Microporous and Mesoporous Materials 277 (2019) 105–114

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Adsorption equilibrium and kinetics of carbon dioxide, methane and T

nitrogen on binderless zeolite 4A adsorbents
Rute Seabraa, Ana Mafalda Ribeiroa,∗, Kristin Gleichmannb, Alexandre F.P. Ferreiraa,
Alírio E. Rodriguesa
a
LSRE-Laboratory of Separation and Reaction Engineering, Associate Laboratory LSRE/LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias,
4200-465, Porto, Portugal
b
Chemiewerk Bad Köstritz GmbH, Heinrichshall 2, 07586, Bad Köstritz, Germany

ARTICLE INFO ABSTRACT

Keywords: In order to evaluate the adsorption properties for CO2, CH4 and N2, from flue gas streams, or for natural gas
Binderless zeolites 4A sweetening, three binderless zeolite 4A adsorbents were studied.
Adsorption equilibrium To characterize these materials, several techniques such as N2 physisorption at 77 K, CO2 physisorption at
Zero length column 273 K, mercury intrusion, Scanning Electron Micrograph (SEM), Energy Dispersive X-ray and X-ray Diffraction
(XRD) were employed.
Adsorption equilibrium isotherms of pure gases (CO2, CH4 and N2) were determined at 303, 343 and 373 K.
The dual site Langmuir model was used to fit the experimental results for adsorption of CO2 and single site
Langmuir model for the adsorption of CH4 and N2. The CO2 was the adsorbate with the highest affinity for all
zeolites 4A and N2 the one with the lowest affinity. In terms of capacity by volume the binderless 4A with high
density has its capacity significantly improved, since it has the same mass based capacity, but due to its higher
density it has a higher volume based capacity. The isosteric heats of adsorption calculated by the Clausius-
Clapeyron equation were in good agreement with literature values.
The adsorption kinetics studies were performed at 308, 323 and 373 K with the Zero Length Column (ZLC)
technique analysing the analytical solution of the mathematical model and the long time response. The results
appear to indicate that the crystal diffusion is the controlling mechanism of the diffusion of CO2 for the high
density binderless zeolites 4A.

1. Introduction The requirement for adequate adsorption capacity restricts the

Due to the increase of world population, industrialization and
technology advancement, the use of fossil fuel has released consider-
able amounts of greenhouse gases such as carbon dioxide which con-
tributes up to 60% of the global warming effects [1]. In order to limit
the CO2 emissions and to decrease its content in natural gas, which is an
energy source with expected consumption growth of 50% over the next
20 years [2], technologies to capture and storage CO2 have been de-
veloped.
The existing techniques for CO2 separation from gas streams include
advanced technologies such as wet scrubber, membranes, cryogenics,
and pressure and temperature swing adsorption [3]. Separation and
purification of gas mixtures by adsorption has gained interest to che-
mical and petrochemical industries due to the low energy requirements
and low capital investment costs [2].
choice of adsorbents for practical separation processes. In order to
avoid pressure drop, nanoporous materials are usually shaped as beads
or pellets. However, the conventional procedure of shaping involves the
addition of an inorganic binder that reduces the adsorption capacity
and influences the transport pore system [4]. To overcome these dis-
advantages, a new synthesis pathway was applied where a temporary
inorganic binder is converted to zeolite matter leading to binderless
beads or pellets [5].
In order to evaluate the performance/potential of these new ad-
sorbents, adsorption equilibrium and kinetics must be assessed. Indeed,
the success of any chromatographic separation process depends in a
good characterization of the intraparticle/intracrystal transport rates
and of the adsorption equilibrium.
In 1943, a pioneering paper of Domain et al. [6] reported the use of
a sufficiently thin bed that, due to the small volume involved, allowed

∗
Corresponding author.
E-mail address: apeixoto@fe.up.pt (A.M. Ribeiro).

