Journal of Natural Gas Chemistry 18(2009)167172

Adsorption separation of carbon dioxide, methane and nitrogen

on monoethanol amine modified -zeolite
Xiaoliang Xu,

Xingxiang Zhao,

Linbing Sun, Xiaoqin Liu

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering,
Nanjing University of Technology, Nanjing 210009, Jiangsu, China
[ Received December 30, 2008; Revised February 27, 2009; Available online June 1, 2009 ]

Abstract
A new type of composite adsorbents was synthesized by incorporating monoethanol amine (MEA) into -zeolite. The parent and MEAfunctionalized -zeolites were characterized by X-ray diffraction (XRD), N2 adsorption, and thermogravimetric analysis (TGA). The adsorption behavior of carbon dioxide (CO2 ), methane (CH4 ), and nitrogen (N2 ) on these adsorbents was investigated at 303 K. The results show
that the structure of zeolite was well preserved after MEA modification. In comparison with CH4 and N2 , CO2 was preferentially adsorbed
on the adsorbents investigated. The introduction of MEA significantly improved the selectivity of both CO2 /CH4 and CO2 /N2 , the optimal
selectivity of CO2 /CH4 can reach 7.70 on 40 wt% of MEA-functionalized -zeolite (MEA(40)-) at 1 atm. It is worth noticing that a very high
selectivity of CO2 /N2 of 25.67 was obtained on MEA(40)-. Steric effect and chemical adsorbate-adsorbent interaction were responsible for
such high adsorption selectivity of CO2 . The present MEA-functionalized -zeolite adsorbents may be a good candidate for applications in
flue gas separation, as well as natural gas and landfill gas purifications.
Key words
-zeolite; monoethanol amine; CO2 ; CH4 ; N2 ; adsorption; separation

1. Introduction
Global warming is an important environmental challenge
facing the world, and carbon dioxide (CO2 ) is one of the major
greenhouse gases [13]. Currently, most emissions of CO2
to the atmosphere from electric power generation plants and
industrial sectors are in the form of flue gas from combustion processes [4]. As a result, the separation and capture of
CO2 from flue gas is an effective way to control CO2 emission. Another important CO2 removal field is the separation
of methane (CH4 ) and CO2 in natural gas [5]. CO2 is often found as a major impurity in natural gas, and its presence
can reduce the energy content of natural gas. Furthermore, in
the presence of water, CO2 will corrupt the transportation and
storage system.
A widely developed commercial technology to separate
CO2 from flue gas and natural gas streams is based on absorption using liquid amines [6,7]. Although this method is
effective for CO2 absorption, it suffers from major drawbacks
such as high energy consumption, equipment corrosion, and

solvent degradation in the presence of oxygen. As an alternative, adsorption is considered to be a promising technology
for separating CO2 from gas mixtures due to its low energy requirement, easy operation, and low maintenance. Therefore,
various materials such as zeolites [8], activated carbons [9],
and carbon molecular sieves [10] have been investigated as
adsorbents for the CO2 separation and capture by selective
adsorption. Although these adsorbents show relatively high
CO2 adsorption capacities at room temperature, their capacities rapidly decline with increasing temperature. Moreover,
the selectivity of these materials is low since such adsorption
is a physical interaction rather than a chemical one.
In order to overcome these limitations, some new adsorbents were prepared by functionalizing the solid supports
with amine groups. Considerable attention has been paid to
the functionalization of mesoporous silicas because of their
large surface areas, uniform mesopores, and tunable pore size
[11,12]. Xu et al. [13] impregnated polyethylenimine (PEI)
on MCM-41, and the resulting material exhibited a CO2 adsorption ability of 2.6 mmol/g at 348 K. Chang et al. [14]

Corresponding author. Tel: +86-25-83587178; Fax: +86-25-83587191; E-mail: liuxq@njut.edu.cn

This work was financially supported by the Major Basic Research Project of Natural Science Foundation of Jiangsu Province Colleges (No. 08 kJA530001)
as well as the Program for Changjiang Scholars and Innovative Research Team in University (No. IRT0732).
Copyright2009, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.
doi:10.1016/S1003-9953(08)60098-5

