Chemical Engineering Journal 260 (2015) 596–604

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Chemical Engineering Journal

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

CO2 sorption and reaction kinetic performance of K2CO3/AC

in low temperature and CO2 concentration
Yafei Guo a, Chuanwen Zhao a,⇑, Changhai Li a, Ye Wu b
a
State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026, China
b
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast University, Nanjing 210096, China

h i g h l i g h t s

 The CO2 sorption capacity of the desired K2CO3/AC was 1.015 mmol CO2/g, and the carbonation conversion was 79.0%.
 The CO2 sorption capacities of K2CO3/AC decrease as the temperature increases from 20 to 60 °C.
 The CO2 sorption performance of K2CO3/AC is enhanced with the increase in C H2 O : C CO2 .
 The sorbent retains stable CO2 sorption capacity during 20 carbonation-regeneration cyclic operations.
 K2CO3/AC shows a higher utilization efficiency of active compound and a higher thermal stability.

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

Article history: Reducing or removing CO2 is critical to the confined spaces such as submarines, space-crafts or aircrafts
Received 10 July 2014 while using solid sorbents has been regarded as a promising method. In this work, K2CO3 loaded on acti-
Received in revised form 13 September vated carbon (K2CO3/AC) was developed as a new and regenerable sorbent for CO2 removing in confined
2014
spaces. CO2 sorption performances of K2CO3/AC were investigated under different conditions by varying
Accepted 15 September 2014
Available online 22 September 2014
the K2CO3 loadings, CO2 concentrations, H2O concentrations, CO2 sorption temperatures and water pre-
treatment durations as well as the purge gas flow rates. The CO2 sorption capacity and carbonation con-
version of K2CO3/AC decrease with increasing temperature and increase with increasing mole ratio of H2O
Keywords:
CO2 removal
concentration over CO2 concentration. Sufficient water vapor pretreatment is found to be beneficial to the
Confined spaces sorption-enhanced performance. Increasing flow rate will weaken the CO2 sorption performance. The car-
K2CO3/AC bonation kinetics was also investigated with the correlation between the shrinking core model and
CO2 sorption performance experimental data. Additionally, the sorbent is proved to be regenerable and stable during 20-cycle
CO2 sorption–desorption experiments. K2CO3/AC presents high carbonation conversion efficiency, high
thermal stability, and low dependency on CO2 partial pressure. Therefore, it can be considered as a
new option for CO2 removal in confined spaces.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction a liquid amine bonded to a polymeric support) [6] have been

CO2 is not regarded as a toxic pollutant at normal conditions as
its concentration in the atmosphere is only 387 ppm. However, CO2
could become hazardous and should be removed from confined
spaces including submarines, space-crafts and aircrafts where the
concentration is likely to reach a relatively high percentage [1].
Recently, the removal of low concentration CO2 in confined spaces
has become one of the key challenges for environmental science
[2]. Although several materials such as LiOH [3], soda lime [4],
aqueous amine solutions [5], HSC+ (the organic solid sorbent using
⇑ Corresponding author. Tel.: +86 551 63603141; fax: +86 551 63601669.
E-mail address: cwzhao@ustc.edu.cn (C. Zhao).
widely used in CO2 removal, new sorbents should be introduced
to improve the aeronautics and navigational technology. As in
the future people might spend very long time in confined spaces
for space or deep sea explorations, long-term CO2 sorption perfor-
mances of the proper sorbent candidates have to be assessed.
Alkali metal carbonates can be used to capture CO2 from fossil
fuel-fired power plants in the presence of H2O to form either
sodium or potassium bicarbonate at temperatures below 100 °C
[7]. Among various alkali metal-based sorbents, K2CO3/AC
(activated carbon) presents relatively high CO2 capture capacity
and carbonation reaction rate under the conditions of 50–100 °C,
5–20% CO2, 5–20% H2O and balance N2 [8–14]. The CO2 sorption
performances of several potassium-based sorbents were

http://dx.doi.org/10.1016/j.cej.2014.09.052
1385-8947/Ó 2014 Elsevier B.V. All rights reserved.
 Y. Guo et al. / Chemical Engineering Journal 260 (2015) 596–604 597

investigated at low temperatures and CO2 concentrations, includ- 7

ing K2CO3/AC [15]. The carbonation reaction induced by K2CO3/
AC was found to consist of two steps which are the hydration reac- 10
tion taking place firstly, and then the KHCO3 being produced rap- 6
AT