https://doi.org/10.1016/j.micromeso.2018.10.024
Received 31 August 2018; Received in revised form 19 October 2018; Accepted 22 October 2018
Available online 23 October 2018
1387-1811/ © 2018 Elsevier Inc. All rights reserved.
R. Seabra et al.
the differential rate equation to be established in terms of operating
variables. Solving these equations, the performance of commercial beds
at large scale and under various conditions could be predicted. This
technique was called shallow bed or zero length columns. In 1947, Boyd
et al. [7] developed a scale-down version of a shallow bed that allowed
the use of only 100 mg of resin and enabled a rapid switching between
different buffer solutions. They were able to quantitatively describe the
rate of adsorption of alkali metal ions on resinous zeolites. Later, this
technique was extensively used to measure ion-exchange rates on all
types of different resins [8] and further extended to study the adsorp-
tion of small organic compounds like phenols and amino-acids [9–12].
In 1988, with the objective of measuring diffusivities of hydrocarbons
in zeolites, a different path was taken with the development of the zero
length technique by Eic and Ruthven [13]. In spite of having an
equivalent experimental set-up to the shallow bed technique, the ZLC
depends on monitoring the desorption of a sorbate from the adsorbent,
when purged by an inert gas at high flow rates. In 1993, this study was
extended to the measurement of diffusivities in pellets by Ruthven and
Xu [14]. In 1996, a complete model which includes macropore and
crystal diffusion in pellets applied to ZLC technique has been developed
simultaneously by Brandani et al. [15] and by Silva and Rodrigues [16]
who also suggested algorithms for data treatment. This technique has
the advantage of elimination of external mass resistances and heat
transfer effects by the use of low adsorbate concentration, small amount
of adsorbent sample and the use of high carrier flow rates during des-
orption.
In this study, different binderless zeolite 4A adsorbents were tested
with the purpose of evaluating their adsorption properties (kinetics and
equilibrium) for carbon dioxide capture from flue gas streams, and for
sweetening of natural gas. Adsorption equilibrium isotherms of pure
gases (CO2, CH4 and N2) were determined by a gravimetric technique at
303, 343 and 373 K. While, adsorption kinetics studies were performed
at 308, 323 and 373 K with the zero length technique, analysing the
experimental results by means of applying the analytical solution of the
mathematical model and by applying the long-time response method.
2. Materials and methods
2.1. Materials
The adsorbents studied were binderless zeolites 4A (4A BFK) with
two particle diameters 1.6–2.5 mm and 2.5–5.0 mm and a binderless
zeolite 4A denominated high bulk density (4A BFK HSD) with
1.6–2.5 mm diameter range (Fig. 1), in form of granulates, provided by
Chemiewerk Bad Köstritz GmbH.
All the studied adsorbents are classified as binder-free molecular
sieves (BFK) as a result of a new synthesis pathway that has been de-
veloped to compensate the fact that in the manufacturing of shaped
zeolites normally 80–83 wt % of zeolite powder and 20–17 wt % of
Fig. 1. Zeolite: a) 4A BFK 2.5–5.0 mm; b) 4A BFK 1.6–2.5 mm; c) 4A BFK HSD 1.6–2.5 mm.
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Microporous and Mesoporous Materials 277 (2019) 105–114
binders are used that despite providing a specific shape and mechanical
strength, reduces the adsorption capacity of the material. Therefore, it
is expected that the tested molecular sieves have an adsorption capacity
comparable to pure zeolites of the same structural types [17].
The adsorption properties of CO2, CH4 and N2 in the different zeolite
samples were determined using gases provided by Air Liquide with the
following specifications: carbon dioxide N48, methane N35 and ni-
trogen N45, which means purity greater than 99.998, 99.95 and
99.995%, respectively. For adsorbent activation and regeneration, he-
lium was used with 99.999% purity, also provided by Air liquid.
The materials were characterized by mercury porosimetry, nitrogen
