ARTICLE IN PRESS

Chemical Engineering Science 65 (2010) 1354–1361

Contents lists available at ScienceDirect

Chemical Engineering Science

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

Thermodynamics and regeneration studies of CO2 adsorption on multiwalled

carbon nanotubes
Shih-Chieh Hsu, Chungsying Lu , Fengsheng Su, Wanting Zeng, Wenfa Chen
Department of Environmental Engineering, National Chung Hsing University, 250 Kuo Kuang Road, Taichung 402, Taiwan

a r t i c l e in f o a b s t r a c t

Article history: Multiwalled carbon nanotubes (CNTs) were fabricated and modified by 3-aminopropyl-triethoxysilane
Received 12 August 2009 (APTS) solutions to study thermodynamics and regeneration of CO2 adsorption from gas streams.
Received in revised form The CO2 adsorption capacities of CNTs and CNT(APTS) decreased with temperature indicating the
7 October 2009
exothermic nature of adsorption process while the thermodynamic analysis gave low isosteric heats of
Accepted 8 October 2009
Available online 31 October 2009
adsorption, which are typical for physical adsorption. The cyclic CO2 adsorption on CNT(APTS) showed
that the adsorbed CO2 could be effectively desorbed via thermal treatment at 120 1C for 25 min while
Keywords: the adsorbed CO2 due to physical interaction could be effectively desorbed via vacuum suction at
Carbon nanotubes 0.145 atm for 30 min. If a combination of thermal and vacuum desorption was conducted at 120 1C and
Isosteric heat of adsorption
0.145 atm, the time for effectively desorbing CO2 could be further shortened to 5 min. The adsorption
Cyclic CO2 adsorption
capacities and the physicochemical properties of CNT(APTS) were preserved during 20 cycles of
adsorption and regeneration. These results suggest that the CNT(APTS) can be stably employed in
prolonged cyclic operation and they are thus possibly cost-effective sorbents for CO2 capture from flue
gases.
& 2009 Elsevier Ltd. All rights reserved.

1. Introduction silica sorbents (Gray et al., 2005; Hiyoshi et al., 2005; Zheng et al.,
2005), mesoporous spherical-silica particles (Lu et al., 2009) and
The CO2 capture and storage (CCS) technologies from flue
mesoporous molecular sieve MCM-41 (Xu et al., 2002, 2005).
gas were considered to be cost-effective means to lessen the
The amine-functionalized carbon nanotubes (CNTs) have
global warning issue after the Kyoto protocol came into force on
reached increasing attention for CO2 capture from flue gas due
16 February 2005. Various CO2 capture technologies, including
to its unique physicochemical properties as well as high thermal
absorption, adsorption, cryogenics, membranes, and so forth, have
and chemical stability (Smart et al., 2006). These sorbents include
been investigated (White et al., 2003; Aaron and Tsouris, 2005).
single-walled CNTs (Cinke et al., 2003) and multiwalled CNTs
Among them, the absorption–regeneration technology has been
(Lu et al., 2008; Su et al., 2009) functionalized with various amine
recognized as the most matured process so far, with amine-based
solutions. The comparisons of CNTs with other commercially
or ammonia-based absorption processes receiving the greatest
available sorbents such as activated carbon and zeolite made by
attention (Bai and Yeh, 1997; Yeh and Bai, 1999; Rao and Rubin,
the foregoing researchers suggest that the amine-functionalized
2002).
CNTs are a promising CO2 sorbent.
However, because the energy penalty to regenerate liquid
Although the amine-functionalized CNTs show potential for
amine or ammonia in the adsorption process is high due to the
CO2 capture from flue gases, the relatively high price currently
high heat capacity of amine/ammonia and large amount of water
restricts their practical use in the field. Therefore, the amine-
(Aaron and Tsouris, 2005), other technologies are being investi-
functionalized CNTs should be regenerated under low energy
gated throughout the world. The Intergovernmental Panel on
penalty and stable reuse through a number of adsorption and
Climate Change (IPCC) special report concluded that the design of
regeneration cycles, and then their practical use becomes feasible.
a full-scale adsorption process might be feasible (IPCC, 2005).
In this article, the CNTs were fabricated and modified by
Possible sorbents include activated carbon (Siriwardane et al.,
3-aminopropyl-triethoxysilane (H2NCH2CH2CH2-Si(OCH2CH3)3,
2001; Prezepiórski et al., 2004), X-type zeolites (Lee et al., 2002;
abbreviated as APTS) solution to study thermodynamics and
Siriwardane et al., 2005; Chatti et al., 2009), SBA-15 mesoporous
regeneration of CO2 adsorption in gas streams. The tests of cyclic
CO2 adsorption on CNT(APTS) via thermal desorption, vacuum
 Corresponding author. Fax: + 886 4 2286 2587. desorption or thermal/vacuum desorption were also conducted to
E-mail address: clu@nchu.edu.tw (C. Lu). evaluate their repeated availability for CO2 capture.

