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Energy Procedia 4 (2011) 356–361 Procedia
Energy Procedia 00 (2010) 000–000 www.elsevier.com/locate/procedia
www.elsevier.com/locate/XXX

GHGT-10

Energy analysis of CaCO3 calcination with CO2 capture

Shiying Lina,1*, Takashi Kigaa, Yin Wangb and Katsuhiro Nakayamac
a
Research & Development Department, Japan Coal Energy Center
b
Institute of Process Engineering, Chinese Academy of Sciences
c National Institute of Advanced Industrial Science and Technology, Japan

Elsevier use only: Received date here; revised date here; accepted date here

Abstract

One method for reducing CO2, the green house gas emissions is to capture CO2 before it releases into the
atmosphere and then sequestrate it. Active lime (main component, CaO) can be used to capture CO2 in the exhaust
gas or in the reactor from fossil fuels utilization effectively. That is calcium oxide (CaO) absorbs CO2 to yield
calcium carbonate (CaCO3) (Eq.(1)), then the CaCO3 is thermally decomposed to CaO again and release nearly pure
CO2 (Eq. (2)) for sequestration.
To obtain a nearly pure CO2 stream from CaCO3 decomposition, the heat for decomposing CaCO3 can be
supplied by combusting fossil fuels, such as coal and natural gas, in a calciner with oxygen fuel combustion. The
oxygen diluted by CO2 (CO2 cycle) or H2O (steam cycle), in order to obtain near pure CO2 stream from CaCO3
decomposition. In our previous studies4-6, it was clarified that calcinations of limestone (main component, CaCO3)
in a fluidized bed calciner can be performed in CO2 cycle atmosphere when the bed temperature was raised above
1293 K, whereas with 60% steam cycle in atmosphere, limestone can be decomposed at comparatively lower
temperature, such as 1173 K. The decomposition conversions of the limestone were about 95% and 98%, in CO2
cycle and in steam cycle atmospheres, respectively. Reducing the calcinations temperature of limestone was helpful
to produce more than 30% active CaO as shown in previous study4-6.
In this study, the energy of CaCO3 calcination process by H2O (steam) cycle was analyzed and compared with
CaCO3 calcination process by CO2 cycle. For process calculations, the mass and energy flows were calculated
iteratively, based on the input and output balances, until err [(input – output)/input] was < 0.01. Analysis showed
that, although H2O (steam) cycle calcination had calcination energy more about 3.6% than CO2 cycle due to water
evaporation latent heat loss, however, the calcination energy per active CaO was lowest for H2O (steam) cycle.
⃝c© 2011
2010 Published by Elsevier
Elsevier Ltd. All rightsLtd.
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Open
vedaccess under CC BY-NC-ND license.

Keywords: CO2 sorbent, Limestone calcinations, Reactivity, Energy, Chemical loop

1. Introduction
The reduction of anthropogenic CO2 emission is becoming increasingly urgent because CO2 contributes to
global warming. One method for reducing CO2 emission is to capture and sequestrate CO2 before it is released into
the atmosphere. Calcined lime (main component, CaO) can be used to capture CO2 in the exhaust gas1 or in the
reactor2,3 during the utilization of fossil fuels. That is calcium oxide (CaO) absorbs CO2 from fuel gas to yield

* Corresponding author. Tel.:+81-3-6400-5198; fax:+81-3-6400-5207.

E-mail address:slin@jcoal.or.jp.

doi:10.1016/j.egypro.2011.01.062
 S. Lin et al. / Energy Procedia 4 (2011) 356–361 357

2 Author name / Energy Procedia 00 (2010) 000–000

calcium carbonate (CaCO3)(Eq.(1)), and the CaCO3 is then thermally decomposed to CaO, releasing nearly pure
CO2 for sequestration (Eq. (2)).

In fact, the heat for decomposing CaCO3 can be supplied by combusting fossil fuels, such as coal and natural
gas, in a calciner.  To obtain a nearly pure CO2 stream from CaCO3 decomposition, CaCO3 could be calcined by
the oxygen fuel combustion with a CO2/O2 or with steam/CO2/O2 (Fig.1). Steam is added to the calcination
atmosphere to reduce CO2 partial pressure, and the reduction of CO2 partial pressure can decrease the decomposition
temperature of CaCO3 (Fig.2). The equilibrium constant KC of CaCO3 decomposition in Figure 2 was calculated by
using a thermodynamic calculation soft HSC 4.0.
CaO  CO 2 o CaCO 3 ; ٌH298= —178 kJ/mol (Exothermic) (1)
CaCO 3 o CaO  CO 2 ; ٌH298=178 kJ/mol (Endothermic) (2)