idly. During the sorption process the adsorption process exists 5 8 11

with the carbonation reaction [16]. Compared with the carbon-
ation process of K2CO3/AC in power plants, the carbonation reac-
tion rate of K2CO3/AC decreased greatly in low temperature and
the CO2 concentration becomes the driving force of reduction.
In order to evaluate the long-term CO2 sorption performance of
K2CO3/AC in confined spaces, several key issues should be investi-
gated including the loadings of K2CO3 retained on the support, the
CO2 sorption reaction kinetics of K2CO3/AC, the effects of reaction
temperature, gas composition, water pretreatment and flow rate
on CO2 sorption performance, and the multiple-cycle operation
behaviors. However, so far little research has been focused on the
CO2 sorption performance of K2CO3/AC in the conditions where
CO2 concentrations are lower than 1% and the temperatures are
lower than 60 °C.
Hence, in the current paper CO2 sorption performance of K2CO3/
AC in low CO2 concentration of 1.0% at 20–60 °C was experimen-
tally studied. The CO2 sorption behaviors and reaction kinetics of
K2CO3/AC with different loadings and the effects of temperature,
gas composition, water pretreatment and flow rate on CO2 sorption
capacity are studied. Moreover, the CO2 sorption capacity and the
change of microscopic structure during multiple cycles are studied
for K2CO3/AC.
2. Experimental section
2.1. Samples
K2CO3, activated carbon (AC) and K2CO3/AC were used in this
study. Analytical reagent K2CO3 and AC were supplied by Research
Institute of Nanjing Chemical Industry Group. The activated carbon
utilized was derived from cocoanut activated charcoal. The surface
area, average pore diameter and pore volume are determined as
579.57 m2/g, 2.30 nm and 0.33 cm3/g, respectively.
K2CO3/AC was prepared by impregnating K2CO3 on AC. 100 g
supports were added to an aqueous solution containing a certain
amount of K2CO3 (the mass of K2CO3 is determined ranging of
5.26–33.33 g, depending on the theoretical loading of K2CO3 vary-
ing from 5% to 25%) in 500 mL de-ionized water. Then, it was
mixed with a magnetic stirrer at ambient temperature for 12 h.
Thereafter, the mixture was dried in a rotary evaporator at
105 °C. The dried samples were then calcined in a muffle furnace
for 2 h at 300 °C.
The as-synthesized sorbents were labeled as KACI5, KACI10,
KACI15, KACI20 and KACI25, where ‘‘K’’ denotes K2CO3, ‘‘AC’’
denotes activated carbon, ‘‘I’’ denotes the impregnation method
and the numbers denote the theoretical loadings of K2CO3. The
actual K2CO3 loading of each sorbent was determined by measur-
ing the mass percentage of potassium using an Inductively Coupled
Plasma Mass Spectrometry. The loadings are 4.43%, 9.21%, 13.95%,
18.42% and 23.14% for KACI5, KACI10, KACI15, KACI20 and KACI25,
respectively.
2.2. Apparatus and procedure
The CO2 sorption performances of these sorbents were assessed
using a modified fixed bed reactor system coupled with a gas ana-
lyzer. The experimental setup is shown in Fig. 1. The apparatus
consists of three sections: a simulated gas production system, a
fixed-bed reactor, and a gas measurement system. The description
of the experimental setup is discussed in depth in Ref. [15].
TC PI
12 13
9 14 15 16
4
MT RH TI
3
1 2
Fig. 1. Schematic for the experimental setup. (1) N2; (2) CO2; (3) pressure
regulating valve; (4) mass flow controller; (5) H2O; (6) high-precision syringe
pump; (7) evaporator; (8) mixture tank; (9) fixed-bed reactor; (10) condenser; (11)
gas analyzer; (12) temperature controller; (13) pressure indicator; (14) mass
transmitter; (15) relative humidity monitor; (16) temperature indicator.
A confined space atmosphere was simulated by a constant flow
of CO2, H2O and balanced N2. CO2 and N2 were supplied by high-
purity cylinders and the flow rates were adjusted by mass flow
controllers. H2O was injected using a high-precision syringe pump
and the feed line was heated to ensure complete vaporization of
water. The stainless fixed-bed reactor with an inner diameter of
0.02 m was packed in an electric heating element. The electric
heating element was used to heat the reactor to the given temper-
ature. A gas analyzer was used to measure the CO2 concentration of
outlet gas. The relative humidity (RH) and temperature of the sim-
ulated atmosphere were also monitored online by the relative
humidity monitor and temperature sensor.
Three grams sorbent was placed in the reactor and the bed
height was 0.01 m. A simulated gas flow containing 1.0% CO2 and
1–2.5% H2O with purge flow rates of 300–700 mL/min was used
for the experiments. The reaction temperature can be adjusted
from 20 °C (ambient) to 60 °C. The reactor needed to be heated
to 200 °C for about 20 min to remove the moisture prior to each
experiment. Then the reactor was cooled down to pre-determined
temperature and the N2 stream was switched to flue gas. The CO2
concentration of outlet gas was monitored with a gas analyzer.
When the outlet CO2 concentration equaled to the inlet CO2 con-
centration, the flue gas was switched to pure N2 to clean the appa-
ratus. At the end, the reactor was heated to 200 °C at pure N2 until
the CO2 concentration reached 0, followed by cooling down for the
next experiment.
3. Theoretical analysis
3.1. CO2 sorption performances of KACIs
The CO2 sorption efficiency (gCO2 ), CO2 sorption capacity (qCO2 )
and carbonation conversion of the sorbent (f(t)) are used to express
the CO2 sorption performances of KACIs.
gCO2 is calculated as:
C CO2;inlet  C CO2;outlet
gCO2 ¼    100% ð1Þ
C CO2;inlet 1  C CO2;outlet
where C CO2;inlet is the inlet CO2 concentration, C CO2;outlet is the outlet
CO2 concentration.qCO2 can be calculated by integrating the break-
through curve as below [17]:
Z t 
1 T0 1
qCO2 ¼ Q g gCO2 dt ð2Þ
W 0 T Vm
598 Y. Guo et al. / Chemical Engineering Journal 260 (2015) 596–604
where qCO2 is the amount of CO2 removed (mmol/g), W is the weight
of sorbent (g), gCO2 is the CO2 sorption efficiency calculated
using Eq. (1), Qg is the gas flow rate in the CO2 sorption process
(mL/min). T0 is 273 K, T is the gas temperature (K), and Vm is
22.4 mL/mmol.
As 1 mol of K2CO3 can react with one mole of CO2 and produce
two moles of KHCO3, f(t) is calculated as:
qec ðq  qep Þ  MK2 CO3
f ðtÞ ¼  100% ¼  100%
nCO2 b  1000
where f(t) is the carbonation conversion, qec and qep are the amounts
