Chemical Engineering Journal 175 (2011) 512518

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Nano CaO grain characteristics and growth model under calcination

Yanqing Zhu, Sufang Wu , Xieqing Wang
Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China

a r t i c l e

i n f o

Article history:
Received 31 May 2011
Received in revised form
12 September 2011
Accepted 13 September 2011

a b s t r a c t
This paper addresses the grain characteristics and growth model of nano CaO under high-temperature
calcination conditions. Nano CaO samples derived from nano CaCO3 were prepared with a chamber
calciner under different calcination times (10480 min) and temperatures (750900 C) to study the
nano CaO grain growth. X-ray diffractometer and the Scherrer formula were used to test and calculate
the grain size of nano CaO. The microstructure and sorption performances of nano CaO were observed
by a nitrogen adsorption/desorption apparatus and a thermogravimetric analysis. The results showed
that the grain size of CaO grew faster as the calcination temperature increased. A growth asymptote
was approached by prolonging the consecutive calcination time. A grain growth model for nano CaO
was built according to solid phase sintering theory for the following conditions: 10120 min isothermal
calcination at 750900 C. The activation energy for nano CaO grain growth was calculated as 120 kJ/mol.
In addition, the relation of grain growth, structural properties and CO2 adsorption performance of nano
CaO are discussed.
2011 Elsevier B.V. All rights reserved.

Keywords:
Nano CaO
Calcination
Grain characteristics
Growth model

1. Introduction
CaO has been identied as the most promising candidate for
CO2 capture because CaO-based adsorbent has the following advantages: a high reactive sorption capacity for CO2 , a low cost and
the abundance of its natural precursors [1]. CaO-based adsorbents for CO2 capture through carbonationcalcination cycles are
widely studied in zero-emission power generation technologies
[2,3], reactive sorption-enhanced reforming for hydrogen production (ReSER) [46] and energy storage systems in chemical heat
pumps [7,8]. In these technologies, CaO are used repeatedly based
on the reversible reactions given in Eq. (1):
carbonation

CaO(s) + CO2 (g)

calcination

CaCO3 (s) H = 178 kJ/mol

(1)

The calcination process determines the structural characteristics of fresh CaO, which is an active sorbent for CO2 . Sun et al.
[9] investigated sintering during repeated cycles of calcination and
carbonation with limestone. And they found that the carbonation
time has little effect on the pore size distribution of sorbents, i.e.
that sintering of limestone largely occurs during calcination processes. Actually, the sintering of CaO is a common phenomenon
that happens simultaneously with calcination. Many researchers
have studied the consequences of sorbent sintering. Borgwardt
[10] studied the sintering rate of CaO in a N2 atmosphere at

Corresponding author. Tel.: +86 571 87953138; fax: +86 571 87953735.
E-mail address: wsf@zju.edu.cn (S. Wu).
1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.09.084

temperatures between 700 and 1100 C. They found that the

surface area and porosity of sorbent sharply decreased with calcination temperature increased. And sintering of CaO may be
accelerated by the presence of CO2 and H2 O in the gas phase
[11]. Furthermore, Borgwardt modeled the rate of surface area
decrease using a correlation proposed by German and Munir [12].
Wu et al. [13] adopted nano CaO/Al2 O3 to capture CO2 with
carbonationcalcination cycles. They compared the SEM images
before and after 20 runs with the CaO/Al2 O3 sorbents. It showed
that some of the sorbent particles increased from about 10 nm to
about 1.4 m caused by sintering. Many literatures showed that
the sintering of CaO resulted in specic surface area and pore volume reductions [10,1416], average particle size increases [11,13]
and the closure of micropores [11,17]. The changes in the CaO
microstructure signicantly decrease the CO2 sorption capacity and
durability [1820].
Sintering researches above focused on the structural properties
as surface area, pore size and particle size. More detailed studies
showed that calcination caused the formation and growth of CaO
grains. When CaCO3 decomposes at high temperatures, small CaO
grains form, and then the contact grains form necks and begin to
grow, resulting in an increase in the average grain size [10,21]. Currently, there are few published studies addressing CaO grain growth
during calcination. Dash et al. [22] adopted high-temperature Xray diffractometer (HTXRD) to test the CaO grain size derived from
CaCO3 (laboratory reagent) calcination at 1273 K and 1473 K. The
grain sizes of CaO calculated by the Scherrer formula were 17 and
47 nm, respectively. Feng et al. [23] used nano CaCO3 as CaO precursors to investigate the CaO sintering characteristics in multiple

