Thermodynamic Modeling of Combustion

Processes
– Applications and Limitations

Daniel Lindberg
What do you associate with
Thermodynamics?

2
 Rudolf Clausius Josiah Willard Gibbs
Ludvig Boltzmann

James Joule William Thomson, Lord James Maxwell

Kelvin
4
Gm   xi Gio  RT  xi ln xi   xi x j  ij
i i i j i

𝜇𝑖= 𝜇𝑖𝑜 + 𝑅𝑇 ln 𝑎𝑖

900

800
Liquid

T / °C
700 Liquid + Liquid +
NaCl(s) Na2SO4(s)

600
NaCl(s) + Na2SO4(s)

500
0 20 40 60 80 100
mol-% Na2SO4

5
 What is thermodynamics?
• Thermodynamics: Science of the relationship between
different types of energy, especially between heat and
mechanical energy and of the conversion of either into
the other.

• Chemical thermodynamics: In thermodynamics, the

study of the interrelation of heat and work with chemical
reactions or with a physical change of state
 Relationships among fields of study
Organizational state
Viewpoint Fields of study
of a system
Energetics Equilibrium thermodynamics Equilibrium state
(thermodynamics)
Irreversible/nonequilibrium Steady state
Macroscopic thermodynamics Transient state

Fluid dynamics

Microscopic Kinetics Statistical

mechanics/thermodynamics

Ultramicroscopic Quantum mechanics

Geochemical thermodynamics, 2nd edition, Darrell Nordstrom & James Munoz

7
Why is chemical thermodynamics relevant for high-T
industrial processes?
• Basis for energy balances in the furnace
related to chemical reactions
• Higher temperaturefaster
reactionschemical equilibrium assumption
more relevant
• Important subtool in process simulation tools
• Important tool to predict chemical reactions
of complex mixtures of solids, liquids and gas
• Also a component in chemical kinetics
 At chemical equilibrium
– No thermal or mechanical (pressure)
gradients
– No chemical potential gradients
– No apparent change in the amounts
and the chemical composition of the
phases in the system
– Forward and reverse reactions occur
at the same rate
– Gibbs energy minimum of a system at
constant P,T

3
 Gibbs energy and the equilibrium constant
• Law of mass action
• jA+kB ⇌ lC+mD
• K = equilibrium constant, a =activity
• Example: 1CO + 1 H2O ⇌ 1CO2 + 1 H2

• ∆G°rxn= -RT lnK or K=e-DG/RT

14
Gibbs energy and equilibrium constant
– Reaction: CO + H2O ⇌ CO2 + H2
– K=[a(CO2)· a(H2)] / [a(CO) · a(H2O)]
– K=e-DG/RT; DG is the change in Gibbs energy for the
reaction (GCO2+GH2-GCO-GH2O)
– DG<0: reaction favors CO2 + H2

dG/dx<0
x=T,n,ξ
Gibbs energy and equilibrium constant
– Reaction: CO + H2O ⇌ CO2 + H2
– K=[a(CO2)· a(H2)] / [a(CO) · a(H2O)]
– K=e-DG/RT; DG is the change in Gibbs energy for the
reaction (GCO2+GH2-GCO-GH2O)
– DG<0: reaction favors CO2 + H2
– DG>0: reaction favors CO + H2O

G
dG/dx>0

x=T,n,ξ
Gibbs energy and equilibrium constant
– Reaction: CO + H2O ⇌ CO2 + H2
– K=[a(CO2)· a(H2)] / [a(CO) · a(H2O)]
– K=e-DG/RT; DG is the change in Gibbs energy for the
reaction (GCO2+GH2-GCO-GH2O)
– DG<0: reaction favors CO2 + H2
– DG>0: reaction favors CO + H2O
– DG=0: chemical equilibrium
G

dG/dx=0

x=T,n,ξ
 Chemical equilibrium
– Gibbs energy of a system is the sum of the Gibbs
energy of all involved phases
– G=∑NG
– N: amount (mol, gram, etc.) of phase 
– G: Gibbs energy of phase  per mol, gram, etc.
– When the G-function has a global minimum (dG=0),
equilibrium is attained
– Gibbs energy minimization
– The basis for complex chemical equilibrium
calculations (mass balance needs to be considered)
 Gibbs energy
• G=f(T,P, ni)= a+∑bTn+∑cPn...

