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Chemical Physics 412 (2013) 7276

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Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

A comparative study of CO2, CH4 and N2 adsorption in ZIF-8, Zeolite-13X


and BPL activated carbon
Joe McEwen 1, Jim-Dario Hayman 1, A. Ozgur Yazaydin
Department of Chemical Engineering, University of Surrey, Guildford, GU27XH, United Kingdom

a r t i c l e

i n f o

Article history:
Received 7 November 2012
In nal form 10 December 2012
Available online 20 December 2012
Keywords:
Adsorption
CO2 capture

a b s t r a c t
Experimental adsorption isotherms of CO2, CH4 and N2 in ZIF-8, Zeolite 13X and BPL activated carbon are
reported at 25 C and up to 1 bar. Results show that the adsorption capacity of Zeolite-13X is very sensitive to the activation temperature used. When properly activated its gas uptake is considerably higher
than BPL activated carbon and ZIF-8. CO2/CH4 and CO2/N2 mixture adsorption isotherms based on IAST
calculations reveal that Zeolite-13X also has signicantly higher selectivities for CO2 compared to BPL
activated carbon and ZIF-8. ZIF-8 performs poorly for CO2 separations within the pressure range investigated; on the other hand, its adsorption capacity shows no dependence of regeneration temperature.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Increasing concerns of the effects that anthropogenic CO2 has
on global climate change has led to the introduction of a number
of carbon mitigation schemes. Globally, 85% of energy is derived
from fossil fuels [1] and the global energy demand is expected
to have increased by 30% in 2040 compared to 2010 [2]. As such,
the total elimination of these principal resources would cause a
global energy crisis, so the need for an effective and commercially
feasible CO2 capture and sequestration method is of great importance. Current methods of CO2 removal from ue gas have had
some industrial success, mainly chemical absorption systems
using alkanolamines such as Monoethanolamine (MEA), Diethanolamine (DEA) and Methyl Diethanolamine (MDEA) [3,4]. These
are among the most mature and effective; however a large
amount of energy is required for regeneration, resulting in considerable reductions in the net power plant output. While suggestions have been put forward to improve the efciency of the
processes, it is clear that a more drastic step forward is needed
if any real advance towards a universal and low-cost CO2 sequestration system is to be made.
Natural gas is predicted to achieve the highest growth rate of all
current energy sources thanks to the discovery of new offshore
elds, its limited environmental impact and more efcient combustion method. By 2020 its use is expected to exceed coal which
is continually being further penalized by stricter emission limits
[5]. Nevertheless treatment of raw gas will always be required
either for transportation or to increase the heating value for ef Corresponding author. Tel.: +44 1483 68 6555; fax: +44 1483 68 6581.
1

E-mail address: a.yazaydin@surrey.ac.uk (A. Ozgur Yazaydin).


These authors contributed equally.

0301-0104/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.chemphys.2012.12.012

cient combustion. This requires removal of contaminants of which


carbon dioxide is one prevalent example. Current removal methods, such as cryogenic processes, are highly energy intensive such
that signicant global energy savings could be realized if more efcient processes were industrialized.
An alternative solution for the separation of CO2 from gas
streams has arisen in the form of solid adsorbent materials.
Adsorption based techniques show promise due to their inherently
simplicity, low operational requirements, ease of control and high
efciency [6]. For an adsorption medium to be practical for industrial CO2 removal, its structure must allow fully reversible uptake
and release of the gas, preferably with mild regeneration conditions, show good structural stability for prolonged use and low tendency for poisoning by trace impurities. Solid adsorbents such as
activated carbons, alumina and zeolites have been investigated
for their potential use in pressure swing adsorption (PSA) for gas
separation and storage [79]. A more recent addition to these porous materials is the class of metalorganic frameworks (MOF).
These materials are formed via coordination between metal clusters and organic linkers [10]. Advantageous properties of MOFs include their large surface areas and the relative ease in which their
pore sizes and chemical functionality can be controlled to suit specic applications. In recent years, extensive research has been carried out on the adsorptive qualities of MOFs for gas separation
[6,11].
Zeolitic imidazolate frameworks (ZIFs) are a MOF sub-class
which have a tetrahedral network that are analogous to zeolites
but use transition metals linked by imidazolate ligands [12]. ZIFs,
and in particular ZIF-8, have shown exceptional thermal, chemical
and water stabilities under a range of conditions which indicates
great promise for industrial adsorption applications [1315].
Although ZIF-8 is bettered by many other MOFs in terms of gas

