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Applied Energy 124 (2014) 241247

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Removal of low concentration CO2 at ambient temperature using several


potassium-based sorbents
Chuanwen Zhao, Yafei Guo, Changhai Li, Shouxiang Lu
State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026, China

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Several potassium-based sorbents

were applied to low concentration


CO2 removal at ambient temperature.
 K2CO3/AC shows high carbonation
conversion efciency and CO2
sorption capacity.
 K2CO3/5A, K2CO3/13X, and K2CO3/SG
show low CO2 sorption capacities.
 K2CO3/Al2O3 shows low carbonation
conversion efciency and needs high
temperature of 350 C to be
regenerated.
 K2CO3/AC is a more efcacious choice
for CO2 removal in conned space.

a r t i c l e

i n f o

Article history:
Received 30 December 2013
Received in revised form 12 February 2014
Accepted 15 February 2014
Available online 1 April 2014
Keywords:
CO2 removal
Conned space
Potassium-based sorbent
Porous support

a b s t r a c t
The requirement for long-duration human operation in a conned space has made removal of low concentration CO2 a critical technology. The incorporation of organic amines into a porous support is thought
to be a promising approach, but the low amine utilization ratio and the loss of amine components due to
evaporation in regeneration process make it necessary to try new sorbents. As K2CO3 are more difcult to
be decomposed than organic amine compound, potassium-based sorbents may be more effective for CO2
removal in conned spaces. In this work, activated carbon (AC), Al2O3, zeolite 5A, zeolite 13X, and silica
aerogels (SG) were chosen as the supports and K2CO3 was provided as the active component. An experimental demonstration of the CO2 sorption performances of these sorbents was present in detail in the
condition of ambient temperature and the CO2 concentration of 5000 ppm. The CO2 sorption capacities
are calculated as 0.87, 1.18, 0.34, 0.53, and 0.15 mmol CO2/g for K2CO3/AC, K2CO3/Al2O3, K2CO3/5A,
K2CO3/13X, and K2CO3/SG, respectively. The reacted products are completely regenerated in the temperature range of 100200 C for K2CO3/AC and K2CO3/SG. Other sorbents, however, require a higher temperature of 350 C in order to be regenerated. K2CO3/Al2O3 shows the highest CO2 sorption capacity, while
K2CO3/AC shows the highest bi-carbonation conversion efciency. The CO2 sorption capacities of
K2CO3/5A, K2CO3/13X, and K2CO3/SG do not reach the expected values. Among these sorbents, K2CO3/
AC is a new, more efcacious choice for CO2 removal in conned space at ambient temperature.
2014 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +86 551 63603141; fax: +86 551 63601669.
E-mail address: sxlu@ustc.edu.cn (S. Lu).
http://dx.doi.org/10.1016/j.apenergy.2014.02.054
0306-2619/ 2014 Elsevier Ltd. All rights reserved.

