Article

pubs.acs.org/jced

Effect of the Adsorbent Pore Structure on the Separation of Carbon

Dioxide and Methane Gas Mixtures
Honghong Yi,†,‡ Yundong Li,‡ Xiaolong Tang,*,†,‡ Fenrong Li,§,‡ Kai Li,‡ Qin Yuan,‡ and Xin Sun‡
†
College of Civil and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
‡
College of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China
§
College of Architectural Engineering, Kunming University of Science and Technology, Kunming 650500, China

ABSTRACT: The role of the pore structure of the adsorbent

in separating CO2/CH4 mixtures was investigated in this study.
Three carbon materials with different pore structures, activated
carbon (AC), superactivated carbon (Super-AC), and ordered
mesoporous carbon (OMC), were used to represent the
different porosity characteristics of adsorbents. Some valuable
conclusions were obtained via the experiments and analysis: (1)
The adsorption capacity and affinity of CH4 are more
dependent on the specific surface area and the micropores
than those of CO2 at low pressure. (2) When the coverage of
CO2 reaches a certain level, the interaction between mesoporous materials and CO2 is stronger than that between microporous
materials and CO2. The mesoporous materials can absorb more CO2 than the microporous materials in high pressure. (3) At
atmospheric pressure, high specific surface area and micropore volume are adverse to adsorption separation of CO2/CH4 gas
mixtures. The mesoporous materials in this work showed higher selectivity at high pressure, and the mesoporous adsorbents have
greater potential for separating CO2/CH4 mixtures. (4) In general, the separation performance of adsorbents is slightly affected
by the pore structure at atmospheric pressure but controlled by the pore structure at high pressure.

1. INTRODUCTION
Recently, adsorption separation of CO2/CH4 gas mixtures is
seen as a very important research area. To date, almost all types
of adsorbents, such as zeolites,1−4 metal−organic frameworks
(MOFs),5−10 activated carbons,11−13 mesoporous molecular
sieves,14−16 and clays,17−20 have been used to separate CO2/
CH4 mixtures.
In past years, microporous adsorbents were used as the main
materials. New microporous materials, especially MOFs, have
become one of the research focuses. Since MCM-4121and SBA-
1522,23 were successfully synthesized, mesoporous materials
have been shown to play some important roles in various
technological fields such as adsorption, catalysis, gas storage,
and sensing.24 They have also attracted many researchers’
interest in developing their potential separation applications.
Recently, Belmabkhout and Sayari16 reported that the CO2
adsorption capacity of MCM-41 in CO2/CH4, CO2 /N2, and
CO2/H2 binary mixtures at high pressure is generally higher than
that of 13X zeolite and comparable to those of different
activated carbons. The relatively large pores of mesoporous
materials provide good modification conditions. Triamine-
grafted pore-expanded mesoporous silica exhibited high CO2
and H2S adsorption capacities as well as high selectivity toward
acidic gases versus CH4.14 Zhou and co-workers reported that
SBA-15 modified with triethanolamine has stable adsorption/
regeneration performance in CO2/CH4 mixtures.15
It is well-known that the porosity is one of the most
important properties for all adsorbents. The surface area, pore
size distribution, and pore volume greatly affect diffusion and
interaction between gases and the surface. Therefore, porosity
may play some important roles in the separation of gas
mixtures. From the existing literature, we have not obtained a
clear answer about the role of the pore structure in the
separation of CO2/CH4 mixtures. Although the adsorption of
CO2 and CH4 is greatly affected by the pore structure of
adsorbents, the separation of CO2/CH4 mixtures may or may
not be greatly affected. Thus, it is meaningful to study the role
of pore structure on the separation of CO2/CH4 mixtures.
Unlike other adsorbents, carbon materials adsorb gas almost
solely by means of nonspecific interactions, including
dispersion energy and close-range repulsion energy.25 The
chemical bonds and electrostatic interactions play an
insignificant role in carbon materials. Nonspecific forces of
different sizes are generated between gases and carbon
materials with different pore structures. Because interference
from electrostatic interactions and chemical bonds is excluded,
carbon materials have become a very ideal material to study the
role of pore structure in the separation of CO2/CH4 mixtures.
In this study, three kinds of carbon materials were used to
represent different pore structures of adsorbents. Both
superactivated carbon (Super-AC) and activated carbon (AC)
are typical microporous adsorbents that have almost no
Received: December 7, 2014
Accepted: April 20, 2015

