Fuel 206 (2017) 10–18

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Fuel
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Full Length Article

Modified carbon nanotubes/tetraethylenepentamine for CO2 capture

Maryam Irani, Andrew T. Jacobson, Khaled A.M. Gasem, Maohong Fan ⇑
Department of Chemical and Petroleum Engineering, University of Wyoming, Laramie, WY 82071, USA

h i g h l i g h t s

Modified carbon nanotubes (MCNTs) were prepared using a KOH reagent.

MCNTs/tetraethylenepentamine was prepared as a CO2 sorbent.

Under optimal conditions, the CO2 sorption capacity reached 5 mmol CO2/g.

High CO2 desorption rate of the sorbent can considerably reduce CO2 capture cost.

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

Article history: In this work, a CO2 sorbent was prepared by immobilizing tetraethylenepentamine (TEPA) onto modified
Received 1 April 2017 carbon nanotubes. Modification of carbon nanotubes (CNTs) using a KOH reagent was done to increase
Received in revised form 28 May 2017 the surface area and pore volume of the CNTs. The prepared sorbents were characterized using X-ray
Accepted 29 May 2017
diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM),
transmission electron microscopy (TEM) thermogravimetric analysis (TGA), and Brunauer-Emmett-
Teller (BET) analyses. At the optimal TEPA loading of 75 wt% on modified CNTs (MCNTs), the CO2 sorption
Keywords:
capacity reached 5 mmol CO2/g-sorbent for 10 vol% CO2 in N2 along with 1 vol% H2O at 60 °C. Kinetic and
CO2 capture
Carbon nanotubes
thermodynamic adsorption studies found activation energies for CO2 adsorption and desorption of
Sorption MCNTs/TEPA being16.2 kJ/mol and 39.9 kJ/mol, respectively. The low activation energy for CO2 desorp-
Kinetics tion using MCNTs/TEPA corresponds with a high CO2 desorption rate, resulting in a low CO2 capture cost.
Therefore, the MCNTs/TEPA sorbent has potential for application to CO2 capture from gas mixtures.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction According to predictions by the Intergovernmental Panel on

The issue of increasing CO2 emissions in the environment has
received much attention because of its association with climate
change. Specifically, CO2 emissions contribute to the greenhouse
effect; a phenomenon where greenhouse gases such as CO2,
methane, nitrous oxide, water vapor, and ozone absorb and release
thermal infrared radiation resulting in an increase of Earth’s tem-
perature [1]. The increase in concentration of greenhouse gases
due to human activities has caused an increase of 0.8 °C in the
Earth’s surface temperature within the past 100 years [2]. Excess
amounts of greenhouse gases in the atmosphere are also responsi-
ble for other environmental problems such as a rising water-level
in the world’s oceans, an increase in the number of ocean storms,
and an upsurge in floods around the world [1]. Among the green-
house gases, CO2 is the major source attributed to climate change.
CO2 alone contributes to roughly 64% of the greenhouse effect [1].
⇑ Corresponding author.
E-mail address: mfan@uwyo.edu (M. Fan).
Climate Change (IPCC) the atmosphere may have a concentration
of up to 570 ppm CO2 by the year 2100, which may result in a
mean global temperature increase of around 1.9 °C and a rise in
mean sea level of 3.8 m [1].
Around 85% of the world’s total energy demand is provided by
fossil fuel thermal power plants. Fossil fuel power plants con-
tribute approximately 40% of total CO2 emissions around the
world. The capture of CO2 from power plant flue gas gives rise to
around 75% of the total cost of carbon capture and storage [1].
CO2 emissions from thermal power plant flue gas can be
decreased through pre-combustion carbon capture, post-
combustion carbon capture, and oxyfuel combustion [1,3]. The
focus of this work falls into the post-combustion capture category,
which describes the process of CO2 removal from flue gas gener-
ated by thermal power plant combustion chambers that utilize
air for combustion. These power plants produce a flue gas at atmo-
spheric pressure with an average CO2 concentration of less than
15% [1].