242

C. Zhao et al. / Applied Energy 124 (2014) 241247

1. Introduction
The requirement for long-duration human operation in a conned space such as underground warehouses, mines, submarines
and space capsules, has made removal of low concentration CO2
a critical technology [1]. The primary method used to remove
CO2 from enclosed inhabited environments until the early 1990s
was based on LiOH [2]. Although the CO2 storage capacity of LiOH
is high, the material cannot be practically regenerated. The longterm occupation of a space station or a submarine would require
a CO2 sorbent that can be easily regenerated to reduce launch
weight and storage volume [3]. Recently, the incorporation of organic amines into a porous support is thought to be a promising
approach, and this process has been widely studied by many
researchers [431]. Various amine solutions were used as the active components. These divide into three categories: primary, secondary, and tertiary amine groups. The widely used supports
include polymers [46], various silica material (SBA series [710],
MCM series [1115], Silica gel [1620], and KIT series [21]), carbon
materials [2227], and zeolites [2831]. Although various aminebased sorbents show high CO2 sorption capacities, the utilization
of amine compound is not high for all sorbents. Their amine utilization ratio was reported as only 2067%. Another signicant
drawback for amine-based sorbents is loss of amine components
due to evaporation when the sorbent is regenerated at a temperature higher than 100 C. The requirement for solving these problems makes it necessary to test new sorbents.
Recently, carbon capture and storage is recognized as a promising option for CO2 emission reduction [3236], and alkali metal
carbonates can be used to capture CO2 in the presence of H2O to
form either sodium or potassium bicarbonate at temperatures
below 100 C [37]. A moderate temperature swing of 120
200 C then causes the bicarbonate to decompose and release a
mixture of CO2/H2O that can be converted into a sequestration-ready CO2 stream by subsequently condensing the steam.
Compared with the amine-based sorbent, alkali metal carbonates
are more difcult to be decomposed; this is even the case if the
temperature is increased to 800 C. These sorbents may therefore
be more effective for CO2 removal in conned space. If the alkali
metal-based sorbents are used for this technology, they should
feature high sorption capacities at low CO2 partial pressures
and at ambient temperature. However, in previous studies most
researchers have only examined the CO2 capture behaviors of alkali metal-based sorbents under the reaction conditions of 50
100 C, 520% CO2, 520% H2O [3746]. It is unclear whether
the carbonation reaction paths change when the temperature is
the ambient temperature and the CO2 concentration is lower
than 1%. It is also unknown if their CO2 sorption capacities keep
high values in this situation.
Firstly, it was reported that K2CO3/AC [3841,43,45] (activated carbon) and K2CO3/Al2O3 [4246] had the potential to be
employed as suitable sorbents for CO2 capture in ue gas from
fossil fuel-red power plants due to their high CO2 capture
capacities and rapid carbonation reaction rates. Secondly, the
zeolites [2831,4750] possess well-dened pore structures and
their pore sizes are of the same magnitude as CO2 molecules,
they are therefore expected to have good afnities for CO2 capture, and these pore sizes can accommodate both the immobilized alkali metal carbonates and the adsorbed CO2. Thirdly,
silica aerogels (SG) possessing an open pore structure, a high
porosity, a high surface area and a low density, have a great potential for utilization as CO2 adsorbents [1620]. Nonetheless in
order to reach high adsorption capacities, SG should be functionalized. Here, AC, Al2O3, zeolite 5A, zeolite 13X, and SG were chosen as the supports, and K2CO3 was chosen as the active

component. An experimental demonstration of the CO2 sorption


performances of these sorbents was presented in detail in the
condition of ambient temperature and the CO2 concentration of
5000 ppm. Additionally, the CO2 sorption capacities of these
potassium-based sorbents were compared with other sorbents
such as amine-tethered solid sorbents.

2. Experimental section
2.1. Samples
The supported potassium-based sorbents were prepared by
impregnating K2CO3 on AC, Al2O3, zeolite 5A, and 13X, and SG,
respectively. K2CO3 was provided as an analytical reagent. Al2O3
and AC were supplied by Research Institute of Nanjing Chemical
Industry Group. Zeolite 5A and 13X were supplied by Shanghai
Zeolite Molecular Sieve Co., LTD. SG was supplied by Shanghai
Shangchen Industrial Co., LTD. The preparation process of these
sorbents consisted of three steps as follows: (1) 10 g of support
material were added to an aqueous solution of anhydrous K2CO3
in 100 ml of deionized water. Then it was mixed with a magnetic
stirrer for 20 h at room temperature. (2) After stirring, the mixture
was dried in a rotary vacuum evaporator at 105 C for dehydration.
(3) The dried samples were calcined in a furnace under a N2 ow
(100 ml/min) for 3 h at 300 C.
All sorbents were prepared with theoretical K2CO3 loadings of
30%. However, the actual loadings are 12.49%, 28.5%, 11.2%,
16.2%, and 37.5% for K2CO3/AC, K2CO3/Al2O3, K2CO3/5A, K2CO3/
13X, and K2CO3/SG, respectively.