© XXXX American Chemical Society A DOI: 10.1021/je501109q

J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

mesopores. Ordered mesoporous carbon (OMC), with 61.5 % where q is the amount adsorbed, P is the equilibrium pressure,
mesopores and 38.5 % micropores, is classed as a mesoporous and the parameters a, b, and c depend on the adsorbent,
adsorbent. On the other hand, Super-AC with the maximum adsorbates, and temperature.
specific surface area is a substitute for adsorbents with high The most important equations used in the IAST calculation
specific surface areas. OMC and AC have similar specific are listed hereafter. The spreading pressure, π, is given by
surface areas. 0
PCO qCO 0
PCH qCH
2 4 πA
All of the data and conclusions reported herein were ∫ 0 P
2
dP = ∫0 P
4
dP =
RT (2)
obtained from pure gas adsorption tests. Both the Henry’s law
constants and adsorption heats were calculated via the virial where qi is related to Pi by any pure-component isotherm, P0i is
model and the Clausius−Clapeyron equation. Mixture the equilibrium “vapor pressure” for adsorption of pure i at the
adsorption and separation were considered via ideal adsorption same spreading pressure, A is the surface area of the adsorbent,
solution theory (IAST) predictions. On the basis of isotherms R is the gas constant, and T is the absolute temperature.
for the pure gases, some primary information about adsorption Raoult’s law is written for both species as follows:
and separation of mixtures on the carbon adsorbents with 0
PyCO = PCO x
2 CO2 (3)
different pore structures has been obtained in this study. 2

0
2. EXPERIMENTAL METHODS PyCH = PCH x
4 CH4
= P20(1 − xCO2) (4)
4

2.1. Materials. Three adsorbents were used to the study. where xi and yi are the mole fractions of component i in the
The AC was commercially available activated carbon. Super-AC adsorbed and gas phases, respectively. These three equations
was obtained from AC through a novel activation method. In (eqs 2, 3, and 4) define the adsorbed mixture. With the values
this method, KOH and AC were mixed at a ratio of about 4/1 of PCO 0 0
, PCH , xCO2, and xCH4 determined, the following
(KOH/AC), and the mixture was heated to 800 °C in an inert 2 4

atmosphere for about 2 h. High microporosity is formed during equations are used to calculate qt, qCO2, qCH4, and the adsorption
the activation. OMC was synthesized with SBA-15 as a selectivity SCO2/CH4:28,29
template. SBA-15 was synthesized as reported by Zhao et 1 xCO2 xCH4
al.23 The synthesis of the OMC was performed according to the = 0
= 0
procedure reported elsewhere.26 qt qCO (PCO2) qCH (PCH 4
) (5)
2 4
2.2. Adsorption Measurements. Equilibrium isotherms
qCO = qtxCO2 (6)
of CO2 and CH4 were measured using a static volumetric 2

