Ind. Eng. Chem. Res.

1996, 35, 2389-2394 2389

Characterization of Reaction between ZnO and COS

Eiji Sasaoka*
Faculty of Health and Welfare Science, Okayama Prefectural University, Kuboki-111,
Soja, Okayama 719-11, Japan

Kazuo Taniguchi, Md. Azhar Uddin, Shigeru Hirano, Shigeaki Kasaoka, and
Yusaku Sakata
Faculty of Engineering, Okayama University, Tsushima-naka, Okayama 700, Japan

In order to understand the behavior of COS in a ZnO desulfurization reactor, the reaction between
ZnO and COS was studied in the presence of gases which compose a coal-derived gas. The
behavior of COS in the reaction zone of a ZnO packed bed can be predicted as follows: H2S in
coal-derived gas reacts more easily with ZnO than COS; most of COS is converted to H2S by
catalytic hydrolysis and then reacts with ZnO, although a part of COS may react directly with
ZnO; H2 accelerates the conversion of COS to H2S; the water-gas shift reaction accelerates the
reaction between ZnO and COS; and CO2 does not affect the reaction.

Introduction controlled by the following reaction:

Solid-oxide fuel cells and molten-carbonate fuel cells,
new technologies using coal-derived gas, are receiving
attention from thermal efficiency and/or environmental
points of view because their high efficiency reduces CO2
emission per unit of electric power without SOx emis-
sion. To establish these highly efficient processes, it is
necessary to develop a high-temperature process for the
desulfurization of coal-derived fuel gas. The highly
efficient removal of sulfur compounds from several
thousand ppm down to ca. 1 ppm has been reported
(Lee, 1987; Lew et al., 1989; Minth, 1991).
From the standpoint of desulfurization efficiency, zinc
oxide is the most attractive among the sorbents reported
because of its favorable sulfidation thermodynamics
(Schrodt et al., 1975; Westmoreland and Harrison,
1976). For this reason, current practical research seems
to be concentrated on zinc oxide (Focht et al., 1988;
Gangwal et al., 1989; Lew et al., 1989; Sa et al., 1989;
Jothimurugesan and Harrison, 1990; Woods et al., 1990;
Ayala et al., 1991; Silaban et al., 1991; Lew et al., 1992;
Sakurai et al., 1994). In particular, a number of studies
of desulfurization using zinc oxide stabilized as zinc
titanate and zinc ferrite have been reported. In these
reports, the practical application of sorbents containing
ZnO to the removal of H2S has been studied, but the
reaction between ZnO and COS has not been clarified.
Although a study of the reaction between MnO and COS
was found (Wakker et al., 1993), the authors were
unable to locate previous studies of the reaction between
ZnO and COS.
From previous papers (Wakker et al., 1993; Akimoto
and Dalla Lana, 1980), it is thought that the catalytic
hydrogenation of COS to H2S, the catalytic hydrolysis
of COS, and the water-gas shift reaction will occur in
addition to the gas-solid reaction of ZnO and COS.
Therefore, to understand the behavior of COS in a
desulfurization reactor, the catalytic activity of ZnO and
ZnS (formed from ZnO) has to be clarified.
We studied the catalytic activity of ZnS formed from
ZnO in order to understand the behavior of COS in the