J. McEwen et al. / Chemical Physics 412 (2013) 7276

storage capacity, its hydrophobicity and stability towards moisture


is unrivalled when compared to most other MOFs [14].
This paper compares two commercial adsorbents, Zeolite-13X
and BPL activated carbon (AC), against ZIF-8 based on experimental
adsorption of CO2, CH4 and N2, and based on the separation of CO2
from binary mixture of CO2/CH4 and CO2/N2 using the Ideal Adsorbed Solution Theory (IAST) calculations.
2. Experimental & computational methods
2.1. Adsorbent materials and characterization
Zeolite-13X (Na exchanged) and BPL AC were obtained from
Sigma Aldrich and Calgon Carbon, respectively. ZIF-8 was synthesized by using the aqueous method reported by Pan et al. [16].
The synthesized ZIF-8 was characterized by PXRD, TGA and SEM.
BET surface areas for all three adsorbents were determined (See
Supplementary data for the details of synthesis and characterization methods used).
2.2. Adsorption experiments
Pure component adsorption isotherms of CO2, CH4 and N2 in
ZIF-8, Zeolite-13X and BPL AC were obtained by gravimetric analysis in the range of 01000 mbar, at a constant temperature of
25 C. The equipment used for the adsorption experiments was a
Hiden Isochema Intelligent Gravimetric Analyser (IGA-001). Samples were outgassed prior to measurements being taken. This
was achieved by reducing the pressure of the sample chamber to
106 mbar at 25 C. Some adsorption experiments were also conducted after the samples were outgassed at 200 C. The samples
were typically kept at these conditions overnight until no further
mass loss was observed. The gases used for analysis were all research grades and obtained from BOC Gases.
2.3. Binary mixture IAST calculations
Numerous studies have shown that the mixed gas adsorption in
microporous materials [1721] can be successfully predicted by
using the IAST [22] based on pure component isotherms. Grand
canonical Monte Carlo (GCMC) simulations of binary mixture
adsorption have also shown good agreement with mixture results
predicted from IAST calculations [23,24].
IAST calculations were undertaken using an in house written
Fortran code. Selectivities were calculated according to the following formula

3.2. Pure component isotherms


Fig. 13 show pure adsorption isotherms for CO2, CH4 and N2 in
ZIF-8, Zeolite-13X and BPL AC, respectively, at 25 C between 0 and
1 bar obtained after outgassing the samples at 25 C.
Adsorption isotherms for all gases in ZIF-8 are within the range
of previously published data [7,13,31], and are linear within the
pressure range considered (Fig. 1). In Zeolite-13X CO2 exhibits a
type I isotherm according to the IUPAC classication, while CH4
and N2 isotherms shows linear behaviour (Fig. 2). CO2 isotherm
seems to be plateauing in Zeolite-13X as it approaches 1 bar. In
BPL AC, only N2 isotherm exhibit a linear behaviour, and CO2 and
CH4 isotherms are type I (Fig. 3). BPL AC shows the highest adsorption capacity for all gases at 1 bar. Both Zeolite-13X and BPL AC adsorbs signicantly more gas compared to ZIF-8. On the other hand,
Zeolite-13X exhibits drastically reduced adsorption capacities
when compared to previously published data [25,32]. Similarly,
the results for BPL AC also show reduced overall adsorption compared to published data [27,32], although the difference is not as
much as it is for Zeolite-13X. This is most probably due to the
low temperature (25 C) used for the outgassing of the samples
and should have a negative effect, particularly, on the adsorption
of CO2. Because, preferred adsorption sites for CO2, such as cations
and surface defects, are easily occupied by other impurities, e.g.
Water.
To test the effect of the outgassing temperature on CO2 adsorption in ZIF-8, Zeolite-13X and BPL AC, we measured the CO2 isotherms after outgassing the samples at 200 C. The results are
given in Fig. 4. There is no change to the CO2 isotherm in ZIF-8
and the CO2 isotherm in BPL AC shows a slight increase. However,
it is the CO2 isotherm in Zeolite-13X which shows a substantial increase, such that at 1 bar it depicts the signs of approaching saturation. The afnity between cations in Zeolite-13X and water
molecules are so strong that 25 C is an insufcient temperature
for complete evacuation of water molecules in Zeolite-13X, which
requires outgassing at signicantly higher temperatures. On the
other hand, it is well known that surface defects on carbonaceous
materials, such as carboxyl and carbonyl groups attract water molecules. However, it seems that outgassing at 25 C removed most of
these water molecules as the difference between the isotherms obtained after outgassing the samples at 25 C and 200 C are not
very signicant. As ZIF-8 is a hydrophobic material there is no difference between the CO2 isotherms obtained after outgassing at