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studied CO2 adsorption and desorption on aminopropyl-SBA15 and reported that the amount of CO2 was only 0.4 mmol/g
at 298 K. Yue et al. [15] developed a new material by incorporating tetraethylenepentamine into as-synthesized SBA-15.
The obtained materials showed a high CO2 adsorption capacity. Nevertheless, the high cost and relatively poor hydrothermal stability of these materials limit their applications under
commercially relevant operating conditions. From the point of
view of industrial applications, researchers focus their attention on zeolites, a type of stable and inexpensive microporous
materials. However, investigations concerning CO2 removal
by use of amine-modified zeolites are very limited. Birbara
et al. [16] proposed zeolites as potential solid supports for
amines. Jadhav et al. [17] recently studied the modification
of zeolite 13X by monoethanol amine (MEA). The modified
zeolite displayed a moderate adsorption selectivity for CO2
over nitrogen (N2 ) at different temperatures.
-zeolite is a large pore size zeolite of great importance
in catalytic processes [18]; however, its functionality as adsorbent in gas separation processes is scarcely explored. In our
previous study, we have investigated the effect of substituting Na+ for H+ on the adsorption properties of carbon dioxide, methane and nitrogen on -zeolite [19]. Aiming at developing new adsorbents with a high selectivity, we employed
MEA to functionalize -zeolite in the present study. The properties of MEA-modified -zeolites were characterized by Xray diffraction (XRD), N2 adsorption, and thermogravimetric
analysis (TGA). The adsorption capacity for CO2 , CH4 , and
N2 on -zeolites with different amine loadings was examined.
The comparison of adsorption performance of MEA--zeolite
with other adsorbents was also conducted.
2. Experimental
2.1. Preparation of aminated -zeolite

-zeolites were degassed at 573 and 343 K, respectively under vacuum for 4 h. BET specific surface areas were calculated using adsorption data in a relative pressure (p/p0 ) ranging from 0.05 to 0.20. The total pore volume was determined
from the amount adsorbed at a relative pressure of about 0.99.
The pore size was estimated by the Horvath-Kawazoe method.
TGA was conducted by using STA Netzch 409PC apparatus.
Thermal characterization was carried out under dynamic conditions with a heating rate of 10 K/min in N2 atmosphere.
2.3. Adsorption measurement
Equilibrium adsorption isotherms of CO2 , CH4 , and N2
were measured at 303 K using a static volumetric adsorption
system (Micromeritics ASAP 2020). The samples were activated at 573 K (for -zeolite) or 343 K (for MEA-modified
-zeolites) under vacuum for 6 h prior to measurement. The
pure component selectivity of two gases A and B is calculated
by means of the following equation:
A/B = [VA /VB ]p,T
where VA and VB are the volumes of gases A and B adsorbed
at pressure p and temperature T .
3. Results and discussion
3.1. Preparation and characterization of MEA-modif ied
-zeolite
The XRD patterns of parent and MEA-modified
-zeolites are given in Figure 1. It can be seen that the location of diffraction lines remained constant, indicating that the
structure of -zeolites was well preserved after introduction
of MEA. Nevertheless, the intensity of diffraction lines decreased as the MEA content increased, which is in agreement
with the reports of Xu et al. [13,20] and Jadhav et al. [17].

-zeolite with a SiO2 /Al2 O3 molar ratio of 25 was supplied by Nankai University in China. MEA was introduced into -zeolite by wet impregnation, as reported by Xu
et al. [13,20]. Typically, a given amount of MEA was added
in 4 g of methanol at room temperature. After the mixture was
stirred for 15 min to form a clear solution, 1 g of -zeolite was
added. The resulting slurry was stirred for a further 30 min,
and then dried at 343 K for 16 h under vacuum (700 mmHg).
The obtained materials were denoted as MEA(x)-, where x
represents the weight percentage of MEA in the sample.
2.2. Characterization of aminated -zeolite
The parent and MEA-modified -zeolites were characterized by XRD, N2 adsorption, and TGA. XRD patterns
of the samples were recorded with a Bruker D8 Advance
diffractometer using CuK radiation and a Ni filter at 40 kV
and 30 mA. N2 adsorption experiments were performed at
77 K using a BELSORP measuring instruments (BELSORPmini II, Japan). Prior to analysis, parent and aminated

