J. Mater. Sci. Technol., Vol.25 No.

3, 2009 329

Effect of Reactivity of Quick Lime on the Properties

of Hydrated Lime Sorbent for SO2 Removal
H.G. Shin1) , H. Kim1) , Y.N. Kim2) and H.S. Lee3)
1) Department of Materials Science and Engineering, Seoul National University, Seoul, Korea
2) Machinery & Materials Testing Center, Korea Testing Laboratory, Seoul, Korea
3) School of Materials Science and Engineering, Pusan National University, Busan, Korea
[Manuscript received January 16, 2008, in revised form May 16, 2008]

The hydration of quick lime and the sulfation of hydrated lime were carried out for verification of relationship
between the reactivity of quick lime and the properties of hydrated lime as a sorbent. The effect of reactivity
of quick lime was investigated with the change of calcination temperature and time. Results obtained showed
that the temperature rise during the hydration of quick limes varied from 31 to 69 C with the variation of
calcination temperature and time. The specific surface area and the sulfation ability of hydrated lime prepared
by hydration of quick lime showed a proportional relationship with the reactivity of quick lime. The hydrated
lime which was prepared by hydration of quick lime calcined at 1100 C had the highest reactivity and showed
41.53 m2 /g of the specific surface area, 0.16 cm3 /g of the pore volume and 87% of the removal efficiency for
SO2 removal.
KEY WORDS: Reactivity; Quick lime; Hydrated lime; Calcination; Hydration; Sorbent

1. Introduction a five-step mechanism[8] . Heat transfer resistances as

Limestone is one of the abundant materials in the
world and is very useful for various applications. Both
quick lime and hydrated lime are produced from lime-
stone by calcination and hydration. The in-duct sor-
bent injection is one of the dry flue gas desulfuri-
sation(FGD) processes. In this process, the sorbent
particles are normally introduced into humidified and
temperature-controlled flue gas in the duct between
the air pre-heater and particulate control device. The
sorbent used widely in the humidified duct injection
processes is hydrated lime(Ca(OH)2 )[1] . However, the
sorbent is not highly converted in the operation of
these processes. How to increase the utilization of
hydrated lime has been an important subject for the
application of the dry processes. The superiority of
calcium hydroxide over calcium carbonate as a sor-
bent has been attributed to the smaller mean particle
size, higher surface area, higher pore volume, larger
mean pore diameter, and plate-like grain structure
(as opposed to sphere-like grain structure) of CaO de-
rived from Ca(OH)2 compared to that derived from
calcium carbonate. In boiler economizer and cool-
side studies, improved SO2 removal performance has
been reported for calcium hydroxide. Thus, it is desir-
able to provide calcium hydroxide having high surface
area, high porosity, and small particle size for use in
SO2 sorption, and for other physical processes relying
on the sorptive capabilities of calcium hydroxide[25] .
The structural properties of the sorbents such as spe-
cific surface area and porosity are believed to play
an important role in SO2 removal. In general, it
has been shown that higher desulfurization reactivity
correlates with higher specific surface area[6,7] . The
uncertainty in predicting the behavior of a particu-
lar limestone in a calcination process is due to the
complexity of the calcination process which involves
Corresponding author. Prof. H.S. Lee; Tel.:+82 51 510 2388;
E-mail address: heesoo@pusan.ac.kr.
well as pore diffusion resistance of the CO2 evolved
might have significant effects on the calcination rate.
As it is reported by Dogu[9] , changes in pore struc-
ture also play a significant role on the calcination
mechanism and the reactivity of a calcined limestone
is strongly dependent on its physical and structural
properties which in turn are highly dependent on cal-
cination conditions[10] . However, there are many as-
pects not well understood about the calcination reac-
tion, and therefore there is no consensus about several
fundamental aspects of the process as particle reaction
model, rate-limiting processes, and total pressure on
the reaction rate etc.[11] .
In this study, the calcination of limestone with var-
ious temperatures, the hydration of quick lime and the
sulfation of hydrated lime have been performed. It is
the aim of this work to relate the reactivity changes of
quick lime during the calcination process to the prop-
erties of the hydrated lime in the removal of SO2 .
2. Experimental
Calcined quick limes were obtained in a muf-
fle furnace at temperatures between 900 C to
1200 C and for calcination time varying from 30 to
180 min. Hydrated lime was achieved by hydra-
tion process using water, ethanol and additive (quick
lime:water:ethanol:additive=100 g:48 ml:72 ml:3 g).
The resultant hydrates were dried off in an oven main-
tained at 105 C to produce a dry sorbents. All sam-
ples were then milled and sieved to a particle size
below 200 being used in the sulfation system.
The temperature rise recorded from a room tem-
perature of 25 C during hydration was used as the
reactivity value of calcined quick lime[12] . The crystal
structure and the crystalline size were analyzed using
a Mac Science M18XHF X-ray diffractometer (XRD).
Crystalline size was calculated from XRD data as
follows[13] :
330 J. Mater. Sci. Technol., Vol.25 No.3, 2009

fraction line measured at half-height of the diffraction

80 peak (in radians), and (0001) is half the diffrac-
tion angle (in radians) of (0001) planes. A scanning
60 electron microscope (SEM), Hitachi S-2700, was used
to observe the sorbent morphology. The specific sur-
face area and the pore volume of the sorbent were
C
o

