Materials Transactions, Vol. 48, No. 10 (2007) pp.
2739 to 2742
#2007 The Mining and Materials Processing Institute of Japan
Absorption and Release of Carbon Dioxide with Various
Metal Oxides and Hydroxides
Kenji Yamauchi*1 , Norihiro Murayama and Junji Shibata*2
Department of Chemical, Energy and Environmental Engineering, Faculty of Environmental and Urban Engineering,
Kansai University, Suita 564-8680, Japan
Lithium silicate (Li4 SiO4 ) and lithium zirconate (Li2 ZrO3 ) absorb CO2 in a lower temperature range and the absorbed CO2 is released
reversibly in a higher temperature region. In this study, various metal oxides and hydroxides and their complex oxides containing Li were
investigated for their CO2 absorption properties at dierent temperatures in order to get better understanding of the related mechanism.
The inection points in the TG curves, at which predominant reaction changes from CO2 absorption to CO2 release, are observed at around
973 K for Li4 SiO4 and Li2 ZrO3 . The CO2 absorption is based on the formation of Li2 CO3 through the decomposition of Li-containing complex
oxides. From the experimental results and thermodynamical calculations, it is noticed that CO2 absorption takes place very slowly in spite of
large equilibrium constant in the lower temperature region below 873 K, while the absorption at 973 K happens quickly. When the absorption at
973 K and the release at 1273 K are repeated 5 times for Li4 SiO4 , the material maintains its crystal structure to give CO2 absorption and release.
On the other hand, CaO shows an inection point at 1173 K in the TG curve. Magnesium oxide and hydroxide do not react with CO2 below
1273 K. [doi:10.2320/matertrans.M-MRA2007877]
(Received November 20, 2006; Accepted July 2, 2007; Published August 29, 2007)
Keywords: lithium silicate, lithium zirconate, carbonation, absorption kinetics, reaction temperature
1.
Introduction
Carbon dioxide concentration in the global atmosphere is
rising rapidly due to mass consumption of fossil fuels and
carbon dioxide gives rise to the greenhouse eect. The Kyoto
protocol adopted in 1997 requires reduction of such greenhouse gases. In order to eliminate a large amount of
greenhouse gases, in particular CO2 , recovery and xation
technologies are required.112) Those technologies are classied as physical and chemical methods. Carbon dioxide
absorption amount into solutions such as water and alkalis
depends on pressure and temperature under several physical
methods. However, CO2 is discharged easily from absorbents
by decompression and heating with the physical methods. In
the case of chemical absorption reactions using monoethanolamine or K2 CO3 , treatment cost of the CO2 -absorbed
solution is very high.
We focus on the carbonation reactions of metal oxides and
hydroxides, which reveals that the absorbents can be used
repeatedly and CO2 can be concentrated, in order to recover
CO2 . Carbon dioxide is xed in a form of solid through
chemical reactions and is discharged reversibly. Carbonation
of various kinds of materials aects atmospheric CO2
concentration in the world. Lithium silicate (Li4 SiO4 ) and
lithium zirconate (Li2 ZrO3 ) were recently recognized as new
CO2 absorbents by Nakagawa et al.15) They absorb CO2
below 973 K and the absorbed CO2 is released reversibly in
the higher temperature region. If those materials are used as
CO2 absorbents, CO2 can be separated selectively from high
temperature gas containing CO2 without cooling. It leads to
the development of a CO2 removal device which can be used
successively. However, the reactivity and mechanism of CO2
absorption under various reaction conditions and the eect of
the kind of metal oxides and metal hydroxides absorbents on
*1Graduate
Student, Kansai University
author, E-mail: shibata@[Link]
*2Corresponding
reaction rate have not been investigated systematically. We
would like to install removal devices for exhaust gas
containing CO2 in high concentration at high temperature
discharged from factories or garbage incineration facilities.
In this paper, various metal oxides and hydroxides and
their complex oxides containing Li were systematically
investigated for their CO2 absorption properties at dierent
temperatures in order to clarify the related reaction mechanism. Reactivity with CO2 was evaluated by measuring
weight changes resulting from CO2 absorption and release
under various temperatures. Carbonation speed at various
temperatures was obtained from weight increase and contact
time of CO2 . Carbon dioxide absorption and release for
Li4 SiO4 was conrmed repeatedly as a CO2 absorbent. The
equilibrium constants for the observed carbonation reaction
below 1273 K were calculated on the basis of thermodynamics and compared with the experimental results.