adsorption at 77 K and carbon dioxide adsorption at 273 K performed at
Málaga University, scanning electron micrograph (SEM/EDS) per-
formed at the Centro de Materiais da Universidade do Porto (CEMUP) and
X-ray Diffraction (XRD) was performed at Universidade de Aveiro.
Mercury intrusion porosimetry was performed using a Pore Size
Analyzer (Micromeritics's AutoPore IV 9500, USA), over a wide range of
pressures (0.0007–227.5 MPa) after activation at 573 K for 12 h in a
vacuum environment.
N2 adsorption experiments at 77 K were performed with an
Accelerated Surface Area and Porosimetry System (Micrometrics' ASAP®
2420, USA), CO2 adsorption experiments at 273 K were executed with
an Accelerated Surface Area and Porosimetry System (Micromeritics'
ASAP® 2020, USA), both analyses were performed after activation at
573 K for 12 h in a vacuum environment.
To study the morphology of the sample, scanning electron microscopy
(SEM)/energy dispersive X-ray spectroscopy (EDS) analysis with High re-
solution (Schottky) Environmental Scanning Electron Microscope with X-
Ray Microanalysis and Backscattered Electron Diffraction Pattern Analysis
(FEI Quanta 400FEG ESEM/EDAX Genesis X4M, USA) was performed.
The XRD analysis for the crystallinity assessment of all zeolite
samples were performed using a Siemens diffractometer D5000, it is a
theta/theta 2 diffraction instrument operating in reflection geometry
using Cu Kalpha1 radiation (λ = 1.54056 Å).
2.2. Adsorption equilibrium isotherms
In order to measure the adsorption equilibrium isotherms of CO2,
CH4 and N2 a magnetic suspension microbalance (Rubotherm,
Germany), with a precision of 0.01 mg was used. The schematic dia-
gram of the experimental set-up is shown in Fig. 2. The balance is
connected to a three port valve, a thermocouple for temperature
monitoring, one pressure transducer to measure the pressure inside the
gas cell and a vacuum pump used for sample activation and cell de-
pressurization. To control the temperature, an electric resistance was
used. The system control and data acquisition are done by a Rubotherm
software.
The adsorbent sample is weighed and placed in a basket linked to a
permanent magnet. The permanent magnet interacts with the
R. Seabra et al.
Fig. 2. Schematic diagram of the experimental set-up for adsorption equilibrium measurements.
electromagnet (magnetic suspension coupling) allowing the measure-
ment of the weight variations inside the cell, which are recorded in a
computer. Before the experiments with the gases under study, the ad-
sorbent was activated at 573 K under vacuum until no mass loss was
observed. To achieve the activation temperature a heating rate of 1 K/
min was used.
The measurements were performed for CO2, CH4 and N2 at 303, 343
and 373 K up to 9 bar.
In all experiments, the values obtained corresponded to the excess
adsorbed phase concentration and in order to correct the buoyancy
effect two helium pycnometries were made assuming that helium is not
adsorbed, one with the adsorbent and the other without. After the
buoyancy correction, the equation to calculate the absolute adsorbed
concentration from the experimental data is:
m+ G (Vs + VC )
q= ads
ms Mw ads G (1)
Where m is the difference of weight between measurements, G is the
density of the gas phase at the measuring conditions (T,P), Vs is the
volume of the solid adsorbent, VC is the volume of the permanent
magnet, the sample basket and the glass wool used to hold the sample,
mS is the adsorbent mass, Mw the adsorbate molecular weight and ads
the density of the adsorbed phase.
The density of the gas phase was calculated assuming the ideal gas
law and the density of the adsorbed phase was calculated according to
Dubinin's assumptions [18,19]:
1) For relatively low temperatures, below boiling point, the molar
volume of the substance in the adsorbed state, v , may be taken as
the molar volume of the substance in the bulk liquid phase.
2) Over the range of temperatures from the boiling point to the critical
temperature, there is a considerable decrease in the liquid phase
density as the critical temperature is approached. However, there is
