DETERMINING THE SELECTIVITY OF

ZEOLITE MOLECULAR SIEVES IN CO2/ CH4

ADSORPTION BY VOLUMETRIC METHOD
F. Mohammadi Nejati1, M. Anbia2, M. Jahangiri1
1
Faculity of Chemical, Petroleum and Gas Engineering, Semnan University, Semnan, Iran
2
Reaserch laboratory of Nanoporous Materials, Faculty of Chemistry, Iran University of Science
and Technology, Narmak, Tehran16846, Iran

SUMMARY: In the present study, two kinds of zeolite molecular sieves, 13X and 4A, were collected
for investigation their ability for separation of CO2 from CH4. In order to study the behaviour of these
zeolites in CO2 separation from CH4, gas adsorption measurement were carried out by the use of static
volumetric method in different temperatures (25, 35, 45 C) and pressures ranging of 1-20 bar. Both
adsorbents showed good selectivity for separation of CO2 from CH4. Comparing with the 4A zeolite
13X exhibited higher adsorption capacity and selectivity for CO2/ CH4 separation.

Keywords: Zeolite molecular sieve, Zeolite 13X, Zeolite 4A, CO2/CH4 Separation, Gas adsorption,
volumetric method.

1. INTRODUCTION
One of the most important stages in natural gas purification process is separation of carbon dioxide from methane. CO 2 acts
as an unpleasant impurity in natural gas wells. Because of its acidic and corrosive nature, it causes serious problems during
storage and transportation of natural gas [1]. In addition from the environmental aspect, capturing of CO2 from power
plants is essential in order to prevent of greenhouse gas emission [2-4]. One of the most common and economically method
for gas separation is adsorption. The most important issue discussed in gas adsorption process is to choose an appropriate
adsorbent with the highest selectivity [5]. Among the adsorbents of CO2, zeolites attract a great attention due to their
superior separation performance and their low costs [6]. A zeolite is a crystalline aluminosilicate with a three dimensional
framework structure that forms uniformly sized pores of molecular dimension. As the pores preferentially adsorbed
molecules that are too large, they act as sieves in a molecular dimension .According to previous studies zeolites 13X and
4A are tow kind of molecular sieves for selective adsorption of CO 2 from CH4 whit high efficiency [7- 9].The aim of our
work is to study the behaviour of 13X and 4A molecular sieves in adsorption and selective separation of CO 2/CH4. For this
purpose the adsorption measurements of methane and carbon dioxide on the mentioned zeolites have been studied at
different temperatures (25, 35 and 45 C) and pressures of 1 to 25 bar. Adsorption properties of CH 4 and CO2 on 13X and
4A have been investigated by volumetric measurements. The potential use of them as an adsorbent for separation of CO 2
from CH4 mixtures is discussed and their selectivity were calculated. The data was modelled using pure isotherm equations
Langmuir.

2. EXPERIMENTAL
2.1 MATERIALS
Zeolites which were selected as adsorbent in this work were commercial 13X (Z10-02/13X) and 4A (Z4-01/4A) that
obtained from Zeochem company. CO2 and CH4 gases with purity more than 99% was used for study their adsorption
behaviour on the selected zeolite molecular sieves. In order to estimating the dead volume of adsorption cell Helium with
the purity more than 99% was utilized.

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2.2 GAS ADSORPTION MEASURMENT
For determining CO2 and CH4 adsorption on the tow zeolites we used volumetric adsorption method. The set up of
apparatus is shown in Figure 1. At rst, 1 gr of a sample was loaded in the adsorption reactor (HP vessel). For vacuuming
the set up system, we opened the valves V- 3 and V-4 and closed other valves, then, the vacuum pump turned on and the
system was vacuumed along with heating temperature of 250C for 1.5 h. After the process of de-gassing, the system was
cooled to ambient temperature. The CO2 adsorbed by opening the valves V-2 and V-3 and closing all other valves. The
pressure of HP vessel decreased because of some dead volume in reactor (including hollow space and the connected tubes)
and some adsorption on samples. Langmuir equation was tted on the experimental data as the best fit. The Langmuir
equation is expressed by Eqn (1), in which q max is the maximum adsorption amount (mmol/gr), P is the equilibrium
pressure of the adsorbate in gas phase (bar), b is the equilibrium constant of adsorption. In the model, q max and b can be
calculated from the linear plots of p/q versus p. Linear form of Langmuir Equation is presented in Eqn (2) [7]:

= (1)
1+

1
= + (2)

Figure 1 Set up of apparatus for gas adsorption measurement

After estimating the adsorption capacity of CO2 and CH4 on both zeolite molecular sieves the ideal selectivity of them in
adsorption process was calculated using Eqn (3) [1]:

2 / 4
= (3)
2 / 4

3. DISCUSSION
Volumetric adsorption isotherms of CO2 and CH4 on molecular sieve 13X and 4A in different temperature are shown in
Figures 2 to 5. Although the isotherms are illustrated in all figures which exhibited successful tting of obtained data to the
Langmuir isotherm model. The parameter of fitted model for equilibrium adsorption measurements are presented in Table
1.