http://dx.doi.org/10.1016/j.fuel.2017.05.087
0016-2361/Ó 2017 Elsevier Ltd. All rights reserved.
 M. Irani et al. / Fuel 206 (2017) 10–18
Aqueous amine technology has been applied to CO2 absorption
in industry, but it suffers from drawbacks including high energy
requirements and corrosion problems [4]. Adsorption on solid
adsorbents is an attractive alternative for efficient CO2 capture from
flue gases. Specifically, carbon based adsorbents are promising due
to their chemical inertness and high surface area [5]. Using solid
adsorbents for CO2 capture have potential advantages compared
to amine scrubbing (aqueous amine technology) including a reduc-
tion in regeneration energy and ease of handling. Several authors
have reviewed and compared aqueous amine technology with
other technologies (e.g. solid adsorbents) comprehensively [6,7].
Recently, studies show that modifications of porous materials
by introducing basic sites can enhance CO2 adsorption capacity
and selectivity due to a strong interaction between basic groups
and acidic CO2. The common functional groups for modification
of porous materials are alkaline carbonates and a number of amine
groups [8]. These solid adsorbents can be prepared by either
chemically bonding amine groups to a support, referred to as
grafting [9], or immobilizing liquid amines within the pores of a
support, known as impregnation [10]. Compared to the grafting
method, impregnation has the advantage of simple preparation
procedures [11]. The wet impregnation of amine-based materials
is generally a physical mixture of amine-based materials and sup-
ports which results in a non-covalent introduction of amine-based
materials into the pores or onto the surface of the support [10].
Carbon nanotubes (CNTs) have a variety of applications due to
their possession of unique properties such as topological hollow
tubular structures, thermal and chemical stability, and large pores
[10,12]. Su et al. [13] modified CNTs using 3-aminopropyl-
triethoxysilane (APTS), and studied CO2 adsorption capacity. The
optimal CO2 adsorption capacity was found to be 1 mmol/g for
15 v.% CO2 at 20 °C. Carbon nanotubes (CNTs) impregnated with
tetraethylenepentamine (TEPA) were prepared by Ye et al. [10] as
a solid amine adsorbent for CO2 capture. The maximum adsorption
capacity was approximately 3.87 mmol g1 for 2 v.% CO2 with 2 v.
% H2O at 40 °C.
Chemical activation is a very efficient method to produce car-
bons with high surface area. Alkaline hydroxides, such as KOH
and NaOH, have been used as common activating agents for
the preparation of activated carbons originating from a variety
of carbonaceous precursors such as coals, carbon nanotubes,
and fibers. Generally, chemical activation using an alkaline
involves solid–solid or solid–liquid reactions, including the
hydroxide reduction and carbon oxidation, to form a porous
structure [14].
In this work, KOH was chosen as an activation agent to modify
multi-walled carbon nanotubes to increase the surface area and
porosity. Several authors [10,15,16] have reported functionalized
unmodified carbon nanotubes (CNTs) with tetraethylenepen-
tamine (TEPA) for CO2 capture, all of which show lower CO2 cap-
ture capacity when compared to TEPA supported on KOH
modified carbon nanotubes (MCNTs/TEPA) used in this work.
The MCNTs/TEPA CO2 capture results are also compared with
experimental results from this study using a sorbent prepared
from unmodified CNTs. To the best of our knowledge the use of
KOH modified carbon nanotubes as a support for the preparation
of an amine-based sorbent through impregnation has not been
reported.
2. Experimental
2.1. Preparation of the MCNT/TEPA sorbents