0009-2509/$ - see front matter & 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2009.10.005
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S.-C. Hsu et al. / Chemical Engineering Science 65 (2010) 1354–1361
2. Materials and methods
2.1. Adsorption experiments
The detailed information for the fabrication and the APTS
modification of CNTs, and the physicochemical characterization
of CNTs and CNT(APTS) is provided elsewhere (Su et al., 2009).
The CO2 adsorption was conducted in a cylindrical column which
was made of pyrex glass having a total length of 16 cm and an
internal diameter of 2 cm. The column was filled with 1.0 g
of sorbents and placed within a temperature oven to maintain
adsorption temperature (Ta) in 20–150 1C. The packing heights of
CNTs and CNT(APTS) are 4 and 2 cm, respectively. The water vapor
in air was kept at 0%.
Compressed air was passed first through a silica gel air dryer to
remove moisture and oil and then was passed through a HEPA
filter (Gelman Science, Ann Arbor, MI, USA) to remove particu-
lates. Two mass flow controllers (MKS Instrument Inc., MA, USA)
were employed to control the influent CO2 concentration by
regulating flow rates of clean air (diluting gas) and pure CO2 gas
(99.95%) entering the mixing chamber. The system flow rate was
controlled at 80 cm3/min equivalent to an empty-bed retention
time of 9.42 and 4.71 s for CNTs and CNT(APTS), respectively. The
influent and effluent gas streams were flowed into a gas
chromatograph (GC) equipped with a thermal-conductivity
detector (TCD) for real-time measurement. All the experiments
are repeated two times and only the mean values were reported.
The influent CO2 concentration (Cin) was in the range of 5–50%,
which was selected to be representative of different CO2
concentrations in combustion gases from many kinds of industrial
activities such as coal-fired power plants (12–14%) (Bosoaga et al.,
2009) or coal gasification systems (30–35%) (Cormos et al., 2008).
The variation of Cin was below 0.2%. The adsorption time (ta) is
10 min, at which effluent CO2 (Ceff) reaches above 99% Cin for all
tests. Blank tests (without sorbents) were conducted with various
influent CO2 concentrations. The adsorption capacities of blanks
were eliminated from the adsorption capacities of CNTs and
CNT(APTS).
2.2. Adsorption/desorption experiments
The adsorption process was conducted with a Cin of 15% and
60 1C. As the CO2 adsorption on CNT(APTS) reached equilibrium,
the adsorption capacity (qe) was measured. Thermal desorption of
CO2 was first tested at 1 atm by changing influent gas to purified
air which was controlled at the same flow rate as adsorption
process. Vacuum desorption of CO2 was subsequently tested at
60 1C. The outlet of the adsorption column was connected to a
vacuum pump which was operated at 0.145 atm for 30 min.
Finally, thermal/vacuum desorption of CO2 was tested to evaluate
the optimum td. The cyclic CO2 adsorption on CNT(APTS) via above
desorption methods was conducted for 20 cycles of adsorption
and regeneration.
2.3. Analytical methods
CO2 concentration was determined via a GC-TCD (Model GC-
2010, Shimadzu Instruments, Tokyo, Japan). A 30 m fused silica
capillary column with 0.32 mm inner diameter and 5.0 mm film
thickness (AB-PLOT GasPro, USA) was used for CO2 analysis. The
GC-TCD was operated at injection temperature of 50 1C, detector
temperature of 100 1C and oven temperature of 55 1C.