ZnS zone of a packed-bed desulfurization reactor (Sasao-
ka et al., 1995). It was found that the ZnS formed from
ZnO was active for the conversion of COS to H2S; if the
contact time of COS with ZnS was sufficient, the
equilibrium of the conversion of COS to H2S was
S0888-5885(95)00370-8 CCC: $12.00
2COS + H2 + H2O S 2H2S + CO + CO2
This experimental work focuses on the characterization
of the reaction between ZnO and COS in the presence
of coal-derived gases.
Experimental Section
Preparation of Zinc Oxide. Zinc oxide was pre-
pared by a precipitation method using a 20% aqueous
solution of Zn(NO3)2 and a 14 wt % aqueous NaOH
solution (containing 10% excess of the theoretical amount
of NaOH required for precipitation). The precipitation
was carried out by adding the raw salt solution to the
NaOH aqueous solution under vigorous mixing at room
temperature. The product of the precipitation was
washed, separated by filtration, dried at 110 °C for 25
h, and then calcined in an air stream (300 cm3/min at
STP) from room temperature to 800 °C (10 °C/min, total
3 h). The product thus obtained was crushed and sieved
to 0.7 and 1.0 mm. In this study, two batches of ZnO
prepared by the above method were used because the
amount of catalyst prepared from one batch was not
enough to test the characteristics of the reaction.
Experimental results obtained from the two batches
were somewhat inconsistent. This will be discussed
later. The BET surface area of the sample ZnO of the
first batch (ZnO(a)) was 3.2 m2/g and its bulk density
was 0.84 g/cm3; the BET surface area and bulk density
of the second batch ZnO(b) were 3.5 m2/g and 0.85 g/cm3,
respectively.
Apparatus and Procedure. The sulfidation experi-
ments were carried out using a flow-type packed-bed
tubular reactor system under atmospheric pressure at
500 °C. The microreactor consisted of a quartz tube of
1.5 cm i.d., in which 0.5 mL of sorbent was packed.
The main compounds in coal-derived gases are H2,
CO, CO2, H2O, N2, H2S, and COS. There are large
differences in gas composition depending on the type of
gasifier, the type of coal used, and the kind of gasifica-
tion reagent. The concentration of H2 varies from 29
to 40%; CO, from 16 to 65%; CO2, from 1 to 31%; and
H2O, from 1 to 20%. In a paper published recently
(Sakurai et al., 1994), a mixture of H2S (1%), H2 (30%),
© 1996 American Chemical Society
2390 Ind. Eng. Chem. Res., Vol. 35, No. 7, 1996
Figure 1. Reactivity of ZnO with COS in the presence of H2S,
H2, CO, CO2, and H2O. Sample, 0.7 mm. Reaction conditions: 520
ppm COS, 1100 ppm H2S, 20% H2, 30% CO, 10% CO2, 9.7% H2O,
N2, 500 °C.
CO (40%), H2O (10%), CO2 (10%), and N2 was used as a
simulated coal-derived gas for molten carbonate fuel
cells.
In these experiments, a mixture of COS (520 ppm),
H2S (1100 ppm), H2 (20%), CO (30%), H2O (9.7%), CO2
(10%), and N2 was fed into the reactor at 200 cm3/min
at STP. The space velocity, SV, was 2.4 × 104 h-1. H2S,
COS, CO2, and CO concentrations of inlet and outlet
gases were measured using GC equipped with TCD
(column packing: Porapak QS + PorapakT for H2S,
COS, CO2; Active carbon for CO).
Results and Discussion
Reaction between ZnO and COS in a Simulated