Multi walled carbon nanotubes (CNTs) with dimensions (O.D. 
I.D.  L) of 10 nm ± 1 nm  4.5 nm ± 0.5 nm  3–6 nm were pur-
11
chased from Sigma-Aldrich. Anhydrous ethanol was purchased
from Decon Labs, Inc. Tetraethylenepentamine (TEPA, technical
grade) and potassium hydroxide (KOH, 85%) were purchased from
Sigma-Aldrich. Hydrochloric acid (HCl, 36%–38%, wt.) was obtained
from Fisher scientific, Inc. All gases used in this work were supplied
by United States Welding, Inc.
Chemical activation of the CNTs was performed by mixing KOH
and CNTs at an activating agent/carbon ratio of 6:1 in 50 ml of
ethanol, and then stirred for 6 h at room temperature. Next the
mixture was dried in an oven at 80 °C for at least 12 h, followed
by heat treatment at a temperature of 600 °C in N2 gas for 3 h.
The materials were then stirred in dilute HCl overnight, filtered,
washed with water until a pH value of 7 was reached, and dried
in the oven at 100 °C. These modified CNTs are given the term
MCNT for the remainder of this work.
The MCNTs/TEPA were prepared by wet impregnation. A speci-
fied amount of TEPA was dissolved in 20 ml of ethanol under stir-
ring. Next, the MCNTs were added into the ethanol/TEPA solution
and stirred for 24 h at room temperature, and then was dried in
an oven at 50 °C. The amount of TEPA and MCNTs added to the solu-
tion was selected for preparation of MCNTs/TEPA samples with
TEPA loadings of 50, 60, 70, 75, and 80 wt%. The unmodified
CNTs/TEPA sorbent was prepared similarly with a maximum TEPA
loading of 50 wt%. TEPA loading over 50 wt% was not achievable
due to the unmodified CNTs sorbent agglomerating from amine
overloading. This most likely can be attributed to the lower surface
area of unmodified CNTs (CNTs without treatment with KOH) com-
pared to modified CNTs (MCNTs).
2.2. Characterization of sorbent
To characterize the functionalities on the sorbents, a Nicolet/
iS50 spectroscope Fourier transform infrared spectrometer (FTIR)
was used with a frequency range of 4000–500 cm1. X-ray diffrac-
tion (XRD) analyses were completed with a Rigaku Smartlab X-ray
diffraction system using a Cu Ka1 line (1.5406 Å) operating at
40 kV/40 mA, with 2h ranging from 10° to 90°. A FEI Quanta 450
field emission scanning electron microscope with a Schottky field
emission gun at an accelerating voltage of 20 kV was applied to
obtain scanning electron microscopy (SEM) images. A Quan-
tachrome Autosorb IQ automated gas sorption analyzer was used
to obtain BET (Brunauer-Emmett-Teller) surface area and BJH
(Barrett-Joyner-Halenda) pore volume. A TA Instruments SDT Q
600 was applied for thermogravimetric analysis (TGA) under N2
gas with a heating rate of 10 °C/min. A Tecnai G2 F20 S-Twin
200 kV High Resolution Transmission Electron Microscope
(HRTEM) was utilized for obtaining TEM images.
2.3. CO2 sorption and regeneration experiments
Reactor preparation consisted of 50 mg of the sorbent being
mixed with 1000 mg of sand and loaded into a quartz tube reactor,
followed by placement into a tube furnace. For sorption experi-
ments10 vol% CO2 in N2 at a flow rate of 300 mL/min was fed to
the reactor. 1 vol% H2O was introduced into this inlet gas stream
by a syringe pump, and heating tape was used to vaporize the
water before entering the reactor. Each sorption test was run until
the outlet CO2 concentration and the inlet CO2 concentration were
equivalent. CO2 desorption was completed using the same experi-
mental setup. The carrier gas, N2 gas (99.9%), at a flow rate of
300 mL/min was used for desorption of CO2 at 90 °C. A schematic
of the experimental set up used for CO2 separation is shown and
labelled (No. 1–14) in Fig. 1.
12 M. Irani et al. / Fuel 206 (2017) 10–18

