Chemosphere 74 (2009) 1348–1353

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Chemosphere
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Enhanced dechlorination of chlorobenzene and in situ dry sorption of resultant

Cl-compounds by CaO and Na2CO3 sorbent beds incorporated with Fe2O3
H. Matsuda a, T. Ito a, D. Kuchar a,*, N. Tanahashi b, C. Watanabe a
a
Department of Energy Engineering and Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
b
Energy Applications Research and Development Center, Chubu Electric Power Co., Inc., Japan

a r t i c l e i n f o a b s t r a c t

Article history: The dechlorination of C6H5Cl and the in situ dry sorption of Cl-compounds produced by C6H5Cl decompo-
Received 2 September 2008 sition in an alkaline sorbent of CaO or Na2CO3 incorporated with Fe2O3 were studied. A sample gas con-
Received in revised form 13 November 2008 taining C6H5Cl at an initial concentration of 500 ppm balanced by either N2, O2 (5%)-N2 or H2O (10%)-N2
Accepted 13 November 2008
carrier gas was introduced into a lab-scale quartz tube reactor where CaO or Na2CO3 sorbent was packed
Available online 19 December 2008
with Fe2O3. Subsequently, the effect of Fe2O3 addition to CaO or Na2CO3 on the removal of C6H5Cl,
achieved by the decomposition of C6H5Cl as well as the dry sorption of Cl-compounds produced by
Keywords:
C6H5Cl decomposition, was investigated.
Calcium oxide
Calcium-ferrite
It was found that the decomposition of C6H5Cl in CaO or Na2CO3 sorbent bed incorporated with Fe2O3
Chlorobenzene occurred in the lower temperatures, compared to the case when only CaO or Na2CO3 sorbent bed was
Dechlorination used. Thus, Fe2O3 was found to play a catalytic role in the oxidative decomposition of C6H5Cl. Further,
Iron oxide the decomposition of C6H5Cl in a bed containing only Fe2O3 was promoted by the presence of O2 and
Sodium carbonate H2O in the reaction atmosphere. Moreover, a higher amount of Cl was absorbed in the combined CaO/
Fe2O3 and Na2CO3/Fe2O3 beds, compared to the absorption of Cl-compounds in only CaO or Na2CO3 sor-
bent bed. Finally, the comparison of CaO and Na2CO3 sorbents showed that the decomposition of C6H5Cl
and the in situ dry sorption of the resultant Cl-compounds in the combined Na2CO3 and Fe2O3 beds were
higher than those in the combined CaO and Fe2O3 beds.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction of C2HCl3 in CaO or Na2CO3 sorbent bed occurred at a lower

The majority of chlorinated organics are chemically stable and
persistent, and therefore, remain in the environment for a long per-
iod and may cause serious problems on ecology. In general, the
chlorinated organics such as dioxins, trichloroethylene and
C6H5Cl can be generated by thermal decomposition or combustion
of Cl-containing materials such as PVC, bleaching agents and even
the inorganic salts such as sodium chloride. To prevent the envi-
ronmental pollution, special attention must be paid in controlling
the treatment conditions, so that the dioxins and other harmful
chloride compounds may not be formed in the thermal treatment
of Cl-containing organic and inorganic materials.
In our previous work (Ando et al., 2007), we have studied the
non-catalytic decomposition of C2HCl3 in a lab-scale quartz reactor
packed with CaO or Na2CO3 sorbent under N2 and H2O–N2 atmo-
sphere, and the in situ dry sorption characteristics of CaO and
Na2CO3 for Cl-compounds produced by C2HCl3 decomposition
were evaluated. As a result, it was found that the decomposition
* Corresponding author. Tel.: +81 52 7893383.
E-mail address: d_kuchar@centrum.cz (D. Kuchar).
temperature, compared to the case when no alkaline sorbent was
present in the reactor, and a higher decomposition rate of C2HCl3
was obtained in the presence of H2O in the reaction atmosphere.