of CO2 removed (mmol CO2/g) by chemical sorption and physical
adsorption, respectively. b is the K2CO3 loading in the sorbents (it
is 1 for pure potassium carbonate). Here, the chemically absorbed
CO2 is determined as the total amount of CO2 removed deducting
the amount of physically adsorbed CO2.
3.2. CO2 adsorption kinetics of KACIs
For the sake of accurate prediction of physical adsorption, the
CO2 adsorption kinetics of KACIs should be investigated. Currently,
many attempts have been carried out to develop a general expres-
sion describing the adsorption kinetics of gases on solid surface,
and the most commonly used ones include the pseudo-first order
equation [18], pseudo-second order equation [19] and the Avrami
model [20]. Recently, a linear driving force (LDF) mass transfer
model is proposed to describe adsorption behaviors of gases on
activated carbon [21–24]. Particularly, the diffusion and adsorption
kinetics of CO2 on activated carbon is found to follow an LDF mode
[25]. Thus, the LDF model is selected to correlate the experimental
adsorption data to reveal the CO2 adsorption kinetics. The LDF
model is proposed to be effective for describing the adsorption
dynamic data based on the assumption that the adsorbent particle
temperature is uniform at all times [26]. The model is generally
expressed as:
qt
¼ 1  expðktÞ
qe
where qt and qe are the adsorption amount at time t and equilibrium
adsorption amount, respectively. k is the kinetic constant.
In order to verify the statistical correctness, the sum of error
squares (SSE (%)) is given by:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P 2
qe;exp  qe;pred
SSE ð%Þ ¼
N
where qe;exp and qe;pred are the experimentally measured and model-
ing predicted adsorption capacity, respectively and N is the number
of data points.
3.3. CO2 sorption kinetics of KACIs
There are little researches focusing on the kinetics of carbon-
ation process of potassium-based sorbents. Onischak and Gidas-
pow [27] proposed a first order homogenous reaction kinetic
model describing the kinetic characteristics between CO2 and solid
K2CO3. The first order model is dependent only on CO2 concentra-
tion while independent of sorbent and H2O concentration [28]. CO2
sorption on potassium-based sorbents is more likely to be a chem-
ical sorption process, which involves the diffusion of CO2 into the
surface and pores, reaction with the active sites and the formation
of compact products layer. The formed products layer would make
the CO2 diffusion process rather difficult. As the carbonation
reaction goes on, the sorbent will gradually deactivate, and the car-
bonation reaction kinetic will be impaired [29]. In recent investiga-
tions, Park et al. [30] performed a systematical comparison of
different kinetic models including homogeneous model, shrinking
core model and deactivation model for simulating the reaction
kinetics of CO2 with K2CO3. They found that the deactivation model
showed promising results in correlating the experimental data.
However, the deactivation model is applicable based on the
assumption of substantially higher H2O concentration compared
to that of CO2. Actually, for the non-catalytic heterogeneous
gas–solid reaction, the internal diffusion resistance cannot be elim-
ð3Þ inated, especially for the sorbents with underdeveloped pore struc-
tures. Therefore, the shrinking core model is adopted to correlate
the experimental data in this paper. It is reported that the carbon-
ation reaction of K2CO3 can be divided as the surface chemical
reaction-controlled region and the internal diffusion-controlled
region [31]. For the carbonation kinetic of KACIs, the global reac-
tion rate can be expressed as the sum of the internal diffusion rate
in the product layer and the reaction rate on the reaction interface.
The integral expression can be derived as:
R 1=3
C K2 CO0 R2 2=3
t¼ ð1  ð1  f ðtÞÞ Þþ 3
ð1  3ð1  f ðtÞÞ
ks C 0CO2 C 0H2 O 6DeC 0H2 O
þ 2ð1  f ðtÞÞÞ ð6Þ
where R (cm) is the radius of particle, ks is the reaction rate constant
per unit reaction interface, C 0CO2 (mol/cm3) and C 0H2 O (mol/cm3) are
the initial concentration of CO2 and H2O, respectively. C 0K2 CO3 (mol/
cm3) is the initial concentration of K2CO3, De is the diffusion coeffi-
cient for H2O in the product layer, and f(t) is the carbonation con-
version. The specific derivation of the expression can be found in
Ref. [31].
4. Results and discussion
4.1. CO2 adsorption performances of KACIs in 1.0% CO2
To determine the CO2 adsorption performances of K2CO3/AC at
ð4Þ ambient temperature, the support of AC, KACI5, KACI10, KACI15,
KACI20 and KACI25 were tested in the conditions of 1.0% CO2 with
balanced N2, and the reaction temperature was maintained as
20 °C. The results are discussed as below.
Fig. 2(a) shows the CO2 adsorption breakthrough curves of
KACIs versus time. The CO2 adsorption capacities can be obtained
by integrating the CO2 adsorption breakthrough curves. The sup-
port of AC shows the highest CO2 adsorption capacity of
ð5Þ 0.2117 mmol CO2/g. The CO2 adsorption capacities of the sorbents
gradually decrease as 0.1934, 0.1830, 0.1585, 0.1572 and
0.1497 mmol CO2/g, with the increase in K2CO3 loadings from 5%
to 25%. Since CO2 adsorption performances of all the sorbents are
mainly displayed as physical adsorption in this condition, the
microscopic structure of the sorbents plays an important role in
this process, thus the more K2CO3 is loaded the less porous of the
sorbent will be, and the smaller CO2 adsorption capacity of the sor-
bent should be [16].
The CO2 adsorption amount of each sorbent versus time is cor-
related using the LDF model, as presented in Fig. 2(b). The CO2
adsorption behaviors of KACIs can be well described by the LDF
model, as indicated by the good correlation regressions. It is
reported that the adsorption of gases on carbon materials, where
the primary transport resistance occurs at the restricted pore
mouths of the carbon, can be exactly described by the LDF model
[26]. This has been proven by the good correlation regressions
between the experimental data and the LDF model.
In order to evaluate the CO2 adsorption kinetic characteristics
and quantify the physical adsorption capacity at different temper-
atures, CO2 adsorption experiments of KACI15 sorbent were per-
formed in 1.0% CO2, 2.0% H2O, and balanced N2, while the
 Y. Guo et al. / Chemical Engineering Journal 260 (2015) 596–604 599

