Flue Gas Desulfurization by Limestone and Hydrated

Lime Slurries
Aye zyuuran*, Ayegl Ersoy-Meriboyu
Chemical and Metallurgical Engineering Faculty, Istanbul Technical University,
34469 Maslak-Istanbul-Turkey
The sulfation properties of six different natural limestone and hydrated lime slurries
were investigated. Sulfation experiments were carried out at the temperatures of 323 K
and 298 K in a gaseous mixture consisting of 5% O2, 10% CO2, 0.5% SO2 and a balance
of nitrogen by volume. Total sulfation capacities of the slurries were found to vary
depending on sulfation temperature, sorbent properties and the sorbent content of the
slurry. It was determined that the total sulfation capacities of all slurries shifted to
higher values as the CaCO3 and Ca(OH)2 contents of sorbents and sorbent content of
slurries increases and sulfation temperature decreases. Depending on sulfation
conditions and the sorbent properties, the total sulfation capacities of limestone and
hydrated lime slurries varied between 14.0-33.1 (mg SO3/ml slurry) and 17.4-40.4 (mg
SO3/ml slurry), respectively. Regression analysis was used to relate the total sulfation
capacity values to the CaCO3 and Ca(OH)2 contents of sorbents and linear empirical
equations were developed.

1. Introduction
Flue gas desulfurization (FGD) processes are usually categorized as wet and dry or
semi-dry systems. In wet FGD processes flue gas is contacted with a slurry consisting of
a sorbent in an aqueous medium, such that the flue gas is cooled to the adiabatic
saturation temperature. Whereas, dry and semi-dry FGD processes involve injection of a
solid sorbent or a sorbent slurry into the furnace or flue gas duct. In wet FGD systems
high degree of SO2 removal is usually achieved with a high level of sorbent utilization
(Berman et al., 2000; Song ang Park, 2002; Warych and Szymanowski, 2002).
However, dry or semi-dry FGD systems are usually exhibit lower SO2 removal
efficiencies because of the short contact time between the flue gas and the sorbent
(Ersoy-Meriboyu, 1999). Thus, several wet FGD systems have been developed and are
in commercial use, including a variety of scrubbing processes involving limestone or
hydrated lime slurries (Ma et al., 2001; Ma et al., 2000).
The aim of the present study is to investigate the sulfation properties of the six different
natural limestone and hydrated lime slurries. The effect of temperature, sorbent
*Corresponding author: E-mail: kmayse@itu.edu.tr

properties and the sorbent content of slurry on the total sulfation capacities of slurries
was determined.

2. Materials And Methods

In the experiments six natural limestone samples originating from different localities of
Turkey were used. Samples were initially crushed and sieved into a powder with a
particle size of < 250 m and their chemical compositions were determined according to
ASTM standarts.
Sulfation experiments were performed in a glass reactor which has been immersed in a
thermostated stirred water bath. Natural limestones and their hydrated limes were used
as sorbents. Powdered sorbents were mixed with enough distilled water to achieve
sorbent contents of 1% and 3% by weight. The slurries which were agitated at 700 rpm
were sulfated at two different temperatures of 298 K and 323 K. During sulfation a
synthetic gaseous mixture consisting of 5% O2, 10% CO2, 0.5% SO2 and a balance of
nitrogen by volume with a constant flow rate of 100 ml/min was fed into the reactor.
The amount of SO3 absorbed by the slurry during sulfation was determined by
iodometric titration method. In this determination, 1 ml of sample was taken from the
reactor every 1 hour and titrated with KI-KIO3 solution using starch as an indicator.

3. Results And Discussion

Chemical composition of the limestone samples used in this study is given in Table 1.
Total sulfation capacity results of the slurries prepared from different limestone and
hydrated lime samples were summarized in Table 2.
It has been reported that the appropriate operation temperature for wet FGD system is
323 K (Kiil et al., 1998; Takashina et al., 2001). Therefore, all of the desulfurization
reactions were performed at 323 K. However, in order to determine the effect of
temperature on the desulfurization efficiency, some of the sulfation reactions were also
carried out at 298 K (Table 2).
As can be seen from Table 2, for the sulfation temperature of 323 K the total sulfation
capacities of the limestone slurries having sorbent content of 1% and 3% by weight
changed between 14.0-17.3 (mg SO3/ml slurry) and 29.6-33.1 (mg SO3/ml slurry),
respectively. On the other hand, the total sulfation capacities of the hydrated lime
slurries having the sorbent content of 1% and 3% by weight were changed between
17.4-22.5 (mg SO3/ml slurry) and 32.9-40.4 (mg SO3/ml slurry), respectively.
Table 1. Chemical composition of limestone samples
Sample
Code
L1
L2
L3
L4
L5
L6

