Improvements of calcium oxide based sorbents for

multiple CO2 capture cycles

Laetitia Vieille, Alexandre Govin, Philippe Grosseau

To cite this version:

Laetitia Vieille, Alexandre Govin, Philippe Grosseau. Improvements of calcium oxide based sor-
bents for multiple CO2 capture cycles. Powder Technology, Elsevier, 2012, 228, pp.319-323.
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Improvements of Calcium Oxide Based Sorbents for multiple CO2 Capture
cycles

Laetitia Vieille*, Alexandre Govin, Philippe Grosseau

Ecole Nationale Supérieure des Mines de Saint-Etienne, Centre SPIN, Laboratoire des
Procédés en Milieux Granulaires (LPMG UMR 5148), 158 Cours Fauriel, 42023 SAINT-
ETIENNE Cedex 2, France

Abstract

This study presents the development of a novel calcium-oxide sorbent for carbon dioxide
capture. In this work, CaO sorbent was impregnated with different molar percentage of
titanium ethoxide. The sorbent prepared with 50 % of titanium ethoxide resulted in the best
uptake characteristics for CO2. Compared to others, a higher BET surface area and a larger
pore volume were observed. An excellent stability during extended carbonation-
decarbonation cycles was also demonstrated. The high titanium content limits the sintering of
particles and thus stabilizes the microstructure of CaO.

Introduction

Carbon dioxide emission into the atmosphere is widely known as to be an important

contributor to global warming. In order to contain the greenhouse effect, the most viable
solution is to find out cost-effective ways to capture and storage CO2 before its releasing into
the atmosphere. Currently, the most common commercial technology to capture CO2 is
amine-based absorption, but its application is limited to small scale, low temperature (40-
150°C) and very high energy cost1. Alternatively, these drawbacks can be overcome by using
metal-oxide-based inorganic sorbents to capture CO2 selectively from flue gas streams.
Suitable sorbents should exhibit fast carbonation and regeneration within the temperature
range of 200-800°C. Actually, CaO based sorbents have been the most promising candidates
for CO2 capture[2-12]. Capture of CO2 by CaO sorbents is based on the reversible reactions
between CaO and CO2, leading to the formation of CaCO3 as follows:

CaO + CO2 CaCO3 (1)

During the carbonation cycle, CO2 uptake increases, reaching the highest value at the end of
the cycle. The carbonation is characterized by the reaction of gaseous CO2 with solid CaO to
yield CaCO3, which can reciprocally be thermally regenerated to CaO and CO2 by heating the
carbonate beyond its decomposition temperature (about 850°C).

Some researchers reported13 that, for the carbonation reaction, after a rapid chemically
controlled initial period, a slower product layer stage diffusion follows. The transition
between the fast and slow reaction stages was attributed to the formation of a CaCO3 product
layer, which limits the carbonation conversions13. The curve in figure 1 confirms that the
performance deteriorates with time (number of cycles). After the reaction of CaO with CO2,
the reaction product CaCO3 must undergo a calcination process in order to regenerate CaO to
be used repeatedly. In the process of calcination, some pores are produced inside the CaO
particle. At the same time, CaO sintering may occur during high-temperature calcination. The
decline of CO2 absorption capacity and cyclic stability with the increasing
carbonation/calcination cycles can be attributed to changes in the particle structure during
calcination. When small CaO particles are heated to certain temperatures high enough but
below the melting point, CaO coalesces and sinters, and the surface area of nascent CaO
decreases with the increase of residence time. Surface area and porosity are very important for
the reaction of CaO with CO2, but sintering reduces surface area and porosity sharply, which
in turn affects the reaction rates and conversion of CaO with CO2.14,15 Abanades et al.13
attributed the decay of CaO conversion to a certain loss of small pores and an increase of
large pores. They carried out observations with SEM, which revealed that the pore
distribution of the calcines was continuously changing with number of cycles; more and
bigger macro-pores were being formed under the condition that micropores decreased.

Currently, many researches focus on the improvement of the performance of CaO-based

sorbents by increasing porosity and improving stability. In the past, Gupta and Fan3
synthesized high-surface-area CaO sorbents from precipitated calcium carbonate (PCC).
Recently, Smirniotis and his coworkers16 obtained high-performance CaO-based sorbents
derived from different organometallic precursors. Some researchers17 promoted CaO sorbents
by using additives, such as NaCl or Na2CO3. The addition of Na2CO3 increased the ions
mobility but the capture of CO2 is unchanged. On the other side, the presence of NaCl
increased the surface area of the precursor material and enhanced its stability. Others5 have
improved the sorbent capacity by doping with alkali metals. Their performance followed the
order Li < Na < K < Rb < Cs, which revealed a strong relationship between the sorption
characteristics and the increase of the atomic radii of the alkali metals. The same researchers
employed a wide range of refractory dopants (Mn, Cu18, Si19, Ti, Cr, Co, Zr and Ce20), and
concluded that good results were obtained for manganese and cerium. In fact, these materials
presented high surface areas and large porous volumes which facilitated the kinetic of
carbonation and the absorption properties of CO2. But the Zr-doped CaO (Zr/Ca 3:10 mol
ratio) was found to exhibit the best CO2-capture performance and the best stability during the
multicyclic carbonation-decarbonation testing.
An other approach21 presented the integration of CaO inside a mineral material of mayenite
(Ca12Al14O33). For 35 wt % of CaO, a significantly improved CO2 absorption capacity was
observed and the cyclic carbonation reactivity of the new absorbent remains constant after 11
cycles.