COCO
2ࠨࠗࠢ࡞ࠞ὾
2 cycle
1000
CaCO
C/O2 3 ࠞ὾Ἱ
Calciner CO2
CaCO
/C/O 1200
1200͠͠ 100 CaCO3=CaO+CO2
2 3
CO2  atm
KC=1/PCO2 [1/atm]

CO2 10 with steam dilution

CaO
1
᳓⫳᳇ࠨࠗࠢ࡞ࠞ὾
H2O (Steam) cycle CO2 1 atm
0.1
CaCO
C/O2 3 ࠞ὾Ἱ
Calciner CO2 ͠ ͠ CaCO3
/C/O
CaCO
2 3 900͠
900 ͠ 0.01
1000 1200 1400
H2O
Temperature [ K ]

Figure 1 Concepts of CaCO3 calcination by the H2O Figure 2 Reaction equilibrium constant for CaCO3
(steam) cycle and CO2 cycle oxygen fuel combustion. decomposition.
Conversion of CaO to CaCO3 [%]

1193PKCO2oxygen
0.04 MPa, 923 K
fuel calcination
100
with H2O(steam 60%) dilution
80 60% steam dilution 1193 K
IncreaseCO2 absorption
60
capacity30%
40
100% CO2 1293 K
20 1293 K oxygen fuel calcination
with CO2 dilution
0
0 20 40 60 80 100
Time [min]

Figure 3 The continuously operating calciner apparatus for Figure 4 Comparison of CO2 absorption capacity of CaO
limestone calcinations by oxygen fuel combustion with H2O obtained by limestone calcination of coal oxygen fuel
(steam) and CO2 cycle4-6. combustion with H2O (steam 60%) cycle and CO2 cycle.
358 S. Lin et al. / Energy Procedia 4 (2011) 356–361

Author name / Energy Procedia 00 (2010) 000–000 3

In previous studies4-6, we experimentally studied a limestone (main content is CaCO3) calcinations with O2
coal combustion in CO2/O2 and steam/O2 atmospheres by used a fluidized bed calciner (Fig. 3). Table 1 shows
limestone decomposition conversion obtained from previous study4-6. Limestone can be near completely
decomposed with the H2O (steam) cycle at comparatively lower temperatures, such as 1173 K.

Table 1 Limestone decomposition conversion in a fluidized bed calciner (%)

1173 K 1193 K 1273 K 1373 K 1473 K
H2O(steam 60%) cycle 98
CO2 cycle 72 89 96 99 (simulated)

After the limestone calcination, we compared the carbonation reactivity of the CaO products with nearly the
same decomposition conversions, 98% obtained with 60% H2O (steam) cycle and 95% obtained with CO2 cycle by
means of TGA (Fig.4). For the carbonation test at 923 K and a CO2 partial pressure of 0.04 MPa, close to 70%
carbonation conversion (CaOCaCO3) was obtained with the CaO produced by H2O (steam) cycle, whereas the
conversion was about 40% for the CaO produced by CO2 cycle, which indicates that the active CaO was greatly
improved by limestone calcinations with H2O (steam) cycle. These results can be explained in terms of the
decreased calcination temperature (due to the fact the steam cycle lowered the CO2 partial pressure) and the
shortening of the average residence time of the particles in the fluidized bed, which effectively prevented the
sintering of particles. Prevention of sintering enhanced the active CaO produced by increasing the specific surface
area and pore volume.
However, there is anxious about that the latent heat loss of water evaporation (Eq.(3)) by H2O (steam) cycle
will increase too much calcinations energy consumption.
H 2O(l ) o H 2O( g ) ; ٌH298=44.03 kJ/mol (3)

Accordingly, in this study, we used thermodynamic calculations to analyze the material and energy balances in
the limestone calcinations process by H2O (steam) cycle and CO2 cycle in which CO2 capture is premised.
Calcination energies per active CaO which produced by H2O(steam) cycle calciantion was examined and compared
with that by CO2 cycle.