CaO
(%)
53.78
52.17
37.45
54.48
54.08
49.91

MgO
(%)
0.54
1.05
4.65
0.26
0.76
2.70

SiO2
(%)
0.68
0.61
12.64
0.22
0.02
3.66

Fe2O3
(%)
0.10
0.08
3.54
0.02
0.10
0.46

Al2O3
(%)
0.25
0.21
6.70
0.54
1.20
2.04

Moisture
(%)
0.08
0.86
0.48
0.10
0.04
0.95

Ignition Loss
(%)
44.24
44.37
32.71
43.80
43.68
41.53

Table 2. Total sulfation capacities of slurries prepared from limestone and hydrated
lime samples

Sample
Code

Sorbent
Content of
Slurry
(weight %)

L1
L2
L3
L4
L5
L6
HL1
HL2
HL3
HL4
HL5
HL6

1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3

Sulfation Temperature
323 K
298 K
Sulfation
Total Sulfation
Sulfation Total Sulfation
Time
Capacity
Time
Capacity
(h)
(mg SO3/ml
(h)
(mg SO3/ml
slurry)
slurry)
4
17.3
4
21.1
6
33.1
6
48.3
4
17.3
------6
31.4
------4
14.0
4
17.4
6
29.6
6
39.5
4
17.3
4
20.9
6
32.8
6
50.9
4
17.0
------6
32.6
------4
15.1
4
17.3
6
31.0
6
41.0
4
20.6
4
24.4
6
38.3
6
53.5
4
21.3
------6
37.8
------4
17.4
4
18.7
6
32.9
6
48.4
4
21.3
4
25.6
6
40.3
6
55.7
4
22.5
------6
40.4
------4
18.9
4
22.3
6
35.1
6
52.7

It is known that the CaCO3 and Ca(OH)2 contents of sorbents play very important role
in the total sulfation capacity values of their slurries. The rate of limestone dissolution
depends on the slurry pH and the pH of the slurry is adjusted by the flow of dissolved
Ca+2 ions (Ma et al., 2001; Ma et al., 2000; Song and Park, 2002; Warych and
Szymanowski, 2002). In this study, the total sulfation capacities of slurries, prepared
from L1, L2, L4 and L5 limestones having the CaCO3 content of 96.04, 93.16, 97.29
and 96.57%, respectively, were found to be higher than the slurries prepared from L3
and L6 limestones, having the CaCO3 content of 66.34 and 89.13%, respectively.
Similarly, the slurries prepared from HL1, HL2, HL4 and HL5 hydrated limes having
the Ca(OH)2 content of 80.77, 79.87, 88.27 and 85.07%, respectively, could remove
more SO2 than the slurries prepared from HL3 and HL6 hydrated limes having the
Ca(OH)2 content of 50.12 and 61.20%, respectively. These results clearly showed
that, the increase of Ca+2 ion concentration in the slurry resulting from the dissolution
of the CaCO3 and Ca(OH)2 components of sorbents creates an improvement in the total
SO2 removal efficiency (Song and Park, 2002 ).

Similar results were also obtained for the sulfation experiments performed at 298 K.
The total sulfation capacities of slurries prepared from L1, L4, HL1, HL4 samples were
found to be higher than those for the slurries prepared from L3, L6, HL3 and HL6
samples (Table 2). The relation between the total sulfation capacities of slurries having
the sorbent contents of 1% and 3% with the CaCO3 and Ca(OH)2 contents of limestone
and hydrated lime sorbents are illustrated in Figures 1 and 2. The experimental results
obtained for the sulfation reactions performed at 323 K clearly showed a strong
dependence between the total sulfation capacities of slurries and CaCO3 and Ca(OH)2
content of the sorbents and following empirical equations were developed.
TSC= 22.787+0.101 CC

(Slurries with the limestone content of 3%)

(1)

TSC= 23.056+0.194 CH

(Slurries with the hydrated lime content of 3%)

(2)

TSC= 6.499+0.101 CC

(Slurries with the limestone content of 1%)

(3)

TSC= 11.634+0.117 CH

(Slurries with the hydrated lime content of 1%)

(4)