The objective of the present investigation is the development of a high-performance CaO-

based sorbents. This study describes the incorporation of titanium as additive into CaO-based
sorbents and its implication on the cyclic carbonation reactivity.

Material and methods

Sorbent preparation

Natural limestone provided by Tamuin quarries (Mexico) was used. CaO was prepared by
calcination of natural limestone at 850°C under nitrogen for 3 hours. Then, CaO powder was
impregnated with predefined quantities of titanium ethoxide (Aldrich), corresponding to
molar percentage of 0.1, 1, 10, 20, 30, 40 or 50. After the impregnation, the material was
dried at 100°C overnight then calcinated at 300°C under air for 12 hours. In fact, the additive
is decomposed under 250°C22. The final product will be noted CaTi-x with x corresponding to
the doping level of titanium ethoxide.
The calculated conversion rate corresponds to the molar number of absorbed CO2 divided by
the molar number of theorical CaO.

Characterizations

X-ray diffraction (XRD) measurements were employed for the identification of phases of the
synthesized CaO-based sorbents. The XRD analyses were conducted on a Siemens D500
powder X-ray diffractometer with a Cu Kα radiation source (wavelength = 1.5406 Å).
BET surface area measurements were performed using nitrogen adsorption and desorption
isotherms at -196°C on a Micromeritics ASAP 2000 volumetric adsorption analyzer. The CaO
sorbents were degassed at 150°C for a night in the degassing port of the apparatus before the
measurements. The adsorption isotherms of nitrogen for BET measurements were collected at
-196°C by using ten values of pressure ranging from about 40 to 240 mmHg.
The porosity was measured by mercury intrusion porosimeter Autopore IV (Micrometrics)
which allows the determination of the pore size distribution.
Scanning electron microscopy (SEM) measurements were performed on selected sorbents to
obtain information on morphology using a JEOL 6500F field-emission scanning electron
microscope. The samples were prepared by placing CaO sorbents on double-sided carbon tape
mounted on the sample holder. Then a gold metallization was realized to improve image
quality.
Volume-weighted particle size distributions of CaO-based sorbents powders were determined
by laser scattering using a Scirocco cell (Mastersizer 2000, Malvern).
Decarbonation-Carbonation. Decarbonation/Carbonation experiments were conducted with
a Setaram 92 thermogravimetric analyzer (TGA). All steps of the carbonation and
decarbonation experiments, heating of the sample, cooling of the sample, and shifting gases
between CO2 (99.995 %) and nitrogen (99.999 %) were programmable. A small amount of
sorbent was placed in an alumina crucible and heated to the decarbonation temperature
(850°C) at a ramp rate of 10°C/min under nitrogen. When the decarbonation process had been
completed, the temperature was decreased to 650°C at a ramp rate of 10°C/min, a mixed of
2/3 of CO2 and 1/3 of nitrogen was automatically switched into the system to replace
nitrogen. When the carbonation process finished, the temperature was increased at 10°C/min
to the decarbonation temperature. A new decarbonation/carbonation cycle began when the
decarbonation temperature was achieved. In this work, the typical carbonation time was set at
120 min to achieve a relatively high uptake capacity of CO2, and the decarbonation time was
set at 60 min to allow the sorbent to be decarbonated completely. During the entire process,
the sorbent weight and the temperature were continuously recorded.

Results and Discussion

In figure 1, the performance results of the natural limestone Tamuin was presented. The curve
confirms that the performance deteriorates with time (number of cycles). After the reaction of
CaO with CO2, the reaction product CaCO3 must undergo a calcination process in order to
regenerate CaO to be used repeatedly. In the process of calcination, some pores are produced
inside the CaO particle. At the same time, CaO sintering may occur during high-temperature
calcination. The decline of CO2 absorption capacity and cyclic stability with the increasing
carbonation/calcination cycles can be attributed to changes in the particle structure during
calcination. When small CaO particles are heated to certain temperatures high enough but
below the melting point, CaO coalesces and sinters, and the surface area of nascent CaO
decreases with the increase of residence time. Surface area and porosity are very important for
the reaction of CaO with CO2, but sintering reduces surface area and porosity sharply, which
in turn affects the reaction rates and conversion of CaO with CO2.14,15 In our study, the
surface area of CaO decreases to 7.2 m²g-1 before calcination to 0.4 m²g-1 after five cycles of
calcination-carbonation. The porosity is closed and it is difficult to CO2 to diffuse inside the
material, its reactivity towards CO2 decreases.