also a sharp increase in the compressibility of the liquid and since an
adsorbed substance in micropores is in a strongly compressed state,
its density is considerable greater than the liquid density and can be
expressed as linear.
Therefore, above boiling point temperature and under critical
temperature, the molar volume is calculated through Equation (2).
T Tb
v = vb + (b vb )
Tc Tb
Microporous and Mesoporous Materials 277 (2019) 105–114
where vb is the molar volume at the boiling temperature, Tb , and Tc the
critical temperature.
3) For temperatures above the critical temperature, the molar volume
is equal to the Van der Waal's volume:
v =b (3)
where b is the Van der Waal's volume.
The system monitors the pressure, the temperature and the weight
variations. In order to obtain one experimental point of the adsorption
isotherm, a small amount of gas is added to the gas cell were the ad-
sorbent sample is placed, when the change in weight is approximately
zero, it is considered that equilibrium has been reached. Then, the gas
cell pressure is increased again, by introducing another amount of gas,
and another point is determined. This procedure is repeated until the
highest desired pressure is achieved. After that, desorption points of the
isotherm are obtained with progressive depressurization.
2.3. Zero length column
In order to obtain the diffusion coefficients of CO2, CH4 and N2, Zero
Length Column tests were performed in a Varian gas chromatograph
with an experimental set-up as represented in Fig. 3.
The adsorbate was prepared by diluting a determined amount of
pure gas in helium. For that, a mixture bottle was first cleaned. Using a
vacuum pump, the bottle was initially cleaned by removing any existing
gas. Then helium was injected and vacuum was again applied to remove
any remaining impurities. A sampling tank of known volume was
connected to the pure adsorbate bottle and filled up to a desired pres-
sure. Then, the sampling tank was connected to the mixture bottle and
the pure gas was expanded into the mixing bottle, and after pressure
equalization the remaining gas was purged from the tank by passing
helium through it, until a total desired pressure was achieved.
The adsorbent was placed in the ZLC cell inside the gas chromatograph,
which allows experiments up to 673 K. The outlet stream was connected to
a thermal conductivity detector (TCD) where the concentration of the gas
was measured and then to a flame ionization detector (FID), which also
ensures that emissions to the laboratory environment are avoided. Prior to
the ZLC cell exists a multiport valve to switch the inlet stream from mixture
(helium plus adsorbate) for saturation and pure helium for desorption. After
the saturation of the column the run started by switching to a pure helium
stream at time zero. The concentration of the adsorbate is followed con-
(2) tinuously for enough time to ensure complete desorption of the sample.
107
R. Seabra et al.
Fig. 3. Zero Length Column experimental set-up.
ZLC experiments of CO2, CH4 and N2 were performed at 308, 323
and 373 K.
In all experiments, the mixture had 0.75% of the adsorbate diluted
in helium so that the velocity variations within the column were re-
duced, the process occurs under isothermal conditions and, above all,
the measurements were carried out in the linear zone of the adsorption
isotherm. The activation of the adsorbents was performed at 573 K at a
heating rate of 1 K/min under a flow of helium. Prior to any ZLC ex-
periment, blank experiments were performed to characterize the
system, using glass beads instead of adsorbent sample.
3. Mathematical model
3.1. Adsorption equilibrium
For the design of separation processes, it is necessary to know the
interactions between adsorbates (fluid) and the adsorbent (solid) since
different bonds involve different energies. For processes where ad-
sorption and desorption are involved, the main focus is in the reversi-
bility achieved by a change of operating conditions as temperature or
pressure. As an exothermic phenomenon, adsorption releases heat and
despite being a dynamic process after a certain amount of time it
achieves an equilibrium state [20].