Fig. 1. Schematic diagram of CO2 separation setup: 1, CO2 cylinder; 2, N2 cylinder; 3(a) CO2 mass flow controller; 3(b), N2 mass flow controller; 4, syringe pump; 5, heat tape
temperature controller; 6, heat tape; 7, tube furnace temperature controller; 8, tube furnace; 9, quartz tube reactor; 10, quartz wool and notch block; 11, sorbent; 12, water
removal unit; 13, gas analyzer; 14, data recording system.

3. Results and discussions

3.1. Characterization

Fig. 2 shows FTIR patterns of the CNTs, MCNTs, and MCNTs/

TEPA. From the spectrum of MCNTs no changes were observed
after modification of the CNTs with KOH, suggesting no functional
groups are present. Compared to the unloaded CNTs and MCNTs,
the FTIR spectrum of MCNTs/TEPA shows additional peaks indicat-
ing the presence of TEPA. The –NH2 and –NH bending vibration of
TEPA are seen in the bands at 1520 and 1420 cm1 , respectively
[15]. Furthermore, the bands at 2870 and 2810 cm1 correspond to
C–H asymmetric and symmetric vibration peaks, respectively.
The XRD patterns of the CNTs, MCNTs, and MCNTs/TEPA are
given in Fig. 3. The strong diffraction peak at 25° and weak diffrac-
tion peaks at 42° and 77° correspond to the graphite (0 0 2), (1 0 0),
and (1 1 0) lattice planes of the CNTs, respectively [15,17]. After
modification of CNTs with KOH at 600 °C, the peak locations do Fig. 3. XRD results of the CNTs, MCNTs and MCNTs/TEPA.
not show any obvious changes indicating that the structure of
the CNTs is retained. It has been reported that KOH is transformed
into K2CO3 at 600 °C [14]. It is proposed that the concentration of MCNT (25°) overlapping the tail of the TEPA peak contributes to
K2CO3 is too low to be detected by XRD, and in part confirmed the increased broadness and intensity of the MCNTs/TEPA peak.
by EDX (image not shown in this work) indicating low concentra- No other obvious changes were seen in the peak locations of
tions of potassium. This low concentration may be due to removal MCNTs after TEPA incorporation.
of K2CO3 through the washing of MCNTs with a hydrochloric acid TGA weight loss curves of the CNTs, MCNTs, and MCNTs/TEPA are
solution. In the XRD pattern of MCNTs/TEPA, the broad diffraction shown in Fig. 4. MCNTs/TEPA displayed a mass loss of approximately
peak spanning 10° –30° with a maximum at 19.6° indicates the 7 wt% from 25 °C to 109 °C, corresponding to the evaporation of
presence of amorphous TEPA. Also, the sharp diffraction peak of