The morphology of sorbents was analyzed by a high-resolution
transmission electron microscope (HR-TEM, JEM-2010, JEOL,
Tokyo, Japan). The porosity characteristics of sorbents were
1355
determined by N2 adsorption/desorption at 77 K via Micromeritics
ASAP 2020 volumetric sorption analyzer (Norcross, GA, USA). N2
adsorption/desorption isotherms were measured at a relative
pressure (PN2/P0) range of 0.0001–0.99 and then employed to
determine surface area, pore volume and average pore diameter
via the Barrett, Johner and Halenda (BJH) method for pore size
range of 1.7–100 nm and the micropore (MP) method for pore size
below 1.7 nm.
The crystal phase and the surface functional groups of sorbents
were characterized by a powder X-ray diffractometer (XRD, Mac
Science Co., Japan) using Cu Ka radiation (40 kV, 30 mA) and by a
Fourier transform infrared ray spectrometer (Spectrum 100 FT-IR
Spectrometer, Perkin Elmer, MA, USA), respectively.
3. Results and discussion
3.1. TEM images
Fig. 1 exhibits the TEM images of CNTs and CNT(APTS). Fig. 1a
and b shows that the isolated CNTs and CNT(APTS) of different
size and direction are usually curved and form an aggregated
structure due to inter-molecular force. After the CNTs were
modified, a large amount of metal catalysts, amorphous carbons
and impurities as indicated by circles in Fig. 1a was removed and
both ends of the CNTs were opened as indicated by arrows in
Fig. 1b. Fig. 1c shows that the isolated CNT has a 10 graphitic
layers structure on both sides with an inner diameter of 4.5 nm
and an outer diameter of 14.5 nm. After the modification, a great
amount of carbon-containing defects along the CNT surface was
detected in Fig. 1d.
3.2. Porosity characteristics
Fig. 2 shows the pore size distributions (PSDs) of CNTs and
CNT(APTS). It is noted that the micropore size distributions of
CNTs and CNT(APTS) only appear in the pore size of 0.2–0.4
and 0.4–0.6 nm, respectively. The pore volume of CNTs reduced
after the modification probably due to the removal of catalysts
which have an average pore diameter of 0.23 nm. The CNTs and
CNT(APTS) have a similar PSD for pore size of 1.7–100 nm, which
can be characterized as a bimodal including a fine fraction and a
coarse fraction. The pores in the fine fraction are the CNT inner
cavities, close to the inner CNT diameter. The pores in the coarse
fraction are likely contributed by aggregated pores, which are
formed within the confined space among the isolated CNTs.
The fine and coarse fractions are located in the pore size range of
1.7–4 and 10–50 nm, respectively.
3.3. Adsorption behaviors
The breakthrough curves of CO2 adsorption on CNTs and
CNT(APTS) showed that initially the CO2 can be efficiently
adsorbed on CNTs and CNT(APTS) with capture efficiencies
497%. The breakthrough time, which represents the capacity
of sorbents to adsorb CO2, appears longer at lower temperatures
or after the APTS modification.
Fig. 3 shows the isotherms of CO2 adsorption on CNTs and
CNT(APTS) at multiple temperatures. It is evident that the qe of
both samples increased with Cin but decreased with temperature.
The qe of CNTs was enhanced after the APTS modification and
the enhancement appears remarkable at low temperatures or
with high Cin. This indicated that the introduction of APTS to CNT
surface improved the adsorption selectivity of CO2 from gas
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Fig. 1. TEM images of CNTs and CNT(APTS).

