL = p dV

p
p1

L = p dV

p2

L12

V1

V2

Is work a state variable?

21

Heat
Heat is energy in transit
due to a temperature difference
Heat is not work. Why?
Convention:
heat supplied to the system is positive
heat removed from the system is negative

Qt = Q + Q f
Total heat absorbed
by the system

Heat generated within

the system due to friction

Heat supplied from

the surroundings
22

Specific heat capacities

dqt
c=
dT

c - denotes specific heat in J/kgK

C - denotes specific heat in J/kmolK

C p Cv = R

number of degrees of freedom

Cv =
R
2

23

Specific heat capacities

JANAF polynomials

Cp
R

= C p ,1 + C p , 2 T + C p ,3 T + C p , 4 T + C p ,5 T
2

Cp in kJ/kmolK

24

8
7
CO2

H2O

Cp/R

N2

CO

O2

H2
O

9/2
Vibrational motions
7/2

Rotational motions
5/2

Translational motions

1
0

500

1000

1500

2000

2500

3000

Temperature in K
25

160000

H(T)-H(298) in kJ/kmol

140000
120000

O2

100000
80000

CO2

Air

H2O

60000

CH4

CO

N2

H2

40000

H,O,N

20000
0

500

1000

1500

2000

2500

3000

Temperature in K
26

Mean Specific Heat Capacities

T

C0

T2

CT

1
= C (T ' ) dT '
T 0
T2

1
'
'
=
C (T ) dT
T2 T1 T1

27

Energy Balance of Thermal Systems (Machines)

dEin dE out = dE
dQt + dL = dU
dQt p dV = dU
control volume

m dq t p d (m v) = d (m u )
dq t p dv = du
28

Energy Balance of Thermal Systems (Machines)

dEin dE out = dE

control volume

dU = dQt p dV + h dm
d (m u) = m dqt p d (m v) + (u + p v) dm
du = dqt p dv
29

Energy Balance of Thermal Systems (Machines)

For any system:

du = dqt p dv

dh = dqt + v dp

dh = dqt

for p=constant

du = dq c

for v=constant

30

J. Warnatz, U. Mass; R. Dibble

Technische Verbrennung
Springer

Ldecke, Ldecke
Thermodynamik
Springer ISBN 3-540-66805-5

31

Mass balance in combustion

Change of
mass with
time (kg/s)

Mass input
kg/s

Mass output
kg/s

d(mass)
= m
input m
output
dt
For a steady state:

m
input = m
output
32

The purpose of making a mass balance is :

(a)

to calculate the accumulation of mass (if any)

(b)

to calculate the out-coming streams

(c)

to calculate composition (make up) of

the outcoming streams

The atoms are conserved (neither created nor

destroyed) and the flow rates in kg/s balance
Molecules are not conserved and the flow rates
in kmol/s may or may not balance
A correct mass balance is a prerequisite to
a subsequent energy balance
33

Example2.1. The task make a mass balance

200 kg/h CH4
BOILER

Combustion products

4000 kg/h air

Mass balance in kmol/h (Chemical Engineering Approach)

CH4 + 2 O2 = CO2 + 2 H2O

Input:
CH4
12.5 kmol/h
N2
109.57 kmol/h
O2
29.13 kmol/h

= 151.20 kmol/h

Output (wet):
CO2
12.5 kmol/h
H2O
25
kmol/h
N2
109.57 kmol/h
O2
4.13 kmol/h

= 1.165
?
why

= 151.20 kmol/h
34

Table 2.2 Composition of the combustion products

Molar fraction

Mass fraction

Species
Wet

Dry

Wet

Dry

Carbon dioxide

0.0827

0.099

0.131

0.1466

Water vapour

0.1653

0.1071

Nitrogen

0.7246

0.8682

0.7304

0.8182

Oxygen

0.0273

0.0327

0.0315

0.0352

0.9999

0.9999

1.0000

1.0000

Establising composition of the out-coming streams is an

integral part of any mass balance

35

Exercise 2.1. The task make a mass balance

200 kg/h CH4
BOILER
Combustion products

4000 kg/h air

Mass balance in kg/h (Combustion Engineering Approach)

CH4 + 2 O2 = CO2 + 2 H2O

16 kg CH4 + 64 kg O2 = 44 kg CO2 + 36 kg H2O
Input:
CH4
200
N2
3,068
O2
932

= 4, 20 0

kg/h
kg/h
kg/h

kg/h

= 1 . 165

Output (wet):
CO2
550 kg/h
H2O
450 kg/h
N2
3,068 kg/h
O2
132 kg/h

= 4, 20 0

kg/h
36

2.3 Reaction Enthalpy (enthalpy of a chemical reaction)

1 A1 + 2 A2 + ........... + n An = 0
n

or

A = 0
i

n =1

The change of the enthalpy in a chemical reaction is called reaction

enthalpy and it is calculated as:

R H temperature = i H i
pressure

To calculate Hi a reference state of zero enthalpy is needed.