• G=H-T·S

• H=H(ref)+∫CpdT Enthalpy

• S=S(ref)+∫(Cp/T)dT Entropy

• Cp=a+bT+cT-2+dTn... Heat capacity

• G=H(ref)+∫CpdT - T· [S(ref)+∫(Cp/T)dT]
 Thermodynamic quantities of compounds
-860 440
Enthalpy for Na2CO3 Entropy for Na2CO3
-900
400
858°C
Enthalpy [kJ/mol]

Entropy [J/molK]
-940
858°C
360
Liquid
-980 Liquid
320
-1020 Hm = 30 kJ/mol Sm = 26.4 J/molK
Solid

-1060 Solid 280 Increases with T,

Increases with T always positive values
-1100 240
500 600 700 800 900 1000 1100 1200 500 600 700 800 900 1000 1100 1200
-1250 240
Gibbs Energy for Na2CO3 Heat capacity for Na2CO3
-1300
220

Heat Capacity [J/molK]

Gibbs Energy [kJ/mol]

-1350 858°C
858°C
200
-1400 Liquid
Gm = 0 Cpm = 3.4 J/molK
180
-1450
Solid
160
-1500 Decreases with T
Always positive values
-1550 140
500 600 700 800 900 1000 1100 1200 500 600 700 800 900 1000 1100 1200
Temperature [°C] Temperature [°C]
Equilibrium state can be determined if we know

- all possible species and phases

- standard Gibbs energy for all species
- total amount of all system components
- non-ideality (excess Gibbs Energy function)

We do not need to use or know

- reaction equations
- equilibrium constants
- state ”before” equilibrium is established
 Gaseous Combustion Equilibria:

Methane combustion as function of

lambda
IN (mol) OUT (mol)

1.000 CH4 CH4

2.400 O2 O2

9.020 N2 N2

CO2

H2O

CO

OH

H2

T ∆fH°298 O
ptot S°298
H
cp(T)
fi(ci, T, …)
T = 1623.00 K
P = 1.01325E+00 bar

Input amount Equil. amount Equil. pressure

(mol) (mol) (bar)
CH4 0.10000E+01 0.28810E–14 0.23503E–15
O2 0.24000E+01 0.39950E+00 0.32590E–01
N2 0.90200E+01 0.90200E+01 0.73583E+00
CO2 0.00000E+00 0.99985E+00 0.81565E–01
H2O 0.00000E+00 0.19987E+01 0.16305E+00
CO 0.00000E+00 0.15127E–03 0.12340E–04
OH 0.00000E+00 0.24237E–02 0.19772E–03
H2 0.00000E+00 0.95625E–04 0.78008E–05
O 0.00000E+00 0.42256E–04 0.34472E–05
H 0.00000E+00 0.23646E–05 0.19290E–06
IN (mol) OUT (mol)

1.000 CH4 CH4 3·10-15

2.400 O2 O2 0.400

9.020 N2 N2 9.020

CO2 0.999

H2O 1.999

CO 2·10-4

OH 0.002

H2 1·10-4

T ∆fH°298 O 4·10-5
ptot S°298
H 2·10-6
cp(T)
fi(ci, T, …)
  = 1100 °C
1.0 106
atm CO2 ppm
H2O
O2
10-2 104
CO

H2

10-4 100
OH

10-6 1.0

H O
10-8 0.01
0.6 0.8 1.0 1.2

Methane/Air Combustion Equilibrium as Function of
Air Factor (at 1100 °C)
Gaseous Combustion Equilibria:

Energy balance and adiabatic

combustion temperature
 Hess’s law
∆H2
T2 A+B AB

∆H1 ∆H4

∆H3
T1 A+B AB
The standard enthalpy of an overall reaction is the sum of the standard enthalpies of the
individual reactions that can be used to describe the overall reaction
Hess’s law
 Hess’s law
∆H2
T2 A+B AB

∆H1 ∆H4

∆H3
T1 A+B AB

∆Hr = ∆H1+∆H2 = ∆H3+∆H4

 Reaction enthalpies

Example:
C + ½ O2 = CO ∆Hr,1000 °C = -113.7 kJ
C + O2 = CO2 ∆Hr,1000 °C = -395.2 kJ
CO2 + C = 2 CO ∆Hr,1000 °C = ?

The standard enthalpy of an overall reaction is the sum of the standard enthalpies of the
individual reactions that can be used to describe the overall reaction
Hess’s law
 Examples
• Is there a difference in the equilibrium
composition of the gas phase at 1000°C for the
reactants:
a) 3 mol CO + 1 mol H2O + 1 mol O2
b) 3 mol C + 1 mol H2 + 3 mol O2
c) 0.5 mol CH4 + 2.5 mol CO2 + 0.5 mol O2

• Will there be a difference for the adiabatic

flame temperature for the reactant mixtures if
the reactants initially are at 25°C and in their
normal state?
70
 Flue gas composition
0 Equilibrium in Combustion
N2
CO2 of CO vs. Air Factor (1500oC)
O2
-2

-4 CO
log(pi/bar)

-6

-8

0.2 0.6 1.0 1.4 1.8

Air factor, 
 0
N2
CO2 Equilibrium in Combustion
-1 of CO vs. Temperature (λ =
O2
1.2)
-2
O
log(pi/bar)

-3 CO

-4

-5
N

-6
1000 2000 3000
Temperature, °C
 3000
Adiab. temp., °C

Equilibrium in Combustion of
2000
CO with Air –
1000
Adiabatic Temperature vs. Air
Factor
0
N2
CO2
-1
O2
log(pi/bar)

-2
CO

-3
O

-4
0 1 2 3
Air Factor, 
Adiab. temp., °C 3000

2000 Equilibrium in Combustion of

CO with Oxygen –
1000 Adiabatic Temperature vs.
0
Lambda
CO2

O2 CO
-1
O
log(pi/bar)

-2

-3

-4
0 1 2 3
Stochiometric Ratio, 
 Gaseous combustion:

How ”true” is the equilibrium

assumption?
  = 1100 °C
1.0 106
CO2
atm ppm
H2O
O2
10-2 104
CO

H2

10-4 100
OH

10-6 1.0

H O
10-8 0.01
0.6 0.8 1.0 1.2

Methane/Air Combustion Equilibrium as Function of
Air Factor (at 1100 °C)
 2.5

H2O
2
Concentration, vol-%

1.5

CH4 CO2
1

0.5

H2 CO
0
0 0.05 0.1 0.15 0.2
Residence time, s

Combustion of methane (1 vol-%) with air, 850 C

Kinetic model calculation.
 106

105 O2
H2O
CH4
104
Concentration, ppmv

CO2
C2-species
103
CH2O

102 CO

CH3 OH
101 H
O
H2
HO2
100
10-2 10-1 100
Residence time, s

Combustion of methane (1 vol-%) with air, 850 C

Kinetic model calculation.
 Gaseous combustion:

How ”true” is the equilibrium

assumption?