Coal-Derived Gas. The reactivity of ZnO was exam-
ined in the presence of the above gas mixture using
ZnO(a) and ZnO(b). As shown in Figure 1, COS and
H2S simultaneously decreased on ZnO. The production
of elemental sulfur and the vaporization of Zn were not
observed. The fractional decrease of COS or H2S was
calculated using the following equation:
fractional decrease of COS (or H2S) )
[outlet concentration of COS (or H2S)]
1- (1)
[inlet concentration of COS (or H2S)]
Apparently, H2S reacted more easily with ZnO than
COS. The fractional conversions of ZnO to ZnS (from
start to 5 h) were calculated as ca. 0.57 [ZnO(a)] and
ca. 0.50 [ZnO(b)] from the data in Figure 1. The activity
dependence on time on stream was similar for the two
samples. Samples a and b were identical within the
author’s ability to reproduce preparation and analytical
testing (Sakurai et al., 1993).
From the results shown in Figure 1, it can be
concluded that COS and H2S are simultaneously re-
moved in the presence of the coal gases, but it is difficult
to compare the reactivity of COS and H2S with ZnO
because of the existence of H2S: COS may directly react
Figure 2. Reactivity of ZnO with COS. Sample, 0.7 mm. Reaction
conditions: 520 ppm COS, N2, 500 °C.
with ZnO but may also be converted to H2S, and a part
of the H2S formed from COS may escape from the
sorbent without being trapped by the sorbent; if H2S
forms from COS, it cannot be distinguished from the
H2S feed. Therefore, to understand the behavior of COS
in the packed bed, it is necessary to examine the
catalytic hydrogenation of COS to H2S and the hydroly-
sis of COS to H2S (Yumura and Furimsky, 1985;
Sasaoka et al., 1994b) in addition to the gas-solid
reaction of ZnO and COS in the absence of H2S.
Reaction between ZnO and COS. Initially, the
reaction between ZnO and COS in the COS-N2 system
(the gas-solid reaction) was examined at 500 °C using
the two samples of ZnO. As shown in Figure 2, ZnO
reacted with COS and produced CO2. The fractional
formation of CO2 was calculated using the following
equation:
fractional formation of CO2 )
[outlet concentration of CO2]
(2)
[inlet concentration of COS]
In both cases, a yellowish material was deposited as
a thin film on the inside wall downstream from the
reactor tube, a part of the reactor which was cooled by
the atmosphere. This material could not be physically
removed from the wall because the amount of material
was too small. Solid-state byproducts which can be
predicted in this system are elemental sulfur and metal
zinc. Therefore, the reactor was taken off from the
reactor system and dipped in HCl (aq). The material
was insoluble in the solution. When the reactor part
was heated, the material melted and changed color from
yellow to dark reddish black (brown) and smelled of
elemental sulfur. From these results, it was confirmed
that elemental sulfur was produced as a byproduct in
both experiments. This is similar to the results reported
in the case of the reaction between ZnO and H2S
(Yumura and Furimsky, 1985; Sasaoka et al., 1994b).
The production of elemental sulfur suggests that the
catalytic decomposition of COS proceeds over ZnO.