2.2. Apparatus and procedure


The CO2 sorption performances of these sorbents were assessed
using a modied xed bed reactor system coupled with a gas analyzer. This experimental setup is shown in Fig. 1.
The atmosphere was simulated by a constant ow of CO2,
H2O and a balance of N2. CO2 and N2 were obtained from
high-purity cylinders and delivered to the experimental apparatus with mass ow controllers. H2O was fed using a high-precision syringe pump and then heated to ensure complete
vaporization. The xed-bed reactor with an inner diameter of
0.05 m was made of stainless steel and was set in an electrically
heated furnace. The electric heating was used to heat the reactor
to the given temperature. A water pipe was buried in the cast
copper. This water-cooling heat exchanger was used to keep
the temperature constant, when the exothermic reaction occurred. A gravimetric sensor was used to detect the change of
the sorbents weight online. The Relative Humidity (RH) and
temperature of the simulated atmosphere were also monitored
online by a hygrothermograph. A gas analyzer was used to measure the CO2 concentration of the outlet gas continuously. A total
of 10 g of the sorbent was placed into the reactor, and the height
of the material was 0.01 m. A simulated gas composition consisting of 5000 ppm CO2 + 1.8% H2O at a total ow rate of 0.05 m3/h
was used for the carbonation reactions. The reaction temperature
is 20 C. When the carbonation reaction was nished, the gas
composition was changed to 100% N2, and the reaction temperature was increased to 400 C. In this way, the regeneration processes of these sorbents were carried out.
The amount of K2CO3 impregnated was determined by an
Inductively Coupled Plasma Mass Spectrometer. An ASAP 2020 system with N2 adsorptiondesorption was used for surface area and
pore structure determination.

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C. Zhao et al. / Applied Energy 124 (2014) 241247

6
5

8
10
4

RH

11 12 13 14 15

Fig. 1. Schematic for the experimental system. (1) N2; (2) CO2; (3) pressure regulating valve; (4) mass ow controller; (5) H2O; (6) high-precision syringe pump; (7)
evaporator; (8) mixture tank; (9) xed-bed reactor; (10) gas analyzer; (11) temperature controller; (12) pressure monitor; (13) gravimetric sensor; (14) relative humidity
monitor; (15) temperature meter.

3. Results and discussion


3.1. Microscopic structure of different sorbents
Because the microscopic structures of these sorbents will play
an important role in their CO2 sorption performances. It should
be investigated that how does the microscopic structure change
after K2CO3 impregnated in these supports. To achieve this objective, all samples were characterized by N2 adsorptiondesorption
analysis. The specic surface areas of these samples were calculated by the BrunauerEmmettTeller (BET) method. The pore volumes and the pore size distribution were obtained using
desorption branches of the isotherms. They are calculated by the

dV/dlog(RP), cm3/(g nm)

1.5

(a)

AC
Al2O3
5A
13X
SG

1.0

0.5

0.0

10

100

Pore radius, nm

BET surface area, m2/g

the supports
the supported sorbents

750

564

454

500
250

71
0

215 186

200

185

7.89

0.99
5

dV/dlog(RP), cm3/(g nm)

1.5

(a)

1000 957

(b)

K2CO3/AC
K2CO3/Al2O3
1.0

K2CO3/5A
K2CO3/13X
K2CO3/SG

0.5

0.0

10

100

Pore radius, nm
Pore volume, 10-3cm3/g

1000

(b)

930

the supports
the supported sorbents

750

445

500

402

372
250

214

305

275

212
21

Fig. 3. Pore size distribution curves for different sorbents (a) the supports, (b) the
supported sorbents.

5.9

Fig. 2. Microscopic structures of samples: (a) BET surface area, (b) pore volume.
(1) K2CO3/AC, (2) K2CO3/Al2O3, (3) K2CO3/5A, (4) K2CO3/13X, (5) K2CO3/SG.

