Drying, devolatilization &

char oxidation of solid fuel

Oskar Karlström
Doctor of Technology

Åbo Akademi 2016:

Chemistry in Combustion Processes
 (IEA 2014)
Coal

Gas Other
Where does the
Oil
electricity come
from globally? Water
Nuclear
Solid fuel combustion
 Solid fuel combustion

fuel
In pulverized fuel
combustion, size of fuel
pieces also called particles
are around 0.1 mm
 Solid fuel combustion
What happens with the mass
of one 0.1 mm single fuel
particle in this furnace?

drying
100%
devolatilization

fuel char oxidation

mass
50%

0.2 s 0.4 s 0.6 s

time
 Terms and concepts
• Small vs large fuel particle
• Devolatilization/pyrolysis of small and large
particles
• Char oxidation of small and large particles
• Kinetic regime
• Mass transfer regime
• Chemical kinetics control
• Mass transfer control
• Char gasification
• Gasification
• Coal types
• Difference in burning between coal and biomass
• Oxy-combustion
H2 O Drying
Volatile matter Devolatilization
Char Oxidation
Ash Ash
 Typical proximate Typical proximate
analysis of wood: analysis of a coal:

H2O H2O
vol vol
char char
ash ash

• less volatile matter, and less moisture in coal than in biomass

• coal forms more char than biomass
 Drying
Fuel + heat → water vapor (endothermal: ΔH >0)
 Energy balance during drying
of a small (<0.1 mm) fuel particle
Energy
Temp.
Convective heat transfer consumption Radiation heat transfer

mpc p
dTp
dt
 hS p Tgas  Tp  
dm p
dt

H  S p p T  T R
4 4
p 
Vaporization
Mass enthalpy
Specific heat

k gas Nu External
h surface area
Surface
d emissivity
Devolatilization - pyrolysis
Fuel + heat → volatiles + char (ΔH≈0)

CO
CO2
H2
Volatiles H2O
Hydrocarbons
Tars

Exact volatile composition

depends on the heating rate
Devolatilization - pyrolysis

As the volatiles are oxidized

a flame can be observed
 Devolatilization of wood

• Hemicellulose start pyrolyzing at 200-350 °C

• Cellulose start pyrolyzing at 280-375 °C
• Lignin start pyrolyzing at 250-500 °C
• Certain extractives such as terpenes (few % in
wood) start pyrolyzing at less than 225 °C
Hemicellulose

Total
Cellulose

Lignin

Di Blasi 2008
 Devolatilization of coal
• Fossil coals can be divided into anthracite,
bituminous coal and lignite
• Volatile matter very low for anthracites
• Volatile content higher for lignite than for
bituminous coals

Anthracite Bituminous coal Lignite

 Devolatilization of lignite
• Lignite: starts to pyrolyse at 300-400 °C
releasing CO and CO2
• At around 400-700 °C also hydrocarbon
vapors, tars and H2 are produced
 Devolatilization of bituminous coals
• Bituminous coals becomes plastic and
can swell remarkably during pyrolysis
• CO and CO2 is formed but to a less
extent than for lignite, due to lower
oxygen content
• Tars, hydrocarbons, and soot are
formed at temperatures higher than
400 °C
 Devolatilization of anthracite
• Low volatile content of anthracite
 What happens with T for a What happens with T for
0.05 mm wood particle if a 6 mm wood particle if
we put in 1000 °C? we put in 1000 °C?
External surface of External surface of
particle particle

1000 °C 1000 °C

600 °C Center of 600 °C Center of

particle particle

200 °C 200 °C
devolatilization

0.02 0.04 0.06 10 20 30

time (s) Time (s)
Drying and devolatilization: in sequences or simultaneously?

• For small particles (< 0.1 mm), drying and

devolatilization occurs in sequences
• For large particles, drying and
devolatilization occurs partly
simultaneously due to temperature
gradients inside the particle
Drying and devolatilization: in sequences or simultaneously?

How do we determine High Bi →

this? temperature
gradient significant
Radius
Heat transfer Low Bi →
coefficient
temperature
rheff
Bi  gradient negligible
k c , particle

Thermal
conductivity
 Char
• Char yield of wood around 15%
on dry basis
• Char yield of coal up to more
than 90% on dry basis
Devolatilization Char Oxidation
 Biomass char

(Di Blasi 2011)

• Biomass char yield slightly

dependent on heating rate
 Coal char
• Coal char yield strongly
dependent on heating rate

(Kobayashi et al. 1976)

 Char
Biomass
Lignite
Bituminous coal
Anthracite
40
HHV (MJ/kg)db

30

20

10

0
0 20 40 60 80 100
Char yield % (dry basis)

Aging
 Biomass
Lignite
Bituminous coal
Anthracite
40 100
HHV (MJ/kg) db

30 80

C %daf
60
20
40
10 20
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Char yield %db Char yield %db
8 60
50
6
40
H %daf