Figure 3. Reactivity of ZnO with COS and H2S. Sample, for
COS: ZnO (a, 0.7 mm); for H2S: ZnO (a, 1.0 mm). Reaction
conditions: 520 ppm COS or 500 ppm H2S, N2, 500 °C.
CO2 was observed in outlet gases from the reactor,
as shown in Figure 2, but only traces (<5 ppm) of CO
were observed.
From these results, it may be concluded that CO2 was
formed from CO produced by the decomposition of COS,
in addition to the COS-ZnO gas-solid reaction. These
reactions are expressed as follows:
-ZnO + COS f Zn-S* + CO2 (3)
X(-Zn-S*) f -Znx-S*x-1 + (1/y)Sy(gas) (4)
-Zn-S* f -ZnS (5)
-Znx-S*x-1 + COS f Zn-S*x + CO (6)
-Zn, and -S* represent an active surface zinc species
and active surface sulfur.
The rate of production of CO2 was not equal to the
rate of COS conversion as shown in Figure 2. The
carbon imbalance may be due to carbon deposition or
CS2 formation. However, carbon deposition was not
confirmed from the color change in the sample before
and after the experiment, and no attempt was made to
detect CS2.
The reactivity of ZnO(a) with COS was higher than
that of ZnO(b), as was the case in Figure 1. Cumulative
amounts of COS reacted with ZnO(a) and ZnO(b) were
ca. 21 cm3 and ca. 14 cm3 at STP, respectively. A
similarity between the samples was observed in the
dependence of the fractional decrease of COS and the
fractional formation of CO2 on time on stream, as well
as the carbon imbalances. As the dependence of the
conversion of COS in the COS-N2 system was consider-
ably different from that in the system of Figure 1, it is
thought that the reactions of eqs 3-6 may not be the
main reactions in the system of Figure 1.
From the results in Figures 1 and 2, it is suggested
that the natures of the two samples are similar although
the reactivity level is not the same. Results using ZnO-
(a) will be primarily shown below.
Comparison of the Reactivity of COS and H2S
for ZnO. To find out the difference in the reactivity of
COS and H2S, the reactivities of COS and H2S for ZnO-
(a) were compared, although the particle sizes of the
samples were not the same (the sample particle for H2S
removal is 1.0 mm in diameter, and that for COS
removal is 0.7 mm in diameter).
As shown in Figure 3, it was confirmed that the
reactivity of H2S with ZnO is considerably higher than
that of COS. This result also suggests that if COS is
partially converted (catalytically) to H2S over the ZnS
Ind. Eng. Chem. Res., Vol. 35, No. 7, 1996 2391
Figure 4. Reactivity of ZnO with COS in the presence of H2.
Sample, ZnO (a, 0.7 mm). Reaction conditions: 520 ppm COS, 20%
H2, N2, 500 °C.
formed and the H2S formed escapes entrapment in the
sorbent in the upstream zone in a packed-bed reactor,
the H2S will react more easily with ZnO than the COS
remaining in the downstream zone. In this H2S-N2
system, the production of elemental sulfur was observed
and confirmed by the same method as in the COS-N2
system. The reactions between ZnO and H2S are
expressed by the following reaction (Sasaoka et al.,
1994b), (eqs 4 and 5):
-ZnO + H2S f -Zn-S* + H2O (7)
Effects of H2 on the Reaction between ZnO and
COS. Figure 4 shows the results of the reaction
between ZnO(a) and COS in the presence of H2. COS
decreased, and a small amount of H2S was produced at
the end of this experiment. The fractional formation
of H2S was calculated using the following equation:
fractional formation of H2S )
[outlet concentration of H2S]
(8)
[inlet concentration of COS]
CO2 was formed at a rate about half that of the COS
decrease. Only traces of CO were formed. In this
system, a whitish (or grayish) film was formed on the
inside wall of the downstream reactor tube which was
cooled by atmosphere. This material could not be
physically removed from the wall because the amount
of material was too small; however, it was insoluble in
water and soluble in HCl(aq). From these results and
published reports (Lew et al., 1989; Sasaoka et al.,
1994a), it is thought that the material is Zn. X-ray
diffraction was used to examine the particles for el-
emental Zn, but no diffraction peaks of Zn were found.
In this system, elemental sulfur was not observed.
From a comparison of Figures 2 and 4, it is clear that,
for the first 2 h, the same COS conversion was observed
both with and without H2, but thereafter the COS
conversion was higher with H2. This effect suggests
that the reaction between ZnO and COS was accelerated
by H2 in the later stage of the reaction. However, the
dependence of the fractional formation of CO2 on the
time on stream in the system with H2 was quite
different from that in the system without H2, and the
carbon imbalance increased in comparison with the
COS-N2 system. From these results, it was suggested
that the reaction mechanism in the system with H2
differed greatly from that in the system without H2: H2
accelerated the reaction between COS and ZnO. To
explain the acceleration of the reaction between ZnO
and COS by H2, the following reactions should be
2392 Ind. Eng. Chem. Res., Vol. 35, No. 7, 1996

