Chemical Engineering Science 60 (2005) 34193423

www.elsevier.com/locate/ces
Shorter communication
Removal of sulfur dioxide using absorbent synthesized fromcoal y ash:
Role of oxygen and nitrogen oxide in the desulfurization reaction
Keat Teong Lee, Subhash Bhatia, Abdul Rahman Mohamed

School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan,14300 Nibong Tebal, Seberang Perai Selatan,
Pulau Pinang, Malaysia
Received 30 July 2004; received in revised form 4 November 2004; accepted 19 January 2005
Available online 23 March 2005
Abstract
Removal of SO
2
from ue gas by the absorbent synthesized from coal y ash and calcium oxide was studied under different reaction
conditions to elucidate the effect of the coexistence of NO and O
2
in the ue gas. The presence of O
2
and NO in the ue gas was found
to be necessary to produce sulfate (SO
2
4
) salts instead of sulte (SO
2
3
) salts as the nal product of the desulfurization reaction. The
roles of O
2
and NO were postulated as an oxidizing agent to oxidize SO
2
to SO
3
, which then reacts with the absorbent. NO itself is not
an oxidizing agent, but with the presence of O
2
, it can be oxidized to NO
2
which acts as an oxidizing agent. It was also found that NO
2
(from NO) is a better oxidizing agent compared to O
2
in oxidizing SO
2
to SO
3
.
2005 Elsevier Ltd. All rights reserved.
Keywords: Absorption; Coal y ash; Flue gas desulfurization; Pollution control; Powders; Separation
1. Introduction
Emissions of hazardous sulfur dioxide (SO
2
) resulting
from the combustion of fossil fuels have created serious air
pollution problems in many parts of the world. In the re-
cent years, many studies have shown that when coal y ash
is mixed with calcium hydroxide (Ca(OH)
2
) or calcium ox-
ide (CaO) in a hydration process, absorbents with SO
2
cap-
ture capacity higher than that of hydrated lime could be at-
tained (Davini, 1996; Fernandez et al., 1997, 2001; Garea et
al., 1995; Ho and Shih, 1992; Ishizuka et al., 2000a, 2001;
Karatepe et al., 1998; Lin et al., 2003; Renedo and Fernan-
dez, 2002; Tsuchiai et al., 1995, 1996b). These absorbents
with a high surface area are a product of the pozzolanic re-
action between silica eluted from the y ash and Ca(OH)
2
or CaO. Upon absorption of SO
2
, the absorbents are con-
verted to SO
2
3
(sulte) and/or SO
2
4
(sulfate) salts. The use
of coal y ash as the base material in absorbent synthesis

Corresponding author. Tel.: +60 4 594 1012; fax: +60 4 594 1013.
E-mail addresses: chktlee@eng.usm.my (K.T. Lee),
chrahman@eng.usm.my (A. R. Mohamed).
0009-2509/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2005.01.002
is attractive both economically and environmentally, as it is
the most voluminous by-product of coal-red power plants.
The extent of SO
2
capture by the absorbent derived from
coal y ash/CaO/Ca(OH)
2
varies signicantly under differ-
ent reaction conditions such as different concentration of
SO
2
, reaction temperature and relative humidity (Garea et
al., 1997; Karatepe et al., 1999; Liu et al., 2002). Apart from
that, the coexistence of other gases in the ue gas such as
nitrogen oxide (NO) and oxygen (O
2
) is also bound to affect
the desulfurization activity of the absorbents. There have
been several reports on the effect of NO on the desulfur-
ization activity of the absorbent (Chu and Rochelle, 1989;
Tsuchiai et al., 1996a). However, the conclusions are not
in agreement. Chu and Rochelle (1989) reported that NO
does not signicantly enhance the reaction of SO
2
removal.
However, Tsuchiai et al. (1996a) reported that the presence
of NO in the ue gas enhances the absorption of SO
2
. It
was assumed that NO plays a catalytic role in the oxida-
tion of SO
2
to SO
3
. In a more recent study, Ishizuka et al.
(2000b) reported that the absorbed NO on the surface of the
absorbent is responsible for the formation of SO
2
4
(sulfate)
salts instead of SO
2
3
(sulte) salts in the absorbent. How-
ever, in their study, pure CaO (which has a different surface
3420 K.T. Lee et al. / Chemical Engineering Science 60 (2005) 34193423
morphology and composition from absorbent prepared by
mixing CaO with y ash) was used as the absorbent. These
ndings therefore suggest that a further study on the role
of NO and O
2
in SO
2
capture by absorbent synthesized
from y ash/Ca(OH)
2
/CaO is warranted. In this work, we
report on the effect of the coexistence of NO and O
2
on the
desulfurization activity of absorbent synthesized from coal
y ash and CaO.
2. Experimental section
2.1. Preparation of the absorbent
The starting materials used to prepare the absorbents were
coal y ash and calcium oxide (CaO). The coal y ash used
in this study was supplied by Kapar Power Plant, Malaysia,
of Tenaga Nasional Berhad. Its chemical composition was
analyzed using Rigaku X-ray Spectrometer RIX 3000 and
was found to consist of 60% SiO
2
, 20%Al
2
O
3
, 4.7% Fe
2
O
3
,
3.0% CaO, 1.1% K
2
O, 1.0% MgO, 7.5% C, 2.4% others and
0.3% ignition loss. The CaO used was of laboratory grade
supplied from BDH Laboratory Supplies, England.
For the preparation of the absorbent, 5 g of CaOwas added
to 100 ml of distilled water at 90