Fig. 2. FTIR spectra of CNTs, MCNTs and MCNTs/TEPA. Fig. 4. TGA curves of CNTs, MCNTs and MCNTs/TEPA with TEPA loading of 75 wt%.
 M. Irani et al. / Fuel 206 (2017) 10–18
adsorbed water. A sharp weight loss (60%) was then observed
between 109 and 246 °C due to the decomposition of TEPA. This
was followed by a third step of weight loss (8%) between 246
and 420 °C that may be due to the loss of the residual TEPA trapped
in the support. Therefore, MCNTs/TEPA are thermally stable below
110 °C which is applicable for CO2 sorption (60 °C) and desorption
(90 °C) in this work.
As shown in Table 1, the surface area of the CNTs increases from
90.3 to 169.8 m2/g after activation with KOH. The generation of lar-
ger pores after KOH activation results in an increase in surface area
of the MCNT. After TEPA loading into the MCNTs, the surface area
and pore volumes decrease, which is an indication that TEPA has
been successfully loaded into the MCNTs structure. Fig. 5 shows
TEM micrographs of unmodified CNTs and modified CNTs. It is
obvious that the nanotubular morphology of CNTs is preserved
after the reaction with KOH (Fig. 5b). The high magnification image
of MCNTs shows that the KOH activation process creates defects in
the nanotubes walls. It has been reported that these defects result
in the increase of pore volumes and surface area of the modified
CNTs [14].
Scanning electron microscopy (SEM) images, Fig. 6, show that
the tubular morphology remained unchanged after modification
of CNTs with KOH. The MCNTs/TEPA image (Fig. 6c) shows a
homogenous morphology with swelling in the tubular structure
of MCNTs, suggesting that TEPA chains were introduced into the
pores of the multilayer MCNTs structure. The schematic represen-
tation of MCNTs/TEPA is illustrated in Fig. 7. It has been reported
that organic solvents with low surface tension (<72 mN/m), such
as ethanol, can act as carriers for the introduction of solutes inside
the nanotubes by capillarity [18,19]. The same process may occur
in this work by introducing TEPA inside MCNTs cavities (Fig. 7)
from the use of ethanol in the preparation of the MCNTs/TEPA
sorbent.
3.2. Effect of TEPA loading on the CO2 sorption capacity
In regards to CO2 sorption, the availability of amine groups in
amine-based sorbents has a crucial role, as the interaction between
the CO2 and amine groups results in adsorption. Hence, the TEPA
loading amount has a direct influence on the CO2 sorption capacity.
Fig. 8 shows that with an increasing TEPA loading (50–75 wt%) CO2
sorption capacity increases from 3 to 5 mmol/g. Further increase in
TEPA loading (80 wt%) results in a reduction of the CO2 sorption
capacity. A decrease in accessible amine groups due to TEPA
agglomeration may describe this reduction in capacity. This parti-
cle agglomeration was visible when TEPA loading was greater than
80 wt%, causing the sorbent to be unusable for CO2 sorption tests.
In addition to MCNTs, unmodified CNTs were tested as a sup-
port, resulting in an optimum TEPA loading of 50 wt% with a max-
imum CO2 sorption capacity of 2.5 mmol/g. These results were
obtained with a gas mixture containing 10 vol% CO2 in N2 with
1 vol% H2O. The lower surface area of unmodified CNTs, compared
to that of MCNTs, may be attributed to the lower observed CO2
capacity. Consequently, the more amine groups loaded, the higher
CO2 sorption capacity.
Table 1
The texture properties of CNTs, MCNTs and MCNTs/TEPA with TEPA loading of 75 wt
%.
Sample BET surface area (m2/g) BJH pore volume (cm3/g)
CNTs 90.3 1.16
MCNTs 169.8 1.97
MCNTs /TEPA 2.2 0.03
13
3.3. Effect of moisture addition
Studying the effect of moisture on CO2 sorption capacity is cru-
cial as CO2-containing gases, such as flue gas, typically contain
water vapor. The addition of 1 vol% moisture increased CO2 sorp-
tion capacity by 56% (3.2–5 mmol/g) compared to dry gas adsorp-
tion, as seen in Fig. 9. Conversely, CO2 adsorption capacity reduced
with a moisture concentration greater than 1%.
This reduction in adsorption capacity may be caused by the
water molecules occupying available adsorption sites, competing
with CO2 [20].
The CO2/amine reactions differ between wet and dry conditions
as seen below. Dry conditions facilitate the formation of carba-
mates between two amine groups, while wet conditions facilitate
the formation of bicarbonates between one CO2 molecule and
one amine group [21,22]. Two types of these amine groups exist
within TEPA including primary (R1–NH2) and secondary (R1–
NH–R2) amines. The maximum adsorption capacity was calculated
using the reaction stoichiometry, resulting in a capacity of 1.0 mol
of CO2 per mole of amine under wet conditions, and 0.5 mol of CO2
per mole of amine under dry conditions [21]. The reactions under
wet conditions include
R1 NH2 þ CO2 þ H2 O ¢ ðR1 NHþ3 ÞðHCO3 Þ ðR1Þ
R1 R2 NH þ CO2 þ H2 O ¢ ðR1 R2 NHþ2 ÞðHCO3 Þ ðR2Þ
The reactions under dry conditions are
2ðR1 NH2 Þ þ CO2 ¢ ðR1 NHþ3 ÞðR1 NHCOO Þ ðR3Þ
2ðR1 R2 NHÞ þ CO2 ¢ ðR1 R2 NHþ2 ÞðR1 R2 NCOO Þ ðR4Þ
ðR1 NH2 Þ þ ðR1 R2 NHÞ þ CO2 ¢ ðR1 NHþ3 ÞðR1 R2 NCOO Þ ðR5Þ
3.4. Effect of sorption temperature on the CO2 sorption capacity
In addition to TEPA loading and moisture content, sorption
capacity is subject to the temperature of adsorption. To study the
effect of adsorption temperature on CO2 capacity, a loading of
75 wt% MCNTs/TEPA was selected. Fig. 10 shows that with an
increasing temperature (25–60 °C) the sorption capacity increased.
It has been proposed in other work [22,23] that the increased tem-
perature may be overcoming the kinetic barrier and enabling mass
transfer of CO2 into the bulk of polymer. The accessibility of amine
sites increase with an increasing temperature, with the maximum
sorption capacity being obtained at 60 °C. The sorption rate is con-
trolled by CO2 diffusion onto the sorbent surface at low tempera-
tures, in this case below 60 °C. A temperature of 70 °C showed a
decrease in capacity, this is due to adsorption being an exothermic
process, which causes a reduced equilibrium sorption capacity. In
other words, the thermodynamics govern over the kinetics, result-
ing in a decrease of CO2 sorption capacity above 60 °C [22].
3.5. Adsorption kinetics and thermodynamics
In this work, the Langmuir adsorption model [24] has been
applied to study the adsorption kinetics of CO2 onto the adsor-
bents. Langmuir adsorption theory is based on the assumptions
that the rates of adsorption and desorption on the surface are equal
at equilibrium, a monolayer of the adsorbed species is formed on
the surface, and the rate constants of adsorption and desorption
are not functions of the number of adsorbed molecules on the sur-
face [25,26].
The CO2 adsorption rate on the surface is shown below [25,26]:
14 M. Irani et al. / Fuel 206 (2017) 10–18

Fig. 5. TEM images of (a) unmodified CNTs, (b) MCNTs.