considered.

-ZnO + H2 f -Zn + H2O (9)

-Zn + COS f -Zn-S* + CO (10)

If the reactions of eqs 9 and 10 occurred, a reasonable
amount of CO should be detected as a product. As CO2
was formed at a rate about half of that of the COS
decrease, it may be supposed that the CO formed from
COS converted to CO and C (disproportionation). How-
ever, carbon formation on the sample was not observed.
This carbon imbalance will be discussed again below.
After ca. 7.5 h from the start of the reaction, the Figure 5. Reactivity of ZnO with COS in the presence of CO.
formation of H2S was detected, although the reaction Sample, ZnO (a, 0.7 mm). Reaction conditions: 520 ppm COS, 30%
between COS and ZnO was still occurring. This result CO, N2, 500 °C.
suggests that active surface sulfur S* as the precursor
of the elemental sulfur reacted with H2 and formed H2S.
The surface reactions of ZnO in the COS-H2-N2
systems were proposed as follows:

-ZnO + COS f -Zn-S* + CO2 (3)

-ZnO + H2 f -Zn + H2O (9)

-Zn + COS f -Zn-S* + CO (10)

-Zn-S* f ZnS (5)

X(-Zn-S*) f -Znx-S*x-1 + (1/y)Sy(gas) (4)

-Zn-S* + H2 f -Zn + H2S (11)
Here -Zn represents an active surface zinc species
(Sasaoka et al., 1994b). -Zn will be vaporized if the
oxygen (which is connected to the zinc) is reduced with
H2. It is possible that vaporization did not occur in the
COS-N2 system because the -Zn could not be reduced
further. If eqs 10 and 11 proceed quickly on the same
surface site, the following catalytic reaction occurs:
COS + H2 f H2S + CO (12)
If the catalytic reaction of eq 12 largely contributed to
the conversion of COS in this system, a large amount
of CO should be produced. However, only traces of CO
were found in this system. Therefore, for the assump-
tion to be correct, eq 12 should be followed by the serial
reactions of the following equations:
-ZnO + H2S f -Zn-S* + H2O (7)
H2O + CO f CO2 + H2 (13)
Effects of CO on the Reaction between ZnO and
COS. As shown in Figure 5, in the presence of CO the
fractional formation of CO2 was equal to the fractional
decrease of COS. No formation of elemental sulfur or
carbon was observed, nor was the vaporization of Zn. A
comparison of Figures 2 and 5 confirms that CO
inhibited the conversion of COS. The inhibition by CO
may be explained by the following surface reaction:
-Zn-S* + CO f -Zn + COS (14)
No carbon imbalance was found in this COS-CO-N2
system. If the imbalance of carbon is due to the carbon
formation by disproportionation of CO, in this system
the carbon should be formed because that reaction can
occur more easily here than in the COS-N2 system
Figure 6. Reactivity of ZnO with COS in the presence of H2O.
Sample, ZnO (a, 0.7 mm). Reaction conditions: 520 ppm COS, 9.7%
H2O, N2, 500 °C.
(Figure 2). The fact that it was not observed suggests
that the disproportionation of CO is not the cause of
the carbon imbalance in the COS-N2 system. The fact
that elemental sulfur was observed in the COS-N2
system but not in the COS-CO-N2 system indicates
that the concentration of surface -Zn-S* species in the
COS-N2 system was higher than that in the COS-CO-
N2 system. Therefore, it may suggest that surface
-Zn-S* species contribute to the carbon imbalance.
Effect of H2O on the Reaction between ZnO and
COS. The effect of H2O or CO2 on the reaction between
ZnO(a) and COS was examined. As shown in Figure 6,
COS reacted with ZnO and formed CO2 and H2S. From
a comparison of Figures 2 and 6, it is clear that H2O
drastically accelerated the decrease of COS. H2S was
found as a byproduct, and the formation of H2S in-
creased with time on stream. The formation of H2S is
explained by the following reactions:
-ZnO + COS f -Zn-S* + CO2 (10)
-Zn-S* + H2O f H2S + ZnO (15)
The reaction of eq 15 is the reverse reaction of the
desulfurization. However, if eqs 10 and 15 occur quickly
on the same surface site of ZnO, the following catalytic
hydrolysis proceeds:
COS + H2O f H2S + CO2 (16)
If this catalytic reaction occurs quickly, COS is readily
converted to H2S. From the results shown in Figure 3,
it is expected that the H2S formed from COS can react
more easily with ZnO than COS. Therefore, the ac-
celeration by H2O can be explained by catalytic hydroly-
sis.