2.
Materials and Experimental
The Li-containing complex oxides (Li4 SiO4 , Li2 ZrO3 and
LiAlO2 ) were synthesized from the mixture containing
Li2 CO3 and each metal oxide (SiO2 , ZrO2 and Al2 O3 ) by
the heat treatment at 1273 K for 10 h in an electric furnace. As
all starting material, the reagents obtained from Wako Co.,
Ltd. were used.
Weight change due to CO2 absorption and release was
recorded on a thermogravimetric instrument (TGA-50,
Shimadzu Co.). Samples were heated to 1273 K at a constant
heating rate of 298 K/min under the CO2 ow of 100 cm3 /
min. The CO2 absorption experiments were carried out under
atmosphere pressure.
In order to measure CO2 absorption rate at various
temperatures, the weight changes were determined by TG
analysis when samples were held at 637 K, 773 K, 873 K
and 973 K under CO2 atmosphere for 10 h. Absorption at
973 K and release at 1273 K were repeated 5 times for
2740
K. Yamauchi, N. Murayama and J. Shibata
Table 1
CO2 absorption and release with various substances.
CO2
absorption
CO2
release
Maximum increase
of weigh (%)
Reaction ratio1
(%)
Tabs (T/K)2
Tth (T/K)3
Li4 SiO4
Yes
Yes
32
87.2
973
973
Li2 ZrO3
LiAlO2
Yes
No
Yes
No
13
28.7
973
973
673
CaSiO3
No
No
573
Li2 O
CaO
Yes
Yes
No
Yes
140
19
95.2
24.1
Substance
1273
1173
1273
1173
MgO
No
No
573
LiOH
Ca(OH)2
No
Yes
No
Yes
33
94.0
1173
1273
Mg(OH)2
No
No
753
Weight change (%)
Li4 SiO4 . The reaction time for CO2 absorption and release
were both 0.5 h.
An X-ray diraction analyzer (JDX-3530, JEOL Co.) was
used to identify the crystal structure of the products obtained
after the reaction with CO2 at various temperatures. After
the determination of the reaction equation with CO2 , the
temperature corresponding to Go 0 for CO2 absorption
was thermodynamically calculated with the HSC chemistry
ver. 5.1 (Chemical Reaction and Equilibrium Software with
Extensive Thermochemical Database, Outokumpu Co. ), and
compared with experimental results.
140
20
135
15
130
10
125
120
115
-5
110
-10
105
-15
100
0
373
473
573
673
773
Experimental results of CO2 absorption and release with
various substances are summarized in Table 1. The feasibility of CO2 absorption and release is indicated by Yes
and No in the table. The maximum increase of weight is
corresponding to the maximum value of weight change in the
observed TG curve. The reaction ratio means the percentage
of the measured weight change compared to theoretical
complete carbonation. The observed temperatures at inection points (Tobs ) and the temperature corresponding to
Go 0 (Tth ) based on thermodynamics are compared. As a
result, CO2 absorption and release reactions take place for
Li4 SiO4 , Li2 ZrO3 , CaO and Ca(OH)2 . Carbonation of Li2 O
proceeds at below 1273 K only. Other materials do not react
with CO2 . More information for CO2 absorption and release
reactions with several materials is described below.
The weight change and equilibrium constant of reaction
between Li4 SiO4 and CO2 are shown in Fig. 1 as a function
of reaction temperature. The inection point in the TG curve,
at which predominant reaction changes from CO2 absorption
to CO2 release, is observed at around 973 K. The maximum
weight increase due to absorption of CO2 is 32% at 973 K.
Reaction ratio is calculated to be 87.2% from measured
weight change compared to theoretical complete carbonation.
Figure 2 shows the XRD patterns of products obtained at
973 K and 1273 K for Li4 SiO4 . Li2 CO3 is veried as a result
of CO2 absorption at 973 K. The CO2 absorption is based on
the formation of Li2 CO3 and the decomposition of Li4 SiO4 .