TSC
: Total sulfation capacity (mg SO3-2/ml slurry)
CC
: Calcium carbonate content of sorbent (%)
CH
: Calcium hydroxide content of sorbent (%)
The correlation coefficients for Eqs. 1-4 were determined as 0.78, 0.97, 0.80 and 0.91,
respectively. The regression analysis of experimental data clearly show that the relation
between Ca(OH)2 contents of hydrated limes and total sulfation capacities of hydrated
lime slurries is stronger than the relation between CaCO3 contents of limestones and
total sulfation capacities of limestone slurries. This conclusion shows the significant
impact of the sorbent type on the total sulfation capacities of slurries. As can be seen
from Table 2, the total sulfation capacities of slurries are increased when the hydrated
lime is used as sorbent material instead of limestone. It is known that, the hydrated lime
possesses higher desulfurization capacity than limestone due to its higher solubility and
higher alkalinity in slurry and better reactivity with SO2 at low temperature (Ma et al.,
2000; zyuuran et al., 2006).
The solubility of Ca(OH)2 in water was determined 0.165% at 293 K, but the solubility
of CaCO3 was found 0.0014% at same temperature (Perrys Handbook, 1998). While
the pH value of a fresh prepared limestone slurry is ranged usually between 8 and 9, this
value is determined as 12 for hydrated lime slurry (Ahlbeck et al., 1993). It is well
known that the increasing the alkalinity will increase dissolution rate of SO2 and the rate
of sulfation reaction, thus the total sulfation capacity increases. The main drawback for
using hydrated lime as a sorbent in wet FGD system is the cost of lime which higher
due to the calcination process. Therefore, when utilizing hydrated lime as a sorbent
material the expenses for calcination, transportation, and slaking must be considered.
A mention earlier, another parameter which effects the total sulfation capacity is the
sorbent content of slurry. This effect was also investigated in this study for the sulfation
experiments conducted at two different temperatures of 298 K and 323 K. As expected,
SO2 removal efficiency increased with the increase in the sorbent content of slurries
since more sorbent content means that more sorbent fed into the reactor for a given inlet
SO2 concentration in the flue gas. Besides, the increment of the sorbent content of slurry
made the Ca+2 concentration higher in the slurries and this leads to an increase in the
internal Ca/S ratio and in the solid-liquid interface area which creates an improvement
in the efficiency of SO2 removal.

18

Total Sulfation Capacity [mg SO3/ml]

Total Sulaftion Capacity [mg SO3 /ml]

34
33
32
31
30
29
28

17

16

15

14

13
60

65

70

75

80

85

90

95

60

100

65

70

75

80

85

90

95

100

CaCO3 [%]

CaCO [%]

(a)
(b)
Figure 1. The relation between CaCO3 content of limestones and the total sulfation
capacities of slurries with a limestone content of a) 3%; b) 1%
25

Total Sulfation Capacity [mg SO3 /ml]

Total Sulfation Capacity [mg SO3/ml]

42
40
38
36
34
32
30

24
23
22
21
20
19
18
17
16
15

45

50

55

60

65

70

75

Ca(OH)2 [%]

80

85

90

95

45

50

55

60

65

70

75

Ca(OH)2 [%]

80

85

90

95

(a)
(b)
Figure 2. The relation between Ca(OH)2 content of hydrated limes and the total
sulfation capacities of slurries with hydrated lime content of a) 3%; b) 1%
During the sulfation reaction, one mole of CaCO3 or Ca(OH)2 react with one mole of
SO2, to form one mole of calcium sulfite dihydrate (CaSO3.2H2O). Thus, a 100%
stoichiometric limestone or hydrated lime requirement means one mole of CaCO3 or
Ca(OH)2 for each mole of SO2 feed. The 150% stoichiometric requirement means 1.5
mole of CaCO3 or Ca(OH)2 for each mole of SO2 feed. Theoretically, higher the
stoichiometry, higher the SO2 absorption. However, it is clearly seen from Table 2 that,
although the amount of sorbent in slurry was tripled, total sulfation capacities of slurries
did not increase at the same ratio due to the effects of other parameters. This is in
agreement with the previously reported studies in literature (Berman et al., 2000; Song
and Park, 2002; Takashina et al., 2001).
The experimental data listed in Table 2 indicate that the total sulfation capacities of all
slurries are shifted to higher values as the sulfation temperature decreased from 323 K
to 298 K. The effect of temperature on the desulfurization efficiency of wet FGD
systems depends on how all reactions in the scrubber are affected by the temperature
changes. In previous studies (Kiil et al., 1998), it has been reported that the solubilities
of calcium carbonate, calcium hydroxide and sulfur dioxide changes depending on the
temperature and this phenomena effects the desulfurization efficiency. The solubility of
SO2 in water decreases with increasing temperature; besides, Ca(OH)2 is rather

insoluble and unlike most soluble metallic hydroxides, its solubility decreases as the
temperature increases; on the other hand, CaCO3 is quite insoluble and its solubility
increases only slightly as the temperature is increases (CRC Handbook, 2001).

4. Conclusions
The present study has shown that the total sulfation capacities of limestone and hydrated
lime slurries were changed depending on origin and chemical composition of limestones
and their hydrated limes. Strong dependence between the total sulfation capacities of
slurries and CaCO3 and Ca(OH)2 content of sorbents were observed. The total sulfation
capacities of all slurries were shifted to higher values as the sorbent content of slurries
increases. The SO2 removal efficiencies of slurries were increased as the sulfation
temperature decreased from 323 K to 298 K. Depending on sulfation conditions and the
sorbent properties, the total sulfation capacities of limestone and hydrated lime slurries
varied between 14.0-33.1 (mg SO3/ml slurry) and 17.4-40.4 (mg SO3/ml slurry),
respectively.

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