Figure 7. Reactivity of ZnO with COS in the presence of H2 and
H2O. Sample, ZnO (a, 0.7 mm). Reaction conditions: 520 ppm COS,
20% H2, 9.7% H2O, N2, 500 °C.
In this system, the fractional formation of CO2 was
smaller than the fractional decrease of COS, but the
difference between them was smaller than that in the
COS-N2 system. Therefore, it is thought that H2O
inhibited the carbon imbalance. The inhibition of
imbalance may be due to the reaction of eq 15 because
this reaction decreased the concentration of -Zn-S*
which may be due to the carbon imbalance as described
in the COS-CO-N2 system.
The effect of CO2 on the reaction between COS and
ZnO was examined by the addition of 10% CO2 to the
COS-N2 system, but no effect was observed.
Effect of H2O on the Reaction between ZnO and
COS in the Presence of H2 or CO. As shown in
Figure 7, in the COS-H2-H2O-N2 system, COS was
not detected for ca. 2 h from the start of the reaction.
Neither the production of elemental sulfur nor the
vaporization of Zn was observed. A comparison of
Figures 2, 4, and 7 confirms that the effect of H2O on
the reaction between ZnO and COS is considerably
larger than that of H2. The formation of H2S in Figure
7 was smaller than that in Figure 6, but the decrease
of COS in Figure 7 was almost the same as that in
Figure 6. Therefore, the fractional desulfurization
()fractional decrease of COS - fractional formation of
H2S) in the case of Figure 7 was larger than that in the
case of Figure 6. This result is consistent with the fact
that H2 accelerates the reaction between ZnO and H2S
in the presence of H2O (Sasaoka et al., 1994b).
As the carbon imbalance in the COS-H2-N2 system
was lessened by the presence of H2O, it is suggested that
the reaction of eq 15 may contribute to the decrease of
the imbalance, as in the COS-CO-N2 system (eq 14).
The reactivity of ZnO(a) in the COS-CO-H2O-N2
system is shown in Figure 8. The production of elemen-
tal sulfur and the vaporization of Zn were not observed.
From a comparison of Figures 7 and 8, it is clear that
CO accelerated the conversion of COS more than H2 in
the presence of H2O. This effect is inconsistent with
the results obtained in the absence of H2O. The
following water-gas shift reaction may explain the
different results obtained in the two systems.
CO + H2O f H2 + CO2 (17)
This reaction was confirmed by the production of CO2;
at 40 min from the start of the reaction, the outlet CO2
concentration was 0.5%, and this value gradually de-
creased to ca. 0.05% at 8 h from the start. From this
result, it is supposed that the H2 formed from H2O by
eq 13 accelerated the decrease of COS. However, the
acceleration by CO in the later stages of the reaction
Ind. Eng. Chem. Res., Vol. 35, No. 7, 1996 2393
Figure 8. Reactivity of ZnO with COS in the presence of CO and
H2O. Sample, ZnO (a, 0.7 mm). Reaction conditions: 520 ppm COS,
30% CO, 9.7% H2O, N2, 500 °C.
Figure 9. Effect of H2S on the reactivity of ZnO with COS in the
presence of H2, CO, CO2, and H2O. Sample, ZnO (b, 0.7 mm).
Reaction conditions: s, 520 ppm COS, 20% H2, 30% CO, 10% CO2,
9.7% H2O, N2; - - -, 520 ppm COS, 1100 ppm H2S, 20% H2, 30%
CO, 10% CO2, 9.7% H2O, N2, 500 °C.
was not explained because the amount of CO2 produc-
tion balanced with the amount of COS decrease. In a
previous paper, iron oxide sorbents were activated by