Figure 1. XRD patterns of parent and MEA-modified -zeolites

Figure 2 displays N2 adsorption isotherms of parent and

MEA-modified -zeolites. All isotherms are of type I and
have a well-defined plateau, exhibiting the characteristic of

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Journal of Natural Gas Chemistry Vol. 18 No. 2 2009

microporous materials. Table 1 summarizes the data of BET

surface area, pore size, and pore volume for the samples under
study. Obviously, the introduction of MEA has a significant
effect on the textual properties [17]. Parent -zeolite possesses a BET surface area of 574 m2 /g and a pore volume of
0.230 cm3 /g. Incorporating 5 wt% of MEA led to a sharp decrease of both surface area and pore volume. It is noteworthy
that very small surface areas (1517 m2 /g) and pore volumes
(0.0630.090 cm3 /g) were detected when the MEA loading
was higher than 15 wt%. Also, the pore size of zeolite de when 5 wt% of MEA was introcreased from 6.5 to 5.7 A
duced. Further increasing the MEA loading to 15 wt%, the
microporous pores in -zeolite were filled with MEA, thus
restricting access of nitrogen into the pores at the liquid nitrogen temperature. Therefore, no valid information on pore size
was available.

450 K, the weight loss on MEA--zeolite samples became evident; moreover, the weight loss increased with the increase of
MEA loading. Such weight losses can thus be attributed to the
desorption and/or decomposition of amine species.
Table 1. Textural properties of parent and aminated -zeolites
Sample
-zeolite
MEA(5)-
MEA(15)-
MEA(40)-
MEA(60)-

BET surface
area (m2 /g)
574
209
17
15
15

Pore volume
(cm3 /g )
0.230
0.190
0.090
0.074
0.063

Pore size

(A)
6.5
5.7

Figure 3. TGA profiles of MEA-modified -zeolites

Figure 2. N2 adsorption isotherms of MEA(x)- samples at 77 K. (1) x = 0,

(2) x = 5, (3) x = 15, (4) x = 40

TGA data for -zeolites before and after MEA

modification are shown in Figure 3. A unique weight loss
up to 450 K was observed on parent zeolite, which is derived
from the desorption of physically adsorbed water. For the zeolites modified by MEA, similar weight losses assigned to water were also detected. When the temperature is higher than

3.2. CO2 , CH4 , and N2 pure component equilibrium adsorption on -zeolite with dif ferent MEA loading
Adsorption of CO2 , CH4 , and N2 on -zeolites with
different MEA loading was measured at 303 K, and the results are given in Figure 4. Apparently, in comparison with
CH4 and N2 , CO2 is preferentially adsorbed on the adsorbents
investigated. The adsorption capacity for CH4 was slightly
larger than N2 . For example, the adsorption amount of CO2

Figure 4. Adsorption isotherms of CO2 , CH4 , and N2 on -zeolites with different MEA loading measured at 303 K

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Figure 5. Effect of MEA loading on the adsorption capacity of -zeolite

was 1.37 mmol/g on MEA(5)-, while the adsorption amount

of CH4 and N2 was only 0.29 and 0.07 mmol/g, respectively.
To clarify the effect of MEA, the adsorption capacity for
different gases obtained from isotherms at 303 K and 1atm
was plotted as a function of MEA loading. As shown in Figure 5, an obvious decrease was observed for the adsorption
capacity of all adsorbates, when the MEA loading enhanced
from 0 to 15 wt%. Further increasing the MEA loading, the
drop in adsorption capacity became gentle. These results are