5 0.015
CNTs
CNT(APTS)

0.010
Volume fraction /nm
Volume fraction /nm

2
0.005

0 0.000
0.2 0.3 0.4 0.5 0.6 1 10 100
Pore width (nm)

Fig. 2. Pore size distributions of CNTs and CNT(APTS).

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120 12
CNTs CNTs
100 20°C 50 mg/g
40°C 40 mg/g
60°C 11 30 mg/g
80 80°C 20 mg/g
100°C 10 mg/g
120°C
150°C
60
10

40
qe (mg-CO2/g-adsorbent)

20 9

lnPCO2
12
0
CNT(APTS) CNT(APTS)

100
11
80

60 10

40

9
20

0.0022 0.0024 0.0026 0.0028 0.0030 0.0032 0.0034 0.0036

0
0 10 20 30 40 50 1/T (K-1)
Cin (%)
Fig. 4. Regression lines of ln PCO2 vs. 1/T at multiple qe via CNTs and CNT(APTS).
Fig. 3. Adsorption isotherms of CO2 via CNTs and CNT(APTS) at multiple
temperatures.
Table 1
Isosteric heats of adsorption under multiple qe.
streams. The temperature dependence of qe is more significant for
qe (mg/g) CNTs CNT(APTS)
CNT(APTS).
The adsorption selectivity of CO2 on CNT(APTS) was subse- Qst (kJ/mol) 2
r Qst (kJ/mol) r2
quently evaluated by measuring the gas flow rate and the CO2
concentration before and after the adsorption column. For a 15% of 10  13.83 0.874  23.77 0.988
20  13.95 0.920  22.49 0.999
CO2/air mixture entering the adsorption column at a flow rate of 30  11.84 0.960  17.76 0.988
80 cm3/min, the effluent flow rate was 65 cm3/min as the Ceff was 40  10.33 0.982  16.25 0.991
0%. This indicated that only CO2 was adsorbed on CNT(APTS). 50  8.97 0.999  14.36 0.996
Chemical interaction between CO2 and CNT(APTS) was respon- Average  11.78  18.92
sible for such high selectivity of CO2.
The qe of CNTs(APTS) at 20 1C is 58 and 114 mg/g with a Cin of
15% and 50%, respectively, which is greater than those of APTS- adsorption (Agnihotri et al., 2005). The Qst (kJ/mol) at a given qe
modified granular activated carbon under the similar conditions was calculated from the Clausius–Clapeyron equation as (Ebbing
(34.6 and 79.5 mg/g with a Cin of 15% and 50%, respectively) (Lu et and Gammon, 1999)
al., 2008). Similar findings have been reported in the literature,
 
showing that the CO2 adsorption capacity of amine-modified CNTs @ðln PCO2 Þ Qst
¼ ð1Þ
is twice that of activated carbon (Cinke et al., 2003). These results @ð1=TÞ qe R
reflect that amine-modified CNTs are efficient CO2 sorbents.
where PCO2 is the CO2 partial pressure (Pa); T is the absolute
temperature (K) and R is the universal gas constant (8.314 J/mol/
3.4. Isosteric heat of adsorption K). For a given qe, the Cin at multiple temperatures was obtained
from Fig. 3 and was subsequently converted to PCO2 . The average
The isosteric heat of adsorption (Qst), which is defined as the Qst of CNTs and CNT(APTS) for a constant qe of 10–50 mg/g
difference between the activation energy for adsorption and (in a 10 mg/g increment) was then determined from the slopes of
desorption, represents the strength of adsorbate–adsorbent inter- the straight lines after plotting ln PCO2 against 1/T, as shown in
action (Szekely et al., 1976). Quantification of Qst is very important Fig. 4 and the results are given in Table 1. It is evident that the
for kinetic studies of adsorption process because the heat released slopes of CNT(APTS) are steeper (more negative) than the slopes of
upon adsorption is partially adsorbed on sorbents which causes CNTs for all surface loading (qe) indicating stronger interaction
a rise in adsorbent temperature and thus influences the rate of between CO2 and CNT(APTS). This could be attributed to chemical
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100