Y. Zhu et al. / Chemical Engineering Journal 175 (2011) 512518

513

Nomenclature
C
d
E

G
0
G
K
M
R
T
t




grain growth rate constant

grain size, nm
activation energy for grain growth, kJ/mol
instantaneous average grain size, nm
initial grain size of CaO after decomposition, nm
Scherrer constant, 0.9
initial mass of sorbent, mg
8.314, J K1 mol1
temperature, K
calcination time, min
main peak breadth in XRD spectra
X-ray wavelength, nm, (=0.15406)
Bragg angle, degree

cycles (carbonation in 100%CO2 and calcination in 100%N2 at temperature of 850 C). He found that the CaO grain size increased from
37 to 62 nm after 6 carbonationcalcination cycles. Li et al. [24]
assumed that limestone modied by acetic acid solution had better sintering-resistance because the modied limestone protected
CaO grain growth. The aforementioned research only studied CaO
grain size change; there has been no detailed investigation of the
grain growth model and its consequences (Table 1).
In this study, nano CaCO3 with a particle size of 70 nm was
adopted as a precursor of nano CaO-based CO2 sorbent. The nano
CaO grain growth characteristics were investigated more systematically under continuous changes in calcination conditions
with X-ray diffractometer (XRD) and Scherrer equation. The grain
growth model of nano CaO related to calcination temperature and
time were investigated. The relation of nano CaO grain growth,
pore size distribution and specic surface area was studied by
nitrogen adsorption isotherm measurement. And the adsorption
performance of CaO sample tested by a thermogravimetric analysis
(TGA) was discussed.

10480 min and then cooled to room temperature to make several

samples.
Samples
of
the
CaO
material
after
multiple
carbonationcalcination cycles were prepared in a vertical
tube in a xed bed. The diagram of gas-solid xed bed reactor
for evaluating CO2 adsorbent was shown in Fig. 3. The inner
diameter of vertical tube reactor is 18 mm. A 10 g sample of nano
CaCO3 was placed around the thermocouple in the tube reactor
to minimize the temperature error. The cyclic CO2 adsorption
tests were conducted under atmosphere pressure. Firstly, heating
the reactor to 800 C and holding for 30 min in a N2 gas ow
(40 mL/min) to complete CaCO3 decomposition. Secondly, cooling
the reactor to 650 C and holding for 40 min, during this period CO2
(10 mL/min) was added to complete carbonation. And then repeat
the calcinationcarbonation cycles. CaO samples were collected
after decomposition period at different cycles.

2. Experimental

2.2. Characterization of nano CaO

2.1. Preparation of nano CaO samples

The X-ray diffraction pattern of CaO was tested by an XRD

(D/MAX-RA, Rigaku, Japan). The characteristic peaks of 2 = 53.9 ,
64.2 and 67.4 in the CaO XRD patterns show that these are single
diffraction apexes without noise interference and are suitable for

Nano CaCO3 (>95% purity) (Hu Zhou Ling Hua Ltd. China) was
used as the CaO-based adsorbent precursor. The X-ray diffraction
pattern tested with XRD and the morphology tested with transmission electron microscope (TEM) were shown in Figs. 1 and 2. Nano
CaCO3 used here is hexagonal calcite with an average particle size
about 70 nm. Nano CaO samples for studying grain growth were
derived from different calcination conditions with a chamber calciner. A 3 g sample of nano CaCO3 was placed in corundum crucible
and put into the chamber of the calciner. The calciner was heated
to 750900 C at a rate of 12 C/min in a N2 ow (0.8 L/min). The
N2 ow was maintained to prevent CaO from reacting with CO2 or
moisture in the atmosphere. The temperature was held constant for

Fig. 1. XRD pattern of nano CaCO3 .