consistent with the data from N2 adsorption at liquid nitrogen temperature (Table 1), thus pointing out the importance
of pore size variation in adsorption. After the introduction of
MEA, the adsorption amounts of three adsorbates decreased,
while the relative decrease magnitude of CO2 adsorption capacity was much lower than that of CH4 and N2 . As a consequence, the difference in the adsorption capacity between CO2
and other adsorbates was enlarged, which results in a high adsorption selectivity for both CO2 /CH4 and CO2 /N2 on these
amine-modified zeolites.
Pure component selectivity of CO2 /N2 , CO2 /CH4 , and
CH4 /N2 at equilibrium pressures of 0.03 and 1.0 atm was calculated from adsorption isotherms and given in Figure 6. In
general, the adsorption selectivity of CO2 over CH4 and N2
at low-pressure region was high. At the optimal loading of
MEA (i.e. 40 wt%), the selectivity of CO2 /CH4 and CO2 /N2
can arrive at 35.86 and 92.85, respectively at 0.03 atm. With
the increase of equilibrium adsorption pressure, the selectivity
of CO2 over CH4 and N2 decreases. At the pressure of 1 atm,
the selectivity of CO2 /CH4 and CO2 /N2 is 4.63 and 12.19, respectively on parent -zeolite. Introducing MEA improves
the selective adsorption performance, a maximum selectivity of CO2 /CH4 (7.70) and CO2 /N2 (25.67) is obtained on
MEA(40)- at 1 atm. Further increasing the loading amount
of MEA, the selectivity declines. It is worth noticing that such
high selectivity is achieved at the pressure of 1 atm.

Figure 6. Adsorption selectivity on -zeolites with different MEA loading at the pressure of (a) 0.03 and (b) 1.00 atm and temperature of 303 K

To examine the factors influencing the adsorption

difference of CO2 , CH4 , and N2 on MEA--zeolite samples,
the steric effect is first taken into consideration. It is known
that the kinetic diameter of CO2 , CH4 , and N2 is 3.30, 3.80,
respectively. After incorporating MEA, the pore
and 3.64 A,
diameter of -zeolite decreases. Obviously, such decrease
in pore diameter has a smaller effect on the adsorption of
CO2 than that of CH4 and N2 . As a result, the selectivity of CO2 over CH4 and N2 on -zeolite after modification
rises. Besides, the adsorbate-adsorbent interaction is considered to be another factor affecting the adsorption behavior.
CO2 is acidic, thus the introduction of basic amine into zeolite can promote the interaction between CO2 and adsorbent,

while the interaction of CH4 or N2 with adsorbent is scarcely

enhanced. Therefore, the stronger interaction of adsorbateadsorbent and the smaller molecular size are responsible for
the higher adsorption amount of CO2 than CH4 and N2 , which
results in a higher selectivity of CO2 /CH4 and CO2 /N2 on
amine-functionalized zeolites.
The mechanism of CO2 adsorption on amine-modified
adsorbents has been reported in many publications. Gray et
al. [21] proposed that amine carbamates and carbonates were
produced from the reaction of alkanolamines with dissolved
CO2 . Amine-modified adsorbents were also expected to
adsorb CO2 by similar pathway, which was supported by
diffuse reflectance infrared Fourier transform spectroscopy

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Journal of Natural Gas Chemistry Vol. 18 No. 2 2009

(DRIFTS) investigation [22]. The in situ infrared (IR) study

during CO2 adsorption on aminated adsorbents confirmed the
proposal [22]. IR peaks corresponding to carbamate and
bicarbonate species derived from the reaction of CO2 with
amine groups were detected. Therefore, the main reactions
responsible for CO2 adsorption with amine should be the formation of carbamate and bicarbonate.
3.3. Cycle adsorption of CO2 by the MEA--zeolite sample
For practical use, the adsorbent should not only possess
high selectivity and high adsorption capacity, but also display
a stable cyclic adsorption performance during long-term cyclical operation. The cyclical adsorption/desorption (at 303 K in
pure CO2 atmosphere) was carried out using MEA(40)- and
the results are shown in Figure 7. The adsorption capacity was
constant after 6 cycles of adsorption and desorption, which indicates that the adsorption performance was stable under the
conditions investigated. The stable adsorption performance