adsorption instrument at 30 °C, 40 °C, and 50 °C. It is

noteworthy that the sample was heated to 100 °C with blowing
inert gas (helium, 99.99 %) to wash the instrument and clear
the adsorbent in the adsorption system before every measure-
ment. CO2 and CH4 were obtained from Foshan Kodi Gas
Chemical Industry Co. Ltd. The purities of the adsorbates were
99.99 % for CO2 and 99.95 % for CH4.
2.3. Characterization. Nitrogen adsorption and desorption
isotherms were measured at −196 °C, and Brunauer−
Emmett−Teller (BET) surface areas, mesopore volumes,
micropore volumes, and total pore volumes were calculated
from the isotherms. The pore size distributions were analyzed
by the Horváth−Kawazoe (HK) method for micropores and
the Barrett−Joyner−Halenda (BJH) method for mesopores.
Nitrogen adsorption and desorption experiments were done on
an Autosorb-iQ physisorption apparatus.
2.4. Prediction of Multicomponent Adsorption Equi-
libria. IAST, proposed by Mayer and Prausnitz, was the first
major theory for predicting mixed-gas adsorption from pure
component isotherms, and it remains the most widely
accepted.25 For the application of IAST, the main condition
to be fulfilled is the availability of (i) good-quality single-
component adsorption data and (ii) an excellent curve-fitting
model for such data.27
In the current work, the single-adsorption data points
showed an orderly characteristic; the Langmuir−Freundlich
model was used to fit the pure-gas isotherms, and a perfect
fitting result was obtained (R2 > 0.999; see Table 3). The
simple formulation of this model is expressed by eq 1:
abP c
q=
1 + bP c (1)
B DOI: 10.1021/je501109q
qCH = qtxCH4
4 (7)
xCO2 yCH4
SCO2 /CH4 = ·
xCH4 yCO (8)
2
2.5. Isosteric Heat of Adsorption. The isosteric heat of
adsorption is a critical parameter for adsorptive separation
processes. It is a measure of the interaction between adsorbate
molecules and the solid surface of the adsorbent. It can be
calculated from the Clausius−Clapeyron equation with the
assumption of an isotherm:
⎛ ∂ ln P ⎞
ΔHs = −RT 2⎜ ⎟
⎝ ∂T ⎠n (9)
where ΔHs is the isosteric heat of adsorption at a specific
loading.
2.6. Henry’s Law Constant. In order to evaluate the
adsorption affinity between the adsorbate and the adsorbent,
the Henry’s law constant, KH, was investigated. This constant is
directly related to the interaction of molecules with the surface
of the adsorbent, since at low pressure molecule−surface forces
predominate.30−32 The Henry’s law constants of CO2 and CH4
on different samples were calculated via the virial equation.
According to the property of the virial model, KH can be
determined as follows:
P 1
= exp(c1q + c 2q2 + c3q3 + ···)
q KH (10)
where c1, c2, c3, ... are the virial coefficients. A plot of ln(P/q)
versus the loading q should approach the axis linearly with slope
c1 and intercept −ln(KH) as q approaches 0.
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Journal of Chemical & Engineering Data
3. RESULTS AND DISCUSSION
3.1. Characterization. In order to understand the role of
the pore structure in adsorption and separation, nitrogen
adsorption/desorption isotherms were determined at −196 °C
(Figure 1a). BET surface areas, pore volumes, and average pore
Figure 1. (a) N2 adsorption/desorption isotherms and (b) pore size
distributions of Super-AC, AC, and OMC.
sizes of samples are shown in Table 1. The pore size
distribution information on the three samples is presented in
Figure 1b. The micropores constitute 90 %, 87 %, and 38.5 % of
the total pore volume for Super-AC, AC, and OMC,
respectively. The mesopores constitute 61.5 % of the total
pore volume for OMC. In Figure 1b, for pore size greater than