BarrettJoynerHalenda (BJH) method for the pores between 1.7


and 300.0 nm, and are calculated by the HorvathKawazoe method
for the pores smaller than 1.7 nm. BET surface areas, pore volumes,
and pore size distributions of these sorbents are shown in Figs. 2
and 3, respectively.
Fig. 3 shows that the specic surface area of AC is much higher
than other supports, but its pore volume is only 0.372 cm3/g, which
is lower than other supports. The reason is that most pores of AC
are distributed in the pore size of less than 5 nm which is shown

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C. Zhao et al. / Applied Energy 124 (2014) 241247

in Fig. 3. After K2CO3 has been loaded on AC, the surface area decreases from 957 to 564 m2/g, and its pore volume decreases to
0.214 cm3/g. Conrmed from the change of pore distribution before and after loading K2CO3 which is shown in Fig. 3, most active
components are distributed in the pore size of 25 nm. The pore
structure with the pore size of less than 2 nm is not lled.
Most pores are distributed in the pore size of 2150 nm for
Al2O3 and zeolite 5A, and most active components are willing to
distribute in this pore size range. After K2CO3 has been loaded
on, the specic surface area of Al2O3 decreases from 185 to
71 m2/g, and its pore volume decreases from 0.445 to 0.27 cm3/g.
For zeolite 5A, the specic surface area and pore volume greatly
decrease from 200 m2/g and 0.402 cm3/g to 7.89 m2/g and
0.021 cm3/g, respectively.
Most pores of zeolite 13X are distributed in two pore size
ranges of 12 nm and 5100 nm. After K2CO3 has been loaded
on, its specic surface area decreases from 454 to 215 m2/g, and
its pore volume decreases from 0.305 to 0.212 cm3/g. It is interesting that most K2CO3 are distributed in the pore size of 12 nm,
while the pore structure with the pore size of 5100 nm is not
lled.
The specic surface area of SG is only 186 m2/g, but its pore volume of 0.930 cm3/g is much higher than other supports. Most
pores of SG are distributed in the pore size of 5150 nm. After
K2CO3 has been loaded on, its pore volume greatly decreases to
0.006 cm3/g, and its specic surface area greatly decreases from
186 to 0.99 m2/g. Most pores of SG are blocked.
3.2. CO2 sorption performances of different sorbents

CO2 sorption efficiency, %

3.2.1. CO2 sorption curves of different sorbents


The CO2 sorption processes were performed in the composition
of 5000 ppm CO2, 1.8% H2O, and N2 balanced at 20 C. The H2O
concentration (corresponding to the RH of 78%) was chosen to

(a)

100
AC
Al2O3

75

5A
13X
SG

50
25
0
0

12

18

24

30

CO2 sorption efficiency, %

Time, min
100

K2CO3/AC
75

(b)

K2CO3/Al2O3
K2CO3/5A

50

K2CO3/13X
K2CO3/SG

25
0
0

60

120

180

240

Time, min
Fig. 4. CO2 sorption performances of different sorbents (a) the supports, (b) the
supported sorbents.