the reduction with H2 followed by reoxidation (Sasaoka
et al., 1992). Therefore, it is possible that the sample
was activated by treatment with the H2 formed from
H2O.
As described above, the production of CO2 balanced
the COS decrease. This result is consistent with that
in Figure 5. Therefore, it is suggested that CO inhibits
the carbon imbalance in the COS-H2O-N2 system.
The effect of CO2 on the reaction between ZnO and
COS was examined in the presence of both H2 and CO.
The effect of CO2 was not observed.
Effect of H2S on the Reaction between ZnO and
COS. As coal-derived gases contain H2S in addition to
COS, H2, CO, CO2 and H2O, the effect of H2S was
examined at 500 °C in the presence of these gases. In
this case, ZnO(b) was used due to lack of the sample
ZnO(a). As shown in Figure 9, H2S inhibited the
decrease of COS (the data in the presence of H2S are
the same data as in Figure 1). COS competes with H2S
to react with ZnO, but H2S is more reactive than COS
(Figure 3). Therefore, this result is reasonable.
Conclusions
To understand the behavior of COS in a desulfuriza-
tion ZnO packed reactor, the effects of coal-derived gases
on the reaction between ZnO and COS were examined.
Generally speaking, a packed-bed reactor is used for
high-temperature desulfurization processes. In the
reactor, it is thought that the gas-solid reactions of
ZnO-H2S and ZnO-COS play an important role in
desulfurization.
2394 Ind. Eng. Chem. Res., Vol. 35, No. 7, 1996
From this work, it is possible to predict the behavior
of COS in the reaction zone of a ZnO packed bed. H2S
in a coal-derived gas reacts more easily with ZnO than
COS. Most of the COS is converted to H2S by catalytic
hydrolysis and then reacts with ZnO, although a part
of the COS may react directly with ZnO. H2 accelerates
the conversion of COS to H2S, and the water-gas shift
reaction accelerates the reaction between COS and ZnO.
CO2 does not affect the reaction.
The practical application of ZnO in desulfurization
reaction usually entails the addition of some support
material to the ZnO in order to improve the mechanical
strength of the sorbent. Al2O3 and TiO2 are sometimes
used as the support (Wood et al., 1990; Wakker et al.,
1993). These metal oxides are known as catalysts for
COS hydrolysis (Akimoto and Dalla Lana, 1980). There-
fore, we expect that sorbents containing these supports
are active for the hydrolysis of COS. From this consid-
eration and the results of this work, it may be concluded
that the most important problem in developing highly
efficient ZnO desulfurization sorbents is the develop-
ment of a highly efficient ZnO sorbent for the removal
of H2S.
Acknowledgment
We gratefully acknowledge that this work was sup-
ported by the Ministry of Education, Science and
Culture, Japan, through the Grant in Aid for Scientific
Research No. 04203111.
Literature Cited
Akimoto, M.; Dalla Lana, I. G. Role of Reduction Sites in Vapor-
Phase Hydrolysis of Carbonyl Sulfide over Alumina Catalysts.
J. Catal. 1980, 62, 84-93.
Ayala, R. E.; Marsh, D. W. Characterization and Long-Range
Reactivity of Zinc Ferrite in High-Temperature Desulfurization
Process. Ind. Eng. Chem. Res. 1991, 30, 55-60.
Focht, G. D.; Ranade, P. V.; Harrison, D. P. High-Temperature
Desulfurization Using Zinc Ferrite: Reduction and Sulfidation
Kinetics. Chem. Eng. Sci. 1988, 43, 3005-3013.