80
Adsorption index (%)

60

40

20
110°C
120°C

0
80 90 100 110 120 130 140 150 0 20 40 60 80 100 120
Temperature (°C) Time (min)

Fig. 5. CO2 adsorption indexes of CNT(APTS) at various desorption temperatures and times (Cin = 15%, ta = 10 min, Ta = 60 1C, P = 1 atm).

interaction of CO2 with available surface amine groups of 40

CNT(APTS). The Qst of both samples is all negative and tend to
less negative with surface loading (qe), suggesting the exothermic
nature of adsorption process and a decrease in the strength of
30
qe (mg-CO2/g-sorbent)

CO2-CNTs and CO2-CNT(APTS) interaction with qe. The change

of Qst with qe is more significant for CNT(APTS). The Qst ranged
from  8.97 to  13.83 kJ/mol for CNTs and from  14.36 to
23.77 kJ/mol for CNT(APTS), which are typical for physical 20
adsorption (Szekely et al., 1976).
The average Qst of CNTs ( 11.78 kJ/mol) and CNT(APTS)
(  18.92 kJ/mol) is lower than those of CO2 adsorption on
activated carbon (   20.3 kJ/mol) (Esteves et al., 2008) and many 10
kinds of zeolites (  55 to 66 kJ/mol) (Siriwardane et al., 2005)
documented in the literature.

0
3.5. Cyclic CO2 adsorption via thermal desorption 100

The optimum desorption temperature (Td) and time (td) must

80
Adsorption index (%)

be determined before the cyclic CO2 adsorption via thermal

desorption. Fig. 5 shows the CO2 adsorption indexes of CNT(APTS)
at multiple Td and td. The adsorption index (%) was calculated 60
based on the percentage ratio of qe of the regenerated sorbents to
the virgin one, thus 100% of adsorption index indicates that the
sorbent is not deteriorated at all. It is seen that the CO2 adsorption 40
index after 120 min of operation slowly increased with Td and
reached maximum at 110–120 1C. Therefore, Td of 110 and 120 1C
were chosen to determine the optimum td. The CO2 adsorption 20
index slightly increased with td and achieved maximum after 60
and 25 min of operation at 110 and 120 1C, respectively. From an
0
operational perspective, the CO2 desorption from the surface of 0 5 10 15 20
CNT(APTS) via 120 1C for 25 min would be more practical and thus n
was selected as in the cyclic CO2 adsorption.
Fig. 6 shows the qe and the CO2 adsorption indexes of Fig. 6. Cyclic CO2 adsorption on CNT(APTS) via thermal desorption (Cin = 15%,
ta = 10 min, td = 25 min, Ta = 60 1C, Td =120 1C, P= 1 atm).
CNT(APTS) conducted at 120 1C and 1 atm for 25 min under
various cycles of adsorption and regeneration (n). It is apparent
that the CO2 can be effectively desorbed from the surface of below 3% attrition after 20 cycles of operation. This suggests that
CNT(APTS) and the qe was preserved during 20 cycles of operation. CNT(APTS) can be employed in prolonged cyclic CO2 adsorption
The CO2 adsorption indexes appeared stable and only showed via a simple temperature swing operation.
 ARTICLE IN PRESS
S.-C. Hsu et al. / Chemical Engineering Science 65 (2010) 1354–1361 1359

40 100

80

Adsorption index (%)

30
qe (mg-CO2/g-sorbent)

60

20
40

10 20

0
0 0.0 2.5 5.0 7.5 10.0 12.5
100 Time (min)

Fig. 8. CO2 adsorption indexes of CNT(APTS) at various desorption times via

thermal/vacuum desorption (Cin = 15%, ta = 10 min, Ta = 60 1C, Td =120 1C, P =0.145
80 atm).
Adsorption index (%)