C. To the slurry 13.1 g

of coal y ash was then added. The slurry was heated up
to 95

C and maintained at that temperature using a heating

thermal mantle for 10 h for the hydration process to occur.
The resulting slurry was then ltered and dried at 200

C for
2 h producing dry powder-type absorbents. The powder-type
absorbents were then pelletized, crushed and sieved to pro-
duce the required particle size range of 250300 m. This
preparation condition was obtained based on the optimiza-
tion of the absorbent preparation conditions reported else-
where (Lee, 2004).
In order to elucidate the role O
2
and NO in the desulfu-
rization reaction, the spent absorbent after being subjected
to a series of desulfurization reaction under different reac-
tion conditions was tested with Fourier transformed infra
red (FTIR) spectroscopy to identify the presence of specic
functional groups in the spent absorbents. The spent ab-
sorbent was initially mixed with potassiumbromide (KBr) in
the ratio 1:5. The mixture of absorbent and KBr was ground
until a uniform, homogeneous and ne mixture of powder
was obtained. The mixture of powders was then poured into
a pellet mold, and then cold pressed at a pressure of 8 tons.
The thin and transparent pellet was then placed in the sam-
ple holder for analysis. The FTIR spectrum was recorded
on a Perkin-Elmer FTIR 2000 spectrophotometer. In order
to determine the reactivity of air (particularly O
2
) towards
the various species absorbed on the spent absorbent, the pre-
pared transparent pellet was analyzed twice; once directly
after its preparation process and another time after leaving it
exposed to air for 2 h. It was found that there were no signif-
icant differences between the two spectra obtained, indicat-
ing that the air is not reactive towards the absorbed species
on the spent absorbent. However, for preventive measures,
Fig. 1. Schematic diagram of the experimental set-up for xed bed desul-
furization.
the time taken to prepare the transparent pellet and analysis
was kept to a minimum time frame.
2.2. Desulfurization activity study
Desulfurization experiments were performed using a xed
bed test rig, as shown in Fig. 1. The reaction zone was con-
tained in a 0.01 m inner diameter stainless steel tube tted in
a furnace for isothermal operation. The sorbent (0.7 g) was
packed in the center of the reactor supported by glass wool.
A stream of feed gaseous mixture containing 800 ppmv of
SO
2
, 0 and 250 ppmv of NO, 12% of CO
2
, 0 and 5% of
O
2
, and balance nitrogen at a reaction temperature of 150