The pure elements in their most stable state at T=298.15 K and
p=1 bar are prescribed zero enthalpy.
The pure elements are: O2, N2, H2, C (graphite)
37

2.4 Standard Enthalpies of Formation

The concept of the standard enthalpy of formation is to measure
enthalpy of any chemical compound
n pure
elements

Chemical reactor operated

at: p=1 bar, T=298.15 K

f H

1 mol of
the compound

0
298.15

The standard enthalpy of formation of a compound is the reaction enthalpy

of its formation reaction from the pure elements in their most stable state
at the temperature T=298.15 K and the pressure p=1bar (indicated by 0)

Note: If the enthalpy of formation of a compound is positive heat

has to be supplied to form the compound and the formation
reaction is endothermic.
38

Standard enthalpies of formation of some compounds (JANAF Tables)

0

f H 298.15 (kJ/mol)

0
S 298

Compound

Aggregation state

(J/mol K)

Oxygen

O2(g)

205.04

Hydrogen

H2(g)

130.57

Nitrogen

N2(g)

191.50

Carbon

C(s,graphite)

5.74

Oxygen atoms

O(g)

249.2

160.95

Hydrogen atoms

H(g)

218.0

114.6

Water vapour

H2O (g)

-241.81

188.72

Water

H2O (l)

-285.83

69.95

Hydroxyl radicals

OH(g)

39.3

183.6

Nitrogen atoms

N(g)

472.68

153.19

Diamond

C(s,diamond)

1.9

2.38

Carbon

C(g)

716.6

157.99

Carbon monoxide

CO(g)

-110.53

197.6

Carbon dioxide

CO2(g)

-393.5

213.7

Methane

CH4(g)

-74.85

186.10

Ethane

C2H6(g)

-84.68

229.49

Propane

C3H8(g)

-103.85

269.91

Ethylen

C2H4(g)

52.10

219.45

Benzene

C6H6(g)

82.93

269.20

Ethanol

C2H5OH(g)

-235.31

282.00

39

Indirect determination of the enthalpy of formation (Hess law)

Since enthalpy is a state function it can be determined using reaction
enthalpy of oxidation reactions that are relatively easy to measure.
Task determine the enthalpy of formation of pure methane knowing
the reaction enthalpies of other oxidation reactions.

CH 4 H

C + 2 H2 = CH4

0
298.15
0
298

(1)

C(s, graphite) + O2 = CO2

R1 H

= 393.5

(2)

H2(g)

R 2 H 298 = 241.81 kJ/mol

kJ/mol

+ 0.5 O2 = H2O

R 3 H 298 = 802.25 kJ/mol

(3)
CO2 + 2 H2O = CH4 + 2 O2
__________________________________________________________________

(1)+2(2)+(3)

C+O2+2H2+O2+CO2+2H2O = CO2+2H2O+CH4+2O2
C + 2 H2 = CH4

CH 4 H

0
298.15

= R1 H

0
298

+ 2R2 H

0
298

+ R3 H

0
298

= 393.5 + 2 (241.81) + 802.25 = 74.87 kJ/mol of CH 4

40

2.5 Lower Calorific Value (LCV) and Gross Calorific Value (GCV)
H2 + 0.5 O2 = H2O (liquid) + 285,830.00 kJ/kmol of H2
GCV (Brennwert)
H2 + 0.5 O2 = H2O (gas) + 241,900.00 kJ/kmol of H2
LCV (Heizwert)

The definition of LCV

unit of fuel
Combustion chamber
p=1 bar
oxidizer (oxygen or air)
Temperature T1

Products of complete
combustion; H2O (g)

LCV

Temperature T2

T1=T2 (usually 0 C, 20C or 25 C)