2. Calculation methods
2.1. Thermodynamic calculation
The calculation program and thermodynamic data from HSC Chemistry 4.0 software were used.7 In the
calculation, the enthalpy of substances is given as
T
H (T ) H f (298)  ³ C P dT  ¦ H tr (4)
298
where Hf(298) is the enthalpy of formation at 298 K, Cp is the heat capacity at constant pressure, T is temperature,
and Htr is the enthalpy of phase transformation of the substance. The temperature dependence of the heat capacity in
the calculation is used by fitting the experimental heat capacities.
Cp A  10 3 B ˜ T  10 5 C ˜ T 2  10 6 D ˜ T 2 (5)
where A, B, C and D are coefficients estimated from experimental data.
Entropy values can be calculated from the heat capacity by using eq. (9) and numerical integration.
T
S S 0 (298)  ³ (C P / T )dT  ¦ H tr / Ttr (6)
298
where S0(298) is the standard entropy of the substance, which can be calculated by integrating the CP/T function
from 0 to 298 K, and Ttr is the temperature of phase transformation.
The Gibbs energy G is defined by as G { H  T ˜ S . The Gibbs energy change, Gr, for a chemical
reaction,
aA  bB  ... cC  dD  ... , (7)
is calculated as the difference in the Gibbs energy between the products and the reactants:
 S. Lin et al. / Energy Procedia 4 (2011) 356–361 359

4 Author name / Energy Procedia 00 (2010) 000–000

'Gr { ¦ vi Gi (products)  ¦ vi Gi (Reactants)

(8)
(c ˜ GC  d ˜ G D  ...)  (a ˜ G A  b ˜ G B  ...)
where a is the stoichiometric coefficient of a species GA in reaction and so on; and v is the stoichiometric coefficient
of a species in the reaction. The equilibrium products for the reactants can be obtained by minimizing the Gibbs
energy of the system under a desired set of conditions (temperature and pressure).

2.2. Mass and energy flow calculation

Given the input mass flow and the operating conditions (temperature and pressure), for a reactor, the output
mass flow is obtained by calculating the equilibrium composition. Then the heat contained in the output mass flow
is calculated. For process calculations, the mass and energy flows were calculated iteratively, based on the input and
output balances, until err ((input –output)/input) was < 0.001.

2.3. CaCO3 Calcination process components

The main components of the limestone calcinations process are one calciner and two heat exchangers for
exhaust gas (heat exchanger (a)) and exhaust solid (heat exchanger (b)). Calciner is a reactor for coal combustion
and for CaCO3 decomposition, which produce CO2 gas and lime (CaO) solid. Heat exchangers (a) and (b) are used
for sensible heat recovery of exhaust gases and solid from calciner.
The operating temperature of calciner is 1173 K for H2O (steam) cycle and 1173 K to 1473 K for CO2 cycle,
as determined from experimental results.4-6

3. Results and discussion

Figure 5 shows the results of energy and material balances for CaCO3 calcination with H2O (steam 60%, O2
40%) cycle. Calcination temperature was set at 1173 K, with limestone decomposition conversion be about 98%
from the fluidized bed calciner shown in previous study4-6. The sensible heat recovery efficiency for heat
exchangers (a) and (b) were suggested as 80%. It can be seen that, the reaction heat of CaCO3 decomposition is
178kJ/mol-CaCO3, and the exhaust heat (423K) after heat exchanger is 43.6kJ/mol-CaCO3 which contained sensible
heat 26% with latent heat of water evaporation 74%. The exhaust sensible heat (423K) after heat exchange (a) and
(b) were 19.07 and 8.8 kJ/mol-CaCO3. The latent heat of water evaporation was 32.3 kJ/mol-CaCO3. The exhaust
heat (423 K) is used about 9.67 kJ/mol-CaCO3 to preheat water. Accordingly, total energy consumption of
calcination is 228.51 kJ/mol-CaCO3, reflected the total heat loss is 50.51 kJ/mol-CaCO3. Accordingly, the energy
excess for the H2O (steam) cycle calcination is as
Total energy consumption of calcination 228.51
Energy excess 1.28
Energy of CaCO3 decomposition 178

Heat and mass balance for H2O (steam) cycle calcination process Heat and mass balance fo CO2 cycle calcination process
㧔calcination temperature 900͠‫ޔ‬sensible heat recovery 80% ) 㧔
calcination temperature 1200͠‫ޔ‬sensible heat recovery 80% )