x1 y 2
x2 y 1

where y and x are the mol fractions of components in the gas and
adsorbed phases, respectively.
3. Results and discussion
3.1. BET surface area and pore volumes
Zeolite-13X recorded a surface area and pore volume of 488 m2/g
and 0.27 ml/g, respectively. These values fall in the range previously reported [25,26]. BPL AC recorded a surface area and pore
volume of 985 m2/g and 0.49 ml/g respectively. This again falls
within the previously reported range [27,28]. BET surface area
and pore volume of ZIF-8 were found to be 1475 m2/g and
0.70 ml/g, respectively, which are higher than most published values for nano-sized ZIF-8 crystals [15,29,30].

73

Fig. 1. Experimental CO2, CH4 and N2 adsorption isotherms in ZIF-8 at 25 C.

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J. McEwen et al. / Chemical Physics 412 (2013) 7276

Fig. 2. Experimental CO2, CH4 and N2 adsorption isotherms in Zeolite-13X at 25 C.

Fig. 3. Experimental CO2, CH4 and N2 adsorption isotherms in BPL AC at 25 C.

25 C and 200 C, which means low temperature activation of ZIF-8


is sufcient for complete evacuation of impurities from this material. ZIF-8 is outperformed by Zeolite-13X and BPL AC for gas
adsorption below 1 bar; however, for gas separations at higher
pressures ZIF-8 can be favored due to its much less energy
intensive activation. Because, as can be seen from Fig. 4, while in
Zeolite-13X and BPL AC CO2 isotherms are already plateauing, in
ZIF-8 CO2 isotherm is still linear thanks to its relatively larger pore
volume.

3.3. IAST calculations for binary mixtures


All the IAST calculations were performed using the pure component isotherms obtained after outgassing the samples at 25 C.
Fig. 5 shows a comparison of the pure component and IAST calculated equimolar CO2/CH4 mixture adsorption isotherms in ZIF-8,
Zeolite-13X and BPL AC. Fig. 6 shows the same comparison for

Fig. 4. Experimental CO2 adsorption isotherms in Zeolite-13X, BPL Activated


Carbon and ZIF-8 at 25 C after being outgassed at 200 C.

the equimolar CO2/N2 mixture. The purpose of these IAST calculations is to ascertain the difference between the adsorption of the
components from a mixture and from pure gas. There is no or
insignicant difference between the CO2 adsorption from both of
the mixtures and pure gas in all three materials, which means
CO2 adsorption is negligibly affected by the presence of CH4 and
N2 in the bulk phase. In ZIF-8, pure component and binary mixture
isotherms of CH4 and N2 are same. On the other hand, in Zeolite13X and BPL AC, both CH4 and N2 show reduced uptake from the
mixture indicating that CO2 molecules exclude them in these two
materials.
To further characterize the separation performance of the
adsorbents for CO2/CH4 mixtures Fig. 7 shows the IAST calculated
selectivities at 1 bar and 25 C with increasing CH4 mol fraction.
Selectivities for both ZIF-8 and BPL AC show almost complete independence of gas composition which is indicated by negligible
selectivity variation, 3 to 2.75 and 3.8 to 4, respectively). However,
their selectivity performance for CO2 over CH4 pale in signicance
when compared to Zeolite-13X. Zeolite 13X shows an exponentially increasing selectivity with by increasing CH4 mol fraction.
At yCH4 0:95, for instance, a selectivity of 23 is achieved. Not only
is this greater than ZIF-8 and BPL AC, 2.75 and 3.98, respectively,
but is also superior to other MOFs, notably HKUST-1 and Mg2
(dobdc) [31,33].
IAST calculations have also been undertaken at CO2/CH4 ratios
across a range of pressures to mimic natural gas and biogas purication. These ratios are 1:9 and 1:1, respectively. Fig. 8 shows this
evaluation with some interesting results. At a 1:1 ratio all adsorbents exhibit preference of CO2 over CH4. Zeolite-13X displays
the best performance with the greatest CO2 and least CH4 adsorption out of the three. Its performance is then relatively closely followed by BPL AC. The worst adsorbent by some margin is ZIF-8.
Results for natural gas purication conditions are more interesting. Both ZIF-8 and BPL AC shows greater adsorbance of CH4 than
CO2 which came as some surprise proving that neither adsorbent
would work under these conditions if used alone. Due to its high
afnity for CO2 Zeolite-13X performs well even at low concentrations. This suggests that electrostatic forces due to the presence
of cations in Zeolite-13X are signicantly better at separating gas
mixtures of adsorbates that have a large difference in polarization
moments than van der Waals forces and molecular sieving.