2 nm, no obvious peaks were found for Super-AC and AC. The
peak values of the pore size distribution curves are 0.50 nm for
Super-AC, 0.49 nm for AC, and 0.46 nm and 3.5 nm for OMC.
Table 1. BET Surface Areas, Pore Volumes, and Average Pore Sizes of the Samples
pore volume/mL·g−1
adsorbent total micropores
Super-AC 0.8668 0.7755
AC 0.6265 0.5445
OMC 1.2326 0.4751
Article
Both Super-AC and AC are typical microporous materials.
OMC is a mesoporous material containing some micropores.
The specific surface areas follow the order Super-AC (1854.803
m3·g−1) > AC (1344.271 m3·g−1) > OMC (1266.179 m3·g−1).
Although Super-AC and AC are all-microporous materials, the
former has the larger specific surface area. The specific surface
areas of AC and OMC are similar. Super-AC has the highest
specific surface area. In the separation process, the role played
by high surface area could be obtained from the experimental
data for Super-AC. In addition, we can also get some
information about the role of mesopores and micropores
from the adsorption experiments and predictions of selectivity.
3.2. Effect of the Pore Structure on Single-Compo-
nent Adsorption. Adsorption equilibrium isotherms for CO2
and CH4 on all of the adsorbents were measured, and the
isotherms at 30 °C, 40 °C, and 50 °C are presented in Figure 2.
It can be observed that the isotherms of carbon dioxide are
much more favorable than those of methane. Additionally, the
critical temperature is considered to be an important factor. A
higher critical temperature is conducive to adsorption on
porous materials.11,33
Both the Henry’s law constant and isosteric heat of
adsorption are useful parameters to measure the interactions
in the adsorption system. The difference is that the Henry’s law
constant shows the interactions at low surface coverage, while
the isosteric heat of adsorption is able to show the trend of the
interaction force with increasing coverage.
The data in Table 2 show that the affinities follow the order
Super-AC > AC > OMC for both CO2 and CH4. This trend is
similar to the orders of the surface areas and micropore
volumes of three adsorbents. In the micropores, the gas
molecules have more strong attraction due to the overlapping
potentials from the surrounding walls.25 The surface area and
micropore volume are important factors affecting the
adsorption of methane and carbon dioxide, as shown in Figure
3. Comparison of the results for the two gases clearly shows
that the relationships of the Henry’s law constant to the
micropore volume and surface area are almost linear for CH4
(R2 = 0.995 and 0.996, respectively) but not for CO2 (R2 =
0.822 and 0.693, respectively). This phenomenon proves that
the adsorption of CH4 is more dependent on the specific
surface area and micropore volume relative to CO2. In other
words, within a certain range, increasing the micropore volume
and surface area will more greatly enhance the affinity for CH4
than that for CO2.
According to the results shown in Figure 4, one common
feature is that the isosteric heat of adsorption decreases with
increasing amount of adsorption. We found that the adsorption
heat of CO2 on OMC is greater than that of AC at high
coverage, showing that OMC maintains a strong force to CO2
at high coverage. OMC has a stronger ability to load a large
number of CO2 molecules than the other two adsorbents at
high pressure.
mesopores surface area/m2·g−1 average pore size/nm
0.0913 1854.803 0.935
0.0820 1344.271 0.932
0.7609 1266.179 1.95
C DOI: 10.1021/je501109q
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Journal of Chemical & Engineering Data Article