41

2.6 What is the relationship between LCV and the reaction enthalpy ?

Example:
H2 +0.5 O2 = H2O (g)

(p=1 bar, T=298.15 K)

The reaction enthalpy is:

R = i H i = H

0
H 20 , 298.15

0
H 2 , 298.15

0.5H

0
O 2 , 298.15

= -241.81 kJ/mol

but LCV of H2 is 241.81 kJ/mol

0
LCV298
.15 = R H =

H
i

For oxidation reaction written

for 1 mol of fuel,
water in gas phase

42

Table 2.5 LCV of some selected fuels (p=1 bar, T=298.15 K)

Fuel
Hydrogen
Carbon oxide
Methane
Ethane
Propane
Butane
Pentane
Ethylene
Propylene
Butylene
Acetylene

Formula
H2
CO
CH4
C2H6
C3H8
C4H10
C5H12
C2H4
C3H6
C4H8
C2H2

Molar mass
g/mol
2.016
28.01
16.03
30.05
44.06
58.08
72.15
28.03
42.05
56.06
26.06

kJ/mol
241.9
283.0
802.5
1,428.0
2,044.1
2,658.5
3,272.9
1,323.1
1,926.0
2,542.8
1,255.9

LCV
kJ/mn3
10,792
12,625
35,805
63,707
91,193
11,860.4
146,014
59,027
8,595.1
113,442
56,029

kJ/kg
119,990
10,104
50,062
47,521
46,394
45,773
45,362
47,203
45,817
45,359
48,123

43

Calculate LCV of methane using values

of the formation enthalpies.
CH4 + 2 O2 CO2 + 2 H2O (g)
-CH4 - 2 O2 + CO2 + 2 H2O (g) = 0

R H = i H i = (1) H CH 4 + ( 2) H O 2 +
i

+ (1) H CO 2 + (2) H H 2 O =

(1) (74.85) + (2) (0) + (393.5) +

2 (241.81) = 802.27kJ
0
298.15

LCV

= 802.27 = 802.27 kJ/mol CH 4

44

2.7 Dependence of LCV on temperature

1 fuel 2O2 + 3CO2 + 4 H 2O = 0

R H T = ?
0

-------------------------------------------------------------------------------------------------------i =4

R H T = i H i
0

i =1

i =4

(H

T
298.15

i =4

i =1

+ i H i0, 298.15 +
i =1

R H T = R H
0

p ,i

dT ) =

298.15

C
i =1

p ,i

dT

298.15

0
298.15

i =4

+ i
i =1

p ,i

dT

298.15

45

Integral
forms

LCV

0
T

LCV T = LCV

= LCV

0
298.15

i =4

0
298.15

i
i =1

C
i

p ,i

p ,i

dT

298.15

reactants
i =1

dT

298.15

products

C
k =1

p ,i

dT

298.15

Kirchhoff law
Differential
forms

i =4
d ( LCV )
= i C p ,i
dT
i =1

products
d ( LCV ) reactants
= i C p ,i i C p , k
dT
i =1
k =1
46

Calculate LCV of methane at T= 1298.15 K. (gases are ideal)

-CH4- 2 O2+CO2+2 H20 = 0
0
298.15

LCV

= 802.5 kJ/mol

LCV T = LCV
0

with T=1298.15 K
and for CH4, CO2, H2O
and for O2

0
298.15

=?

0
1298.15

LCV
i=4

i
i =1

p ,i

dT

298.15

cp=33.3 kJ/kmol K
cp=29.1 kJ/kmol K

0
3
LCV1298
=
802
.
5

1
)

33
.
3

10
(1298.15 298.15)
.15

(2) 29.1 103 1000 1 33.3 103 1000

3

2 33.3 10 1000 = 802.5 8.4 = 794.1kJ / mol

47

Energy Balance of a Furnace

when p= const (dh=dqc)
L=0
(most of furnace and process applications)

H
in = H
out + Q

Hin

Hout
Furnace p=const
Heat sink

48

Energy Balance (cont)

H
in = H
out + Q

In order to calculate Hin and Hout both the amount and composition
of the incoming and out-coming streams have to be known.
These are obtained from a mass balance
in _ species

n
i ( H

f ,i

T in

p ,i

Chemical Engineering
Approach

dT ) =

298 . 15
out _ species

n
k ( H

f ,k

T in

p ,k

dT ) +Q

298 . 15

where
ni

is in

kmol/s

H f ,i

is in

kJ/kmol

Cp,i

is in

kJ/kmol K
49

Energy Balance (cont)

