COAL TECHNOLOGIES

M.Sc. Chemical Engineering

Delivered by:
Dr Usman Ali
usmanali@uet.edu.pk

Department of Chemical Engineering

University of Engineering & Technology, Lahore
 Chemistry of Sulfur Oxide (SO2/SO3) Formation

Sulfur in coal occurs in three forms: as pyrite,

organically bound to the coal, or as sulfates.
The distribution between pyritic and organic sulfur is
variable with up to approximately 40% of the sulfur
being pyritic.
During combustion, the pyritic and organically bound
sulfur are oxidized to SO2 with a small amount of SO3
being formed.
The SO2/SO3 ratio is typically 40:1 to 80:1
 Generation of SOx
The overall reaction for the formation of SO2 is:
S + O2 → SO2 ΔHf = 128,560 Btu/lb mole
and the overall reaction for the formation of SO3 is:
SO2 + 1/2O2 ←→ SO3 ΔHf = 170,440 Btu/lb mole
It is proposed that SO is formed early in the reaction
zone and is intermediate product. The major SO2
reactions are:
SO + O2 → SO2 + O
SO + OH → SO2 + H
The reactions involving SO3 are reversible. The
reactions for SO3 is the three-body process:
SO2 + O +M → SO3 +M
where M is a third body that is an energy absorber. The
major steps for removal of SO3 are thought to be :
SO3 + O → SO2 + O2
SO3 + H → SO2 + OH
SO3 +M → SO2 + O +M
 Generation of NOx
 The majority of nitrogen oxides emitted from power plants
are in the form of nitric oxide (NO), with only a small fraction
as nitrogen dioxide (NO2) and nitrous oxide (N2O).
 NO originates from the coal-bound nitrogen and nitrogen in
the air used in the combustion process and is produced
through three mechanisms:
Thermal NO, Prompt NO, and Fuel NO.
 The factors that influence NOx emissions in pulverized coal-
fired boilers can be generally categorized as boiler design,
boiler operation, and coal properties; however, NOx
formation is complex, and many parameters influence its
production.
 Thermal NO
 Thermal NO formation involves the high-temperature (>
2370◦F) reaction of oxygen and nitrogen from the combustion
air.
 The principal reaction governing the formation of NO is the
reaction of oxygen atoms formed from the dissociation of O2
with nitrogen, referred to as the Zeldovich mechanism, are:
N2 + O• ←→NO +N•
N• + O2 ←→ NO + O•
 These reactions are sensitive to temperature, local
stoichiometry, and residence time.
Thermal NO is of greater significance in the post-
flame region than within the flame.
Consequently, several technologies have been
developed for reducing thermal NO by;
 lowering the peak temperature in the flame,
 minimizing the residence time in the region of the highest
temperature,
 and controlling the excess air levels.
 Prompt NO
Prompt NO is the fixation of atmospheric
(molecular) nitrogen by hydrocarbon fragments in
the reducing atmosphere in the flame zone.
The proposed mechanism is:
CH• +N2 ←→ HCN +N•
HCN + O• ←→NH• + CO
NH• + O• ←→NO• + H•
The main reaction product of hydrocarbon radicals
with N2 is HCN, and the amount of NO formed is
governed by the reactions of the nitrogen atoms with
available radical species.
 Fuel NO
Nitrogen in the coal, which typically ranges from 0.5
to 2.0 wt.%, occurs mainly as organically-bound
heteroatoms in aromatic rings or clusters.
Pyrrolic (5-membered ring) nitrogen is the most
abundant and contributes 50 to 60% of the total
nitrogen.
Pyridinic (6-membered ring) nitrogen comprises
about 20 to 40% of the total nitrogen. The remaining
0 to 20% nitrogen is thought to be in amine or
quaternary nitrogen form.
Coal nitrogen is first released during volatilization in
the coal flame as an element in aromatic compounds
referred to as tar.
The tar undergoes pyrolysis to convert most of the
nitrogen to HCN as well as some NH3 and NH.
The partitioning of nitrogen between volatiles and
char is important in NOx formation.
C + NO ←→ 1/2N2 + CO
CH• + NO ←→ HCN + O•
 Nitrogen Dioxide and Nitrous Oxide
Comprise less than 5% of the total NOx
production.
The oxygen levels are too low and the
residence times are too short in high
temperature coal flames for much of the NO
to be oxidized to NO2.
O• +N2 ←→ N2O
NH• + NO ←→ N2O + H•
NCO• + NO ←→ N2O + CO
 References
Miller, B. G., Coal Energy Systems. Elsevier,
2005. Chapter 6