The Li4 SiO4 is formed again by releasing CO2 in the
Li2CO3(s) + Li2SiO3(s)
Fig. 1 Weight change and equilibrium constant for reaction between
Li4 SiO4 and CO2 at various temperatures.
1500
(a) Original material (Li4SiO4)
Li4SiO4
1000
Li2SiO3
Li2CO3
500
Intensity [cps]
Results and Discussion
-20
973 1073 1173 1273
Heating Temp., T / K
(a) Li4SiO4(s) + CO2(g)
3.
873
ln KT[-]
Reaction ratio1 : percentage calculated from the measured weight change compared to theoretical complete carbonation 2 Tabs : temperature at inection
point 3 Tth : temperature corresponding to Go 0
1500
(b) After absorption of CO 2 at 973K
Li2CO3
1000
Li2SiO3
500
1500
(c) After release of CO 2 at 1273K
Li4SiO4
1000
500
0
0
10
20
30
40
50
60
70
2 (deg.) [Cu-K ]
Fig. 2
XRD patterns of reaction products for Li4 SiO4 .
temperature region from 973 K to 1273 K. The reaction
equation between Li4 SiO4 and CO2 is given as follows;
Li4 SiO4 CO2 Li2 SiO3 Li2 CO3
The temperature corresponding to Go 0 for the reaction
(1) is found to be 973 K from thermodynamical calculations.
This temperature is very close to the experimental results.
When the above reaction occurs, the weight of solid is
estimated to increase by 36.7%. CO2 absorption is found
Absorption and Release of Carbon Dioxide with Various Metal Oxides and Hydroxides
Weight change (%)
135
Weight change (%)
(d)
(a) 673K
(b) 773K
(c) 873K
(d) 973K
130
125
120
115
(c)
114
25
112
20
110
15
108
10
106
5
104
102
110
105
100
(b)
(a)
100
0
-5
373
473
573
673
773
(a)
Reaction time, t / h
Li2ZrO3(s) + CO2(g)
1200
600
400
110
200
100
0
0
Li2CO3
500
Intensity [cps]
800
120
Li2CO3(s) + ZrO2(s)
(a) Original material (Li2ZrO3)
Li2ZrO3
Reaction temp., (T / K)
Weight change (%)
1000
130
973 1073 1173 1273
Fig. 5 Weight change and equilibrium constant of reaction between
Li2 ZrO3 and CO2 at various temperatures.
1000
140
873
Heating Temp., T / K
10
Fig. 3 Change in absorption rate at (a) 673 K, (b) 773 K, (c) 873 K and (d)
973 K.
ln KT[-]
140
2741
1000
(b) After CO 2 absorption at 973K
Li2ZrO3
Li2CO3
500
ZrO2
1000
(c) After CO 2 release at 1273K
Li2ZrO3
Reaction time, t / h
Fig. 4 Weight change for reaction between Li4 SiO4 and CO2 during
repetition of absorption and release.
500
0
0
10
20
30
40
50
60
70
2 (deg.) [Cu-K ]
predominant over CO2 release from the calculations, at a
temperature lower than 973 K. However, the weight change
does not appear actually below 673 K in spite of large
equilibrium constant in the lower temperature region.
Reaction kinetics of absorption is thought to be more
decisive.
In order to measure CO2 absorption ratio for Li4 SiO4 in a
lower temperature region, samples were kept at various
temperatures above 673 K under CO2 ow for 10 h. The
results are shown in Fig. 3. At 973 K, weight increase takes
place quickly for 0.5 h and the maximum increase is 34% for
10 h. At 873 K, the weight increase by absorbing CO2 is
12.2% for 10 h. On the other hand, weight change is hardly
observed at 673 K and 773 K after reaction with CO2 for 10 h.
CO2 absorption takes place very slowly below 873 K.
The absorption at 973 K and the release at 1273 K were
repeated 5 times for Li4 SiO4 in order to examine the cyclic
behavior. The results are shown in Fig. 4. The material
obtains 30% of increase in weight in the initial stage of
carbonation. The CO2 absorption and release are found to
occur promptly at the corresponding temperatures. The
material recovers the original weight after every CO2 release.