In 1918, Langmuir gave the first coherent theory of adsorption as a
dynamic equilibrium with equal rates of adsorption and desorption.
This model assumes that the surface is energetically homogeneous, that
there is no interaction between adsorbed molecules and that each site
has the same probability of adsorbing, being able to accommodate only
one molecule [20].
The Langmuir model equation is:
Ki P
qi = qm, i
1 + Ki P (4)
where qi is the adsorbed concentration of the component i, qm, i is the
maximum adsorption capacity of the adsorbent (only considering
monolayer adsorption) of component i, Ki is the adsorption constant for
component i and P is the pressure. The adsorption constant, also known
as the Langmuir constant, and it dependence on temperature can be
expressed by the Van't Hoff equation:
H
Ki = K i0 e Rg T
(5)
where K i0 is the adsorption constant at infinite temperature, ( H ) is
the heat of adsorption on the homogeneous surface, Rg is the universal
gas constant and T is the temperature of the system.
Under high values of pressure the term Ki P 1 and so the
Langmuir isotherm reduces to qi = qm, i , which means the capacity sa-
turation of the adsorbent is complete. For low values of pressure the
term Ki P 1, reducing then the Langmuir model equation to the linear
q
isotherm model: q i = Ki P .
m, i
For real adsorbents, the heterogeneous surface may provide two (or
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Microporous and Mesoporous Materials 277 (2019) 105–114
more) types of adsorption sites with different characteristic energies
[21–23]. Therefore, the single site Langmuir model can be extended to
a dual-site Langmuir model (Equation (6)), where the strongest ad-
sorption energy sites will be filled first, followed by the weak adsorp-
tion energy sites. When both sites reached equilibrium each one can be
modelled by two separate equilibrium constants (K1 and K2), and both
constants can be calculated through Van't Hoff's equation.
K1, i P K2, i P
qi = qm1, i + qm2, i
1 + K1, i P 1 + K2, i P (6)
3.2. Zero length column
The mathematical model that describes the ZLC system is based on
the following assumptions: (1) the adsorbent pellet has a bidisperse
porous structure containing macropores and crystals (micropores), (2)
Fick's law for diffusion is valid for macropore and crystal diffusion, (3)
macropore and crystal diffusion are mechanisms in series, (4) adsorp-
tion in macropores is negligible, (5) adsorption equilibrium in crystals
is described by a linear isotherm and (6) the ZLC cell is equivalent to a
continuous stirred tank adsorber [24]. Taking all the assumptions into
account, the analytical solution for slab, infinite cylinder and sphere
geometries were determined and the outlet concentration of ZLC can be
obtained through Equation (7).
Dap 2j t
exp l2
C
= 2L
C0 j =1
2
j + L (L + 1 n) (7)
where n is equal to 0, 1 or 2 for slab, infinite cylinder, and sphere,
respectively, C and C0 are the instantaneous and initial gas phase
concentrations, respectively, Dap is the apparent diffusivity, l is the re-
presentative spatial dimension of the pellet (radius for sphere and in-
finite cylinder, and half-length for slab), L is the ZLC parameter given
by Equation (8).
Qp l2
L=
(n + 1) K Vs Dap (8)
where Qp is the purge flowrate, Vs is the volume occupied by the pellets
in the cell, K = p + (1 p ) K eq where p is the porosity of the pellet
and K eq = s HRg T where s is the density of the solid and H the Henry
constant.
It must be taken into attention that in order to avoid heat effects in
ZLC experiments, the adsorbate concentration must be kept as small as
possible [25]. However, at very high purge flow rates (high values of L)
the effluent concentration can be very diluted, being too small for ac-
curate measurement. Yet, one must keep in mind that the purge flow
rate cannot be too much decreased, as the desorption equilibrium can
became the controlling phenomenon [26]. According to Ruthven and
Brandani, in order to properly apply this method, it is necessary to
ensure that the adsorbent is in equilibrium with the gas phase before
R. Seabra et al. Microporous and Mesoporous Materials 277 (2019) 105–114