CaCO3(1mol)/ CO2(1.56 mol) 㧔

㗼ᾲ11.30 kJ㧕 Fuel excess＝
H2O(0.84mol) Fuel excess＝ CaCO3(1mol)/
CO2(1.56 mol)
C(0.56mol) 75͠ Calcination Energy
150͠(43.6kJ) Loss:8.15%
(220.36 kJ) Calcination Energy C(0.56mol)
(2.97kJ) Loss:16.87%
＝1.24
25͠
7.77 kJ ＝1.28 (220.36kJ) Energy for CaCO3 decomposition
Heat
ᾲ੤឵
Exchanger
Energy for CaCO3 decomposition 25͠ Heat
24.35kJ
(a) ᾲ੤឵
Exchanger
Ԙ
H2O㧔g: 0.12mol, Ԙ(a) CO2㧔 0.84mol㧕
CaCO3(1mol)/ CO2(1.56 mol)
L:0.72mol). 100͠ 75͠
C(0.56mol) H2O(0.84mol) Terms input output error
(9.67 kJ) CaCO3(1mol)/ CO2(2.4 mol) (1.59kJ)
(80.94+220.36 kJ) 900 ͠ Terms input output error
C(0.56mol) 1200͠
705͠ (132.29kJ) C [mol] 1.56 1.56 0
C [mol] 1.56 1.56 0 (115.13+220.36 kJ) (144.55 kJ)
CaO(1mol) Loss:7% H [mol] 0 0 0
3.1kJ H [mol] 1.68 1.68 0 950͠ CaO(1mol) Loss:16.54%
900 ͠
౉ᾲ,QSXWKHDW
8.15kJ 1200͠ 10.12kJ O [mol] 4.12 4.12 0
(CN-
0.021mol
Calciner
⍹Ἧ⍹ 44.61 kJ ᾲ੤឵ Heat O [mol] 4.96 4.96 0
ࠞ὾ Exchanger Calciner
⍹Ἧ⍹ 61.18kJ Heat Ca [mol] 1 1 0
Άᢱ⚂3.7 %ࠕ࠶ࡊ)
for calcination ԙ
(b) Ca [mol] 1 1 0 Loss:0 % ᾲ੤឵
Exchanger
178kJ
178 kJ ࠞ὾
for calcination ԙ(b) Chemical 220.36 178.00 -
H2O㧔0.84mol㧕 0 kJ 178 kJ178kJ
Chemical 220.36 178.00 +0.000 heat [kJ] 0.002
O 320͠ CaO(1mol) heat [kJ] +8.15 CO2㧔 0.84mol㧕
㉄⚛ 2 sensible 41.92
45.45kJ 1150͠
(0.56mol)
150 ͠
sensible 50.53 ㉄⚛O2 48.17kJ
CaO(1mol)
heat[kJ]
5.73kJ 125͠
25͠ heat[kJ] (0.56mol)
4.48 kJ
25͠

Figure 5 Calculation result of mass and heat balance for H2O Figure 6 Calculation result of mass and heat balance for CO2
(steam) cycle calcination. cycle calcination.
360 S. Lin et al. / Energy Procedia 4 (2011) 356–361

Author name / Energy Procedia 00 (2010) 000–000 5

Figure 6 shows the results of energy and material balances for CaCO3 calcination with CO2 cycle (CO2 60%,
O2 40%) cycle. Calcination temperature was set at 1473 K, with limestone decomposition conversion be about 99%
from the fluidized bed calciner shown in previous study4-6. The sensible heat recovery efficiency for heat
exchangers (a) and (b) were suggested as 80%. It can be seen that, with the heat for CaCO3 decomposition
178kJ/mol-CaCO3, the exhaust sensible heat (348K) after heat exchanger (b) is 2.97 kJ/mol-CaCO3 while the
exchange loss is 24.35 kJ/mol-CaCO3. The exhaust sensible heat after heat exchange (a) and (b) were 2.97 and 4.48
kJ/mol-CaCO3. Accordingly, total energy consumption of calcination is 220.36 kJ/mol-CaCO3, reflected the total
heat loss is 42.36 kJ/mol-CaCO3. Accordingly, the energy excess for the CO2 cycle calcination is as
Calcination energy 220.36
Energy excess 1.24 .
Energy of CaCO3 decomposition 178
*  1 
UVGCO E[ENG

-% C% 1  EQPXGTUKQP
% 1  E[ENG

-% C% 1  EQPXGTUKQP
300 300 % 1  E[ENG
H2 O (steam) cycle (1173 K) Calcination Energy [kJ/mol-CaCO3)
Calcination Energy [kJ/mol-CaCO3)