O %daf
4 30
20
2
10
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Char yield %db Char yield %db
 Char
• Char Oxidation generally
significantly slower than
Devolatilization: important to
consider in the design of
combustion units
Devolatilization Char Oxidation
 Char
• Organic and inorganic part
• Organic part consists of C, N, O, S, H
• Of the organic part,
almost 100% on mass basis is C
• Oxidation of char refers to heterogeneous
oxidation of solid carbon, C(s)
• Heterogeneous combustion:
C(s) + O2(g) → CO2(g)
• Homogeneous combustion:
2CO(g) + O2(g) → 2CO2(g)
 Char oxidation
O2 C(s)+ O2 (g) → CO/CO2(g) (ΔH<0)

C(s)

CO/CO2

mpc p
dTp
dt
 hS p Tgas  Tp  
dm p
dt

H  S p p TR4  Tp4 
<0
Tp  Tgas
 Char oxidation
• Char is porous
• Oxidation reactions occurs
inside char particle and at the
external surface of the char
particle
 Char oxidation
O2

C(s)

CO/CO2

• The faster the reaction (kinetics), the shorter

way the oxygen will penetrate inside the char
• If the reactions are very fast, all the reactions
take place at the external surface
O2 concentration inside and outside char particle

0.6 Inside particle Outside particle

0.5

0.4 RI
O2 conc.

0.3 RII
0.2

0.1 RIII
0
0 0.2 0.4 0.6 0.8 1

Particle Radius
 Char oxidation
• limited by mass transfer if Regime III
particles are large (>1 mm)
• limited by chemical kinetics if
particles are small (<0.05 mm) Regime I
• Otherwise limited by the
combined effects of chemical Regime II
kinetics and mass transfer
 2000
Temp. ( oC)

1500 RIII

RII
1000

500 RI
-4 -3 -2 -1
10 10 10 10
particle diameter (m)

(For a typical bituminous coal char, note

that the diagram is fuel dependent)
 Chemical kinetics Mass transfer control
control (Regime I) (Regime III)
• Fuel type and mass limits • External surface limits char
the char oxidation rate oxidation rate
• Char oxidation rate is • Char oxidation rate is not
strongly temperature strongly temperature
dependent dependent
• Rate not limited by
external mass transfer
2000
Temp. ( oC)

1500 RIII

RII
1000

500 RI
-4 -3 -2 -1
10 10 10 10
particle diameter (m)
 Chemical kinetics control (Regime I & Regime II)
• High internal surface area gives high
kinetic rate
• Biomass chars have higher internal surface
area (up to 1000 m2/g) than coal chars (10-
100 m2/g)
• Catalytic elements such as Na, K, Mg, Ca
can reduce activation energy and enhance
rate
• Biomass char has higher fraction of
catalytically important elements than coal
char

Biomass chars significantly

more reactive than coal chars
with respect to O2
Internal Efficiency Activation energy
surface area Mass factor Concentration

Temperature
dm  E / RT p
 Ai mcO 2 Ae
dt
RIII =>  0 • Low E gives high rate
• High Tp gives high rate
RI =>  1

• For coal chars E is around 160 kJ/mol for char oxidation by O2

• For biomass chars E is generally around 100 kJ/mol for char
oxidation by O2
 Char oxidation and char gasification
• In combustion, char is always oxidized to some
extent by CO2 and H2O
• Char oxidation by CO2 and H2O is called char
gasification
• Char gasification reactions are important in
combustion systems and gasification systems
• Note: char gasification and gasification have
different meaning
Char Char
oxidation gasification

O2 CO2 H2O

Char Char Char

particle particle particle

CO 2CO H2
CO

exothermic endothermic
 Combustion Gasification

electricity CO, H2

N2, CO2 Some CO2

heat

Combustion Gasification

Fuel Fuel
Air Insufficient
amount of air
 Gasification
• In combustion the carbon and hydrogen
reacts to CO2 and H2O
• In gasification, the goal is to produce a gas
rich in CO and H2 that for example can be
burned in a gas boiler
• In gasification systems an insufficient amount
of air is used, so that the oxidation of gases is
incomplete → high levels of CO and H2
 Waste gasification in Lahti
5.

3.

4.
1. 1.Fuel handling
2.FB gasifier
3.Gas cooling
4.Gas filter
5.Gas fired boiler

2.
 Oxy-combustion
• A combustion technique for the future?
• Fuels are combusted in O2 instead of air
• To avoid extremely high temperatures, the
CO2 is partly recirculated
• The goal is to produce electricity, but so that
the formed CO2 is stored
 Combustion Oxy-combustion
Storage

electricity electricity

N2, CO2 CO2

heat heat

Combustion Oxy-
Combustion

Coal Coal
Air O2
 Terms and concepts
• Small vs large fuel particle
• Devolatilization/pyrolysis of small and large
particles
• Char oxidation of small and large particles
• Kinetic regime
• Mass transfer regime
• Char gasification
• Gasification
• Coal types
• Difference in burning between coal and biomass
• Mass transfer control
• Chemical kinetics control
• Oxy-combustion
...stay tuned for part II of this course