The kinetic diameter of CO2 is 0.33 nm, and the pore

diameter of AC is concentrated between 0.4nm and 0.5 nm, as
was shown in Figure 1. It is impossible that the adsorption
phenomenon of multimolecular layers is generated in the
micropores of AC. OMC has a larger pore size (2 nm to 4 nm)
and pore volume (196.7 % of that for AC and 142.2 % of that
for Super-AC). Under high pressure, the characteristics of
mesoporous materials (larger pore size and volume) show great
advantages.
3.3. Effect of the Pore Structure on Adsorption
Separation. IAST is well-known to give accurate predictions
of mixture adsorption isotherms on the basis of isotherms of
single components in many materials.27,34 The pure-gas
adsorption isotherms of CO2 and CH4 on all of the samples
were fitted using the Langmuir−Freundlich model, and perfect
fitting results were obtained (Figure 2 and Table 3). IAST was
then applied to these pure-gas isotherms. The adsorption
isotherms of CH4/CO2 mixtures at 0.1 MPa were calculated for
50 % CH4 in the bulk phase (Figure 5). Similar to the single-
component isotherms, all of the adsorbents favor CO2 over
CH4 in the mixtures, and the microporous adsorbents (Super-
AC and AC) similarly have stronger attraction than the
mesoporous adsorbent (OMC) for both gases. In contrast with
the single-component adsorption, the adsorption amounts of
both gases have a certain degree of reduction because of the
competitive adsorption. Furthermore, CO2 has the competitive
advantage.
From Figure 6, it is clear that the selectivity factors SCO2/CH4
at 0.1 MPa follow the order OMC > AC > Super-AC. Table 1
shows that both the micropore volume and surface area follow
the order OMC < AC < Super-AC. A conclusion can be
speculated that high specific surface area and micropore volume
may not favor the adsorption separation of CO2/CH4 mixtures
under our experimental conditions. Adsorption of CH4 more
strongly depends on the specific surface area and micropore
volume relative to CO2.
In porous materials, the pore diameter is a very important
property. All absorbents are classified on the basis of pore
diameter as microporous (0 nm to 2 nm), mesoporous (2 nm
to 50 nm), and macroporous (>50 nm) materials. In this work,
carbon adsorbents with typical pore size distributions (Super-
AC, AC, and OMC) have been used to study effect of pore
structure on the separation of CO2/CH4 gas mixtures.
Figure 6 shows that at atmospheric pressure (0.1 MPa),
OMC has a slightly higher SCO2/CH4 than Super-AC. The
SCO2/CH4 values of those two adsorbents are within the range
2.26 to 2.82. The SCO2/CH4 values of Super-AC and OMC have
not shown a large difference. Thus, the effect of pore diameter is
not very remarkable at atmospheric pressure. In order to
illustrate further the effect of pore diameter on separation, we
Figure 2. Adsorption isotherms of CO2 and CH4 at (a) 303 K, (b) 313
K, and (c) 323 K. predicted SCO2/CH4 values at up to 5 MPa using the
extrapolation method. In this case, the extrapolation method
Table 2. Henry’s Law Constants of CO2 and CH4 on the is a powerful forecasting tool. For simple comparison
Three Samples illustration, its reliability can be guaranteed. Figure 7 compares
the extrapolated results with values obtained from adsorption
KH/mmol·MPa−1·g−1 isotherms for several microporous and mesoporous materials at
adsorbent CO2 CH4 KH(CO2)/KH(CH4) high pressure from the reported literature. In Figure 7, Super-
Super-AC 124.61 75.73 1.65
AC and 13X1 belong among typical microporous materials, and
AC 113.42 34.06 3.33
SBA-15,35 MCM-41,16 MIL-100,36 and OMC37 belong among
OMC 102.17 22.01 4.64 mesoporous materials. All of above adsorbents have different
physical, chemical, or interfacial characteristics, but some
D DOI: 10.1021/je501109q
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Figure 3. Relationships between the Henry’s law constant and (a) the micropore volume and (b) the surface area.

pressure. According to the results at atmospheric pressure

Figure 4. Isosteric heats of adsorption for CO2 and CH4 as functions
of the amounts adsorbed on the samples.
uniform trends can be seen. Figure 7 shows that SCO2/CH4
decreases as the pressure increases for the two kinds of
microporous materials (Super-AC, 13X) and slightly increases
after a decrease with pressure for the five kinds of mesoporous
materials. Relative to the two microporous materials, the five
mesoporous materials show obvious advantages at high
and higher pressures, important conclusions can be acquired:
mesopores may promote the separation performance of
adsorbents to some extent, and this effect is intensified with
increasing pressure.
In Figure 7, zeolite 13X has the highest SCO2/CH4 below 0.5
MPa. We believe that the high SCO2/CH4 should be not ascribed
to micropores because many previous studies have proved that
the high SCO2/CH4 of zeolites for CO2/CH4 mixtures at low
pressure is caused by electric field and extra-framework
cations.2,25,38,39 Besides, Super-AC that likewise contains a
large micropore volume shows the lowest SCO2/CH4 whether at
low or high pressure. Generally speaking, the adsorption
capacity of zeolites for CO2 is controlled by the pore structure
at high pressures.39,40 Therefore, the SCO2/CH4 values of zeolites
at high pressure could explain the role of the pore diameter.
Taken together, these results suggest that micropores work
against separating CO2 from CH4 at high pressure.
Theoretically, it can be explained why mesoporous
adsorbents have a certain degree of superiority for separating
CO2/CH4 gas mixtures. As is known to all, the critical
temperature of CO2 is 31.3 °C, which is higher than the
experiment operating temperature (30 °C). Thus, multi-
molecular layer adsorption of CO2 can occur in the mesopores.
Conversely, the critical temperature of CH4 is −82.45 °C, which
is lower than the experiment operating temperature (30