Typical time to equilibrium:

For T = 850 °C, time = 0,1 - 1 s
For T=1500 °C, time = 1 – 10 ms
 Solid-Gas Equilibria:

Capture of SO2, HCl, HF by

Limestone
Secondary
Air

Fuel
Limestone

Primary Flue Gas

Air Recirculation

Bubbling Fluidized Bed Combustion with Limestone Addition

IN (mol) OUT (mol)

C 14.00 CO2 CO H2O

H 36.80 O2 H2 OH

S 0.080 H2S S2 SO

Cl 0.035 SO2 SO3 N2

F 0.006 HCl HF Cl2

O 23.36 F2

N 63.60

Ca 0.300 CaCO3 (s) CaO (s)

CaSO4 (s) CaSO3 (s)

350 . . . 1300 °C
CaS (s) CaCl2 (s)

CaF2 (s) Ca(OH)2 (s)

 650 °C 1050 °C
mol %-absorption mol %-absorption

SO2 (g) 6·10-10 100.0 0.0017 97.9

CaSO4 (s) 0.080 0.0783

HCl (g) 0.0346 1.2 0.0350 0.0

CaCl2 (s) 0.0002 –

HF (g) 0.0018 69.8 0.0060 0.0

CaF2 (s) 0.0021 –
 100
In CaSO4
 = 1.3
80

Absorbed Sulfur. %
60

40

20

0
500 600 700 800 900 1000 1100 1200
Temperature, °C

Sulfur Captured in CaSO4 at  = 1.3

 100
In CaSO4
 = 1.3
80
In CaS
Absorbed Sulfur. %  = 0.7
60

40

20

0
500 600 700 800 900 1000 1100 1200
Temperature, °C

Sulfur Captured in CaSO4 at  = 1.3, and in CaS at  = 0.7

 100
F captured
in CaF2
80

Absorbed share, %
60

40
Cl captured
in CaCl2
20

0
500 600 700 800 900 1000 1100 1200
Temperature, °C

Captured HCl and HF vs. Temperature ( = 0.7)

 Solid-Gas Equilibria
• Equilibrium modelling gives boundary
conditions to gas reactions
• Equilibrium percent capture or percent solid
conversion case (input) dependent and not
generalizable
• Kinetic information needed about solid
reactivity and conversion rate
Equilibrium and NOx
Nitrogen species in a typical flue gas under chemical
equilibrium conditions

• Most abundant ones

λ=1.1: N2, NO, NO2, N2O
λ=0.9: N2,HCN, NH3

• Equilibrium conc. of NOx decreases with temp.:

data from flue gas with λ=1.1:
T=1800 K 1200 ppm
T=500 K <1ppm
 T = 1900 K, p = 1 atm,  = 1
0 H2O 1000000
N2 volume
ppm
-1

-2 10000
log(pi/atm) H2
O2
-3
OH
[NO]eq.
H
-4 O 100
H2O2

-5
NO
HO2
-6 1
-8 -6 -4 -2 0
log(0/s)

Combustion of Natural Gas with Air. Kinetic Modelling.

Schematic view of NO Formation in Boilers
- Chemical Equilibrium vs. Kinetics

Time

Equilibrium concentration
(λ=1.1)
NO concentration

Typical measured
concentration

Furnace Superheaters
Temperature
 Equilibrium and NOx

• Forget - except at very high temperatures (2500+ °C)

• Formation chemistry slow and sensitive to intial
form of input nitrogen (N2, org-N)
• Decomposition chemistry ”frozen” at below 1500 °C
Feasibility of chemical equilibrium analysis
in combustion

BETTER WORSE
Rapid reactions Slow reactions
– High T - Low T
– Long residence time - Short residence time

Isothermal conditions Temperature gradients

Good mixing Composition gradients

GLOBAL ANALYSIS LOCAL ANALYSIS

50/50
 Equilibrium Modelling (EM) and
Combustion - Conclusions

• Gas phase: EM standard and relevant (but T > 800 °C)

• Solid-gas: EM gives boundary conditions for gas-solid
reactions.
• Kinetic information needed of extent of solid
conversion.
• NOx: Forget EM except > 2500 °C! (Kinetic models
available).