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Chemical Physics
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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
0301-0104/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.chemphys.2012.12.012
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].
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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.
75
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. 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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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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