40 determined by nitrogen physisorption at 77 K in an

T/

Autosorb-1(Quantachrome) analyser.
900 C
o

20 1000 C o

1100 C o 3. Results and Discussion

1200 C o

0
0 300 600 900 1200 The variation of temperature rise during hydra-
Time / s tion of quick limes calcined at temperature ranges of
9001200 C for 1 h is shown in Fig. 1. The tem-
Fig. 1 Temperature rise during hydration of quick limes
calcined at various temperatures perature rises accompanied by hydration of quick
lime increased with calcination temperature up to
1100 C and decreased above the calcination temper-
6 ature. When quick lime calcined at 1100 C for 1 h
was hydrated, the maximum temperature rise was
Specific surface area / (m /g)

69 C which is the highest rise among quick limes cal-

2

5 cined at 900, 1000, 1100 and 1200 C. These results

indicated that quick lime calcined at 1100 C has the
4
highest reactivity for hydration. When quick lime cal-
cined at 1200 C for 1 h was hydrated, the tempera-
ture rise was lower than that of quick lime calcined
3 at 1100 C and the time required to maximum tem-
perature rise became much longer. This means that
quick lime calcined at 1200 C becomes less reactive.
2
900 1000 1100 1200 The reactivity of quick lime calcined at 1200 C seems
Temp. /
o
C
to decrease because of the grain growth and densifica-
tion of quick lime structure. In order to verify these
Fig. 2 Variation of specific surface area of quick limes as results, the specific surface areas and microstructures
a function of calcination temperature
of quick limes were analyzed.
Figures 2 and 3 show the variation of specific
0.9 surface area of quick lime as a function of calci-
(1) t=
B(0001) cos (0001) nation temperature and SEM photographs of quick
where is the wavelength of X-rays (0.15405 nm for lime calcined at 900, 1000, 1100 and 1200 C, respec-
CuK), B(0001) is the broadening of the (0001) dif- tively. Quick lime calcined at 1100 C, which showed

Fig. 3 SEM photographs of quick limes calcined at various temperatures: (a), (b) 900 C, (c) 1000 C, (d) 1100 C
and (e) 1200 C
 J. Mater. Sci. Technol., Vol.25 No.3, 2009 331
Table 1 Crystalline sizes of hydrated limes
Calcination temp. of quick lime (Hydrated Lime) Average Crystalline size/nm
900 C 13.2
1000 C 13
1100 C 11.3
1200 C 12.1

60
Ca(OH)
50 CaCO
2

(101)
(001)
40

(110)
C

(100)
Intensity / a.u.

(111)

(021)
o

(013)

(022)
Temp. /

30
1200 C
1100 C
o
o
Calcined at
20 30 min
60 min
o
1100 C

10 120 min
180 min 1000 C
o

0
0 500 1000 1500 2000 2500 900 C
o

Time / s 10 20 30 40 50 60 70 80 90

Fig. 4 Reactivity of quick limes as a function of calcina- 2 / deg.

tion time Fig. 5 XRD patterns of hydrated limes with variation of

calcination temperature of quick limes
the highest reactivity for hydration, had the largest
specific surface area. As shown in Fig. 3(d), a lot of
pores, which were created due to thermal decomposi- 0.5

tion of limestone, existed on the surface of particles

Specific surface area (m /g)

and therefore quick lime calcined at 1100 C was very

40
0.4
2

Pore volume / (cc/g)

porous. There were less pores on the surface of quick
limes calcined at 900 and 1000 C because of incom- 0.3