1.0 (a) 0.20

Dimensionless concentration of CO2

20°C
30°C

Adsorption amount, mmol/g

0.8
0.15 40°C
50°C
0.6 60°C

AC 0.10
0.4 KACI5
KACI10
0.2 KACI15 0.05
KACI20
KACI25 (a)
0.0
0 5 10 15 20 0.00
Time, min 0 3 6 9 12 15
Time, min

0.20
(b) -0.7
y=-853.3x+1.8577
Adsorption amount, mmol/g

2
R =0.9735
0.15 -0.8

AC

ln k
0.10 KACI5 -0.9
KACI10
KACI15
0.05 KACI20 -1.0
KACI25
(b)
0.00
0 5 10 15 20 0.0030 0.0031 0.0032 0.0033 0.0034
Time, min -1
1/T (K )
Fig. 2. CO2 adsorption performances of different sorbents [(gas flow rate: 500 mL/
min; CO2 concentration: 1.0%; temperature: 20 °C). (a) CO2 adsorption break- Fig. 3. CO2 adsorption kinetic characteristics of KACI15 [(gas flow rate: 500 mL/
through curves; (b) CO2 adsorption amount fit to LDF model]. min; CO2 concentration: 1.0%; temperature: 20–60 °C). (a) CO2 adsorption amount
fit to LDF model; (b) Arrhenius plot of adsorption rate constant].

temperature varies from 20 to 60 °C. The results are plotted in

Fig. 3.
The LDF model is applied to correlate the experimental data, the Table 1
corresponding kinetic parameters obtained from the model is sum- Kinetic parameters obtained from LDF model for CO2 adsorption at different
temperatures.
marized in Table 1. The model is found to provide good fitting
results, as indicated by the high R2 values and small SSE values. T (°C) 20 30 40 50 60
From Fig. 3(a), the CO2 adsorption amount of KACI15 decreases k (min1) 0.3528 0.3753 0.4306 0.4541 0.4914
with increasing temperature. The adsorption capacities of the sor- qe (mmol  g1) 0.1585 0.1849 0.1802 0.1216 0.1011
bent under 20–60 °C are determined to be 0.1585, 0.1858, 0.1799, R2 0.9995 0.9995 0.9995 0.9995 0.9989
SSE (%) 0.1257 0.0800 0.0780 0.0220 0.0400
0.1222 and 0.1019 mmol CO2/g, respectively. Fig. 3(b) gives the
Arrhenius plot for the kinetic constants obtained from LDF model.
Based on the kinetic coefficients at various temperatures, the
apparent activation energy and pre-exponential factor are calcu-
lated as 7.09 kJ/mol and 6.41 min1, respectively. The empirical
Dimensionless concentration of CO2

1.0
kinetic equation is determined as:

7:09 0.8
k ¼ 6:41 exp  ð7Þ
RT
0.6
AC
4.2. CO2 sorption performances of KACIs in 1.0% CO2 + 2.0% H2O KACI5
0.4 KACI10
As reported in previous publications [8–14], K2CO3/AC can be KACI15
used to capture CO2 to form potassium bicarbonate in the reaction 0.2 KACI20
conditions of 5–20% CO2 and 5–20% H2O at 50–100 °C. However,
KACI25
the CO2 sorption performances of KACIs at low CO2 partial pres-
sures and low temperatures have not been revealed. Thus the 0.0
0 5 10 15 20 25
regrading experiments were conducted and the results are shown
Time, min
in Fig. 4.
Fig. 4 presents the CO2 sorption breakthrough curves versus Fig. 4. CO2 sorption performances of different sorbents (gas flow rate: 500 mL/min;
time. It can be seen that support of AC shows fast breakthrough CO2 concentration: 1.0%; H2O concentration: 2.0%; temperature: 20 °C).
600 Y. Guo et al. / Chemical Engineering Journal 260 (2015) 596–604

5.6
80

y=-8.25+4.02x
Carbonation conversion, %

5.2 2
60 R =0.9916

4.8

ln ks
40
20 °C
30 °C 4.4
40 °C
20
50 °C
4.0
60 °C
(a)
0
0 5 10 15 20 25 30 3.0 3.1 3.2 3.3 3.4
-3 -1
Time, min 1/T (10 K )

Fig. 5. Carbonation conversions of KACI15 at various temperature fitted to -14.5

shrinking core model (gas flow rate: 500 mL/min; CO2 concentration: 1.0%; H2O
y=-35.48+6.17x
2
concentration: 2.0%; temperature: 20 °C). R =0.9901
-15.0

-15.5

ln De
Table 2
Kinetic parameters obtained from shrinking core model for carbonation at different -16.0
temperatures.

T (°C) 20 30 40
ks 244.11 151.59 96.56
De (107) 5.81 2.40 1.54
R2 0.9977 0.9951 0.9970
for the physical adsorption process. The sorbent of KACI15 shows
the best sorption performance with the longest sorption break-
through time. Further increase in loading amount leads to a
decrease in sorption breakthrough time. The CO2 sorption capacity
of AC is calculated as 0.2015 mmol CO2/g, which is close to the
physical adsorption capacity. The CO2 sorption capacities for KACIs
are calculated to be 0.4027, 0.5301, 1.0147, 0.6558 and
0.4481 mmol CO2/g, respectively. Deducting physical adsorption
capacity and considering the complete conversion of K2CO3 to
KHCO3 via carbonation reaction, the corresponding conversion effi-
ciencies are determined through Eq. (3) as 58.0%, 48.0%, 79.0%,
34.4% and 16.5% for KACI5, KACI10, KACI15, KACI20 and KACI25,
respectively. The above results can be explained that the higher
K2CO3 loadings will result in less dispersed K2CO3 thus less conver-
sion, as elaborated in Ref. [16].
In order to investigate the CO2 sorption kinetics of the sorbent,
CO2 sorption performance of KACI15 were studied in 1.0%
CO2 + 2.0% H2O at the temperature range of 20–60 °C. The carbon-
ation conversions of the sorbent at different temperatures are cal-
culated and correlated using the shrinking core model, and the
results are plotted in Fig. 5. The corresponding kinetic parameters
obtained are tabulated in Table 2.
Good correlation regressions are achieved between the kinetic
model and experimental data, as indicated by the high R2 values.
This implies that the sorption kinetics of CO2 can be well described
using the shrinking core model. Based on the kinetic parameters,
the Arrhenius plots of kinetic constants for surface chemical reac-
tion-controlled region and the diffusion-controlled region are
found to satisfy linear correlation, as presented in Fig. 6.
Related parameters can be obtained from the values of the slope
and the intercept of the fitting lines. The apparent activation ener-
gies for the surface chemical reaction-controlled region and the
diffusion-controlled region are determined as 33.42 and 51.30 kJ/
mol, respectively. The corresponding pre-exponential factors are
calculated as 2.61  104 and 3.90  1016 cm2/min. This indicates
50 60 -16.5
61.97 48.95
0.82 0.42 (b)
0.9980 0.9965 -17.0
3.0 3.1 3.2 3.3 3.4
-3 -1
1/T (10 K )
Fig. 6. CO2 sorption kinetic characteristics of KACI15 obtained from the fitting
results of shrinking core model [(gas flow rate: 500 mL/min; CO2 concentration:
1.0%; H2O concentration: 2.0%). (a) Arrhenius plot of the reaction rate for surface
chemical reaction-controlled region; (b) Arrhenius plot of the rate for internal
diffusion-controlled region].
that the internal diffusion is the rate limiting step for the whole
carbonation process.
4.3. Factors affecting the CO2 sorption performances of KACI15
Compared with other KACIs sorbents in this study, KACI15
presents both higher carbonation conversion efficiency and CO2
sorption capacity. Consequently, it was utilized for further investi-
gation on the effect of reaction conditions including carbonation
temperature, gas composition, water pretreatment and flow rate
on the CO2 sorption performances.
4.3.1. Temperature
The CO2 sorption processes of KACI15 in gas flow of 1.0% CO2,
2.0% H2O, and balanced N2 were carried out at different tempera-
tures. The results are presented in Fig. 7.
Fig. 7 presents experimental CO2 sorption breakthrough data
measured at different temperatures. It can be seen that the break-
through time is reduced with increasing reaction temperature and
it presents a faster breakthrough pattern. The best sorption perfor-
mance is achieved when the temperature is 20 °C. This indicates
that a lower temperature is favorable for CO2 sorption performance
of KACI15, which is ascribed to the exothermic nature of carbon-
ation reaction. This is in conformity with the change of carbonation
conversion with temperature shown in Fig. 5. It is reported that the
sorption of CO2 should be more economically promising when
operated at ambient temperature. Thus, KACI15 sorbent turns as
 Y. Guo et al. / Chemical Engineering Journal 260 (2015) 596–604 601