Gangwal, S. K.; Harkins, S. M.; Woods, M. C.; Jain, S. C.; Bossart,
S. J. Bench-Scale Testing of High Temperature Desulfurization
Sorbents. Environ. Prog. 1989, 8, 265-269.
Jothimurugesan, K.; Harrison, D. P. Reaction between H2S and
Zinc Oxide-Titanium Oxide Sorbent. 2. Single-pellet Sulfidation
Modeling. Ind. Eng. Chem. Res. 1990, 29, 1167-1172.
Lee, A. L. DOE Report MC/ 220045-2364: Internal Reforming
Development for Solid Oxide Fuel CellssFinal Report; Depart-
ment of Energy Report MC/220045-2364; U.S. Government
Printing Office: Washington, DC, 1987.
Lew, S.; Jothimurugesan, K.; Flytzani-Stephanopoulos, M. High-
Temperature H2S Removal from Fuel Gases by Regenerable
Zinc Oxide-Titanium Dioxide Sorbents. Ind. Eng. Chem. Res.
1989, 28, 535-541.
Lew, S.; Sarofim, A. F.; Flytzani-Stephanopoulos, M. Sulfidation
of Zinc Titanate and Zinc Oxide Solids. Ind. Eng. Chem. Res.
1992, 31, 1890-1899.
Minth, N. Q. High-Temperature Fuel Cells. CHEMTECH 1991,
120-126.
Sa, L. N.; Focht, G. D.; Ranade, P. V.; Harrison, D. P. Modeling
High Temperature Desulfurization in a Fixed-Bed Reactor.
Chem. Eng. Sci. 1989, 44, 215-224.
Sakurai, T.; Okarnoto, M.; Miyazaki, H.; Nakao, K. High-Tem-
perature Desulfurization Performance and Durability of Fine
Zinc Ferrite Particles Prepared by the Coprecipitation Method.
Kagaku Kogaku Ronbunshu 1993, 20, 275-282.
Sakurai, T.; Okarnoto, M.; Miyazaki, H.; Nakao, K. High-Tem-
perature Desulfurization Performance and Durability of Fine
Zinc-Iron-Aluminum Oxide. Kagaku Kogaku Ronbunshu 1994,
20, 275-282.
Sasaoka, E.; Ichio, T.; Kasaoka, S. High-Temperature H2S Re-
moval from Coal-Derived Gas by Iron Ore. Energy Fuels 1992,
6, 603-608.
Sasaoka, E.; Hirano, S.; Kasaoka, S.; Sakata, Y. Stability of Zinc
Oxide High-Temperature Desulfurization Sorbent For Reduc-
tion. Energy Fuels 1994a, 8, 763-769.
Sasaoka, E.; Hirano, S.; Kasaoka, S.; Sakata, Y. Characterization
of Reaction between Zinc Oxide and Hydrogen Sulfide. Energy
Fuels 1994b, 8, 1100-1105.
Sasaoka, E.; Taniguchi, K.; Hirano, S.; Uddin, M. A.; Kasaoka,
S.; Sakata, Y. Catalytic Activity of ZnS Formed from Desulfu-
rization Sorbent ZnO for Conversion of COS to H2S. Ind. Eng.
Chem. Res. 1995, 34, 1102-1106.
Schrodt, J. T.; Hilton, G. B.; Rogge, C. A. High-temperature
Desulfurization of Low-CV Fuel Gas. Fuel 1975, 54, 269-272.
Silaban, J. T.; Harrison, D. P.; Berggren, M. H.; Jha, M. C. The
Reactivity and Durability of Zinc Ferrite High Temperature
Desulfurization Sorbents. Chem. Eng. Commun. 1991, 107, 55-
71.
Wakker, J. P.; Gerritsen, A. W.; Moulijin, J. A. High Temperature
H2S and COS Removal with MnO and FeO on δ-Al2O3 Accep-
tors. Ind. Eng. Chem. Res. 1993, 32, 139-149.
Westmoreland, P. R.; Harrison, D. P. Evaluation of Candidate
Solids for High-Temperature Desulfurization of Low-Btu Gases.
Environ. Sci. Technol. 1976, 10, 659-661.
Woods, M. C.; Gangwal, S. K.; Jothimurugesan, K.; Harrison, D.
P. Reaction between H2S and Zinc Oxide-Titanium Oxide
Sorbent. 1. Single-pellet Kinetic Studies. Ind. Eng. Chem. Res.
1990, 29, 1160-1167.
Yumura, M.; Furimsky, E. Comparison of CaO, ZnO, and Fe2O3
As H2S Adsorbents at High Temperature. Ind. Eng. Chem.
Process Des. Dev. 1985, 24, 1165-1168.
Received for review June 19, 1995
Accepted April 1, 1996X
IE950370+
X Abstract published in Advance ACS Abstracts, June 1,
1996.