It is observed from the XRD patterns of reaction products that
the material maintains its crystal structure through the
repeated CO2 absorption and release. Though slight amount
of CO2 absorption decreases with the number of repeating
operations, repeated use of Li4 SiO4 is expected.
Weight change and equilibrium constant for the CO2
absorption and release with Li2 ZrO3 is given in Fig. 5. An
Fig. 6
XRD patterns of reaction products for Li2 ZrO3 .
inection point is observed at around 973 K like the result
with Li4 SiO4 . Li2 ZrO3 exclusively absorbs CO2 below 973 K
and releases above 973 K. The maximum gain of weight is
13%, which is less than that with Li4 SiO4 . The XRD patterns
of the products which reacted with CO2 at 973 K and 1273 K
are shown in Fig. 6. Li2 CO3 is found at 973 K. By heating to
1273 K, Li2 ZrO3 appears again while Li2 CO3 disappears.
The reaction equation between Li2 ZrO3 and CO2 is given as
follows;
Li2 ZrO3 (s) CO2 (g) ZrO2 (s) Li2 CO3 (s)
The temperature corresponding to Go 0 is calculated to
be 973 K for the above equation. This value coincides with
the inection point. Reaction ratio is calculated to be 28.7%
from the ratio between the observed weight increase and
theoretical one. Li2 ZrO3 xes CO2 in the form of lithium
carbonate up to 973 K.
Though it is not shown in the gure for LiAlO2 , any
increase of weight is not observed in the TG analysis results.
The weight of solid is expected to increase by 31.5%
theoretically when LiAlO2 fully absorbs CO2 . It is found
from thermodynamical calculation that CO2 absorption
reaction can proceed below 673 K and CO2 release reaction
becomes predominant above 673 K. The reason why no
weight increase appears for LiAlO2 is caused by the slow
carbonation rate below 673 K. It is supposed that LiAlO2
2742
K. Yamauchi, N. Murayama and J. Shibata
15
130
10
120
110
-5
100
-10
ln KT[-]
Weight change (%)
(a)
-15
90
(b)
-20
-25
80
0
373
473
573
673
773
873
-30
973 1073 1173 1273
Heating Temp., T / K
(a) Ca(OH)2(s) + CO2(g)
(b) CaCO3(s)
CaCO3(s) + H2O(g)
CaO(s) + CaO(g)
Fig. 7 Weight change and equilibrium constant of reaction between
Ca(OH)2 and CO2 at various temperatures.
does not react with CO2 . In the case of CaSiO3 , the weight
would increase by 37.9% if the material fully absorbs CO2 .
According to thermodynamical calculations, CO2 absorption
by CaSiO3 occurs below 573 K. From the results of TG and
XRD, however, no weight change is observed at dierent
temperatures below 1273 K. Since CO2 absorption rate is
very slow in the lower temperature region, it is thought that
contact time with CO2 gas is not enough.
Carbon dioxide absorption and release were examined
using other various metal oxides and hydroxides. Weight
increase of Li2 O is observed to occur rapidly above 773 K.
The maximum increase is 140%. When Li2 O transforms
Li2 CO3 completely, it is calculated that the weight increases
up to by 147%. The reaction ratio is calculated to be 95.2%.
Carbonation of Li2 O is observed below 1273 K only. When
CaO is used as a CO2 absorbent, the weight change is
observed above 673 K and the maximum increase of weight
is 19% at 1173 K. The observed temperature to obtain the
maximum weight is close to the thermodynamically calculated results. In the case of Ca(OH)2 , carbonation and
dehydration occur at the same time below 1173 K as
presented in Fig. 7. The maximum weight change is 33%.
Above 1173 K, CO2 is released by decomposition of CaCO3 .
At 1273 K, weight decreases to 27% from the original weight.
It coincides with the calculated values of weight change by
dehydration. On the basis of thermodynamics, carbonation of
Ca(OH)2 is a predominant reaction below 1273 K. In fact, the
CO2 absorption reaction occurs below 1173 K because
CaCO3 decomposes severely above 1173 K. The temperature
corresponding to Go 0 for CO2 absorption by MgO and
Mg(OH)2 are calculated to be 573 K and 753 K, respectively.