In order to find an appropriate high-temperature CO2 absorbent, we doped pristine CaO with
titanium ethoxide. Different ratios of additive were added. Their cyclic reaction characteristics
are observed and recorded as shown in Figure 2. The calculated conversion rate corresponds
to the molar number of absorbed CO2 divided by the molar number of theorical CaO. The
conversion rate increases with the molar percentage of additive. It can be seen from figure 2
that at weak doping level (0.1 and 1 %), the additive does not impact the absorption of CO2 by
the material. The shape of the curve changes when the rate of titanium is higher than 20 %.
The cyclic reaction capacity of CaTi-40 and CaTi-50 with CO2 are almost the same and very
stable. It decreases slowly with the increase of cycles. Particularly, no significant changes
with number of cycles suggests that these samples are promising CO2 absorbents. No molar
fraction of titanium ethoxide higher than 0.5 was tested because the reactivity toward CO2 is
the same for CaTi-40 and CaTi-50, a maximum conversion rate seems to be attained.
CO2 should interact chemically with CaO rather than with TiO2 because CO2 and TiO2 are
acidic oxides. Some studies show that only CO is adsorbed at the surface of TiO223 or CO2 is
converted to CO when it is adsorbed at the TiO2 surface24,25.

The BET surface specific area values of titanium ethoxide doped sorbents are presented in
table 1. All measurements were made twice.

Surface specific area

Pore volume (cm3.g-1)
Sorbents (m2.g-1)
CaCO3 1.2 0.80
CaO (obtained after
7.2 1.75
calcination of CaCO3)
CaTi-0.1 8.0 1.83
CaTi-1 8.2 1.88
CaTi-10 9.4 2.15
CaTi-20 8.4 1.93
CaTi-30 9.6 2.20
CaTi-40 11.7 2.69
CaTi-50 13.8 3.30

Table 1 : BET SSA and Pore volume of various sorbents

All of the surface areas are higher than for pristine CaO. CaTi-40 and CaTi-50 exhibit the
highest surface areas and porosities among the various sorbents investigated in this study.
Sorption capacity depends on the degree of microporosity development, high surface area and
high pore volume facilitate the diffusion of CO2 inside these materials.
 Figure 1 : Carbonation of the limestone in 66 vol % CO2 gas stream and completely
regenerated in nitrogen

Figure 2 : Carbonation/decarbonation cycles (rate of titanium ethoxide : 0.1 % ■, 1 % □, 10

% x, 20% +, 30 % □ , 40 % ●, and 50 % ■) and limestone Tamuin : ●
The XRD patterns of the various rate of incorporated titanium ethoxide are presented in figure
3. From figure 3, the formation of crystalline CaCO3, CaO, Ca(OH)2 and TiO2 were noted in
all of the materials. CaCO3 and Ca(OH)2 are formed during the impregnation process, after
the calcination at 850°C under nitrogen, they are decomposed to CaO, only CaO and TiO2 are
present for the first carbonation cycle. The content of TiO2 increases with the percentage of
titanium ethoxide. However, TiO2 peaks were visible only from 20% molar. No mixed oxide
such as CaTiO3 was observed during the thermal treatment. The low temperatures could be
responsible for such behavior.
If we put on a graph, the content of titanium according to TiO2, we obtain a straight line with
a correlation coefficient R2 = 0.98 and the intercept is 4.81. So, nearly 5% of titanium is
introduced inside the CaO lattice.
In order to study surface morphology and explore the structural features at the grain level,
SEM studies were performed on various CaO sorbents with different ratios of titanium
ethoxide. The corresponding SEM images obtained are presented in figure 4. The limestone
Tamuin is dense and compact, some small particles of nearly 2 µm are observed. After
calcination, the departure of CO2 creates some cavities and the material becomes very porous.
The SEM images of doped-CaO show fine particles of CaO dispersed into dense block of
TiO2. The size and crystallinity of blocks increase with the titanium content. The presence of
TiO2 limits the sintering of CaO particles.

Figure 3 : XRD patterns of CaTi-20, CaTi-30, CaO (starting material) (on left) and CaTi-40,
CaTi-50, CaO (starting material) (on right) (CaCO3 : jcpds number, 00-047-1743; Ca(OH)2 :
jcpds number, 00-044-1481; TiO2, jcpds number, 00-004-0477)
 CaCO3 CaCO3

CaO (obtained after calcination of CaCO3) CaO (obtained after calcination of CaCO3)

20 % 20 %
 30 % 30 %

40 % 40 %

50 % 50 %
Figure 4 : SEM images of CaCO3, CaO and CaO doped with titanium ethoxide

A study of aging was done on the best absorbent (CaTi-50), under 30 cycles of carbonation-
calcination. After 30 cycles, its reactivity towards CO2 is clearly superior to that of pure
limestone Tamuin (see figure 5).
 Figure 5 : Carbonation-decarbonation cycles of CaTi-50 : □ and limestone Tamuin : ●

Conclusion

CaTi-40 and CaTi-50 were identified as promising sorbents for CO2 capture, they exhibit very
high CO2-capture capacity and a strong stability during the course of multicyclic carbonation-
decarbonation testing. The high titanium content limits the sintering of particles and stabilizes
the microstructure of CaO.

Acknowledgment
We are grateful to the ADEME (Agency of environment and energy management) for
financial support. We would also like to thank the different partners of CARGESE project:
IFP new energy and ATANOR.
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