Thereby, it was concluded that CaO and Na2CO3 alkaline sorbents
promoted the decomposition of C2HCl3 by the in situ absorptive re-
moval of Cl-compounds produced by C2HCl3 decomposition. As the
Cl-containing reaction products, only CaCl2 and NaCl were de-
tected. Regarding the sorbents, the conversion of CaO to CaCl2 de-
creased at a temperature higher than 1073 K, due to a partial
decomposition of CaCl2 back to CaO. Given these results, the opti-
mum temperature for effective dry sorption of Cl-compounds on
CaO and Na2CO3 during C2HCl3 decomposition was determined to
be 873 K for both sorbents.
Furthermore, non-catalytic decomposition of chlorinated ben-
zenes in the presence of adsorbents such as CaO, Na2CO3 and
MgO has been reported by several authors (Hooker and Klabunde,
1994; Ito et al., 2008). More specifically, Ito et al. (2008) studied
the non-catalytic decomposition of C6H5Cl, which is considered
to be a precursor of dioxins, in a lab-scale quartz reactor packed
with CaO or Na2CO3 alkaline sorbent under N2 or O2-N2 atmo-
sphere. As the results, CaO and Na2CO3 alkaline sorbents were re-
ported to enhance the decomposition of C6H5Cl, by lowering the

0045-6535/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2008.11.029
 H. Matsuda et al. / Chemosphere 74 (2009) 1348–1353
decomposition temperature. Similarly to the study on C2HCl3
decomposition (Ando et al., 2007), the Cl-compounds produced
by the decomposition of C6H5Cl in CaO or Na2CO3 sorbent bed were
absorbed and stabilized in the form of CaCl2 or NaCl. The highest
conversion values of CaO–CaCl2 of 0.23 and Na2CO3–NaCl of 0.38
were obtained at 1073 and 873 K, respectively.
In addition, Sakurai et al. (2002) reported that some volatile or-
ganic compounds such as C2HCl3 were effectively decomposed by
Fe2O3 in aqueous solution. They concluded that Fe2O3 possessed
a catalytic activity which was higher than that of reduced iron. Fur-
ther, Weber et al. (2002), Fujii et al. (2003) reported that the
decomposition of dioxins in the fly ash increased in the presence
of Ca(OH)2. In particular, more than 99% of dioxins in fly ash dis-
charged from municipal solid waste combustors were decomposed
when the fly ash mixed with Fe2O3, Ca(OH)2 and triethanolamine
was kept at 623 K for 35 min (Fujii et al., 2003). Similarly, the
catalytic activity of Fe2O3 towards chlorinated organics was con-
firmed for hexachlorobenzene and carbon tetrachloride (Hooker
and Klabunde, 1994; Ma et al., 2005a,b). In details, Ma et al.
(2005a,b) studied the effect of CaO and Fe2O3 on the dechlorination
of hexachlorobenzene. In their work, they demonstrated that the
extent of dechlorination of hexachlorobenzene was higher when
CaO was mixed with Fe2O3, than when CaO and Fe2O3 were used
separately.
Hence, to further enhance the dechlorination of chlorinated
organics, we studied the catalytic effect of Fe2O3 on the decompo-
sition of C6H5Cl, and also the in situ dry sorption of Cl-compounds
produced by C6H5Cl decomposition using CaO or Na2CO3 sorbent
bed combined with Fe2O3. In particular, the dry sorption capacities
of CaO and Na2CO3 and C6H5Cl decomposition were evaluated un-
der N2, H2O–N2 and O2–N2 atmospheres at the temperatures rang-
ing from 673 to 1273 K. Then, the optimum conditions for effective
removal of C6H5Cl as well as by-products in CaO or Na2CO3 sorbent
bed incorporated with Fe2O3 were investigated.
Fig. 1. Experimental apparatus.