H
in = H
out + Q

m

fuel

T in

( LCV +

p , fuel

dT ) + m
oxidiser

298 . 15

all _ products

T in

p , oxidiser

dT =

298 . 15

m
k

Tout

c p ,k dT

Combustion
Engineering
Approach

+ Q

298.15

where
mfuel

is in

kg/s

LCV

is in

kJ/kg

cp,i

is in

kJ/kg K

50

Example 2.4
Make the energy balance of the boiler in exercise 2.1 knowing
that 2 MW of heat is extracted by the water tube wall (heat sink).
Calculate Tout (Tin = 298.15 K).
200 kg/h CH4
BOILER
4000 kg/h air

Since the gases are ideal:

for O2 and N2
for CH4, CO2, H2O

Combustion products

Cp=29.1 kJ/kmol K
Cp=33.3 kJ/kmol K

To do:
Energy balance
Calculate Tout
Calculate efficiency of the boiler
51

Energy balance using enthalpies of formation

200 kg/h CH4
BOILER
Combustion products

Heat sink

4000 kg/h air

INPUTS

Q=2 MW
298.15

CH4

12.5 ( 74.85 10 3 +
298 . 15

N2

109 . 57 (

33.3dT ) / 3600 = 259.9

kJ/s

298.15

29 . 1dT ) / 3600

=0

kJ/s

298 . 15
298.15

O2

29.13 (

29.1dT ) / 3600 = 0

kJ/s

298.15

TOTAL INPUTS

-259.9 kJ/s
52

Energy balance using enthalpies of formation (cont.)

200 kg/h CH4
BOILER
4000 kg/h air

Combustion products

Heat sink

OUTPUTS

Q=2 MW
CO2

12.5(-393.5x103+33.3x(Tout-298.15))/3600 = -1,366.32 + 0.11563 (Tout-298.15)

H2O
25(-241.81x103+33.3x(Tout-298.15))/3600 = - 1,679.24 + 0.23125(Tout-298.15)

N2
109.57(

29.1x(Tout-298.15))/3600

0.8856 (Tout-298.15)

=
= 2,000.00

0.0334 (Tout-298.15)

O2
4.13(
29.1x(Tout-298.15))/3600
Heat extracted (Q)

TOTAL OUTPUTS

-1,045.56 + 1.2659 (Tout-298.15)

53

Energy balance using enthalpies of formation (cont.)

-259.9 = -1,045.56 + 1.2659 (Tout-298.15)

and Tout = 918.81 K

What is the thermal input into the boiler?

Physical enthalpy
Chemical enthalpy

0
kJ/s
-(-1,366.32-1,679.24-(259.9)) = 2,785.66 kJ/s

TOTAL ENTHALPY

= 2.786 MW

and Hout = 2.786 2 = 0.786 MW

BOILER

Heat sink

2.786 MW
Chemical Enthalpy
of CH4

Q=2 MW

Nil Physical Enthalpy

Tin=298.15 K

2
=
= 0.72
2.786

0.786 MW
Physical Enthalpy
of Combustion
Products
Tout=918.81 K
54

Energy balance using LCV

200 kg/h CH4
BOILER
Combustion products

Heat sink

4000 kg/h air

Q=2 MW

INPUTS

298 . 15

CH4

200 (50 , 062 +

33 .3dT / 16 ) / 3600

= 2 ,781 .2 2

kJ/s

298 . 15

298.15

N2

39,068(

29.1dT / 28) / 3600 = 0

kJ/s

298.15
298.15

O2

932(

29.1dT / 32) / 3600 = 0

kJ/s

298.15

TOTAL INPUTS

2,781.22

kJ/s
55

Energy balance using LCV (cont.)

200 kg/h CH4
BOILER
4000 kg/h air

Combustion products

Heat sink

OUTPUTS

Q=2 MW

CO2
550(33.3(Tout-298.15)/44/3600
H2O
450 (33.3 (Tout-298.15)/18/3600 )
N2
3,068(29.1(Tout-298.15)/28/3600
O2
132(29.1(Tout-298.15)/32/3600
Heat extracted
TOTAL OUTPUTS

0.11563 (Tout-298.15)

0.23125 (Tout-298.15)

0.8856 (Tout-2898.15)

=
=

0.0334(Tout-298.15)
2,000.00

2,000.00 + 1.2659 (Tout-298.15)

56

Energy balance using LCV (cont.)