Table 1
Experimental data for CaO grain size during calcination.
t/min

T/K
d/nm

10
60
120
240

1023.5
35.9
42.2
51.7
58.9

1073.5
41.8
51.5
63.0
75.1

1123.5
55.6
63.3
85.2
101.8

1173.5
65.2
91.8
102.7
133.8

Fig. 2. TEM image of nano CaCO3 .

514

Y. Zhu et al. / Chemical Engineering Journal 175 (2011) 512518

Fig. 3. Diagram of the xed bed reactor system.

use in grain size calculations. The mean grain size was determined
by the Scherrer equation, as follows:
d=

K
cos 

(nm)

(2)

where can be tted by XRD characteristic peaks.

TGA (Pyris1, Perkin-Elmer, USA) was used to measure the reactive sorption capacity of nano CaO. Samples of less than 3 mg were
placed into the platinum nacelle of TGA. The sorption process was
conducted at 600 C for 10 min with 0.02 MPa of CO2 in N2 . The
detailed operation of the test is described elsewhere [25]. The reactive sorption capacity was calculated according to Eq. (3):
reactive sorption capacity =

CO2 sorption mol amount

M
1000 (mol/kg)

(3)

The BrunauerEmmerTeller (BET) surface area and the

BarrettJoynerHalenda (BJH) desorption pore size distribution
analyses of samples were conducted by nitrogen physisorption in
liquid N2 using a Belsorp apparatus (BEL II-mini, Japan). And TEM
(JEM-1230, JEOL, Japan) was used to investigate the morphology
of nano CaCO3 and nano CaO. Powder materials were dispersed
in anhydrous alcohol and then ultrasonically dispersed for 20 min.
After pretreatment the samples were observed with high multiple
electron microscope.

were found in Fig. 5 and no CaCO3 was existed because of complete decomposition. The image of CaO was shown in Fig. 6. From
Fig. 6 we found that CaO derived from nano CaCO3 decomposition agglomerated in some extent, and the separated grains were
80100 nm.
3.2. The grain growth characteristic of nano CaO under
calcination
To investigate the effect of calcination temperature and accumulation of the consecutive calcination time on CaO grain growth, four
calcination temperatures (750 C, 800 C, 850 C and 900 C) and
ve isothermal times (10, 60, 120, 240 and 480 min) were selected.
The grain size of the nano CaO under the different calcination conditions is shown in Fig. 7. When raising the calcination temperature
for a xed isothermal time, the grain size of CaO grew signicantly.
Prolonging the calcination time at a xed temperature led to a rapid
increase in the CaO grain size; an asymptote can well describe the
growth curve for longer calcination times.
We also found that the CaO grain size increased 64% at 750 C
after 240 min and gradually accelerated to 105% at 900 C after
240 min. The higher the calcination temperature was, the faster
1.6
594.4 C

1.5
1.4

3. Results and discussion

TGA was adopted to investigate the decomposition temperature of nano CaCO3 . The quality curve of nano CaCO3 was shown in
Fig. 4 when temperature programmed heating from 150 to 850 C
at a rate of 15 C/min in N2 atmosphere. From Fig. 4 we found that
the starting and the complete decomposition temperature of nano
CaCO3 were 594.4 C and 721.1 C respectively. To investigate nano
CaCO3 decomposition in the xed bed, 750 C calcination for 10 min
in N2 atmosphere was adopted. The component and morphology
of decomposition product were examined with XRD and TEM. The
X-ray diffraction pattern was shown in Fig. 5. Typical peaks of CaO

weight(mg)

1.3

3.1. The decomposition of nano CaCO3

1.2
1.1
1.0
0.9
0.8

721.1 C
100

200

300

400

500

600

700

temperature (C)
Fig. 4. Decomposition curve of nano CaCO3 .

800

900

Y. Zhu et al. / Chemical Engineering Journal 175 (2011) 512518

515

110
100
90

grain size(nm)

80
70
60
50
40
30
20

10

20

30

40

runs
Fig. 5. XRD pattern of CaO derived from nano CaCO3 decomposition (decomposition
conditions: N2 atmosphere, 750 C, 10 min in xed bed).