1349
2. Experimental
2.1. Preparation of samples
In the present work, calcium oxide and sodium carbonate were
used as alkaline sorbents. The samples of CaO and Na2CO3 were
prepared by calcinating the commercial CaCO3 and NaHCO3 of re-
agent grade (Wako Chemicals, Japan) in a muffle furnace at 1073 K
for 1 h and at 673–873 K for 1 h, respectively. As a catalyst, the iron
oxide (a-Fe2O3) of reagent grade (Wako Chemicals, Japan) was
used. Further, calcium ferrites of CaFe2O4 or Ca2Fe2O5 provided
by Nippon Steel Co., Japan were used as the chemically bound sor-
bent-catalyst samples.
Prior to the experiments, CaO, Na2CO3, Fe2O3, CaFe2O4 and Ca2-
Fe2O5 were ground in an agate mortar, and were sieved to a mean
particle size ranging from 5 to 20 lm.
2.2. Experiments
A gas flow type tubular reactor packed with CaO or Na2CO3 and
Fe2O3, as illustrated in Fig. 1, was used for the dechlorination of
C6H5Cl and in situ dry sorption of by-products. The reactor con-
sisted of a double tube made of quartz glass. The alkaline sorbents
of CaO or Na2CO3 were placed at the bottom of an inner tube of
20 mm inner diameter. A 20 mg of CaO or Na2CO3 was mixed with
a-Al2O3 particles of 20 lm (mean particle diameter) to adjust the
weight ratio of CaO to a-Al2O3 and Na2CO3 to a-Al2O3 to 0.01. Prior
to the experiments, the effect of a-Al2O3 on C6H5Cl decomposition
was investigated, and as a result, no significant effect of a-Al2O3 on
the thermal decomposition of C6H5Cl was observed in the temper-
ature range of 673–1273 K.
In the case of Fe2O3, Fe2O3 was incorporated with the mixture of
CaO or Na2CO3 with a-Al2O3, and the amount Fe2O3 used was equi-
molar to the respective molar amount of CaO or Na2CO3. Then, the
1350 H. Matsuda et al. / Chemosphere 74 (2009) 1348–1353
following sorbent and catalyst arrangements were studied; (i) mix-
ing Fe2O3 particles with CaO or Na2CO3 particles, (ii) setting Fe2O3
particles bed in the upper stream apart from CaO or Na2CO3 sor-
bent bed, and (iii) using calcium ferrite of CaFe2O4 or Ca2Fe2O5 as
a chemically bound mixture of CaO and Fe2O3.
Quartz wool (SiO2) was placed on the upper surface of the par-
ticles bed to prevent the fine particles of sample from being blown
off the reactor. The quartz wool was also inserted between the sor-
bent bed of CaO or Na2CO3 and Fe2O3 in order to prevent these
samples from contacting. The temperature of the reactor was set
at a prescribed temperature from 673 to 1073 K by adjusting elec-
trical power supply to the electric furnace. The reaction tempera-
ture was monitored continuously by a thermocouple of K-type
which was located at the outer surface of the reaction tube, just
at the center of the packed bed height.
The initial concentration of C6H5Cl was set at 500 ppm, in accor-
dance with the experimental conditions of our previous work on
the decomposition of C6H5Cl in CaO or Na2CO3 packed bed (Ito
et al., 2008). A sample gas of C6H5Cl (500 ppm)-N2 (carrier gas),
C6H5Cl (500 ppm)-H2O (10%)-N2 (carrier gas) or C6H5Cl
(500 ppm)-O2 (5%)-N2 (carrier gas) was supplied to the reactor at
a total gas flow rate of 3  104 m3 min1. It was confirmed that
the mass transfer resistance through a gas film around the alkaline
sorbent particle was negligible at the gas flow rate used.
2.3. Analyses
The effluent gas from the reactor was dehydrated and sampled
at a given time interval. The concentrations of C6H5Cl and by-prod-
ucts in the effluent gas were determined by a gas chromatograph
(GC-2014, Shimadzu, Japan) equipped with porapack Q column.