60
50

40
40
qe (mg-CO2/g-sorbent)

20
30

0
0 5 10 15 20
20
n

Fig. 7. Cyclic CO2 adsorption on CNT(APTS) via vacuum desorption (Cin =15%,
ta = 10 min, td =30 min, Ta = 60 1C, P = 0.145 atm). 10

3.6. Cyclic CO2 adsorption via vacuum desorption

0
Fig. 7 shows the qe and the CO2 adsorption indexes
of CNT(APTS) conducted at 60 1C and 0.145 atm for 30 min under
100
various n. It is seen that the qe decreased from 37.7 to 30.1 mg/g
while the CO2 adsorption index decreased from 100% to 79.8% at
Adsorption index (%)

the first cycle of operation. This could be attributed to the 80

chemical interaction of CO2 and CNT(APTS), which is unable to
desorbed from the surface of CNT(APTS) via vacuum suction.
60
However, the qe of regenerated CNT(APTS) reached stable during
the following 19 cycles of operation. This suggests that the
physical interaction of CO2 and CNT(APTS) can be effectively 40
recovered via vacuum suction in prolonged cyclic operation.

20

3.7. Cyclic CO2 adsorption via thermal/vacuum desorption

In order to make CO2 desorption from the surface of spent
CNT(APTS) become more practical in the field, the CO2 desorption
via a combination of thermal treatment and vacuum suction was
further tested at 120 1C and 0.145 atm. Fig. 8 shows the
CO2 adsorption indexes at various td. As can be seen, the CO2
adsorption index slightly increased with td and achieved near
100% after 5 min of operation, which is much shorter than those
via thermal treatment (25 min) or vacuum suction (30 min).
Fig. 9 presents the qe and the CO2 adsorption indexes of
CNT(APTS) conducted at 120 1C and 0.145 atm for 5 min under
various n. It is seen that no attrition of CO2 adsorption on
CNT(APTS) was observed during 20 cycles of operation.
0
0 5 10 15 20
n
Fig. 9. Cyclic CO2 adsorption on CNT(APTS) via thermal/vacuum desorption
(Cin = 15%, ta =10 min, td = 5 min, Ta = 60 1C, Td = 120 1C, P = 0.145 atm).
The CO2 purity in the desorbed gas was also evaluated. This
study employed the purified air as the purge gas for CO2
desorption from the surface of CNT(APTS) at the same flow rate
as adsorption process. Therefore, the CO2 purity in the desorbed
gas depends on desorption time and reached a maximum Ceff of
17% via thermal/vacuum desorption. This is not acceptable in the
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1360 S.-C. Hsu et al. / Chemical Engineering Science 65 (2010) 1354–1361

field. However, the CO2 purity in the desorbed gas can be

improved by replacing the purge gas air with the steam. After (a) Virgin
condensation of steam to liquid H2O, the CO2 purity in the (b) After n = 20
desorbed gas should be significantly increased.

Intensity (a.u.)
3.8. Stability of the adsorbents

The pore structure, the crystal phase and the surface functional (b)
groups of CNT(APTS) before and after 20 cycles of adsorption and
thermal regeneration were characterized by BET, XRD and FTIR,
respectively. Fig. 10 presents the N2 adsorption/desorption
isotherm curves of virgin and regenerated CNT(APTS). It is clear
that both samples have similar N2 isotherm curves which exhibit
(a)
a type II shape according to IUPAC classification (Gregg and Sing,
1982), with a rounded knee at a very low PN2/P0 (about 0.01)
representing some micropores in CNT(APTS). After a very slow
20 40 60 80
increase up to a PN2/P0 of 0.9, the isotherm curves display a sharp
2θ
increment with PN2/P0 showing largely mesoporous nature of
CNT(APTS). A small closed adsorption/desorption hysteresis loop Fig. 11. XRD patterns of CNT(APTS) before and after 20 cycles of operation via
is also observed with a PN2/P0 above 0.9 probably due to the thermal desorption.
mesopores with a capillary condensation.
Fig. 11 shows the XRD patterns of virgin and regenerated
CNT(APTS). It is evident that both samples have similar XRD
a: Virgin
patterns showing a typical peak of CNTs or graphite at 2y =26.11
b: After n = 20
which illustrate the characteristics of a typical multi-walled CNT
structure (Zhu et al., 2008). a
Fig. 12 presents the IR spectra of virgin and regenerated
Transmission (%)