Fig. 4. SEM images of zeolites: a) 4A BFK 2.5–5.0 mm, b) 4A BFK 1.6–2.5 mm, c) 4A BFK HSD 1.6–2.5 mm.

starting the desorption step. When the L values is large (> 10) the in-
terpretation of an experimental ZLC desorption curve is trustworthy
providing reliable values for diffusion [27].
Finally, j are the roots obtained from the transcendental equation,
which for sphere geometry (geometry of the studied materials) is given
by Equation (9).
cot( j ) + L 1=0
j
Despite that, the use of all the information of the experiment provides a
more reliable analysis, which can be modelled using more terms (β
roots) of equation (7). In this study, the two approaches were applied.
4. Results and discussion
(9)
4.1. Adsorbent characterization

In the case of crystal control, the Dap has to be replaced by the

/l2
crystal diffusivity and the spatial coordinate is the crystal re- SEM images of the zeolite 4A samples are presented in Fig. 4.
presentative spatial dimension (Dc / rc2 ). For the case of macropore con- Crystals with an average size of 1 μm can be observed. The character-
trol, the pore diffusivity (Dp) is calculated through Equation (10). istic cubic shape of the zeolite 4A crystals is observed for the three
samples. However, some intergrowth of the crystals is also visible for
p Dp
Dap = the three samples. From the EDS spectra, the expected elements were
p + (1 p ) K eq (10) found (O, Na, Al, Si).
The pore diffusivity (Dp) is related with the interaction of the ad- From the mercury intrusion, it can be concluded that all the samples
sorbate molecules with the pore walls (Dk ) and the interaction between have similar pore distribution and average pore diameter. The high
molecules (Dm) . The Bosanquet equation (Equation (11)) translates this density sample has the higher solid density (measured by Hg intrusion
relation, where p is the tortuosity. at 200 MPa) and apparent density (measured by Hg intrusion at
0.035 MPa), due to the lower pore volume.
1 1 1 A summary of the main measured properties is presented in Table 1. The
= p +
Dp Dm Dk (11) pellet density (apparent density, ap = mass /pellet volume ) and the solid
density ( s, Hg = mass/(pellet volume (macro + meso) pore volume) ) obtained by
Using the first term of the series represented by Equation (7), the
mercury intrusion are given as well as the skeleton solid density
response at long times can be approximated by straight lines as pre-
( sk, He = mass/ solid volume = mass/(pellet volume (macro + meso + micro) pore volume) )
sented in Equation (12) [24], called the long-time response (LTR).
obtained by helium picnometry.
C 2L
2
1 Dap t As the diffusion of nitrogen at 77 K in zeolite 4A is kinetically re-
ln ln
C0 2
+ L (L + 1 n) l2 stricted, it is not possible to obtain meaningful physical values through
1 (12)
this procedure. From the adsorption of carbon dioxide at 273 K, as the
The use of the long-time response to model the experimental ZLC temperature is higher and therefore the kinetic energy of the molecules
results is justified by the direct calculation of the long-time asymptote is greater, the diffusion into the pores is faster allowing the determi-
slope, which has the information of the adsorption kinetics. One of the nation of the surface area presented in Table 1. The adsorption iso-
main problems of this approach is the difficulty in the determination of therms of carbon dioxide at 273 K are presented in Fig. 5.
the range of points to be included [28]. Such a problem can lead to The X-Ray diffraction results of the zeolites 4A studied as well as the
large differences in the value of the intercept resulting in low re- one obtained from the International Zeolite Association (IZA) [29] are
producibility of the method [26]. On the other hand, the initial part of represented in Fig. 6. A good match can be found, indicating that no
the desorption curve may be affected by the washing of the cell and by other crystalline material/zeolite type might be present in the samples.
dead volume effects that may hide the real diffusivity values [28].

Table 1
Total intrusion volume, surface area, average pore diameter, apparent and solid density obtained from mercury intrusion, surface area from carbon dioxide phy-
sisorption at 273 K and solid density obtained from helium picnometry in the zeolites 4A.
4A BFK 2.5–5.0 mm 4A BFK 1.6–2.5 mm 4A BFK HSD 1.6–2.5 mm

−1 −4 −4
Total Intrusion Volume m³ kg 3.01 × 10 3.15 × 10 1.61 × 10−4
Surface Area (Mercury intrusion) m2 kg−1 3.84 × 103 3.49 × 103 2.00 × 103
Surface Area (CO2 Physisorption) m2 kg−1 5.10 × 105 5.01 × 105 5.10 × 105
Average Pore Diameter m 3.14 × 10−7 3.61 × 10−7 3.20 × 10−7
Apparent Density kg m−3 1091 1109 1406
Solid Density kg m−3 1624 1707 1819
Skeleton Density kg m−3 2201 2225 2245