After each run of the experiments, the alkaline sorbent of CaO or
Na2CO3 was removed from the reactor and was subjected to an
XRD analysis (RINT-2500TTR, Rigaku, Japan) for qualitative analy-
sis of the reaction products formed on the alkaline sorbent. Subse-
quently, the same sample was dissolved in ion-exchanged water,
and the content of Cl in the alkaline sorbent was determined by
an ion chromatograph (LC-10A, Shimadzu, Japan).
2.4. Evaluation of Cl-sorption on alkaline sorbent
The Cl-sorption in CaO or Na2CO3 was determined by the fol-
lowing relations, and the Cl-sorption ratio was based on the
amount of Cl absorbed in CaO or Na2CO3 measured by the ion
chromatograph
MCaCl2
For CaO XCl ¼
MCaO
MNaCl
For Na2 CO3 XCl ¼
2MNa2 CO3
3. Results and discussion
3.1. Decomposition behavior of C6H5Cl under N2, H2O–N2 and O2–N2
atmospheres
The thermal decomposition behavior of C6H5Cl under N2, H2O–
N2 and O2–N2 atmospheres were examined. Fig. 2 shows the con-
version of C6H5Cl obtained at the pseudo-equilibrium conditions
of each reaction atmosphere of C6H5Cl (500 ppm)-N2 (carrier
gas), C6H5Cl (500 ppm)-H2O (10%)-N2 (carrier gas) and C6H5Cl
(500 ppm)-O2 (5%)-N2 (carrier gas), at temperatures of 673–
1273 K. It is seen in the figure that there was no big difference in
the C6H5Cl decomposition obtained under N2 and H2O–N2 atmo-
spheres. Under these reaction atmospheres, gaseous reaction prod-
Fig. 2. Effect of reaction atmospheres on C6H5Cl decomposition.
ucts of HCl, C6H6, C2H2, CH4 were identified, and also carbonaceous
deposit was detected on the surface of quartz wool.
On the other hand, the decomposition of C6H5Cl under O2–N2
atmosphere started already at a temperature below 673 K which
was far lower than 1073 K, observed for the decomposition of
C6H5Cl under N2 and H2O–N2 atmospheres. When the temperature
was raised from 673 to 1073 K, more than 90% of C6H5Cl was
decomposed under O2–N2 atmosphere and HCl, C6H6, CH4, CO,
CO2 and H2O were detected as the reaction by-products. Further,
no carbonaceous deposit was detected on quartz wool and in the
reaction tube under O2–N2 atmosphere, which suggested that a
part of carbon element in C6H5Cl was oxidized to CO2 or CO by
the coexisting O2 gas.
3.2. Decomposition behavior of C6H5Cl in Fe2O3 bed under N2, H2O–N2
and O2–N2 atmospheres
Before studying the decomposition behavior of C6H5Cl in CaO or
Na2CO3 sorbent bed incorporated with Fe2O3 particles, the effect of
only Fe2O3 on the decomposition of C6H5Cl was studied using a
packed bed of 500 mg of a-Fe2O3 particles, under N2, H2O–N2
and O2–N2 atmospheres in the temperatures of 873 and 1073 K.
Fig. 3a shows the concentration profiles of C6H5Cl at the outlet
of a-Fe2O3 bed at 873 K. The concentrations of C6H5Cl at the outlet
of the reactor operated without a-Fe2O3 at 873 K under various
atmospheres are indicated by the chained-lines. As shown in
Fig. 2, the decomposition of C6H5Cl did not occur at 873 K under
N2 and H2O–N2 atmospheres without a-Fe2O3, and thus the
chained line for N2 and H2O–N2 atmospheres shown in Fig. 3a cor-
ð1Þ
responds to the C6H5Cl initial concentration of 500 ppm. As for the
O2–N2 atmosphere, partial decomposition of C6H5Cl was observed
ð2Þ at 873 K without a-Fe2O3 (see Fig. 2), hence the chained line for O2-
N2 atmosphere corresponds to the C6H5Cl concentration of
400 ppm.