200 kg/h CH4
BOILER
Combustion products

Heat sink

4000 kg/h air

Q=2 MW

INPUTS

2,781.22

OUTPUTS
=

2,000.00

1.2659 (Tout 298.15)

Tout = 915.28 K

2
Efficiency =
= 0.72
2.78
57

Adiabatic combustion temperature

For adiabatic combustion Q=0

m
fuel ( LCV +

Tin

p , fuel

Tin

dT ) + m
oxidiser

298.15

= ( m
fuel + m
oxidiser )

p , oxidiser

dT

298.15
Tout

p , products

dT

298.15

One may calculate Tout for any excess air ratio

Thus, Tout is uniquely defined for any fuel and excess air ratio

58

Adiabatic combustion temperature (cont.)

=1

For stoichiometric combustion

m
oxidiser = lair , max m
fuel

and

LCV +

T in

p , fuel

dT + l air

, min

298 . 15

= (1 + lair ,min )

T in

p , air

dT

298 . 15
Tad

p , products

dT

298.15

Tad
Tad

is a maximum temperature obtainable from combustion of the fuel

is uniquely determined for any fuel (it is a fuel property)
59

Adiabatic combustion temperature (cont.)

Adiabatic combustion temperature for stoichiometric
combustion in air (Tin=298.15 K, p= 1bar).
H2

2,473 K

CH4

2,285 K

C2H2 2,936 K

C2H6 2,357 K

C3H8 2,400 K

CO

2,624 K

Assumption:
CO2 and H2O are the only combustion products
60

2.11 Furnace exit temperature

Hin
Hout
Furnace p=const
Heat sink
Energy balance:

Tin , fuel

m
fuel ( LCV +

p , fuel

dT ) + lmin,air m fuel

Tin ,air

p , air

dT =

298

298

Tout

(m
fuel + lmin,air m
fuel ) c p , products dT + Q

Tout is furnace exit temperature

298

61

2.11 Furnace exit temperature (cont)

Definition of a new variable TTI
TTI TOTAL THERMAL INPUT
FUEL THERMAL INPUT

TTI = m
fuel LCV +

Tin , fuel

(m
fuel

c
dT
+

l
m
,
,
min
p
fuel
air
fuel

298

Tin ,air

p , air

dT )

298

PHYSICAL ENTHALPY (PREHEAT)

62

2.11 Furnace exit temperature (cont)

Tout

Q

= 1
TTI

(1 + lair ,min ) c p , products dT

298

Tin , fuel

LCV +

Tin ,air

c p , fuel dT +

298

c
dT
p
air
,

298

Q

= f ( , Tout )
TTI

0
if Q

Tout Tad

63

Exercise 2.4.
Generate a graph showing the relationship Q/TTI as a function of
excess air and furnace exit temperature for combustion of methane
Assume:
Tin,fuel=298 K, Tin,air=298 K and LCV = 50,062 kJ/kg of CH4

Tout

Q

= 1
LCV

(1 + lmin,air ) c p , products dT
298

LCV
64

Exercise 2.4 (cont)

16 kg CH4 + 64 kg O2 = 44 kg CO2 + 36 kg H2O
lmin,air = 64/16/0.233=17.1674 kg of air/kg of CH4
Composition of combustion products:

wCO2
wH2O
wN2
wO2

=
=
=
=

cp, products= wCO2

2.75/(1+17.1675 )
2.25/(1=17.1675 )
13.1675 /(1+17.1675 )
4( 1)/(1+17.1675 )

cp,CO2
44

+ wH2O

cp,H2O
18

+ wN2

cp, N2
28

+ wO2

cp,O2
32
65

Exercise 2.4 (cont)

Assumption: cps are constant (independent of temperature)

for CO2, H2O
for O2,N2

Tout

p , products

Cp=33.3 kJ/kmol K
Cp=29.1 kJ/kmol K

dT =

298

33.3
33.3
29.1
29.1
( wCO 2
+ wH 2O
+ wN 2
+ wO 2
) (Tout 298)
44
18
28
32
66

1.0
Combustion of pure CH4
constant cp values

0.8
=1.0

Q/TTI

0.6

=1.05
=1.1

0.4

0.2

0.0

=3.0

=1.15
=1.2

Tin=298 K

=1.3

=2.0
=1.5

500

1000

1500

2000

Furnace exit temperature in K

2500

3000
67

Exercise 2.4 (cont)

