The forms of sulphur

The forms in which sulphur generally exists in

coal
1)pyritic, (2) sulphate, (3) organic, (4) free.
When coal is carbonised or burnt these
different forms of sulphur behave differently
and are split up into forms as follows
Fixed sulphur: It is the amount of sulphur
retained by the coke when the coal is carbonised
 The forms of sulphur
Volatile sulphur: It is the portion of sulphur which
volatilises when the coal is carbonised at 950C
Combustible sulphur: This is the sulphur that is
expelled during the
complete combustion of coal. The combustible
sulphur, however, includes the
total amount of volatile sulphur
Non-combustible sulphur : This is the sulphur left in
the ash after the coal is completely burnt
Sulphur capture in fluidised bed
combustors
Calcium-based sorbents such as limestone (CaCO3) and dolomite
(CaMg(CO3)2) are widely used for removing of sulfur dioxide in
fluidized bed combustion (FBC) of coal or other sulfur containing
fuels. Two steps can describe the reactions between limestone and
sulfur dioxide sulphur capture reactions are following:
CaCO3 (s) CaO (s) + CO2 (g) ----(1)
CaO (s) + SO2 (g) + O2 (g) CaSO4 (s) ----(2)
During FBC, usually in the temperature range of 800 -
950 Deg C, CaCO3 is calcined to CaO and CO2 (Eq. 1). Then
CaO reacts with SO2 and O2 to form CaSO4
 Ca/S ratio
A main parameter controlling desulfuration is the Ca/S
ratio. Theoretically, 1 mol of Ca of a sorbent can react with
1 mol of S. However, more moles of Ca may be needed to
absorb 1 mol S under normal conditions. The sulfation
reaction (2) takes place at the surface and the pores in the
sorbent. In the reaction, the volume of the solid phase is
increased, as 1 mol of CaSO4 (46.0 cm3/mol [2]) occupies
more volume than 1 mol of CaCO3 (36.9 cm3/mol [2]). The
progress of limestone or dolomite sulfurization is eventually
hindered by pore blocking and the product layer which
separates the sorbents from the gas phase
 How to Calculate Ca/S ratio

Basic reactions of sulfur capture in BFBC by limestone

CaCO3 = CaO + CO2
SO2 +CaO+ 1/2 O2 = CaSO4
64 kg + 56 kg + 16 kg = 136 kg
1 kg of SO2 + 0.875 kg of CaO + 0.25 kg O2 = 2.125 kg of CaSO4
or 1 kg of S with 70% S capture will produce 0.7 x 2 x 2.125 kg of CaSO4
or 1 kg of S with 70% S capture will produce 2.975 kg of CaSO4
1 kg of S with 70% S capture will use 0.7 x 2 x 0.875 kg of CaO
or 1 kg of S with 70% S capture will use 1.225 kg of CaO
In reality of 70% capture itself, Ca/S molar ratio has to be 4
S + O2 = SO2
32 + 32 = 64
1 kg of S produces 2 kg of SO2
 How to Calculate Ca/S ratio
1 2 S in kgmoles 0.03125
CaCO3 = CaO + CO2
100 = 56 + 44
1 kg of CaCo3 gives 0.56 kg of CaO Ca in kgmoles 0.125
1 kg of CaCo3 gives 0.44 kg of CO2
1 kg of CaCo3 gives 0.40 kg of Ca Ca/S ratio 4
Every kg of S needs 12.5 kg of CaCo3 to achieve Ca/S ratio of 4
 PARAMETERS INFLUENCING
SULFUR CAPTURE REACTION

Physical properties of lime stone

Reaction Temperature
Chemical propertieslime stone
 Physical properties of Sorbent
Grain size
Mean pore size
Overall pore vloume
Specific surface area
porosity
Physical properties of lime stone
Effect of characteristic of five sorbents on their sulfur
capture capability at a fluidized bed condition
was investigated Calcium conversion for capture of
sulfur by sorbents is strongly influenced by the
element components and the morphology and
microstructure of the sorbents. Large specific
surface area and suitable mean pore size are most
important factors
Physical properties of lime stone

For limestones, while the overall pore

volume
increasing rate after calcination of a limestone
decreases, its porosity and specific surface
area increasing rate decrease either. However,
its absolute value of porosity and specific
surface area may determine the conversion
rate. An optimum temperature for the
limestones conversion is 900 Deg C
 Physical properties of lime stone
.
 Physical properties of lime stone
.
 Physical properties of lime stone
.
 Physical properties of lime stone
Summary of conversion of five sulfurization sorbents
Item Grain size (mm) Conversion of calcium (%)
Chemical Integration of
analysis SO2 emission

Limestone
L-1 0.15- 0.4 25.0 28.1
L-2 0.6- 2 38.9 42.8
L-3 1.2- 2.5 36.6 38.0
Seashell
S-1 1.2- 3 29.0 33.1
S-2 0.8- 3 32.4 37.2
 Sulfurization conversion of the five
sorbents
Sulfurization conversion of the five sorbents
 Conversion rate of the five sorbents at
different temperature
.
 ORIGINAL CALCINED
(850 Deg C,3 Hr) AND SULFURIZED (850 Deg C,1 Hr)

.
 Chemical properties of Sorbent
Cao
Mgo
Sio2
Fe2O3
Al2O3
MnO2
Na2O
 Chemical properties of Sorbent
The main constituent of the lime stone is CaO
and there is a certain amount of MgO in the
sorbents. Metal elements as Fe, Al and Na are
small proportions.
 Wet Process
Lime stone + Water
stack

Sluryy tank

Slurry pump

ESP
Stack
scrubber

Recirculation pump

Gupsum transfer pump

Hydro cyclone

Root blower

RVDF
 FGD Process Chemical Reaction

CO2
(Carbon dioxide)

H2O
(Water)

SO2
(Sulfur dioxide)
CaCO3
(Calcium carbonate, CaSO42H2O
limestone) (Calcium sulfate,
gypsum)
O2
(Oxygen)

SO2 + CaCO3 + O2 + H2O CaSO42H2O + CO2

Thanks