Figure 7. CO2 adsorption capacity as a function of adsorption cycle for

MEA(40)-

suggests that the amine-modified zeolite is promising for the

potential application in selective adsorption of CO2 .
3.4. Comparison of adsorption performance of MEA-zeolite and other adsorbents
Table 2 compares the adsorption capacity and equilibrium
selectivity for CO2 , CH4 , and N2 of different adsorbents. For
unmodified zeolites, the selectivity of CO2 /CH4 (1.66) and
CO2 /N2 (5.40) on ZSM-5 is very low. Some other zeolites
such as SAPO-43, Na-SAPO-34, and NaETS-4 possess relatively higher selectivity, and the selectivity of CO2 /CH4 and
CO2 /N2 on NaETS-4 can reach as high as 6.93 and 18.35, respectively. Several amine-modified samples were also concerned, while only the selectivity on PEI-functionalized oil
palm shell was reported. As can be seen from Table 2, the selectivity of both CO2 /CH4 (3.26) and CO2 /N2 (7.79) is moderate. As for the sample of MEA(40)-, a high CO2 /CH4 selectivity of 7.70 was obtained. Especially, the selectivity of
CO2 /N2 can reach as high as 25.67, which is much higher
than that on other adsorbents shown in Table 2. Additionally, MEA(40)- exhibits relatively higher CH4 /N2 selectivity
(3.33). The high selectivity of CO2 /N2 on MEA(40)- makes
it a promising adsorbent for CO2 removal from flue gases of
power plants (mainly consist of N2 and CO2 ). Also, it has
potential for recovering CH4 from natural gas and landfill gas
(contain CH4 , CO2 , and a small amount of N2 ).
Works are in progress to increase both the selectivity and
adsorption amount at the same time. For microporous materials, the decrease of adsorption amount is ascribed to the
introduction of a large number of basic groups. Hence, incorporating a small amount of basic groups with a high CO2
adsorption capacity is beneficial to the improvement of both
the selectivity and adsorption amount. Additionally, mesoporous materials with a large pore size may be a good host for
the development of novel CO2 adsorbents.

Table 2. Comparison of adsorption capacities and equilibrium selectivities for CO2 , CH4 , and N2 on different adsorbents at 1 atm
Adsorbent

T (K)

SAPO-43
Na-SAPO-34
NaETS-4 degassed at 373 K
ZSM-5
Activated palm shell (B800)a
PEI-oil palm shellb
PEI(50)-MCM-41b
-zeolite
MEA(40)-

298
298
303
313
298
298
298
303
303

Adsorbed amount (mmol/g)

CO2
CH4
N2
1.07
0.16
0.07
3.50
0.60
0.30
3.03
0.44
0.17
1.08
0.65
0.20
0.83
0.09
0.11
2.28
0.70
0.29
0.74

1.76
0.38
0.14
0.77
0.10
0.03

Pure component equilibrium selectivities

CO2 /CH4
CO2 /N2
CH4 /N2
6.68
15.28
2.29
5.83
11.66
2.00
6.93
18.35
2.65
1.66
5.40
3.25
9.20
7.55
0.82
3.26
7.79
2.39

4.63
12.19
2.63
7.70
25.67
3.33

Reference
[23]
[24]
[25]
[26]
[10]
[27]
[13]
this study
this study

Deposited by benzene, b PEI: polyethylenimine (PEI)

4. Conclusions
A type of composite adsorbents was prepared by incorporating monoethanol amine (MEA) into -zeolite. The
introduction of MEA did not deteriorate the structure of
-zeolite. Among the three adsorbates (i.e. CO2 , CH4 and

N2 ), CO2 was preferentially adsorbed on the adsorbents investigated. The incorporation of MEA improved the selectivity of both CO2 /CH4 and CO2 /N2 , and the optimum selectivity
of CO2 /CH4 and CO2 /N2 can reach as high as 7.70 and 25.67
respectively on MEA(40)- at 1 atm and 303 K. Such high adsorption selectivity can be ascribed to steric effect as well as
chemical adsorbate-adsorbent interaction.

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Xiaoliang Xu et al./ Journal of Natural Gas Chemistry Vol. 18 No. 2 2009

Acknowledgements
The authors are grateful for financial supports of the Major
Basic Research Project of Natural Science Foundation of Jiangsu
Province Colleges (No. 08 kJA530001) as well as the Program for
Changjiang Scholars and Innovative Research Team in University
(No. IRT0732).

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