Further, regarding the C6H5Cl decomposition in the presence of
Fe2O3, the concentration of C6H5Cl at the outlet of the reactor de-
creased and the extent of this decrease in C6H5Cl concentration de-
pended on the gas atmosphere. Specifically, the concentrations of
C6H5Cl at the outlet of the reactor operated at 873 K approached
the constant values of 470, 400 and 230 ppm under N2, H2O–N2
and O2–N2 atmospheres, respectively. And these concentration val-
ues of C6H5Cl were lower than 500, 500 and 400 ppm under N2,
H2O–N2 and O2–N2 atmospheres, respectively, obtained in the
pseudo-equilibrium conditions of thermal decomposition of
C6H5Cl at 873 K without Fe2O3. It is also seen in Fig. 3a that
Fe2O3 had a catalytic effect on the decomposition of C6H5Cl, even
under N2 atmosphere, but the catalytic effect of Fe2O3 on decompo-
sition of C6H5Cl decreased with time.
 H. Matsuda et al. / Chemosphere 74 (2009) 1348–1353
Fig. 3. Concentration-time curves of C6H5Cl at the outlet of Fe2O3 bed under N2,
H2O–N2, O2–N2 atmospheres at (a) 873 K and (b) 1073 K.
To summarize the experiments at 873 K, the decrease of C6H5Cl
concentration in Fe2O3 bed was found to be in the order, O2–
N2 > H2O–N2 > N2. Therefore, it was concluded that C6H5Cl was
decomposed mainly by catalytic oxidation with Fe2O3, to which
the oxygen was supplied from H2O–N2 and O2–N2 atmospheres.
Further, when the temperature was raised from 873 to 1073 K,
higher decomposition of C6H5Cl was obtained and the results are
presented in Fig. 3b. It can be seen that, at this temperature of
1073 K, the thermal decomposition of C6H5Cl occurred under N2
or H2O–N2 atmosphere even without Fe2O3 presence (see Fig. 2),
and the chained line shown in Fig. 3b for N2 and H2O–N2 atmo-
spheres corresponds to C6H5Cl concentration of 460 ppm, which
was 40 ppm lower than the initial concentration of 500 ppm. How-
ever, the concentration of C6H5Cl was remarkably reduced when
the atmosphere was changed to O2–N2 atmosphere, and the ther-
mal decomposition observed at 1073 K under O2–N2 atmosphere
without Fe2O3 is in Fig. 3b expressed by the chained line at 50 ppm.
As for the results obtained in the reactor operated with Fe2O3
bed at 1073 K, the outlet concentrations of C6H5Cl obtained in
the presence of Fe2O3 under N2 and H2O–N2 were significantly low-
er than those obtained without Fe2O3. And after about 80 min of
the reaction period, the concentration of C6H5Cl approached a cer-
tain constant value. Finally, in the case of O2–N2 atmosphere, the
concentration of C6H5Cl was kept virtually zero for the whole reac-
tion time, and the concentration of benzene produced by the
decomposition of C6H5Cl was kept at a value less than 1 ppm.
After the experiments, Fe2O3 samples obtained after C6H5Cl
decomposition at 1073 K under N2, H2O–N2 and O2–N2 atmo-
spheres were subjected to XRD analyses. In the case of N2 atmo-
sphere, diffraction peaks of Fe3O4 and FeO were observed, which
suggested that the following reductive reactions of Fe2O3 to
Fe3O4 and Fe2O3 to FeO might have taken place, as expressed in
Eqs. (3) and (4). In this process, the O2 released from Fe3O4 and
Fe2O3 was considered to play a role of an oxidant for the oxidative
decomposition of C6H5Cl.