Fig. 8. Nano CaO grain size over multiple cycles (carbonation conditions: 650 C,
40 min (N2 : 40 mL/min, CO2 : 10 mL/min); calcination conditions: 800 C, 30 min (N2 :
40 mL/min)).

The CaO grain growth over multiple cycles was examined, and
the results are shown in Fig. 8. The CaO grain size grew from 47.6
to 82.8 nm after the rst 6 cycles and then leveled out at approximately 90 nm over a total of 40 cycles. This result indicates that the
intermittent calcination time scattered over multiple cycles had a
cumulative effect on the grain growth speed only in the rst few
cycles. The grain size also approached an asymptote as the number
of cycles increased.
3.3. Nano CaO grain growth kinetics

Fig. 6. TEM image of CaO derived from nano CaCO3 decomposition (decomposition
conditions: N2 atmosphere, 750 C, 10 min in xed bed).

2 = Ct
2 G
G
0

140

750 C

120

grain size(nm)

The grain growth kinetics of nano CaO derived from the decomposition of fresh CaCO3 was investigated. CaCO3 calcination to
regenerate CaO is actually a process of simultaneous decomposition
and sintering. Small CaO grains emerge after decomposition and
then migrate to the growth interface of large grains, growing larger
during calcination. This process is similar to the sintering process
of solid-phase materials. The grain growth model of solid-phase
sintering is as follows [20]:

800 C

850 C
900 C

100

80

(4)

is a
In Eq. (4), the instantaneous average grain size of CaO, G,
parabola (opening to the right) for growth as a function of calcination time. Here, we treated C as a grain growth rate constant that
can be used to represent the speed of grain growth. The initial grain
0 , and C are both a function of the
size of CaO after decomposition, G
calcination temperature. C follows the Arrhenius equation, which
can be written as given in Eq. (5). The E in Eq. (5) represents the
activation energy of the grain growth.

E
RT

60

C = C0 exp

40

To determine the activation energy for the grain growth by data

tting, Eq. (5) can be written in a linear form, as follows:

-50

50

100 150 200 250 300 350 400 450 500

t(min)
Fig. 7. CaO grain size under different calcination conditions.

the CaO grains grew. The CaO grain size increased as the consecutive calcination time increased, but the growth was not unlimited.
Increasing the calcination temperature caused the CaO grain size
to increase and the growth rate to accelerate.

ln C = ln C0

(5)

E1
.
RT

(6)

First, Eq. (4) was applied to t the experimental data shown in

2
2 with t, the slope C and intercept G
Fig. 7. By linearly tting G
0
0 has a linear relationship
were obtained. The results showed that G
with the calcination temperature. Eq. (7) is the regression equation
0 and temperature T.
obtained by linearly tting G
0 = 163.7 + 0.19T
G

R2 = 0.9537

(7)

516

Y. Zhu et al. / Chemical Engineering Journal 175 (2011) 512518

By linearly tting ln C and 1/T, the value of C0 and the activation

energy E can be calculated as follows:

140

C0 = 1.25 107

120

0 , we obtain the grain growth

Combining the results of C0 , E and G
kinetics equation:

 120000 

2 = (0.19T 163.7)2 + 1.25 107 exp

G

RT

(8)

A comparison of the CaO grain sizes predicted by Eq. (8) and

the experimental data are shown in Fig. 9. The average relative
deviation is 4.66%. It seems that the grain growth kinetic equation derived here fairly depicts the grain size of nano CaO in a
specic range of the calcination process. As Eq. (4) was derived
from grain boundary movement mechanism [26] without the limitation of particle size. Theoretically, it can be applied to CaO with
0 varied
a wide range of particle size. But the parameters C and G
with different particle sizes.

calculated data(nm)

E = 120kJ/mol

100

80

60

40

20
20

40

60

80

100

120

140

experimental data(nm)
Fig. 9. Comparison of the calculated and experimental data.