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 Figure 2 Adsorption isotherms of CO2 on 13X Figure 3 Adsorption isotherms of CO2 on 4A

Figure 4 Adsorption isotherms of CH4 on 13X Figure 5 Adsorption isotherms of CH4 on 4A

By comparison of CO2 and CH4 isotherms it can be understood that adsorption capacity increase with enhancing the
pressure. Although, for both adsorbent, amount of CO 2 adsorbed increase too fast by increasing pressure at low pressures,
but in higher range of pressure its increment is not significant. This behaviour shows that zeolite molecular sieves 13X and
4A have high performance for utilizing as a CO2 adsorbent in atmospheric pressure. Also, It can be observed from Figure 2
to 5 and Table 1 that both zeolites type-X and type-A have high adsorption performance for CO2 adsorption in compare
with CH4. This kind of behaviour is due to higher adsorbent affinity toward CO2 compared to CH4. Higher adsorption
capacity of CO2 is due to its smaller molecular size and the interaction of quadrupole moment of CO 2 with polar surface of
both zeolite 13X and 4A, On the other hand, CH4 with no dipole moment and larger molecular size do not attract to the
pores and surface of the zeolites at low pressures, but at high pressures because of induced polarity and London forces
shows weak interaction with the adsorbent surface. The adsorption capacity of CO2 for molecular sieve 13X was higher
than 4A. The average pore diameter of zeolite 4A and 13X are 4 and 10 angstrom, respectively. Kinetic diameter of CO2
molecules is 3.9 A, which is a little lower than average pore diameter of zeolite 4A .So the movement of CO2 molecules
may be surrounded inside the pore of molecular sieve 4A. This is the reason for better preferences of zeolite 13X in CO 2
adsorption. By comparing the CO2 and CH4 isotherms it can be understood that adsorption capacity increase with
increasing the pressure. Also, it can be observed from Table 1 that, ranging of correlation coefficients R2 is 0.995 to 0.998,
which shows good agreement between experimental data and Langmuir model.

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 Table 1. Parameters of Langmuir equation for the obtained data
Adsorbent Gas q max b ( 1/bar ) R2 Temperature
(mmol/gr)
( C)
CO2 4.16 2.63 0.999
25
CH4 1.47 0.56 0.999
CO2 3.79 2.35 0.998
13X 35
CH4 1.41 0.43 0.997
CO2 3.45 2.24 0.998
45
CH4 1.30 0.364 0.998
CO2 3.08 2.93 0.995
25
CH4 1.44 0.64 0.999
CO2 2.87 2.58 0.998
4A 35
CH4 1.39 0.45 0.995
CO2 2.66 2.45 0.997
45
CH4 1.28 0.40 0.998

Carbon dioxide selectivity over methane for both adsorbent at different temperatures is shown in Figures 6 and 7
respectively. As can be seen, both type of zeolites exhibited high CO2/CH4 selectivity at the atmospheric pressure.
Selectivity of CO2 over CH4 was reduced by increasing of adsorption pressure. This is due to high adsorption capacity of
CO2 at low range of pressures. In addition, it is obvious that increasing of temperature lead to higher selectivity. According
to CO2 adsorption properties, temperature has the stronger effect on CH 4 desorption from the surface, which resulted in
higher selectivity at higher temperatures. Selectivity of CO2/CH4 is near 8.5 for 13X molecular sieve at the temperature of
45 C, but due to consideration of saving energy, it is better to utilize it at lower rang of temperatures.

Figure 6 Selectivity of CO2 over CH4 for 13X

Figure 7 Selectivity of CO2 over CH4 for 4A

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4. CONCLUSIONS
The equilibrium adsorption tests were performed by the volumetric method at three different temperatures of 25, 35 and 45
C and pressures ranging of 0 to 20 bar. Both selected sorbents, molecular sieves 13X and molecular sieves 4A showed
preferential adsorption of CO2 over CH4 at all pressures. The molecular sieve 13X showed better CO2 uptake than
molecular sieves 4A. Although 13X molecular sieves showed better performance for utilizing in ambient temperature and
atmospheric pressure.

5. REFERENCES
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Modied Zeolite 13X for CO2 Adsorption at Different Temperatures, (Energy & Fuels) ,pp. 35553559, 2007.

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atmospheric pressure( Chemical engineering journal), pp.50-56, 2013.

7. Z.Zhang, W.Zhang, X.Chen, Q.Xia, Z.LiAdsorption of CO2 on Zeolite 13X and Activated Carbon with Higher
Surface Area( Separation Science and Technolog),pp.710-719,2010.

8. K. T. Chue, J. N. Kim, Y. J. Yoo, S. H. Cho,Comparison of Activated Carbon and Zeolite 13X for CO2 Recovery
from Flue Gas by Pressure Swing Adsorption, pp.591-598 ,1995.

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6. AUTHOR DETAILS

Fariba Mohammadi Nejati :Master Student at the University of Semnan

Email address: elnaz_nejati2000@yahoo.com

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 Mansoor Anbia: Associate Professor of Department of Chemical of Iran University
of Science and Technology
Email address : abnia@iust.ac.ir

Mansour Jahangiri: Assistant Professor of Semnan University

Email address : Mjahangiri@Semnan.ac.ir

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