Table 3. Parameters of the Langmuir−Freundlich Model

CO2 CH4
T/K parameter Super-AC AC OMC Super-AC AC OMC
303 a 16.2465 123.788 111.204 20.6264 6.34393 14.2043
b 1.84741 0.126810 0.133630 0.781941 3.14143 0.761844
c 0.757641 0.710263 0.723831 0.758633 0.932190 0.830813
R2 0.999353 0.999652 0.999840 0.999632 0.999413 0.999691
313 a 20.2242 10.0879 7.38893 5.61147 231.050 6.19421
b 1.41331 2.20308 2.36756 4.42853 0.04096 1.40081
c 0.06960 0.09176 0.10310 −0.03766 0.14406 0.14149
R2 0.99901 0.99978 0.99994 0.99945 0.99945 0.99926
323 a 30.6560 234.974 193.542 10.5525 720.684 2.84174
b 0.57497 0.06689 0.06720 1.25259 0.01308 4.47237
c 0.07329 −0.01220 −0.01449 −0.00122 −0.04742 −0.15913
R2 0.99952 0.99963 0.99938 0.99904 0.99909 0.99916

E DOI: 10.1021/je501109q
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Journal of Chemical & Engineering Data
Figure 5. Adsorption isotherms for the pure gases (A, CO2; B, CH4) and a binary mixture (CO2/CH4 = 50/50).
Figure 6. Adsorption selectivity at a total pressurce of 0.1 MPa.
Figure 7. IAST CO2 selectivity over CH4 vs pressure for a CO2/CH4
= 50/50 mixture on several kinds of micro- and mesoporous materials.
IAST predictions for OMC2, MCM-41, SBA-15, MIL-100, and 13X
were calculated on the basis of experimental single-component data
from refs 37, 16, 35, 36, and 1, respectively.
F DOI: 10.1021/je501109q
Article
°C). Thus, only a monolayer of CH4 molecules can be adsorbed
on the adsorbent surface in the micropores or mesopores. When
the environment temperature is higher than the critical
temperature of the gas, the gas molecules cannot be liquefied.
Multilayer adsorption formation is equivalent to the liquefaction
process. Therefore, the mesoporous structure is an important
reason that OMC exhibits better separation performance.
Mesoporous materials may exhibit more excellent separation
performance at higher pressure because multi-molecular layer
adsorption will become stronger at higher pressure and
mesoporous materials will be able to load more CO2 molecules.
In addition, the large pore volume of mesoporous materials
provides the possibility for them to be filled with a large amount
of CO2.
4. CONCLUSIONS
In this work, adsorption equilibrium data for CO2 and CH4 on
three carbon materials with different pore structures were
obtained using a static volume experiment. IAST was used to
predict the SCO2/CH4 and adsorption isotherms of a binary gas
mixture. Through the analysis of experimental data, we have
obtained some conclusions about the effect of the pore
structure on the separation of CO2 from CH4:
(1) The affinity follows the order Super-AC > AC > OMC for
both CO2 and CH4. The micropore volume and surface
area are important factors affecting the adsorption of CO2
and CH4, but CH4 is more dependent on the specific
surface area and the micropore volume than CO2.
(2) When the coverage reaches a certain level, OMC has a
stronger interaction with CO2 than AC does. The
mesoporous materials can absorb more CO2 than the
microporous materials because of the huge pore volume
and mesopore structure.
(3) At atmospheric pressure, SCO2/CH4 follows the order OMC
> AC > Super-AC. The order of SCO2/CH4 is opposite to
that of micropore volume and surface area. Thus, high
specific surface area and micropore volume are adverse to
adsorption separation of CO2/CH4 gas mixtures.
(4) At high pressure (up to 5 MPa), all of the mesoporous
materials in this work show higher SCO2/CH4 than
microporous materials. The mesopores may promote
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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adsorbents’ separation performance to some extent, and
this effect is intensified by pressure.
(5) In general, the separation performance of adsorbents is
slightly affected by the pore structure at atmospheric
pressure but is controlled by the pore structure at high
pressure.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: txiaolong@126.com. Fax: +86 10 6233 2747.
Funding
This work was supported by the Fundamental Research Funds
for the Central Universities (06101046).
Notes
The authors declare no competing financial interest.
■
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H DOI: 10.1021/je501109q
J. Chem. Eng. Data XXXX, XXX, XXX−XXX