1351
3Fe2 O3 ! 2Fe3 O4 þ ð1=2ÞO2 ð3Þ
Fe3 O4 ! 3FeO þ ð1=2ÞO2 ð4Þ
Further, in the case of samples obtained under H2O–N2 and O2–
N2 atmospheres, the characteristic XRD peaks of Fe3O4 and Fe2O3
were observed in Fe2O3 sample after C6H5Cl decomposition. Simi-
larly to N2 atmosphere, Fe2O3 was reduced to Fe3O4 releasing the
oxygen during C6H5Cl decomposition under H2O–N2 atmosphere.
In contrast, Fe2O3 remained unchanged under O2–N2 atmosphere,
discharging the same amount of O2 as that received by Fe2O3 from
H2O–N2 atmosphere. In this case, Fe2O3 worked as catalyst of O2
donor and O2 acceptor. Given this, it was considered that an en-
hanced decomposition of C6H5Cl in Fe2O3 bed was achieved under
O2–N2 atmosphere.
It is supposed that the amount of O2 became insufficient for the
complete decomposition of C6H5Cl under N2 atmosphere, since the
O2 present in Fe2O3 was consumed by the reaction with C6H5Cl.
Nevertheless, as seen in Fig. 3a and b, the a-Fe2O3 particles still
kept the catalytic ability for C6H5Cl decomposition even after 80
min under N2 atmosphere. To understand the reason why C6H5Cl
decomposition continued to some extent in Fe2O3 particles bed,
even under N2 atmosphere, the Fe2O3 samples recovered after
experiments at different temperatures were subjected to chloride
determination by an ion chromatograph.
Consequently, the soluble chloride content was found to in-
crease from about 1.1  102 mol/mol1 of a-Fe2O3 at 673 K to
about 1.5  102 mol/mol1 of a-Fe2O3 at 1073 K. Such a result
suggested that a part of a-Fe2O3 was reduced to FeCl2 during the
decomposition of C6H5Cl. Consequently, the newly formed FeCl2
was supposed to also work as a catalyst together with a-Fe2O3,
since it has been reported that FeCl2 possessed the catalytic ability
to dechlorinate some chlorinated organics (Lingaiah et al., 1999).
3.3. Decomposition behavior of C6H5Cl and in situ dry Cl-sorption
capacity in CaO sorbent bed incorporated with Fe2O3
The effect of Fe2O3 coexisting with CaO on the dechlorination of
C6H5Cl and the in situ dry sorption of the resultant Cl-compounds
was studied only under N2 atmosphere, and the following three
sorbents and catalyst arrangements were used; (i) mixing Fe2O3
particles with CaO particles, (ii) setting Fe2O3 particles bed in the
upper stream apart from CaO sorbent bed, and (iii) setting CaFe2O4
and Ca2Fe2O5 as chemical compounds of CaO and Fe2O3 in a packed
bed.
Fig. 4 shows the comparison of the three sorbents and catalyst
arrangements in terms of C6H5Cl concentration profiles at the out-
Fig. 4. Time-change of C6H5Cl concentration during C6H5Cl decomposition in CaO
particles bed incorporated with Fe2O3, under N2 atmosphere at 873 K.
1352 H. Matsuda et al. / Chemosphere 74 (2009) 1348–1353
let of CaO sorbent bed coexisting with Fe2O3, under N2 atmosphere
at 873 K. As seen in Fig. 4, the amount of C6H5Cl decomposed with-
in 90 min of the experiment was in the order, (i) > (ii) > (iii). There-
by, it can be said that more effective decomposition of C6H5Cl was
achieved in CaO sorbent bed incorporated with Fe2O3 particles.
It was also found that calcium ferrite of CaFe2O4 showed a high-
er reactivity towards C6H5Cl compared to Ca2Fe2O5, which is in
agreement with the results of Jin et al. (2000), Ciambelli et al.
(2001) who reported that calcium ferrite with higher content of
iron showed higher catalytic oxidation activity (Jin et al., 2000;
Ciambelli et al., 2001). Thereby, a higher C6H5Cl decomposition ra-
tio of CaFe2O4 to Ca2Fe2O5 was attributed to a higher amount of tri-
valent iron in CaFe2O4.