J. McEwen et al. / Chemical Physics 412 (2013) 7276

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Fig. 5. Pure CO2 and CH4 isotherms and IAST calculated equimolar CO2/CH4 mixture isotherms at 25 C in (a) ZIF-8, (b) Zeolite-13X and (c) BPL AC.

Fig. 6. Pure CO2 and N2 isotherms and IAST calculated equimolar CO2/N2 mixture isotherms at 25 C in (a) ZIF-8, (b) Zeolite-13X and (c) BPL AC.

Fig. 7. IAST predicted CO2 selectivities at 1 bar and 25 C in Zeolite-13X, BPL AC and
ZIF-8 with increasing mol fraction of CH4 in a CO2/CH4 mixture.

Fig. 9 shows the selectivities of ZIF-8, Zeolite-13X and BPL AC


for CO2 over N2 in a CO2/N2 mixture with increasing N2 mol fraction at 1 bar and 25 C. Zeolite-13X exhibits the greatest CO2 selectivity, ranging from 300 to 100. This is somewhat lower than
previously reported in literature [32] but this could be attributed
to the 25 C activation temperature used for the sample. Both
BPL AC and ZIF-8 have very modest selectivities in comparison
with Zeolite-13X. The selectivity of BPL AC shows good agreement
with the literature [32]. The selectivity for ZIF-8 is higher than reported elsewhere [34]. While Zeolite-13X has an almost negative
linear relationship between selectivity and increasing mol fraction
of N2, ZIF-8 and BPL activated carbon remain relatively constant
across the same range, varying between 20 and 26 for BPL AC,
and between 8.4 and 7.6 for ZIF-8. It is interesting to note that
the order in which the adsorbents appear in terms of BET surface
area and pore volume is reversed for their selectivities. Fig. 10
shows the IAST calculated adsorption isotherms for a CO2/N2 mixture containing 8 mol% CO2 (approximate composition of ue gas

Fig. 8. IAST calculated isotherms at 25 C for CO2/CH4 mixtures with ratios of (a) 1:1 and (b) 1:9.

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J. McEwen et al. / Chemical Physics 412 (2013) 7276

tigated, its adsorption capacity shows no dependence of activation


temperature. ZIF-8 can perform better for gas separations at higher
pressures thanks to its relatively large pore volume and milder
activation requirements.
Acknowledgements
We thank Dr. Izabela Jurewicz for the SEM images.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.chemphys.2012.
12.012.
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Fig. 9. IAST predicted CO2 selectivities at 1 bar and 25 C in Zeolite-13X, BPL AC and
ZIF-8 with increasing mol fraction of N2 in a CO2/N2 mixture.

Fig. 10. IAST calculated isotherms at 25 C for CO2/N2 mixtures in Zeolite-13X, BPL
AC and ZIF-8. CO2 content in the mixtures is 8%.

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4. Conclusions
Experimental adsorption isotherms of CO2, CH4 and N2 at 25 C
and up to 1 bar show that Zeolite-13X has higher gas adsorption
capacities compared to BPL AC and ZIF-8. It also has signicantly
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calculations. However, Zeolite-13X is the most vulnerable to the
presence of impurities among the three adsorbents, thus requires
a more energy intensive regeneration process. Although ZIF-8 performs poorly for CO2 separations within the pressure range inves-

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