3.4. Structural properties related to nano CaO grain growth

The calcination conditions have a strong effect on CaO grain
growth, which further inuences the adsorbent microstructure
properties. The pore size distributions of nano CaO under different
calcination conditions were investigated and shown in Fig. 10.
From Fig. 10(a) we can see that mesopores (approximately 20 nm)
and micropores (<2 nm) were both generated during the initial
calcination under 750 C. As calcination proceeded to 120240 min,

(a)

-3

3.5x10

the number of mesopores clearly decreased and the number of

micropores slightly increased. The similar trend was found under
800 C calcination in Fig. 10(b), and the micropores increased more
obvious when calcination proceeded to 120 min. When calcination
temperature continued to increase to 850 C, more micropores
than mesopores appeared within 120 min calcination. But both
types of pores signicantly decreased in number when the sample

(b)

-3

3.0x10

3.0x10
10min
60min
120min
240min

-3

2.0x10

2.5x10

dvp/drp

-3

2.5x10

dvp/drp

3.5x10

-3

1.5x10

-3

1.0x10

2.0x10
1.5x10
1.0x10

-4

5.0x10

5.0x10

0.0

0.0
0

20

40

60

80

-3

10min
60min
120min
240min

-3

-3

-3

-3

-3

-4

100

20

40

3.5x10
3.0x10

dvp/drp

2.5x10
2.0x10
1.5x10
1.0x10
5.0x10

-3

80

100

(d)

3.5x10

80

100

-3

-3

10min
60min
120min
240min

-3

-3

3.0x10
2.5x10

dvp/drp

(c)

60

rp(nm)

rp(nm)

-3

2.0x10
1.5x10

-3

1.0x10
-4

5.0x10

0.0

-3

10min
60min
120min
240min

-3

-3

-3

-3

-4

0.0
0

20

40

60

rp(nm)

80

100

20

40

60

rp(nm)

Fig. 10. The pore size distribution of CaO for different calcination times (a) C = 10 (750 C calcination); (b) C = 17 (800 C calcination); (c) C = 33 (850 C calcination); (d) C = 57
(900 C calcination).

Y. Zhu et al. / Chemical Engineering Journal 175 (2011) 512518

was calcined for 240 min under 850 C (shown in Fig. 10(c)).
And under 900 C calcination, many micropores appeared within
60 min calcination but sharply decreased in number when the
sample was calcined more than 120 min (shown in Fig. 10(d)).
Under different calcination temperature the trends of pore size
distributions of nano CaO were not uniform. The grain growth rate
constant C was determined by the calcination temperature according to Eq. (5). Under calcinations at 750 C, 800 C, 850 C and 900 C,
C was calculated as 10, 17, 33 and 57, respectively. When C was
1017, the grain growth of nano CaO was relatively slow. Small
grains coalesced and grew to large grains resulted to the original
mesopores between small grains disappeared and transformed to
micropores with smaller space. The pore size tended to be microporous. However, when C continued to increase to 33, the small
grains grew rapidly and the micropores sharply decreased when
the grain size of CaO grew over 100 nm. When C was 57, the grain
size of CaO was already more than 100 nm over 120 min calcination.
The pore size tended to be nonporous. As discussed above, this nding indicated that when sintering was mild, the pore size tended to
be microporous at low grain growth speeds, whereas the material
tended to be nonporous at rapid grain growth speeds, which was
attributed to severe sintering.
The BET-specic surface areas of the CaO samples derived from
different calcination conditions were shown in Fig. 11. It appeared
that the specic surface areas of the CaO were little change at
750800 C calcination within 120 min, and only a slight decline
was observed at 240 min of calcination. However, the specic surface areas of the CaO were little larger during initial times (<60 min)

(a)

20
750 C

surface area(m2 /g)

50

150

200

250

Fig. 11. Specic surface area of CaO derived at different calcination conditions.

at 850900 C calcination and sharply reduced for long calcination

times (>60 min). As the grain size of nano CaO grew for the entire
temperature range investigated, the specic surface area was supposed to decrease with the ongoing calcination. The reason for the
almost unchanged specic surface area at 750800 C calcination
within 120 min and the larger surface areas during initial time at
higher calcination temperatures may be the increase in micropores
(shown in Fig. 10). The emergence of more micropores provided

7
6
5
4
10min
60min
120min
240min

8
7
6
5
4
3

10min
60min
120min
240min

2
1
0
-1

-1
0

t(min)

(d)

reactive sorption capacity(mol/kg)

10min
60min
120min
240min

0
2

t(min)

10min
60min
120min
240min

7
6
5
4
3
2
1
0
-1

t(min)

(c)
reactive sorption capacity(mol/kg)

100

t(min)

reactive sorption capacity(mol/kg)

reactive sorption capacity(mol/kg)

900 C

12

(b)

850 C

800 C

16

517

t(min)

Fig. 12. The reactive sorption capacity of the 1st cycle (a) 750 C calcination; (b) 800 C calcination; (c) 850 C calcination; (d) 900 C calcination.