simulate a typical condition in a submarine. The CO2 sorption efciency, which is used for expressing the CO2 sorption performance
of the sorbent, is calculated by the change of CO2 concentration between the outlet gas and the inlet gas. The results are shown in
Fig. 4.
As shown in Fig. 4(a), CO2 sorption efciencies of all supports
decrease to zero in less than 20 min. The CO2 sorption capacity
can be easily obtained by integrating the data of their CO2 removal
curves. The CO2 sorption capacities are 1.37  10 1, 1.38  10 1,
9.48  10 2, 1.09  10 1, and 1.20  10 1 mmol CO2/g for AC,
Al2O3, zeolite 5A, zeolite 13X, and SG, respectively. Because CO2
sorption performances of all supports are mainly depended on
the physical adsorption process in this condition, the microscopic
structure of the sample plays an important role in this process.
Several results were obtained from the adsorption isotherms of
pure CO2 on adsorbents at 2530 C. It was reported that the CO2
sorption capacity of AC increased from 0.2 to 8 mmol/g when the
pressure increased from 0.05 to 60 atm [47,5154]. The similar
conclusion was obtained for some zeolite materials. The CO2 sorption capacities of zeolite b, 5A, 4A, and 13X increased from 0.3, 4.8,
2.8, and 3.2 to 1.7, 6.3, 4.9, and 5.1 mmol/g respectively, when the
pressure increased from 0.1 to 60 atm at 30 C [30,47,51]. The CO2
sorption capacity of AC decreased as the temperature increased at
the same pressure of pure CO2 [47,5154]. Some other results were
obtained by passing the mixture 20% CO2 + 80% N2 at 1 atm total
pressure. The CO2 sorption capacity decreased from 0.734 to
0.072 mmol/g for AC when the temperature increased from 28 to
150 C [27,55]. The CO2 sorption capacity of zeolite 13X decreased
from 1.25 to 0.18 mmol/g as the temperature increased from 30 to
120 C [28,29,48]. It can be concluded that the CO2 sorption capacities of these materials will be greatly affected by temperature and
CO2 partial pressure. In the reaction conditions of this paper, low
temperature is an advantage factor, but the low CO2 partial pressure is an adverse factor for CO2 sorption capacities of these sorbents. A chemical active component is needed to improve the
CO2 sorption capacities of these materials.
Except for K2CO3/SG, CO2 sorption capacities are greatly improved for these supported sorbents. The time for nearly 100%
CO2 removal is longer for K2CO3/AC as 27 min than that of other
sorbents, and its total reaction time is 132.8 min. The total reaction
time is longest for K2CO3/Al2O3 as 215 min. Their CO2 sorption
capacities are calculated as 8.73  10 1, 1.18, 3.45  10 1,
5.27  10 1, and 1.54  10 1 mmol CO2/g for K2CO3/AC, K2CO3/
Al2O3, K2CO3/5A, K2CO3/13X, and K2CO3/SG, respectively. It is deduced that these potassium-based sorbents can be used to remove
CO2 at ambient temperature by chemical reactions. Based on that
one mole of K2CO3 can absorb one mole of CO2, the theoretical
bi-carbonation conversion efciencies are calculated as 96.4%,
57.3%, 42.5%, 44.9%, and 5.7%, respectively. K2CO3/Al2O3 shows
the highest CO2 sorption capacity, while K2CO3/AC shows the highest bi-carbonation conversion efciency. The CO2 sorption capacities of K2CO3/5A, K2CO3/13X, and K2CO3/SG do not reach the
expected values.
3.2.2. Mass changes of different sorbents
To achieve the objective of nding out the carbonation reaction
paths of different sorbents at ambient temperature, mass changes
in the reaction process of all sorbents were measured with the
gravimetric sensor. The results are shown in Fig. 5.
Fig. 5(a) shows that the reaction rate and the nal mass change
of AC are the lowest among these support materials. The curves of
mass change are similar for zeolite 5A, zeolite 13X, and SG. Calculated from the curves of CO2 removal, the amounts of CO2 removal
are 60.1, 60.7, 41.7, 47.9, and 52.8 mg for AC, Al2O3, zeolite 5A, zeolite 13X, and SG, respectively. The nal mass change of each sample
is higher than this value. The extra increment is attributed to the

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C. Zhao et al. / Applied Energy 124 (2014) 241247

(a)
AC
Al2O3

180

5A
13X
SG

90

12

18

24

30

Time, min
1200

(b)

3.3. Regeneration behaviors of different sorbents

800

m, mg

K2CO3/AC
K2CO3/Al2O3
K2CO3/5A

400

K2CO3/13X
K2CO3/SG
0

60

120

180

240

Time, min
Fig. 5. Mass changes of different sorbents (a) the supports, (b) the supported
sorbents.