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R. Seabra et al. Microporous and Mesoporous Materials 277 (2019) 105–114

4.2. Adsorption equilibrium isotherms

Adsorption equilibrium isotherms of CO2, CH4 and N2 on zeolite 4A

BFK 1.6–2.5 mm were determined at 303, 343 and 373 K in the pressure
range of 0–9 bar. The experimental results as well as adsorption iso-
therm model fittings (as described below) are presented in Fig. 7 for
CO2 and in Fig. 8 for CH4 and N2.
As some equilibrium points were determined with increasing pres-
sure - adsorption branch (closed symbols) -and others with decreasing
pressure - desorption branch (open symbols) - it was possible to con-
clude that inside the experimental error the 4A BFK 1.6–2.5 mm sample
did not show any hysteresis for any adsorbate at the three different
temperatures.
The results obtained for zeolite 4A BFK 1.6–2.5 mm were fitted with
the Dual-site Langmuir model (Equation (6)) in the case of CO2 and
with the Langmuir model (Equation (4)) in the case of CH4 and N2 as
this model proved to be sufficient. The parameters qm1, i , qm2, i , K1,0 i , K2,0 i ,
( H )1 and ( H )2 for the CO2 fitting and the parameters qm, i , K i0 and
Fig. 5. Adsorption equilibrium isotherms of carbon dioxide at 273 K in the
the ( H ) for CH4 and N2 were obtained by minimizing the sum of the
zeolites 4A.
absolute error between the experimental and calculated values. In all
cases a good fitting was achieved. The adsorption equilibrium isotherm
parameters for CO2, CH4 and N2 on 4A BFK 1.6–2.5 mm are reported in
Table 2.
The three samples were provided by Chemiewerk Bad Köstritz
GmbH and have the same composition, similar pore distribution, si-
milar average pore diameter and similar surface area obtained from
CO2 physisorption. Furthermore, the results from the X-Ray diffraction
of the 4A zeolites as well as the one obtained from IZA, indicate that no
other crystalline material is present in the samples. In this way, it is
expected that the materials present the same adsorption equilibrium. To
show this, some adsorption equilibrium points were measured for CO2
adsorption, in the other two zeolite 4A samples at 303 K and 373 K and
the results are presented in Fig. 7a and b. It can be seen that, the 4A BFK
2.5–5.0 mm and 4A BFK HSD 1.6–2.5 mm zeolites interactions with the
Fig. 6. X-Ray diffraction data of the zeolite 4A samples.
adsorbate were equally well described by the model determined for the

Fig. 7. CO2 adsorption equilibrium isotherms on 4A BFK

1.6–2.5 mm, 4A BFK 2.5–5.0 mm and 4A BFK HSD
1.6–2.5 mm: experimental points (closed symbols adsorp-
tion, open symbols desorption) and Dual site Langmuir fit-
ting (lines). (a) 303 K, (b) 343 K and (c) 373 K. (d)
Comparison between the CO2 adsorption capacities per vo-
lume of adsorbent (ρap) in zeolites 4A at 303 K.

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R. Seabra et al. Microporous and Mesoporous Materials 277 (2019) 105–114

Fig. 8. Adsorption equilibrium isotherms of a) CH4 and b) N2 adsorbed on 4A BFK 1.6–2.5 mm zeolite: experimental points (closed adsorption, open desorption) and
Langmuir fitting (lines).