1.0 1.0

Dimensionless concentration of CO2

Dimensionless concentration of CO2

0.8 0.8

0.6 0.6

20°C
0.4 30°C 0.4 1:1
40°C 1.5:1
50°C 0.2 2:1
0.2
60°C 2.5:1

0.0 0.0
0 5 10 15 20 25 0 5 10 15 20 25
Time, min Time, min

Fig. 7. Effect of temperature on the CO2 sorption performances of KACI15 (gas flow Fig. 8. Effect of C H2 O : C CO2 on the CO2 sorption performances of KACI15 (gas flow
rate: 500 mL/min; CO2 concentration: 1.0%; H2O concentration: 2.0%). rate: 500 mL/min; CO2 concentration: 1.0%; temperature: 20 °C).

a potential option in application of ambient CO2 removal from con-
fined space.
The CO2 sorption capacities under different temperatures are
calculated as 1.0147, 0.5434, 0.4022, 0.3117, 0.2548 mmol CO2/g.
Noticeable drop in CO2 sorption capacity can be observed when
the reaction temperature increase from 20 to 60 °C. The low CO2
sorption capacity at high temperature is attributed to the reduction
of concentration driving force because the reaction is reversible
and exothermic. It was reported that the CO2 sorption capacity of
amine-based sorbent of CNTs-TEPA-30 in similar confined space
atmosphere increased steadily from 2.0 to 3.56 mmol CO2/g as
the temperature increased from 10 to 40 °C [17]. This indicates that
the effect of temperature on the sorption capacity of KACI15 and
amine-based sorbent is opposite. Besides, amine-based sorbent
shows more stable performance for CO2 sorption with the change
of temperature.
Deducting the physical adsorption amount (Fig. 3), the corre-
sponding carbonation conversion efficiencies of KACI15 under each
temperature can be calculated as 79.0%, 33.0%, 20.4%, 17.4% and
14.1%, respectively. It is found that the carbonation conversion effi-
ciency of KACI15 decreases from 79.0% to 14.1%, when the temper-
ature increases from 20 to 60 °C. The carbonation conversion has
previously been reported to be higher than 90% for K2CO3/AC at
the reaction temperature of 50–80 °C [8–14]. The reason is that
the CO2 concentration and H2O concentration greatly decreased
from 10–20% to 1.0–2.0% (in this paper), respectively. H2O concen-
tration is not changed for all these processes, but RH decreases
from 78% to about 15%, when the temperature increases from 20
to 60 °C. This may be another reason for the decrease of CO2 sorp-
capacity and carbonation conversion. This should be deduced as
the increasing quantity of CO2 in the quasi-liquid layer between
bulk gas and solid phases in the heterogeneous CO2 sorption sys-
tem, due to the increase in H2O concentration [32]. Besides, It is
reported that K2CO3 will be converted into K2CO31.5H2O in the
presence of water vapor with low partial pressure. While it is more
likely to be converted into K4H2(CO3)31.5H2O when exposed in
water vapor of high concentration. The unstable intermediate of
K4H2(CO3)31.5H2O is readily to trap CO2 to form KHCO3, which
immensely facilitate the CO2 removal process [10,33]. The
improvement in carbonation kinetics might be another reason for
the sorption-enhanced process.
4.3.3. Water pretreatment
Water vapor at high concentration is beneficial for improving
the reaction activity. A suggested way to obtain effective CO2 sorp-
tion performance is to increase the carbonation conversion and
reaction kinetic involving sufficient water pretreatment. To inves-
tigate the effect of water pretreatment on the CO2 sorption perfor-
mance of KACI15, the sorbent are pretreated with water vapor of
2.0% for different durations prior to CO2 removal. The CO2 sorption
breakthrough curves measured under different pretreatment dura-
tions are presented in Fig. 9.
The CO2 sorption capacities of the sorbent are integrated as
1.0147, 1.1017, 1.1592, 1.1826 and 1.0797 mmol CO2/g when the
time for water pretreatment increases from 0 to 80 min. The
1.0
Dimensionless concentration of CO2