CNT(APTS). It is seen that both IR spectra are very similar

displaying significant bands at 3480, 2950, 1560 and 1030 cm  1,
1600
which are associated with hydroxyl groups (–OH), CH stretching b 3370 2950
from CH2CH2CH2–NH2 groups, NH2 deformation of hydrogen
bonded amine group (Chang et al., 2003; Huang et al., 2003) C-H2
and Si–O–Si(C) vibrations (Jing et al., 2002), respectively. The
N-H 1030
abundance of surface amine groups provides numerous chemical N-H & N-H2
sites for CO2 adsorption.
The pore structure, the crystal phase and the surface functional
Si-O-Si(C)
groups of virgin and regenerated CNT(APTS) via vacuum deso-
rption or thermal/vacuum desorption also show analogous results
to Figs. 10–12. This reflects that CNT(APTS) are stable nanomater- 3500 3000 2500 2000 1500 1000
ials in cyclic operation regardless of via thermal, vacuum or Wavenumber (cm-1)
thermal/vacuum desorption.
It is apparent that CNT(APTS) not only show good adsorption Fig. 12. IR spectra of CNT(APTS) before and after 20 cycles of operation via thermal
desorption.
capacity of CO2 but also display stable behavior in prolonged

cyclic operation. The energy penalty for the regeneration of spent

25
CNT(APTS) via thermal/vacuum desorption is expected to be low.
Quantity adsorbed (mmol-N2/g-sorbent)

Virgin These advantages make CNT(APTS) that appear possibly cost-

20 After n = 20
effective CO2 sorbents. Since the production and the use of non-
functionalized multiwalled CNTs have now reached several
million tons (Global Industry Analysts, 2009), it is anticipated
15
that the price of CNTs can be further reduced in the foreseeable
future. Thus, the CNT(APTS) appear promising for CO2 capture
10 from flue gas.

5
4. Conclusions

0 APTS-functionalized CNTs were selected as sorbents to study

thermodynamics and regeneration of CO2 adsorption from gas
streams. The thermodynamic analysis indicated that the CO2
0.0 0.2 0.4 0.6 0.8 1.0 adsorption on CNTs and CNT(APTS) is exothermic and typical for
Relative pressure (PN /P0) physical adsorption. The cyclic CO2 adsorption on CNT(APTS)
2
showed that the adsorbed CO2 can be effectively desorbed at
Fig. 10. N2 adsorption (solid line) and desorption (dash line) isotherms of 120 1C for 25 min while the adsorbed CO2 due to physical
CNT(APTS) before and after 20 cycles of operation via thermal desorption. interaction can be effectively desorbed at 0.145 atm for 30 min.
 ARTICLE IN PRESS
S.-C. Hsu et al. / Chemical Engineering Science 65 (2010) 1354–1361
The regeneration time can be further shortened to 5 min via a
thermal/vacuum desorption and thus reduces a significant
amount of energy penalty. The adsorption capacity, the pore
structure, the crystal phase and the surface functional groups of
CNT(APTS) were preserved in the 20 cycles of adsorption and
regeneration. This suggests that the CNT(APTS) can be used in
prolonged cyclic operation. The CNT(APTS) are thus possible cost-
effective CO2 sorbents in the predictable future.
Acknowledgment
Supported from the National Science Council, Taiwan, under a
contact number NSC97-ET-7-005-001-ET is gratefully acknowl-
edged.
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