However, no weight increase is observed in the TG curves of
both materials. As stated above, CO2 absorption ratio is the
most responsible for the phenomena.
From a series of CO2 absorption tests with various metal
oxides and metal hydroxides, Li4 SiO4 is found to be the best
absorbent to separate CO2 from a viewpoint of reaction ratio
with carbonation.
4.
Conclusion
Various metal oxides and hydroxides and their complex
oxides containing Li were investigated for the reactivity,
performance and feasibility as CO2 absorbents.
Carbon dioxide absorption is based on the formation of
Li2 CO3 and the decomposition of Li4 SiO4 . The inection
point in the TG curve is found to be 973 K for Li4 SiO4 . It
absorbs CO2 to increase by 33% in weight up to 973 K and
decomposes to Li2 CO3 and Li2 SiO3 above 973 K. Carbonation of this material is a predominant reaction below 973 K
according to the thermodynamic calculation, but, CO2
absorption reaction almost does not proceed in the lower
temperature range below 673 K. The carbonation and
decomposition could be carried out 5 times repeatedly at
the most suitable temperature. Li2 ZrO3 reacts with CO2 in
the same way as Li4 SiO4 below 973 K. The weight increase is
13%, which is less than that of Li4 SiO4 at 973 K. The
inection point of CaO is found to be 1127 K. The temperature at inection point is very close to the thermodynamically calculated results. CO2 absorption takes place very
slowly in the lower temperature region below 673 K, while it
happens quickly at 973 K.
On the other hand, no weight increase is observed for some
materials examined in this study even if CO2 absorption
reaction is expected thermodynamically. For example,
magnesium oxide and hydroxide do not react with CO2
below 1273 K.
Consequently, Li4 SiO4 is found to be the best material in
our study to separate CO2 from exhaust gas. The weight
increase and reaction ratio of Li4 SiO4 after carbonation are
the largest among the studied materials. The observed
carbonation speed is fast at the optimal temperature of 973 K.
Acknowledgment
This work was supported by the MEXT, Grant-in-Aid for
Scientic Research (A)(1), (17206091) and the MEXT,
Grant-in-Aid for Scientic Research (C)(1), (16636027).
REFERENCES
1) K. Essaki, K. Nakagawa, M. Kato and H. Uemoto: J. Chem. Eng. Jpn.
37 (2004) 772777.
2) K. Essaki, K. Nakagawa, M. Kato and H. Uemoto: J. Chem. Eng. Jpn.
37 (2004) 772777.
3) B. N. Nair, T. Yamaguchi, H. Kawamura, S. Nakao and K. Nakagawa:
J. Am. Ceram. Soc. 87 (2004) 6874.
4) M. Kato and K. Nakagawa: J. Cer. Soc. Jpn. 109 (2001) 911914.
5) K. Nakagawa and T. Ohashi: J. Electrochem. Soc. 145 (1998) 1344
1346.
6) Y. Takada, H. Shiomi, T. Isshiki, T. Shiono, M. Kitamura, T. Oosugi
and M. kamitani: J. Soc. Mat. Sci., Japan 52 (2003) 571575.
7) S. Goto, K. Suenaga and T. Kado: J. Am. Ceram. Soc. 78 (1995) 2867
2872.
8) H. Bearat, M. J. McKelvy, A. V. G. Chizmeshya, R. Sharma and R. W.
Carpenter: J. Am. Ceram. Soc. 85 (2002) 742748.
9) J. C.-S. Wu, J.-D. Sheen, S.-Y. Chen and Y.-C. Fan: Ind. Eng. Chem.
Res. 40 (2001) 39023905.
10) Y. Uchiyama: Chem. Eng. (1995) 4045.
11) K. Yamauchi, N. Murayama and J. Shibata: Proceeding of the third
Japan/Korea international symposium on resources recycling and
materials science (2006) 5762.
12) Y. Kawatsu, K. Ishida, N. Murayama, H. Yamamoto and J. Shibata:
Proceedings of MMIJ annual meeting, II (2004) 5354.