adsorption of H2O. The amounts of H2O adsorption are calculated


as 19.6, 108.2, 265.1, 302.7, and 295.7 mg for AC, Al2O3, zeolite
5A, zeolite 13X, and SG, respectively. Compared the curve of mass
change with the curves of CO2 removal, the H2O adsorption performances can be obtained for these materials. The average H2O sorption efciencies are 10%, 50%, 94%, 94%, and 90% through the whole
CO2 sorption process for AC, Al2O3, zeolite 5A, zeolite 13X, and SG,
respectively. This result is in consistent with the results shown in
pure water vapor adsorption isotherms on various sorbents at
25 C [51].
The nal mass changes through the whole CO2 sorption process
are 541.8, 1175.6, 357.6, 1082.8, and 97.1 mg for K2CO3/AC, K2CO3/
Al2O3, K2CO3/5A, K2CO3/13X, and K2CO3/SG, respectively. Based on
that one mole of K2CO3 can adsorb one mole CO2 and one mole H2O
to produce two mole of KHCO3, the theoretical nal mass changes
of these sorbents are 541.2, 733.6, 213.6, 326.7, and 95.5 mg,
respectively, which are calculated from their CO2 removal curves.
The values obtained from these two curves are similar for K2CO3/
AC and K2CO3/SG. On the contrary, the mass changes are much
higher than these theoretical values for K2CO3/Al2O3, K2CO3/5A,
and K2CO3/13X. It is deduced that, except for the chemical reaction
to remove CO2, the adsorption processes of H2O take place in the
same time for these samples. It is reported that zeolites and zeolite-based sorbents show preferable water adsorption capacities,
hence their CO2 sorption capacities are greatly reduced by
moisture [28,29]. The reason is deduced that the increase of the liquid lm or water layer on the solid surface leads to a decrease in
the concentration of CO2 in the liquid lm, or an increase in the
HCO3 transport resistance and thus a decrease in the interaction
between and the active sites on support [18]. This conclusion is
in consistent with it for zeolite 5A, zeolite 13X, and K2CO3/13X,
because they show high H2O adsorption capacities, and low CO2
sorption capacities. The H2O adsorption capacity of K2CO3/5A is
much lower than it of zeolite 5A, because its pore volume is greatly
decreased from 402 to 21 cm3/g. It was reported that the CO2

In practical application of CO2 removal in a closed loop environmental control system, the sorbent after CO2 sorption process
should be regenerated by increasing temperature, or entering
high-temperature steam. In this section, the effect of temperature
on the regeneration behaviors of these reacted sorbents is investigated, and the results are shown in Fig. 6.
It is shown that the regeneration processes for all sorbents had
nished before the reaction temperature increased to the nal value of 375 C. The nal mass changes for all sorbents are equal to
the values increased through their whole CO2 sorption processes.
It means that all sorbents are completely regenerated in this process. They are completely regenerated in the temperature range
of 100200 C for K2CO3/AC and K2CO3/SG. It was reported that
the decomposition of KHCO3 started at 117.2 C and ended at
219.7 C [56]. The regeneration processes of K2CO3/AC and
K2CO3/SG could be explained by the decomposition of KHCO3.
The regeneration processes of K2CO3/Al2O3, K2CO3/5A, and K2CO3/
13X consists of two steps as the temperature increases: the rst
step is carried out in the temperature range of 60150 C, and
the next step is carried out in the temperature range of 150
350 C. Because a large amount of H2O is adsorbed on these sorbents, the rst step of regeneration is mainly attributed to the
desorption of H2O for K2CO3/Al2O3, K2CO3/5A, and K2CO3/13X.
KAl(CO3)2(OH)2 was found in the carbonation product of K2CO3/
Al2O3 in a xed-bed reactor [41] and a uidized-bed reactor [46].
The decomposition of KAl(CO3)2(OH)2 was reported in the temperature range of 260350 C [41,46]. As a result, it is deduced that
KAl(CO3)2(OH)2 was produced in the carbonation process of
K2CO3/Al2O3 at ambient temperature, its second step of regeneration is attributed to the decomposition of KHCO3 and KAl(CO3)2(OH)2. It was reported that zeolite 13X after CO2 removal had to
be regenerated at 350 C [20]. It is deduced that the regeneration

400

300
-400

K2CO3/AC
K2CO3/Al2O3

200

K2CO3/5A

-800

K2CO3/13X

100

K2CO3/SG

-1200

25

50

0
75

Time, min
Fig. 6. Regeneration behaviors of different sorbents.