Fig. 6. SEM images of the (a) CNTs and (b) MCNTs, and (c) MCNTs/TEPA with TEPA loading of 75 wt%.

Fig. 7. Schematic illustration of TEPA loaded on MCNTs via introduction inside cavities, where black, white, and blue spheres represent C atoms, H atoms, and N atoms,
respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
 M. Irani et al. / Fuel 206 (2017) 10–18 15

Fig. 10. The effect of temperature on CO2 sorption capacity at a CO2 concentration
Fig. 8. The effect of TEPA on CO2 sorption capacity at a CO2 concentration of 10 vol%
of 10 vol% with the balance as N2 gas, a gas flow rate of 300 mL/min, a TEPA loading
with the balance as N2 gas, a gas flow rate of 300 mL/min, an adsorption
of 75 wt%, 1 vol% moisture (H2O) and 50 mg sorbent.
temperature of 60 °C, 1 vol% moisture (H2O) and 50 mg of sorbent.

which describes surface coverage in terms of capacity q, and maxi-

mum capacity, qmax, results in

q ¼ qmax ½1  expðka C 0 tÞ ðE4Þ

q ¼ qmax expðkd tÞ: ðE5Þ

Adsorption measurements are applied to calculate values of ka
and kd by regressing Eqs. (4) and (5), respectively. A representative
fit for adsorption and desorption data is illustrated in Fig. 11. A
quality fit was achieved with correlation coefficients of 0.999 and
0.998 for the adsorption and desorption curves respectively. It
should be noted that the Langmuir adsorption model assumes that
the adsorbed species form a monolayer on the surface. Although
the adsorption in this work may indeed be multilayer, the Lang-
muir model was applied for our quantitative analysis because of
its simplicity.
An efficient CO2 sorbent should have fast adsorption and des-
orption kinetics at low temperatures. In this work, the adsorption
and desorption kinetics were evaluated using the Arrhenius equa-
tion described below [27]
Ea
Lnk ¼  þ LnA ðE6Þ
Fig. 9. The effect of moisture on CO2 sorption capacity at a CO2 concentration of RT
10 vol% with the balance as N2 gas, a gas flow rate of 300 mL/min, an adsorption
temperature of 60 °C, a TEPA loading of 75 wt%, and 50 mg of sorbent. which includes the reaction rate constant (k), the activation energy
(Ea), the molar gas constant (R), the reaction temperature (T), and
the frequency factor (A). The activation energy and frequency factor
are calculated by plotting Ln k versus (1/T) with a linear fit as illus-
dh trated in Fig. 12.
¼ ka C 0 ð1  hÞ ðE1Þ
dt Complete desorption of CO2 from the sorbent occurred at a low
where h is the fraction of surface coverage, t is time, ka is the temperature (90 °C) within a short time period (5 min). The
adsorption rate constant, and C0 is the concentration or partial pres- MCNTs/TEPA CO2 adsorption and desorption Ea values of 16.2 kJ/-
sure of CO2 in the gas. The CO2 desorption rate from the surface is mol and 39.9 kJ/mol, respectively, are relatively low. These results
written as show that the sorbent rate of CO2 adsorption and desorption is
high. Lower CO2 capture costs can be achieved due to this high
dh sorption rate, thus decreasing the necessary sorbent content.
¼ kd h ðE2Þ
dt Decreased sorbent content can result in a decreased operating cost
where kd is the desorption rate constant. The integration and com- because of a reduced temperature change and pressure drop in the
bination of these two equations in conjunction with the flue gas [27]. Compared to literature Ea values of aqueous amine-
relationship based absorption (40–50 kJ/mol), reported solid adsorption Ea val-
ues are generally lower [16,28]. The activation energy for desorp-
q ¼ qmax h ðE3Þ tion in this work is comparable to the results of other solid
16 M. Irani et al. / Fuel 206 (2017) 10–18

Fig. 11. The CO2 adsorption (a) and the CO2 desorption (b) curves MCNT/TEPA (blue lines: experimental data, red lines: Langmuir model fit to obtain ka and kd) [CO2
concentration: 10 vol%; balance gas: N2; gas flow rate: 300 mL/min; H2O: 1 vol%; adsorption temperature: 60 °C; TEPA loading:75 wt%; desorption temperature: 90 °C;
desorption carrier gas: N2 with a flow rate of 300 mL/min; weight of sorbent: 50 mg].

