kinetic models use the ultimate volatile

yield as an input parameter to

determine the volatile yield as a
function of devolatilisation time. They
are relatively simple but restricted to a
particular coal and combustion
condition. Network models are based
on a structural description of the coal,
and allow for predictions of the volatile
yield, rate of evolution and volatile
composition. Generally, they are more
complicated and can be applied to a
wide range of coals and process
conditions.
Volatiles oxidation
The volatiles released react with
oxygen in the air surrounding the
particle, producing CO
2
and H
2
O. The
reaction is rapid and, thus, has a
negligible effect on the overall
combustion time. However, it is
important with respect to NO
formation.
Global oxidation kinetics have been
used to predict the reaction rate. It
assumes that the volatiles are
represented as a single species and the
combustion rate is controlled by mixing
with oxygen. However, this results in
inaccurate predictions. A more
advanced approach is to use the
measured or computed volatile species
as input into a flamelet model to
calculate the reaction. This allows
modelling of major species oxidation
and NO formation. Generally,
knowledge of volatiles oxidation
remains limited.
Char oxidation
Char oxidation dominates the total
burning time of a coal particle. It
Fundamentals of pulverised coal
combustion
Profiles
Coal combustion is a complex
physical and chemical process. It
involves drying and heating,
devolatilisation, oxidisation of volatiles,
and oxidisation of the residual char.
The process produces substantial
amounts of heat but also various
gaseous and solid pollutants.
Drying and heating
Particle drying starts once a coal
enters the furnace. It is a heat transfer
limited process and influenced by the
furnace temperature, coal particle size,
moisture content, and porosity. On
completion of drying, the particle is
further heated to the pyrolysis
temperature. Heating rates differ
significantly between types of
laboratory experiments or, types of
burners. It also depends highly on the
coal particle size. Drying and heating
may cause particle shrinking, a
reduction in the pore size, internal
cracking or particle breakup.
Devolatilisation
Devolatilisation of coal produces
light gases, tar and a residual char.
During devolatilisation, coals exhibit
various degrees of bubbling and
swelling. The volatile yield depends on
the type of coal and pyrolysis
conditions. Generally, bituminous coals
yield larger amounts of tar than other
coals, whilst lower rank coals release
less tar but larger amounts of light
gases. However, some studies showed
no clear correlation between the tar
yield and coal rank.
Devolatilisation models can be
divided into two groups: global kinetic
models and network models. Global
involves oxidation of carbon to CO or
CO
2
at the particle surface. Oxidation
to CO
2
dominates at low temperatures.
However, at high temperatures,
oxidation to CO becomes important.
Hence, the main carbon oxidation
becomes a two-step reaction, with the
CO being subsequently oxidised to CO
2
away from the char particle.
Char oxidation is controlled by the
rate of oxygen diffusion to the particle
or the rate of chemical reactions, or a
combination. At low temperatures, char
oxidation is controlled by the rate of
chemical reactions. At moderate
temperatures, both the rates of chemical
reaction and oxygen pore diffusion are
important, whilst at high temperatures,
oxygen diffusion to the particle surface
becomes dominant.
The reaction rates can be predicted
by either global reaction models or
intrinsic reactivity models. Global
reaction models are based on the
apparent activation energy, limiting
accurate predictions. Intrinsic reactivity
models use an absolute rate of reaction
and express the char reactivity on a
common basis of the heterogenous
processes. Thus, more accurate
predictions of char burnout are
expected.
Char fragmentation may occur
during combustion. It reduces the initial
particle mass, thus increasing the total
external particle surface area and hence
the char reaction rate. Fragmentation is
highly associated with char structure.
Pollutant formation
Nitrogen oxides consist mostly of
NO with much lower levels of NO
2
and
N
2
O. NO is formed by three routes:
Coal combustion is a
complex physical and
chemical process
March 2005
PF 05-02
Modelling has become
an increasingly important
tool
Considerable advances in
understanding have been
achieved but many areas
require further work
thermal NO, prompt NO, and fuel NO
that dominates the total NO formation.
Fuel NO formation is a complex
process. During devolatilisation, fuel-N
is split into char-N and volatile-N that
mainly includes tar-N, HCN and NH
3
.
The distribution of N depends on the
type of coal and temperature. Most of
the tar-N is converted to soot-N and
HCN. Soot-N is largely oxidised to NO
through heterogenous reactions. HCN
and NH
3
are then converted to NO or
N
2
, depending on the stoichiometry and
the total volatile-N concentration. Char-
N undergoes heterogenous oxidation to
largely form NO. However, part of the
NO formed is reduced to N
2
by char,
CO or soot. The final NO production
decreases with increasing bulk gas NO
concentration, char particle size, char
loading, and char reactivity.
Sulphur oxides are produced from
pyritic sulphur and organic sulphur
present in the coal. Pyrite first
decomposes to iron sulphide and
elemental sulphur. At higher
temperatures, the iron sulphide reacts
with oxygen to form iron oxide and
further elemental sulphur. The sulphur
released from both reactions is then
oxidised to SO
2
. A small percentage of
the SO
2
is converted to SO
3
. Organic
sulphur in coal is present as thiols,
sulphides and thiophenes. Its oxidation
mechanism is more complex and not
well understood.
Ash is formed from included
minerals, excluded minerals, and
organically-bound inorganic elements
in the coal. During combustion,
included minerals tend to coalesce to an
extent depending on char structure.
Excluded minerals do not coalesce but
evolve independently and may fragment
into small particles. Organically-bound
inorganic elements form vapour that
subsequently condenses to produce fine
particles. Most modelling has focussed
on the transformation of included and
excluded minerals. Organically-
bounded inorganic elements receive
little attention. Consequently, the
models are only applicable to high-rank
coals.
As seen from the above,
considerable advances in understanding
pulverised coal combustion have been
achieved. However, there are a number
of areas requiring further work. These
include:
G the effect of coal rank on the relative
yields of gases and tar during coal
devolatilisation;
G volatiles oxidation kinetics;
G formation of NOx, SO
2
and ash
IEA Clean Coal Centre is a
collaborative project of member
countries of the International
Energy Agency (IEA) to provide
information about and analysis of
coal technology, supply and use.
IEA Clean Coal Centre has
contracting parties and sponsors
from: Australia, Austria, Canada,
Denmark, the European Union,
India, Italy, Japan,
the Netherlands, New Zealand,
South Africa, Sweden, the UK
and the USA.
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e-mail: mail@iea-coal.org.uk
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Each issue of Profiles is based on a
detailed study undertaken by IEA
Clean Coal Centre, the full report of
which is available separately. This
particular issue of Profiles is based on
the report:
Fundamentals of pulverised coal
combustion
Zhangfa Wu
CCC/95, ISBN 92-9029-410-8, 36 pp,
March 2005, 255*/85/42.50
* non-member countries
member countries
educational establishments within member
countries
original
coal
1. drying 2. devolatilisation 4. char burning
3. volatile combustion
Coal combustion processes