tion capacity. 0min

20min
0.8
4.3.2. Mole ratio of H2O concentration over CO2 concentration 40min
CO2 and H2O play significant role in CO2 sorption performance. 60min
The effect of C H2 O : C CO2 (mole ratio of H2O concentration over CO2 0.6 80min
concentration) on CO2 sorption performance of KACI15 was inves-
tigated by keeping CO2 concentration as 1.0% while varying the 0.4
H2O concentration from 1.0% to 2.5%. The temperature was main-
tained at 20 °C. The results are presented in Fig. 8.
0.2
The CO2 sorption capacities increase from 0.6490 to
1.0193 mmol CO2/g when C H2 O : C CO2 mole ratio increases from 1
to 2.5. Based on the empirical kinetic equation (Eq. (7)), the phys- 0.0
ical adsorption capacities of the sorbent can be predicted using Eq. 0 5 10 15 20 25 30
Time, min
(4) as 0.1577, 0.1638, 0.1585 and 0.1580 mmol CO2/g. Thus the cor-
responding carbonation conversion efficiencies can be determined Fig. 9. Effect of water pretreatment on the CO2 sorption performances of KACI15
through Eq. (3) as 45.2%, 70.4%, 79.0% and 79.2%. It is noted that the (gas flow rate: 500 mL/min; CO2 concentration: 1.0%; H2O concentration: 2.0%;
increase of C H2 O : C CO2 mole ratio enhances the CO2 sorption temperature: 20 °C).
602
corresponding carbonation conversion efficiencies are determined
as 79.0%, 86.8%, 92.1%, 94.2% and 84.7%. Previous investigation
indicated that the K2CO31.5H2O phase could be formed from the
new species of K4H2(CO3)31.5H2O during water vapor pretreat-
ment process. Besides, sufficient water pretreatment had provided
high relative humidity to activate the sorbent as well as to prevent
the new formed active species from transforming to K2CO3 phase
[10,33]. These are favorable for achieving higher CO2 sorption
capacity and carbonation conversion. However, this does not nec-
essarily mean that CO2 sorption performance can be everlastingly
improved with water vapor pretreatment as sufficient as possible,
for overexposure of sorbent to water vapor would eventually result
in agglomeration of active components [34]. This is not beneficial
for maintaining adequately high reaction activity. This should be
reasonable interpretation for the declined CO2 sorption capacity
and carbonation conversion of the sorbent with 80 min water
vapor pretreatment.
4.3.4. Flow rate
Flow rate is a critical factor affecting CO2 sorption performance
of potassium-based sorbents in fixed bed reactor. To evaluate the
effect of flow rate on CO2 sorption performances of KACI15, several
experiments were carried out in the conditions of 20 °C, 1.0%
CO2 + 2.0% H2O, to measure the CO2 sorption breakthrough curves
at different flow rates of 300–700 mL/min. The results are illus-
trated in Fig. 10.
The CO2 sorption capacities of KACI15 are confirmed as 0.9896,
0.9838, 1.0147, 0.8107 and 0.7029 mmol CO2/g as the flow rate
increases from 300 to 700 mL/min. The carbonation conversion effi-
ciencies of KACI15 are determined to be 76.5%, 76.0%, 79.0%, 60.0%
and 52.2%. It is noticed that when the flow rate is kept at lower
value, the CO2 sorption capacity and carbonation conversion are
not significantly affected. When the flow rate increases to a high
value, both the CO2 sorption capacity and carbonation conversion
show a decline tendency. For the condition of larger flow rate, the
space time of the gaseous reactant is shortened. The shortening of
effective contact time between gaseous mixtures and solid reactant
will result in insufficient carbonation conversion and eventually
cause the decrease of CO2 sorption capacity. However, for gas–solid
non-catalytic heterogeneous reaction, the mass transfer should
take an important part in the whole reaction process. The mass
transfer process is primarily induced by the difference of gaseous
reactant concentration between gas bulk and external surface of
sorbent. For the reactions controlled by mass transfer, the reaction
rate will increase as the flow rate increases. Considering the
1.0
Dimensionless concentration of CO2
0.8
0.6
0.4
0.2
0.0
0 10 20
Time, min
Fig. 10. Effect of flow rate on the CO2 sorption performances of KACI15 (gas flow
rate: 300–700 mL/min; CO2 concentration: 1.0%; H2O concentration: 2.0%; tem-
perature: 20 °C).
Y. Guo et al. / Chemical Engineering Journal 260 (2015) 596–604
necessary flow rate needed for CO2 diffusion in pore channel and
adsorption onto active sites during mass transfer process and the
adverse effect of high flow rate on CO2 sorption performance, the
designing of the CO2 removal process should take the parameter
at moderate level in practical application.
4.4. Multiple-cycle behavior of KACI15 for CO2 removal in confined
space
In order to evaluate the long-term stability of KACI15 in cyclic
operations, 20 carbonation-regeneration cycles were carried out.
The CO2 sorption process of KACI15 was carried out in simulated
confined space atmosphere of 1.0% CO2, 2.0% H2O, and N2 balanced
at 20 °C. The regeneration process of the sorbent was carried out in
100% N2 at 130 °C. The CO2 sorption capacities and the carbonation
conversion efficiencies of KACI15 changing against the cycle num-
bers are shown in Fig. 11. In order to investigate the change of
microscopic structure with the cycle numbers, the samples after
every 5 cyclic intervals were characterized by N2 adsorption–
desorption analysis. The BET surface areas, pore volumes and pore
size distributions of these samples are shown in Fig. 12.
Fig. 11 shows that the CO2sorption capacity of KACI15 decreases
from 1.0147 to 0.9866 mmol CO2/g after 20 cycles. In comparison
to the theoretical value, it is found that the carbonation conversion
efficiency decreases from 79.0% to 77.6% as the cycle runs from the
1st to the 20th. KACI15 retains considerable long-term stability
with slight decreasing percentages of 3.0% and 1.8% after 20 cycles
for CO2 sorption capacity and carbonation conversion efficiency,
respectively. It was reported that the CO2 sorption capacity of
HSC+ diminish quickly to 68% of its original value in the second
cycle [6]. The sorbents using SBA-15 and MCM-41 impregnated
with tetraethyenepentamine suffered from amine loss as the sorp-
tion capacity decreased by 8.6% after just 6 cycles of regeneration
at 100 °C [35–37]. It was also reported that the CO2 sorption capac-
ities of SBA(P)-50 [35], MCM-41-PEI-50 [38,39], amine-functional-
ized SG [40], AM-50 [41], amine modified activated carbon [42],
and Y60(TEPA) [43], KIT-6-PEI [44], supported amine sorbents
(TEPAN and ME-100) [45], aminated-SBA-15 [46] dropped drasti-
cally as the number of cycles increases. All these conclusions show
that compared with the amine-based sorbent, KACI15 retains more
stable CO2 sorption performance for long-term cyclic operation.
Fig. 12 shows that the surface area and pore volume of KACI15
decrease as the number of cycle increases. After 20 cycles, the
reduction in surface area and pore volume are 20 m2/g and
1.1
80
Carbonation conversion efficiency, %
CO2 sorption capacity, mmol CO2/g
1.0
60
300 mL/min 40 0.9
Carbonation conversion efficiency
400 mL/min
500 mL/min
20 CO2 sorption capacity
600 mL/min
0.8
700 mL/min
0
30 40 0 4 8 12 16 20
Cycle number
Fig. 11. Multiple sorption–desorption performances of KACI15 [sorption (gas
composition: CO2-1.0%; H2O-2.0%); gas flow rate: 500 mL/min; temperature:
20 °C), desorption (N2 flow rate: 833 mL/min; temperature: 130 °C)].