Temperature, oC

m, mg

270

sorption capacity increased in presence of moisture for aminemodied silica gels [18,20]. However, both the CO2 sorption capacity and the H2O adsorption capacity are much lower than expected
for K2CO3/SG. The reason is that their microscopic structure is completely destroyed by the impregnating of K2CO3. Both the CO2 sorption capacity and the H2O adsorption capacity are excellent for
K2CO3/Al2O3. Its carbonation reaction path is deduced that H2O is
adsorbed rst, and then CO2 reacts with the adsorbed H2O and
K2CO3 to produce KHCO3. The H2O adsorption capacity of AC is
poor. However, it was reported that moisture played a promoting
role in the removal of CO2 for K2CO3/AC [40]. The reason is deduced
that the hydration reaction occurs rst and then KHCO3 is produced for the CO2 sorption process of K2CO3/AC at ambient
temperature.

m, mg

360

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C. Zhao et al. / Applied Energy 124 (2014) 241247

behaviors of K2CO3/5A and K2CO3/13X depend mainly on their


supports.
3.4. Comparison of CO2 sorption capacities for these sorbents with
other sorbents

CO2 sorption capacity, mmol


CO2/g sorbent

The CO2 sorption capacities of these sorbents are compared


with that of potassium-based sorbents with same supports
[3746] which were obtained under the reaction conditions of
50100 C, 520% CO2, 520% H2O, the support materials
[4755], and amine-modied sorbents with same supports
[1620,2531]. Their CO2 sorption capacities are listed in Fig. 7.
The CO2 sorption capacity of AC is in the range of 0.05
0.734 mmol/g. As mentioned above, it is greatly affected by temperature and CO2 partial pressure. The CO2 sorption capacity of
K2CO3/AC is 0.772.32 mmol CO2/g under the ue gas from fossil
fuel-red power plants conditions. It of amine-modied AC sorbent
is 0.571.17 mmol/g, which is lower than that of other aminebased sorbents. The reason is that, most pores of AC are distributed
in the pore size of less than 2 nm, but no active components can ll
in such small pores which lead to a limited loading amount of active component. In this paper, AC was lled with 30% aqueous
K2CO3, but its actual loadings is only 12.49%. As a result, its CO2
sorption capacity is only 0.87 mmol/g. With an increase in the
ingredient ratio of K2CO3/AC in preparation, the amount of impregnated K2CO3 could increase to 23.1% [38]. The CO2 sorption capacity will increase for K2CO3/AC with higher K2CO3 loadings.
The CO2 capture capacity of K2CO3/Al2O3 is 1.822.43 mmol
CO2/g under the ue gas from fossil fuel-red power plants conditions. In this paper, K2CO3/Al2O3 shows the highest CO2 sorption
capacity of 1.18 mmol/g. However, KAl(CO3)2(OH)2 was produced
in the carbonation process of K2CO3/Al2O3 at ambient temperature,
K2CO3/Al2O3 after CO2 removal had to be regenerated at 350 C. To
fulll the specic task for the application in a closed loop environmental control system such as submarines and space craft, regeneration of the sorbent should be possible at low temperature to
reduce the energy demand.
Zeolites have shown promising results for separating CO2 from
gas mixtures and can potentially be used in the pressure swing
adsorption (PSA) process [4750]. The CO2 sorption capacities are
0.360.5 mmol/g for zeolite 5A, and 0.71.25 mmol/g for zeolite
13X, respectively. Several previous works were to synthesize novel
adsorbents by immobilization of different primary and secondary
amines on zeolite matrix [2831]. This immobilization was expected to impart high sorption capacity for CO2 as compared to
the bare zeolite matrix. The CO2 sorption capacities increased to
0.521.11 and 2.062.56 mmol/g for amine modied zeolite 5A
and 13X, respectively. The CO2 capture capacities of K2CO3/zeolites
are only 0.350.52 mmol CO2/g under the ue gas from fossil fuelred power plants conditions. In this paper, they are only 0.34 and
0.53 mmol CO2/g for K2CO3/5A and K2CO3/13X, respectively. The
4

In this work
potassium-based sorbents in Ref. 34-43
support materials in Ref. 44-52
amine-modified sorbents in Ref. 18-22, 27-33