-% C% 1  EQPXGTUKQP
280 280 % 1  E[ENG
CO2 cycle (1473 K)
-% C% 1  EQPXGTUKQP

260 260
Calcination Energy comsumption
Calcination energy H2O (steam) cycle energy
240
energy
3.6
3.6%
% increase
larger CO2 capacity 240 consumption increase
2.1 % less about30% CO2 cycle 1473 K, 3.60%
220 up 220
CO2 cycle 1373 K, 6.48%
Energy of CaCO 3 CO2 cycle 1273 K, 8.49%
Energy of CaCO 3
200 decomposition 200 decomposition

180 180
40 50 60 70 80 90 100 40 50 60 70 80 90 100
Sensible heat recovery [%] Sensible heat recovery [%]

Figure 7 Comparison of energy consumption of Figure 8 Comparison of calcinations energy consumption

H2O (steam) cycle with CO2 cycle under various of H2O (steam) cycle with CO2 cycle witch calcinations
sensible hear recovery temperature changed from 1273 K to 1473 K.

The sensible heat in exhaust gas and solid after H2 O(60%) CO2 cycle
calcianer for CO2 cycle is larger than that for H2O cycle
(steam) cycle, since the calcianation temperature is 100 1200
higher for CO2 cycle (1473 K) than that for H2O
Content of active CaO [%]

E- calcination [kJ/mol-CaCO3]

1000
CaCO3 conversion [%]

(steam) cycle (1173K). Figure 7 shows effect of the 80

E-active CaO [kJ/mol-CaO]

sensible heat recovery on the calcination energy for 800

both of H2O (steam) cycle and CO2 cycle. It is seen 60
that, the sensibe heat recovery strongly affects 600
calcination energy for CO2 cycle than for H2O (steam) 40
400
cycle, such as when the sensible heat be recovered over
70%, the calcination energy for H2O (steam) cycle is 20 200
larger than CO2 cycle, whereas calcination energy of
H2O(steam) cycle will be smaller than CO2 cycle. It is 0 0
1150 1200 1250 1300 1350 1400 1450
seen that at the sensible heat recovery 80%, calcination
energy of H2O(steam) cycle is 3.6% more than CO2 Temperature [ K ]
Figure 9 Comparison of CaCO3 conversion, active CaO content,
cycle, and at the sensible heat recovery efficiency 60% , energy of calcinations consumption and energy consumption per
calcinations energy of H2O (steam) cycle is 2.1 % less active CaO of H2O (steam) cycle with CO2 cycle witch
than CO2 cycle. calcination temperature changed from 1273 K to 1473 K.
Figure 8 shows the energy consumption of CO2
 S. Lin et al. / Energy Procedia 4 (2011) 356–361 361

6 Author name / Energy Procedia 00 (2010) 000–000

cycle under various operating temperature. It is seen that calcinations energy for CO2 cycle falls with the decrease
of operating temperature of CO2 cycle calcination. However, as reported in previous experimental, low operating
temperature may causes reducing calcination rate of CaCO3 particle, consequently reduces CaCO3 decomposition
conversion (Table 1).

Since the property of the limestone calcinations is that to produce active lime (CaO) for CO2 capture, here, an
estimation of “calcination energy per active CaO” must be given. Figure 9 shows the CaCO3 decomposition
conversion, the active CaO content, the calcinations energy and the calcinations energy per active CaO, with H2O
(steam) cycle under 1173 K and with CO2 cycle under a temperature range of 1193 K to 1473 K. It is seen that the
CaCO3 decomposition conversion and active CaO for H2O (steam) cycle were highest since the CO2 partial pressure
and calciantion temperature were low. Caclination for CO2 cycle also have been performed at low temperature, but
the CaCO3 decomposition conversion was much lower than that for H2O (steam) cycle. The CaCO3 decomposition
conversion of CO2 cycle shown an increase with calcination temperature, however, active CaO content was decrease
quickly with increase of calcination temperature. Consequently, as a result shown in the Figure 9, the calcination
energy per active CaO is lowest for H2O (steam) cycle.

Conclusion
The mass and energy balances of a limestone (CaCO3) calcination process with CO2 capture for producing
active lime (CaO) were analyzed by means of thermodynamic calculations. This process involves a calciner with
oxygen fuel combustion by CO2 cycle or H2O (steam) cycle, and two heat exchanges for exhaust gas and solid
sensible heat recovery. Analysis showed that, although H2O (steam) cycle calcination had a higher calcination
energy than CO2 cycle due to water evaporation latent heat loss, however, the calcination energy per active CaO is
lowest for H2O (steam) cycle.

ACKNOWLEDGMENT
This work was carried out under the frameworks of the project of the high performance coal gasification
project for the next generation. The authors give their great thanks to NEDO for their financial support.

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