C
was passed through the absorbent. Prior to that, the N
2
gas
stream was humidied using a humidication system, which
consists of two 250 ml conical ask immersed in a water
bath at constant temperature. The total ow rate of the gas
stream was controlled at 150 ml/min using mass ow con-
troller. The concentration of the SO
2
in the ue gas was
measured using a Portable ue gas analyzer IMR2800P be-
fore and after the absorption process. The concentration of
SO
2
was recorded continuously until 60 min. Two or three
replicate measurements were made for each activity test and
the relative standard deviation was less than 3%. For clarity,
only the averages are presented in this paper. The desulfur-
ization activity in this study is reported as the breakthrough
curves of the desulfurization reaction (C/C
0
vs. t) where C
is the outlet concentration of SO
2
(ppmv) from the reactor
and C
0
is the initial feed concentration of SO
2
(ppmv). The
utilization of Ca
2+
ions in the reacted absorbent or solid
conversion was determined by taking the ratio of the mol of
SO
2
absorbed into the absorbent per mol of Ca
2+
contained
in the absorbent. The mol of SO
2
absorbed into the absorbent
was measured by integrating the difference between the in-
let and outlet concentrations (Tsuchiai et al., 1996a) while
the content of Ca
2+
in the absorbent was determined using
EDTA titration (Lin et al., 2003).
K.T. Lee et al. / Chemical Engineering Science 60 (2005) 34193423 3421
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0 15 30 45 60 75
Time (min)
C
/
C
o
NO: 0 ppmv ; O
2
: 0%
NO: 250 ppmv ; O
2
: 0%
NO: 0 ppmv ; O
2
: 5%
NO: 250 ppmv ; O
2
: 5%
Concentration of NO & O
2
Fig. 2. Desulfurization activity of the absorbent derived from y ash/CaO
at various concentration of NO and O
2
. Feed gas composition at 150

C
and 40% RH: 800 ppmv SO
2
, 0 to 250 ppmv NO, 0 to 5% O
2
, 12%
CO
2
, and the balance N
2
.
3. Results and discussion
In order to elucidate the role O
2
and NO in the desul-
furization reaction, the absorbent synthesized from coal
y ash and CaO was tested for its desulfurization activ-
ity in four series of experimental runs. Fig. 2 shows the
breakthrough curves of the four experimental runs. The
spent absorbents after the desulfurization activity were
tested using FTIR analysis and the spectrum are shown in
Fig. 3 a3d.
In the rst experimental run, the absorbent was subjected
to feed gas without the presence of NO and O
2
. The desul-
furization activity curve (Fig. 2) shows that the absorbent
exhibited a 100% removal of SO
2
for the rst 8 min with a
solid conversion of 57.8%. Referring the FTIR spectrum of
the spent absorbent after the desulfurization reaction under
this condition (in the absence of NO and O
2
), it was found
that the vibration absorption peaks ascribed to SO
2
3
(sul-
te) was detected (Fig. 3a). This result indicated that the
SO
2
in the feed gas was absorbed on the absorbent in the
form of sulte salts (such as CaSO
3
) when NO and O
2
were
not present in the feed gas.
In the second experimental run, the absorbent was sub-
jected to the desulfurization reaction in the presence of
250 ppmv NO and absence of O
2
. Referring to Fig. 2, it was
found that the desulfurization activity of the absorbent un-
der this condition was similar to the desulfurization activity
of the absorbent without the presence of NO and O
2
with a
solid conversion of 56.9%. Referring to Fig. 3b, the FTIR
spectrum of the spent absorbent was also similar to the FTIR
spectrum of the spent absorbent subjected to desulfuriza-
tion reaction without the presence of NO and O
2
, whereby
only the vibration absorption peaks ascribed to SO
2
3
(sul-
te) were detected. Therefore, the presence of NO alone in
the feed gas did not signicantly inuence the desulfuriza-
tion reaction.
In the third experimental run, the absorbent was subjected
to desulfurization reaction in the presence of 5% of O
2
but
without the presence of NO. The desulfurization activity
curve (Fig. 2) shows that there was a substantial increase in
the desulfurization activity of the absorbent. The time the
absorbent could maintain 100% removal of SO
2
increased
to 12 min from the previous 8 min. There was also an in-
crease in the solid conversion of the absorbent to 69.2%.
The presence of O
2
in the feed gas has managed to increase
the desulfurization activity of the absorbent. In order to un-
derstand the role played by O
2
, the FTIR spectrum of the
spent absorbent was studied. Fig. 3c shows that not only the
vibration absorption peaks ascribed to SO
2
3
(sulte) but the
vibration absorption peaks ascribed to SO
2
4
(sulfate) were
also detected in the spent absorbent. Thus, in the presence
of O
2
, the SO
2
in the feed gas is now absorbed in the form
of sulte and sulfate salts. The formation of sulfate salts in-
dicated that SO
2
in the ue gas has been oxidized to SO
3
.
Therefore, it can be concluded that O
2
played a role in the
absorption of SO
2
by initially oxidizing SO
2
to SO
3
. SO
3
then reacted with the absorbent to form the sulfate salts.
However, the stronger peaks ascribed to SO
2
3
as compared
to the peaks ascribed to SO
2
4
in Fig. 3c indicate that most
of the SO
2
in the feed gas was still absorbed in the form of
sulte salts instead of sulfate salts. This nding also showed
that SO
3
can react with the absorbent much faster than SO
2
itself as the activity of the absorbent increased when some
of the SO
2
was absorbed in the form of sulfate salts.
In the nal experimental run, the absorbent was subjected
to a feed gas with the presence of 250 ppmv of NO and 5%
of O
2
. It was observed that the time the absorbent could
maintain 100% removal of SO
2
further increased to 15 min
(Fig. 2) while the solid conversion increased to 79.5%. The
FTIR spectrum of the spent absorbent after being subjected
to desulfurization reaction in the presence of NO and O
2
(Fig. 3d) shows noticeable changes as compared to the FTIR
spectrum of the spent absorbent after subjected to desul-
furization reaction with only the presence of O
2
(Fig. 3c).
It can be seen that the vibration absorption peaks ascribed
to SO
2
3
became weaker, while the vibration absorption
peaks ascribed to SO
2
4
became stronger, indicating that
most of the SO
2
was now absorbed in the form of sulfate
salts instead of sulte salts. The detection of a weak vibra-
tion absorption peak ascribed to NO