Assumption: cps are calculated using JANAF polynomials
Tout

p , products

dT =

298

wi
1
2
2
R
(
(
298
)
C
T

+
C
2
(
T

298
)+
pi ,1 out

pi ,
out
Mi
2
product _ species

1
1
3
3
4
4
+ C pi ,3 (Tout 298 ) + C pi , 4 (Tout 298 ) +
4
3
1
5
+ C pi , 5 (Tout
298 5 ) }
5

68

1.0
Combustion of pure CH4
0.8
=1.0

=1.05

0.6

Q/TTI

cp values from JANAF polynomials

=1.1
=1.15

0.4
=3.0

=1.2

0.2
Tin=298 K

=1.3

=2.0
=1.5

0.0
500

1000

1500

2000

Furnace exit temperature in K

2500

3000
69

Exercise 2.4 (cont)

Adiabatic temperature for stoichiometric oxidation

of CH4 in air (Tin = 298) have been calculated as:

constant cp values

Tad

2,810 K

cp from JANAF polynomials

2,285 K

70

1.0

Combustion of various gaseous fuels in air

0.8

Groningen Natural Gas

=1.0

Q/LCV

0.6

=1.1

0.4

=1.0

Coke Oven Gas

=1.0

Blast Furnace Gas

0.2

Tin= 298 K

=1.1

=1.1

0.0

500

1000

1500

2000

Furnace exit temperature in K

2500

3000
71

A BLAST FURNACE

72

73

74

SMELTING of IRON ORE

Reducing agent
Iron ore
Fe2O3 (Hematite)
Fe3O4 (Magnetite)

CO

A chemical reactor
BLAST FURNACE

Pig Iron
Fe

S
M
E
L
T
I
N
G

75

REMOVAL OF OXYGEN FROM IRON OXIDES

2 Fe2O3 + CO = CO2 + 2 Fe3O4

Begins at 450 C

Fe3O4 + CO = CO2 + 3 FeO

Begins at 600 C

FeO + CO = CO2 + Fe

Begins at 700 C

Production of CO and heat

C + O2 = CO2
CO2 + C =2 CO

76

REMOVAL OF SULPHUR FROM IRON OXIDES

Pyrites
FeS, FeS2

Reactions:

Limestone CaCO3
is added to remove S

Pig Iron
Fe

CaCO3 = CaO + CO2

FeS + CaO + C = CaS + FeO + CO

77

BLAST FURNACE
incoming and out-coming streams

INCOMING
Iron ore (0.5 1.5 )
Pellets (lower iron content ore)
Sinter (fine ore, small coke, fine limestone)
Coke
Limestone (flux)
Hot blast (hot air)
Oxygen

OUT-COMING
Pig Iron (molten)
Slag
Blast Furnace Gas

78

A TYPICAL COMPOSITION OF A PIG IRON

Iron (Fe)
Carbon (C)
Silicon (Si)

93.5 - 95 %
4.1- 4.4 %
0.30 0.90 %

Sulphur (S)

0.025 0.050 %

Manganese (Mn)

0.55 0.75 %

Titanium (Ti)

0.02 0.06 %

79

A COKE-OVEN

80

81

COAL to COKE TRANSFORMATION

Steps:
Heat is transferred into the coal charge
A plastic layer near walls is formed
(375-475 C)
Evolution of tars and aromatic
hydrocarbons
Coke stabilization phase
(600 1000 C)

82

COKE OVEN
incoming and out-coming streams

INCOMING
Blended coals
Air (reducing atmosphere)
Heat

OUT-COMING
Coke
Coke oven gas
83

A TYPICAL COMPOSITION OF A BLAST FURNCACE COKE

Carbon (C)

96-97 %

Hydrogen (H)

0.4-0.6 %

Oxygen (O)

0.5 %

Nitrogen (N)

1%

Sulphur (S)

0.9 %

84

1.0
Oil and Coals

Q/LCV

Light Oil
=1.0

0.5

=1.1
=1.1

Coal Fettnuss mvb

=1.0

=1.0

=1.1

Vietnamese Antracite
0.0
500

1000

1500

2000

Furnace exit temperature in K

2500

3000
85