3
2
1
0

II

III

IV

Fig. 7. Comparison of CO2 sorption capacities for these sorbents with different
support. I: AC, II: Al2O3, III: zeolite 5A, IV: zeolite 13X, V: SG.

reason is that their CO2 sorption capacities are greatly reduced


by moisture. For application of potassium-based sorbent, the CO2
sorption performance is deeply depended on the existing of H2O
and its concentration. Moreover, the sorbent can be regenerated
in water vapor in real operations to improve its CO2 sorption
capacity. As a result, zeolites are not good choices as potassiumbased sorbent for CO2 removal.
The CO2 sorption capacity of SG is in the range of 0.75
1.31 mmol/g. One promising way for the improvement of the CO2
sorption capacity of silica gels is the incorporation of amino into
the silica structure [1620]. Functionalisation of aerogels with
amine groups was also used for improving their strength and elasticity. It was reported that the CO2 sorption capacity of amine functionalized SG achieved such a high value of 6.97 mmol/g [18].
However, the CO2 sorption capacity of sorbents prepared by
impregnating K2CO3 on SG is only 0.120.31 mmol/g. The reason
is that their microscopic structure is completely destroyed by the
impregnating process. It is deduced that the CO2 sorption capacity
of K2CO3/SG can be improved by optimizing the prepared method
for this sorbent.
Among these sorbents, K2CO3/AC may be a new choice for CO2
removal in conned space at ambient temperature as it shows
the highest bi-carbonation conversion efciency. Because K2CO3/
AC can be easily regenerated at low temperatures of 100200 C,
this sorbent can be used in a continuous CO2 sorptiondesorption
operation system. The CO2 sorption performance is mainly determined by the gas residence time and the reaction rate, as the process is carried out in the continuous solid circulation mode.
4. Conclusions
The CO2 sorption performances of K2CO3/AC, K2CO3/Al2O3,
K2CO3/5A, K2CO3/13X, and K2CO3/SG were detailed investigated
in the condition of ambient temperature and the CO2 concentration
of 5000 ppm using a modied xed bed reactor system coupled
with a gas analyzer. It is found that the CO2 sorption capacities
are 1.37  10 1, 1.38  10 1, 9.48  10 2, 1.09  10 1, and
1.20  10 1 mmol CO2/g for AC, Al2O3, zeolite 5A, zeolite 13X,
and SG, respectively. After K2CO3 has been loaded on, their CO2
sorption capacities are greatly improved to 0.87, 1.18, 0.34, 0.53,
and 0.15 mmol CO2/g, respectively. K2CO3/AC shows the highest
bi-carbonation conversion efciency, it can be completely regenerated in 100200 C. The CO2 sorption capacity will increase for
K2CO3/AC with higher K2CO3 loadings. K2CO3/Al2O3 shows the
highest CO2 sorption capacity, but it has to be regenerated at
350 C as the product of KAl(CO3)2(OH)2 in the CO2 sorption process. Zeolites and amine modied zeolites show promising results
for separating CO2 from gas mixtures. However, the CO2 sorption
capacities of K2CO3/zeolites are only 0.350.52 mmol CO2/g, because their CO2 sorption capacities are greatly reduced by moisture. The CO2 sorption capacities of SG and amine functionalized
SG are high. However, the CO2 sorption capacity of sorbents prepared by impregnating K2CO3 on SG is only 0.120.31 mmol/g, because their microscopic structure is completely destroyed by the
impregnating process. Among these sorbents, K2CO3/AC may be a
new choice for CO2 removal in conned space at ambient temperature. Besides a high CO2 sorption capacity, a high reaction rate is
needed for the sorbent in such a low temperature and a low CO2
partial pressure. Future research will investigate the CO2 sorption
reaction rate of these sorbent at ambient temperature.
Acknowledgments
Financial support from the National Natural Science Foundation
(No. 51206155) and the China Postdoctoral Science Foundation

C. Zhao et al. / Applied Energy 124 (2014) 241247

(Nos. 2011M501061 and 2012T50579) are sincerely acknowledged. The authors wish to thank Mr. Christopher Love for his help
in English revision of this article.
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