3
(nitrate), as shown in
Fig. 3d, indicated that a small amount of NO was absorbed
in the absorbent in the form of nitrate salts. This nding in-
dicated the presence of nitrogen dioxide (NO
2
) in the feed
gas. The presence of NO
2
in the feed gas is most proba-
bly due to the oxidation of NO by O
2
. With the presence of
NO
2
, SO
2
could now be oxidized to SO
3
by NO
2
or O
2
.
With the presence of NO and O
2
in the feed gas, as men-
tioned, more of the SO
2
was absorbed in the form of sulfate
salts instead of sulte salts. Therefore, it can be concluded
that NO
2
(formed from the oxidation of NO by O
2
) was a
better oxidizing agent to oxidize SO
2
to SO
3
than O
2
alone.
These ndings therefore validate the assumption made by
Tsuchiai et al. (1996a) that NO plays a catalytic role in the
3422 K.T. Lee et al. / Chemical Engineering Science 60 (2005) 34193423
Fig. 3. FTIR spectrum of spent absorbent after desulfurization reactions with (a) NO: 0 ppmv and O
2
: 0% (b) NO: 250 ppmv and O
2
: 0% (c) NO:
0 ppmv and O
2
: 5% and (d) NO: 250 ppmv and O
2
: 5%.
oxidation of SO
2
to SO
3
. It was also concluded that NO/NO
2
did not compete with SO
2
for the same absorption sites as
only a weak vibration absorption peak ascribed to NO