600
surface area
pore volume
560
BET surface area, m /g
2
520
480
440
400
1 2 3 4
Samples
1.40
1.12
dV/dlog(RP), cm /(g nm)
0.84
3
0.56
0.28
0.00
1 10
Fig. 12. Microscopic structures of KACI15: (a) surface area and pore volume, (b)
pore size distribution. Sample 1: the fresh sorbent; Sample 2: the sorbent after one
cycle; Sample 3: the sorbent after 5 cycles; Sample 4: the sorbent after 10 cycles;
Sample 5: the sorbent after 15 cycles; Sample 6: the sorbent after 20 cycles.
0.013 cm3/g, respectively. The change in surface area and pore vol-
ume are not obvious. The pore size distribution behavior shows no
change in 20 cycles.
All these conclusions indicate that K2CO3/AC retains stable CO2
sorption performance for long-term cyclic operation, and the sor-
bent should be considered as a new choice for ambient CO2
removal from confined space.
5. Conclusions
The CO2 sorption performances of K2CO3/AC with different
K2CO3 loadings were investigated under different conditions by
varying the CO2 concentrations, H2O concentrations, sorption tem-
peratures, water pretreatment durations and flow rates. A set of
experiments were conducted using a modified fixed bed reactor
system with a gas analyzer. It is found that the CO2 sorption capac-
ities and carbonation conversion efficiencies of K2CO3/AC decrease
as the temperature increases from 20 to 60 °C. The shrinking core
model is adopted to correlate the experimental carbonation data
to study the reaction kinetics of CO2 sorption. CO2 sorption perfor-
mance of K2CO3/AC is enhanced with increasing C H2 O : C CO2 . With
sufficient water pretreatment, CO2 sorption capacity and carbon-
ation kinetics can be improved. Excessive water pretreatment
duration is found to weaken the CO2 sorption performance. When
the flow rate is relatively low, the CO2 sorption performance is not
significantly affected by the flow rate. However, a higher flow rate
is found to weaken the CO2 sorption performance. Besides, the
Y. Guo et al. / Chemical Engineering Journal 260 (2015) 596–604 603
0.40 sorbent is found to retain stable CO2 sorption capacity and carbon-
(a) ation conversion efficiency during 20 carbonation-regeneration
cyclic operations. Due to the features of high CO2 sorption capacity,
0.32
preferable carbonation conversion efficiency and excellent long-
BJH pore volume, cm /g
term stability, K2CO3/AC should be taken as a new agent for CO2
3
0.24 removal in confined spaces.
0.16 Acknowledgments
Financial support from the National Natural Science Foundation
0.08
of China (No. 51206155), the Science Foundation of Key Laboratory
of Energy Thermal Conversion and Control of Ministry of Education
0.00 and the Fundamental Research Funds for the Central Universities
5 6 of China (WK2320000023) are sincerely acknowledged. The
authors wish to acknowledge Dr. Kaiyuan Li for the English editing
for this article.
(b)
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