Fig. 5a shows the dry Cl-sorption capacities of different CaO par-
ticles beds coexisting with Fe2O3 during C6H5Cl decomposition un-
der N2 atmosphere at 873 K, in accordance with the above given
three cases of (i) to (iii). The ratio, XCl, 90 min defined by Eq. (1) rep-
resents the amount of Cl absorbed in CaO within 90 min of the
reaction time. In the calculation of XCl, 90 min, the amount of Cl of
1.24  102 absorbed in one mol of Fe2O3 was subtracted from
the total amount of Cl absorbed in CaO + Fe2O3 mixture and cal-
cium ferrites (CaFe2O4 and Ca2Fe2O5). As seen in Fig. 5a, the ratio
of Cl-sorption, XCl, 90 min of only CaO was about 0.18, and the ratio
became higher when CaO was incorporated with Fe2O3. However,
the ratios of Cl-sorption, XCl, 90 min of the two calcium ferrites of Ca-
Fe2O4 and Ca2Fe2O5 were lower, compared to that of only CaO.
Table 1 shows the pore volume and the specific surface area of
CaO, CaFe2O4 and Ca2Fe2O5 measured by an Autosorb-1 (Yuasa
Ionics Co., Japan). As indicated in Table 1, the pore volume and
Fig. 5. (a) Comparison of dry Cl-sorption capacities of CaO particles bed coexisting
with Fe2O3 under N2 atmosphere at 873 K. (b) Comparison of dry Cl-sorption
capacities of CaO and Na2CO3 during C6H5Cl dechlorination.
Table 1
Pore volume and specific surface area of CaO and calcium ferrites.
Pore volume [m3 kg1] Specific surface area [m2 kg1]
CaO 1.7  105
1.0  104
CaFe2O4 2.8  106 1.7  103
Ca2Fe2O5 8.4  107 7.2  102
the specific surface area of CaO used in this study were 1.7 
105 m3 kg1 and 1.0  104 m2 kg1, respectively. But, both values
decreased when CaO and Fe2O3 formed the chemical compounds
known as calcium ferrites. It has been reported that the absorption
capacity of CaO for the dry HCl sorption was closely related to the
pore volume of CaO (Hirabayashi et al., 2002). Therefore, it is con-
sidered that the lower Cl sorption capacity of the calcium ferrites
could be attributed to their low pore volumes.
To investigate the difference in Cl-sorption capacities of the CaO
and Fe2O3 mixed bed with those of CaO and Fe2O3 separate beds,
the sample was recovered from the CaO and Fe2O3 mixed bed
and was subjected to XRD. As a result, the specific XRD peaks of Ca-
Fe2O4 were detected, together with those of the unreacted CaO and
the reaction product of CaCl2.
It has been reported that CaFe2O4 was formed when a mixture
of CaO and Fe2O3 was heated in the temperature range of 873 to
1722 K under O2 atmosphere (Suzuki and Hirabayashi, 2006). From
this report as well as the present findings of the detection of Ca-
Fe2O4, the following reaction of CaO with Fe2O3 was considered
to occur at a temperature higher than 873 K.
CaO þ Fe2 O3 ! CaFe2 O4 ð5Þ
Consequently, the formation of CaFe2O4 in the mixture of CaO
and Fe2O3 caused a drop in Cl sorption capacity, due to a decrease
in the pore volume of CaFe2O4 (see Table 1).
3.4. Comparison of CaO and Na2CO3 dry Cl-sorption capacities during
C6H5Cl decomposition
A comparison of the dry Cl-sorption capacities of CaO with
those of Na2CO3 during C6H5Cl decomposition was carried out,
and in these experiments, the sorbents beds and Fe2O3 were placed
separately. Fig. 5b summarizes the obtained results of the dry Cl-
sorption capacities of CaO and those of Na2CO3 at 673 and 873 K.