518

Y. Zhu et al. / Chemical Engineering Journal 175 (2011) 512518

larger surface areas. This effect in some extent counteracted the

decrease of surface areas caused by grain growth. However, at
severe calcination conditions the rapid growth of grains and the
loss of porous structure reduced the specic surface area. We can
conclude that nano CaO grain growth was not the only factor
determining the specic surface area. The specic surface area of
nano CaO was determined by both pore size distribution and grain
growth.
3.5. CO2 adsorption performance related to nano CaO calcination
conditions
The calcination conditions determined the grain growth and the
microstructure characteristics of nano CaO, which further inuenced the CO2 capture performance. TGA was adopted to measure
the sorption capacity of CaO during the rst carbonation, and the
results are shown in Fig. 12. From Fig. 12(a) and (b) we found that
the CO2 sorption capacity was 7.57.8 mol/kg when CaO derived
from 750 to 800 C calcination within 120 min. And a slight decline
was observed in the 240 min calcination samples. Alternatively, the
results from the samples derived from 850 C calcination (Fig. 12(c))
showed that the sorption capacity was 8 mol/kg for 10 min calcination and gradually reduced with calcination time increase
especially more than 60 min. The sorption capacity decreased 50%
and 67% when calcination for 120 min and 240 min. At 900 C calcination shown in Fig. 12(d) high sorption capacity was reached
during initial time and sharply decreased 55% and 76% when calcination for 120 min and 240 min respectively. Compared with the
surface areas of CaO derived from different calcination conditions
(shown in Fig. 11), we found that the sorption capacity of fresh nano
CaO was consistent with the specic surface area evolution.
4. Conclusions
In this paper, the grain growth characteristics and the growth
model of nano CaO derived from fresh nano CaCO3 under different
calcination conditions were studied. The microstructure properties
and the CO2 sorption performance as a function of the nano CaO
grain growth were determined. It was found that the grain size of
CaO grew signicantly and approached an asymptote as isothermal
calcination proceeded. The grain growth kinetic equation was built,
and the activation energy was 120 kJ/mol calculated. The pore size
distribution of nano CaO was determined by the calcination temperature and time and varied at different grain growth speeds. The
specic surface area evolution can be explained by combining the
effects of the grain growth and the pore size distribution, and the
reactive sorption capacity of CaO was consistent with the specic
surface area evolution.
Acknowledgments
We are grateful for support from the National Science Foundation of China (grant no. 20876142) and the State 863 High
Technology R&D Project of China (grant no. 2009AA05Z104).