3
(ni-
trate) was detected while the vibration absorption peak as-
cribed to NO

2
(nitrite) was not detected at all in the spent
absorbent.
4. Conclusion
The roles of NO and O
2
in the desulfurization reaction by
absorbent synthesized from coal y ash and calcium oxide
were studied. The presence of O
2
and NO in the feed gas
was found to be necessary to produce sulfate (SO
2
4
) salts
instead of sulte (SO
2
3
) salts as the nal product of the
desulfurization reaction.
Acknowledgements
The authors would like to thank ASEAN University Net-
work/Southeast Asia Engineering Education Development
Network (AUN/SEED-Net), JSPS-VCC (Program on En-
vironmental Science, Engineering and Ethics), Ministry of
Science, Technology and Environment Malaysia (Project no.
08-02-05-2040EA001) and Universiti Sains Malaysia (USM
short term grant) for the funding and support on this project.
References
Chu, P., Rochelle, G., 1989. Removal of SO
2
and NO
x
from stack gas
by reaction with calcium hydroxide solids. Journal of Air Pollution
Control Association 39, 175.
Davini, P., 1996. Investigation of the SO
2
adsorption properties of
Ca(OH)
2
-y ash systems. Fuel 75, 713716.
Fernandez, J., Renedo, M.J., Garea, A., Viguri, J., Irabien, J.A., 1997.
Preparation and characterization of y ash/hydrated lime absorbents
for SO
2
removal. Powder Technology 94, 133139.
Fernandez, J., Renedo, M.J., Pesquera, A., Irabien, J.A., 2001. Effect of
CaSO
4
on the structure and use of Ca(OH)
2
/y ash absorbents for
SO
2
removal. Powder Technology 119, 201205.
Garea, A., Viguri, J.R., Irabien, J.A., 1995. Desulfurization rate at low
temperatures using calcium hydroxide and y ash. Coal Science 58,
18631866.
Garea, A., Viguri, J.R., Irabien, J.A., 1997. Kinetics of ue gas
desulphurization at low temperatures: y ash/calcium (3/1) absorbent
behavior. Chemical Engineering Science 52, 715732.
Ho, C.S., Shih, S.M., 1992. Ca(OH)
2
/y ash absorbents for SO
2
removal.
Industrial and Engineering Chemistry Research 31, 11301135.
Ishizuka, T., Tsuchiai, H., Murayama, T., Tanaka, T., Hattori, H., 2000a.
Preparation of active absorbent for dry-type ue gas desulphurization
from calcium oxide, coal y ash and gypsum. Industrial and
Engineering Chemistry Research 39, 13901396.
Ishizuka, T., Kabashima, H., Yamaguchi, T., Tanabe, K., Hattori, H., 2000b.
Initial step of ue gas desulfurizationan IR study of the reaction
of SO
2
with NO
x
on CaO. Environmental Science & Technology 34,
27992803.
Ishizuka, T., Yamamoto, T., Murayama, T., Tanaka, T., Hattori, H., 2001.
Effect of calcium sulphate addition on the activity of the absorbent
for dry ue gas desulphurization. Energy and Fuels 15, 438443.
K.T. Lee et al. / Chemical Engineering Science 60 (2005) 34193423 3423
Karatepe, N., Mericboyu, A.E., Demirler, U., Kucukbayrak, S., 1998.
Determination of the reactivity of Ca(OH)
2
y ash absorbents for SO
2
removal from ue gases. Thermochimica Acta 319, 171176.
Karatepe, N., Mericboyu, A.E., Yavuz, R., Kucukbayrak, S., 1999.
Kinetic model for desulphurization at low temperatures using hydrated
absorbent. Thermochimica Acta 335, 127134.
Lee, K.T., 2004. Flue gas desulfurization studies using absorbent prepared
from coal y ash. Ph.D. Thesis, School of Chemical Engineering,
Universiti Sains Malaysia, Penang, Malaysia.
Lin, B.L., Shih, S.M., Liu, C.F., 2003. Structural properties and reactivities
of Ca(OH)
2
/y ash absorbents for ue gas desulphurization. Industrial
and Engineering Chemistry Research 42, 13501356.
Liu, C.F., Shih, S.M., Lin, R.B., 2002. Kinetics of the reaction of
Ca(OH)
2
/y ash absorbent with SO
2
at low temperatures. Chemical
Engineering Science 57, 93104.
Renedo, M.J., Fernandez, J., 2002. Preparation, characterization
and calcium utilization of y ash/Ca(OH)
2
absorbents for dry
desulphurization at low temperature. Industrial and Engineering
Chemistry Research 41, 24122417.
Tsuchiai, H., Ishizuka, T., Ueno, T., Hattori, H., Kita, H., 1995. Highly
active absorbent for SO
2
removal prepared from coal y ash. Industrial
and Engineering Chemistry Research 34, 14041411.
Tsuchiai, H., Ishizuka, T., Nakamura, H., Ueno, T., Hattori, H., 1996a.
Removal of sulfur dioxide from ue gas by the absorbent prepared
from coal y ash: effects of nitrogen oxide and water vapor. Industrial
and Engineering Chemistry Research 35, 851855.
Tsuchiai, H., Ishizuka, T., Nakamura, H., Ueno, T., Hattori, H., 1996b.
Study of ue gas desulfurization absorbent prepared from coal y ash:
effects of the composition of the absorbent on the activity. Industrial
and Engineering Chemistry Research 35, 23222326.