plete and partial thermal decomposition of limestone, 30

while the pores on the surface of quick lime calcined at 0.2

1200 C decreased because of grain growth and den-

sification of quick lime. Figure 3(b) shows that the 20
0.1

limestone calcined at 900 C was not completely de-

composed into quick lime and was left with quick lime 900 1000 1100 1200
0.0

after calcination. Calcination temperature /

o
C

The reactivity of quick lime calcined at 1100 C
as a function of calcination time is shown in Fig. 4.
The calcination time is critical during the calcina-
tion process. It is desirable that the calcination time
should be as short as possible. However, enough
time must be allowed for heat to transfer to the in-
side of CaCO3 particles and for carbon dioxide gas
to be exhausted from the inside of particles. Calci-
nation should be carried out either at low tempera-
ture for long duration time or at high temperature for
short duration time. The calcination time of 120 min
showed the highest reactivity of quick lime in this
work.
The hydration of quick lime was carried out using
water-alcohol mixture. According to Oates[14] , the
hydrated lime that is produced in this process has
high specific surface area and good handling proper-
ties, disperses well and is far more effective in the
removal of acid gases compared to a normal hydrated
lime. Depending on the reactivity of calcined lime,
the form of the final products was a wet paste or a
dried powder after hydration. The hydrates prepared
from quick limes calcined at 900 and 1000 C were wet
paste forms after hydration, while the hydrates from
quick limes calcined at 1100 and 1200 C were dried
powder forms. The XRD patterns of hydrated limes
are shown in Fig. 5. In hydrated samples from quick
limes calcined at 900 and 1000 C, calcite (CaCO3 )
Fig. 6 Variation of specific surface area and pore volume
of hydrated limes as a function of calcination tem-
perature
was found because of uncalcined CaCO3 , while hy-
drated limes from quick limes calcined at 1100 C and
1200 C had no peaks of calcite. It could be related to
the forms of hydrates such as a paste and a powder
as stated above. The crystalline size calculated from
XRD patterns is reported in Table 1. The difference
of crystallinity, which took place during hydration, is
shown at (0001) diffraction peak. Crystals with sizes
ranging from 11.3 to 13 nm appear in the hydrated
lime. The hydrated lime prepared with the quick lime
calcined at 1100 C showed the lowest crystalline size
of 11.3 nm.
The variation of specific surface area and the pore
volume of hydrated lime as a function of calcination
temperature are shown in Fig. 6. The specific sur-
face area and the pore volume of hydrated limes were
analyzed by nitrogen adsorption measurement (BET
method[15] ). This graph shows that the variation of
specific surface area and the pore volume of hydrated
lime has a similar trend with that of specific surface
area and reactivity of quick lime. Hydrated lime from
quick lime calcined at 1100 C showed the highest spe-
cific surface area of 41.53 m2 /g and the highest pore
332 J. Mater. Sci. Technol., Vol.25 No.3, 2009
Table 2 Sulfation test results of hydrated limes
Calcination temp. of quick lime Removal efficiency at 1 min
(Hydrated Lime)
900 C
1000 C
1100 C
1200 C
volume of 0.16 cm3 /g. The low values of hydrated
limes from quick limes calcined at 900 and 1000 C
were caused by low surface area and reactivity of quick
limes including uncalcined limestone. In case of hy-
drated lime from quick lime calcined at 1200 C, an
impervious layer forms on the surface of the quick
lime particle making it difficult for hydration solu-
tion to penetrate, to start and proceed the hydration
process[16] . From these results, it is clear that the
main factors of hydration process are the specific sur-
face area and the reactivity of quick limes in the case
of the same hydration condition. The sulfation test
results were reported in Table 2[17] . The hydrated
lime using quick lime calcined at 1100 C showed 87%
of SO2 removal efficiency. This suggests that the high
specific surface area of hydrated lime increases the re-
moval efficiency for SO2 and it can be related with
the properties of quick lime.
4. Conclusions
The effect of reactivity of quick lime was inves-
tigated with the change of calcination temperature
and time. Hydration and sulfation were carried out
in order to relate the reactivity changes of quick lime
during the calcination process to the properties of the
hydrated lime in the removal of SO2 . From the results
obtained, it is obvious that the higher the homogene-
ity of quick lime and the degree of thermal decompo-
sition of limestone are, the higher the specific surface
area and the reactivity of quick lime become. The
close relationship between the reactivity of quick lime,
the specific surface area of hydrated lime and the SO2
removal efficiency appears to be confirmed from the
results of hydration and sulfation. The physical prop-
erties and the removal efficiency for SO2 of hydrated
limes were affected by the reactivity and the specific
surface area of quick lime in the same hydration con-
dition. The properties of hydrated lime as a sorbent
could be improved by the controlling of hydration con-
dition in consideration of the value of reactivity and
specific surface area of quick limes.
Conditions
/%
56 Reaction temp.: 500 C
SO2 Concentration : 500 ppm
62 SO2 flow rate: 20 l/min
Air flow rate: 200 l/min
87 Pressure: 1 atm
73 Sorbent : 150 g/min
Acknowledgements
This work was supported by the KEMCO grant
funded by the Korea government (MKE, No. 2006-R-
RU-11-P-15-0-000) and partially supported by grants-in-
aid for the National Core Research Center Program from
MEST/KOSEF (No. R15-2006-022-01001-0).
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