It can be seen that both Cl-sorption capacities of CaO and Na2CO3
were remarkably improved when Fe2O3 was incorporated. More
precisely, the ratio of Cl-sorption, XCl, 90 min of CaO calculated for
90 min of the reaction time increased from 0.07 to 0.18 at 673 K
and from 0.18 to 0.35 at 873 K. Similarly, the ratio of Cl-sorption,
XCl, 90 min of Na2CO3 increased from 0.20 to 0.40 at 673 K and from
0.38 to 0.60 at 873 K. This increase in Cl-sorption capacities of CaO
and Na2CO3 incorporated with Fe2O3 may be attributed to the
enhancement in oxidative decomposition of C6H5Cl by Fe2O3. Fur-
ther, as mentioned above, it is considered that the reaction product
of FeCl2 took part in the catalytic decomposition of C6H5Cl as well.
After the dechlorination, the HCl generated from the decomposi-
tion of C6H5Cl was liable to be absorbed on CaO and Na2CO3.
Finally, as a comparison, the values of XCl, 90 min obtained under
O2–N2 atmosphere, are also shown in Fig. 5b, and in can be seen
that the ratio of Cl-sorption, XCl, 90 min of CaO decreased, when O2
was introduced to C6H5Cl–N2 atmosphere. It was found that the
O2 was effective for the enhancement of oxidative decomposition
of C6H5Cl. But, CO2 generated by the decomposition of C6H5Cl
was most likely absorbed on CaO to yield CaCO3, which resulted
in a lower HCl absorption on CaO. Such a conclusion is in an agree-
ment with the results obtained by Duo et al. (1995) who reported
that HCl sorption capacity of CaCO3 was lower than that of CaO.
 H. Matsuda et al. / Chemosphere 74 (2009) 1348–1353
By contrast, the ratio of Cl-sorption, XCl, 90 min of Na2CO3 was in-
creased, when O2 was introduced to C6H5Cl-N2 atmosphere. Simi-
larly to CaO, C6H5Cl was oxidatively decomposed to generate
CO2. However, under present experimental conditions, the gener-
ated CO2 was unlikely to neither be absorbed on Na2CO3 nor react
with Na2CO3 in any other way.
4. Conclusions
The experiments on the decomposition of C6H5Cl and the in situ
dry sorption of by-products were conducted in a lab-scale packed
bed reactor. As alkaline sorbents, CaO or Na2CO3 incorporated with
Fe2O3 were used and the experiments were performed in the tem-
perature range of 673–1073 K. As sample gases, C6H5Cl (500 ppm)-
N2 (carrier gas), C6H5Cl (500 ppm)-H2O (10%)-N2 (carrier gas) and
C6H5Cl (500 ppm)-O2 (5%)-N2 (carrier gas) were used.
The results showed that enhanced decomposition of C6H5Cl oc-
curred in CaO or Na2CO3 sorbent beds and Fe2O3 worked as a cat-
alyst for the oxidative decomposition of C6H5Cl. The amount of Cl
absorbed on CaO was higher when CaO sorbent bed was incorpo-
rated with Fe2O3. However, the amount of Cl absorbed on calcium
ferrites (CaFe2O4 and Ca2Fe2O5) was lower, due to their smaller
pore volume and specific surface. Under O2–N2 atmosphere, it
was found that O2 promoted the decomposition of C6H5Cl. But,
the CO2 generated by the decomposition of C6H5Cl was liable to
absorption on CaO, which led to the reduction of HCl absorption
by the produced CaCO3.
Further, it was recognized that the dry Cl-sorption capacity of
Na2CO3 was higher than that of CaO during C6H5Cl decomposition
and the maximum dry sorption of Cl-compounds was achieved for
Na2CO3 sorbent bed combined with Fe2O3 sorbent bed. It was un-
likely that Na2CO3 was affected by CO2 generated by the oxidative
decomposition of C6H5Cl in O2–N2 atmosphere, since Na2CO3 did
not react with CO2.
1353
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