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.cej.2011.09.084.
References
[1] B. Feng, H. An, E. Tan, Screening of CO2 adsorbing materials for zero emission
power generation systems, Energy Fuels 21 (2007) 426434.
[2] K. Lackner, A guide to CO2 sequestration, Science 300 (2003) 16771678.
[3] H. Gupta, L.S. Fan, Carbonation-calcination cycle using high reactivity calcium
oxide for carbon dioxide separation from ue gas, Ind. Eng. Chem. Res. 41 (2002)
40354042.
[4] C. Han, D.P. Harrison, Simultaneous shift reaction and carbon dioxide separation for the direct production of hydrogen, Chem. Eng. Sci. 49 (1994)
58755883.
[5] D.P. Harrison, Sorption-enhanced hydrogen production: a review, Ind. Eng.
Chem. Res. 47 (2008) 64866501.
[6] S.F. Wu, L.B. Li, Y.Q. Zhu, X.Q. Wang, A micro-sphere catalyst complex with
nano CaCO3 precursor for hydrogen production used in ReSER process, Eng.
Sci. 8 (2010) 2226.
[7] M. Gadalla, Z. Olujic, P. Jansens, M. Jobson, R. Smith, Reducing CO2 emissions
and energy consumption of heat-integrated distillation systems, Environ. Sci.
Technol. 39 (2005) 68606870.
[8] Y. Kato, N. Harada, Y. Yoshizawa, Kinetic feasibility of a chemical heat pump
for heat utilization of high-temperature processes, Appl. Therm. Eng. 19 (1999)
239254.
[9] P. Sun, J.R. Grace, C.J. Lim, E.J. Anthony, The effect of CaO sintering on cyclic CO2
capture in energy systems, AlChE J. 53 (2007) 24322442.
[10] R.H. Borgwardt, Sintering of nascent calcium oxide, Chem. Eng. Sci. 44 (1989)
5360.
[11] R.H. Borgwardt, Calcium oxide sintering in atmospheres containing water and
carbon dioxide, Ind. Eng. Chem. Res. 28 (1989) 493500.
[12] R.M. German, Z.A. Munir, Surface area reduction during isothermal sintering, J.
Am. Ceram. Soc. 59 (1976) 379383.
[13] S.F. Wu, Q.H. Li, J.N. Kim, K.B. Yi, Properties of a nano CaO/Al2 O3 CO2 sorbent,
Ind. Eng. Chem. Res. 47 (2008) 180184.
[14] J.C. Abanades, The maximum capture efciency of CO2 using a carbonation/calcination cycle of CaO/CaCO3 , Chem. Eng. J. 90 (2002) 303306.
[15] V. Fierro, J. Adanez, F. Garcia-Labiano, Effect of pore geometry on the sintering
of Ca-based sorbents during calcination at high temperatures, Fuel 83 (2004)
17331742.
[16] J.C. Abanades, D. Alvarez, Conversion limits in the reaction of CO2 with lime,
Energy Fuels 17 (2003) 308315.
[17] G.S. Grasa, J.C. Abanades, CO2 capture capacity of CaO in long series of carbonation/calcination cycles, Ind. Eng. Chem. Res. 45 (2006) 88468851.
[18] J.C. Abanades, E.J. Anthony, D.Y. Lu, C. Salvador, D. Alvarez, Capture of CO2 from
combustion gases in a uidized bed of CaO, AlChE J. 50 (2004) 16141622.
[19] S. Dobner, L. Sterns, R.A. Graff, A.M. Squires, Cyclic calcination and recarbonation of calcined dolomite, Ind. Eng. Chem., Process Des. Dev. 16 (1977) 479486.
[20] H. Lu, E.P. Reddy, P.G. Smirniotis, Calcium oxide based sorbents for capture of carbon dioxide at high temperatures, Ind. Eng. Chem. Res. 45 (2006)
39443949.
[21] W.Q. Liu, N.W. Low, B. Feng, G.X. Wang, J.C.D. da Costa, Calcium precursors
for the production of CaO sorhents for multicycle CO2 capture, Environ. Sci.
Technol. 44 (2010) 841847.
[22] S. Dash, M. Kamruddin, P.K. Ajikumar, A.K. Tyagi, B. Raj, Nanocrystalline and
metastable phase formation in vacuum thermal decomposition of calcium carbonate, Thermochim. Acta 363 (2000) 129135.
[23] Z.X. Feng, Y. Zheng, L. Zhang, C.G. Zheng, Research on high temperature sintering behavior of CaO sorbent used in multi-cyclic CO2 capturing, J. Eng.
Thermophys. 30 (2009) 537539.
[24] Y.J. Li, C.S. Zhao, H.C. Chen, C. Liang, L.B. Duan, W. Zhou, Modied CaO-based
sorbent looping cycle for CO2 mitigation, Fuel 88 (2009) 697704.
[25] S.F. Wu, Y.Q. Zhu, Behavior of CaTiO3 /Nano-CaO as a CO2 reactive adsorbent,
Ind. Eng. Chem. Res. 49 (2010) 27012706.
[26] G.W. Cui, Defects, diffusion and sintering, Tsinghua University Press, Peking,
1990.