Fig. 12. Arrhenius plots of MCNT/TEPA for adsorption (a) and desorption (b). [CO2 concentration: 10 vol%; balance gas: N2; gas flow rate: 300 mL/min; H2O: 1 vol%; TEPA
loading: 75 wt%; desorption carrier gas: N2 with a flow rate of 300 mL/min; weight of sorbent: 50 mg].

amine-based sorbents, for example, Liu et al. [16] prepared a sor-
bent using impregnation of tetraethylenepentamine (TEPA) in
industrial grade multiwalled carbon nanotubes (IG-MWCNTs)
and calculated the activation energy of CO2 adsorption/desorption
using the Arrhenius equation. Their results showed that the activa-
tion energy for desorption was in the range of 41–46 kJ/mol, with a
CO2 capacity of around 4 mmol/g using 2 vol% CO2 gas at 16 °C.
Therefore, MCNTs/TEPA has potential to be an efficient CO2 adsor-
bent because of its low energy requirement and its high CO2 sorp-
tion capacity.
 M. Irani et al. / Fuel 206 (2017) 10–18
Fig. 13. Cyclic CO2 sorption and desorption [sorption conditions: CO2 concentra-
tion, 10 vol%; gas flow rate, 300 mL/min; H2O: 1 vol%; sorption temperature, 60 °C;
TEPA loading: 75 wt%; desorption conditions:N2 flow rate, 300 mL/min; desorption
temperature, 90 °C; weight of sorbent:50 mg].
Furthermore, the heat of the reaction can be studied as follows
[27]
DH ¼ Ea;ads  Ea;des ðE7Þ
where DH is the heat of the reaction, and Ea;ads and Ea;des are the acti-
vation energies of adsorption and desorption, respectively, obtained
from the Arrhenius equation (E6). DH was calculated to be
23.7 kJ/mol for MCNTs/TEPA. The sorption of CO2 onto MCNTs/
TEPA is confirmed to be exothermic by the negative value of DH.
3.6. Regenerability
In an industrial settings, an effective sorbent should have not
only high sorption capacity but also needs to be regenerable
through several sorption–desorption cycles. In this work, the study
of sorbent regenerability was performed in 10 sorption-desorption
cycles. The results from Fig. 13 show that the sorption capacity
reduced with an increase in cycle number, with a reduction of
about 20% (5 mmol/g to 4 mmol/g) after 10 cycles. TEPA degrada-
tion [8] and evaporation, most likely due to the low molecular
weight of TEPA, may be attributed to the loss of CO2 sorption
capacity. It is suggested that using amine functional components
with higher molecular weights than that of TEPA may give greater
thermal stability, lessening the likelihood of evaporation and
decomposition during sorption–desorption cycles, resulting in bet-
ter regenerability of the sorbent.
4. Conclusions
A sorbent for CO2 capture has been developed by loading TEPA
on modified carbon nanotubes (MCNTs). An optimal TEPA loading
of 75 wt% obtained the maximal CO2 sorption capacity of 5 mmol/g
for a gas mixture containing 10 vol% CO2 in N2 with 1 vol% H2O.
Unmodified CNTs as a support showed a maximal CO2 sorption
capacity of 2.5 mmol/g with an optimal TEPA loading of 50 wt%.
Thermal stability studies indicate that MCNTs/TEPA is stable below
110 °C. MCNTs/TEPA kinetic data of CO2 adsorption and desorption
show a low energy requirement and a short-time cycle for regen-
eration; therefore, MCNTs/TEPA can greatly decrease the overall
cost of capturing CO2.
17
Acknowledgment
Authors highly appreciate the support of the state of Wyoming.
They would like to thank Sabrina Kaufman, Kyle Summerfield and
Emma Jane Alexander from Shell 3D Visualization Resources at
School of Energy and Resources. Authors would like also thank to
Joshua Stecher for TEM images.
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