Table 2
Fitting parameters of the Langmuir model for CO2, CH4 and N2 adsorption
equilibrium on 4A BFK 1.6–2.5 mm.
Species qm (mol kg−1) K 0i (bar−1) ( H ) (kJ mol−1)

qm1 qm2 0
K1, i
0
K2, i
( H)1 ( H )2

CO2 1.81 3.68 2.01 × 10−8 1.76 × 10−5 42.3 36.6

CH4 3.47 5.88 × 10−5 20.5
N2 3.24 3.98 × 10−5 19.7

4A BFK 1.6–2.5 mm zeolite when presented in terms of amount ad-

sorbed per mass of dry adsorbent. However, Fig. 7d shows a comparison
of the CO2 adsorption equilibrium isotherms given as adsorbed amount
per volume of particle where it can be clearly seen that in terms of
capacity per volume the 4A BFK HSD zeolite is significantly better. At
1.0 bar and 303 K an adsorbed concentration of 5776 mol m−3 was
determined for 4A BFK HSD 1.6–2.5 mm showing a gain of 29% in
comparison with the 4556 mol m−3 determined for 4A BFK 1.6–2.5 mm
zeolite. The advantages of this material in terms of adsorption capacity
are obvious, significantly smaller equipment can be used.
In terms of amount adsorbed, CO2 is the most adsorbed gas in the
zeolite 4A samples studied, and N2 is the less adsorbed. The value of the
heat of adsorption is higher for CO2 and smaller for N2.
In the literature, a maximum CO2 loading capacity of 5.020 mol kg−1
was obtained in a zeolite 4A provided by UOP Co. [30], this quantity shows
to be smaller than the one found in the present study with a binderless 4A.
According to a study with zeolite 4A powder [31], provided by Sigma-
Aldrich (pure zeolite 4A powder), an amount adsorbed of 3.1 mol kg−1 was
found, at 0.1 bar of CO2 and 298 K, which is similar to the one obtained in
this study.
4.3. Isosteric heat of adsorption
The isosteric heat of adsorption determines the extent of tempera-
ture changes within the adsorber during the adsorption and desorption
steps of the processes [32]. It can be estimated by the Clausius-Cla-
peyron equation:
lnP
( Hiso) = Rg T 2
T q = const
where Hiso is the isosteric heat of adsorption of component i, Rg is the
universal gas constant, P is the gas pressure, and T is the temperature of
the system. The derivative is evaluated at constant adsorbed con-
centration, q. From the slope of the plot of lnPi as a function of 1/ T the
isosteric heat of adsorption can be estimated.
Fig. 9 shows the single component isosteric heats of adsorption on
Fig. 9. Single-component isosteric heats of adsorption on 4A BFK 1.6–2.5 mm
for CO2, CH4 and N2 as function of the adsorbed concentration in the tem-
perature range of 303–373 K; Lines are the values obtained through the SSL and
DSL model.
4A BFK 1.6–2.5 mm zeolite as a function of the adsorbed concentration
as well as the heat of adsorption obtained from the Langmuir isotherm
model and dual site Langmuir isotherm model (lines).
In the literature, values of the isosteric heat of adsorption in zeolite
4A of 47.8 kJ mol−1 for the adsorption of CO2 [33], 23.8 kJ mol−1 for
N2 and 16.72 kJ mol−1 for CH4 [34] were found. Comparing the heats
of adsorption of this material with the values reported in literature it
can be concluded that in the case of CO2 and N2 the values in the
present work are slightly lower and slightly higher for CH4.
4.4. Zero length column
In order to determine the diffusivity coefficients and the diffusion
control mechanism of CO2, CH4 and N2 in the binderless zeolites 4A, several
experiments with different flow rates and at different temperatures were
performed. The temperatures studied were 308, 323 and 373 K. To achieve
a kinetic-controlled process in ZLC experiments, it is necessary to achieve
high values of the parameter L [35]. As this is obtained by increasing the
flow rate, experiments with different flowrates were performed leading to
the optimal value of 6.8 × 10−7 m3 s−1 (STP) used in the trials shown
below.
To allow the adsorption equilibrium to be described by the Henry's
Law, a mixture of Helium with 0.0075 bar (partial pressure) of ad-
(13)
sorbate was used. In order to properly apply this method it is necessary
to allow the system to reach full equilibrium between the fluid and the
adsorbent [27]. If the saturation step is performed for a short period of
time, the desorption curve has almost the same final slope but the
amount adsorbed is not the same [36]. For this reason, in all experi-
ments, when equilibrium in the gas phase was apparently reached, an
additional period of 20 min was added to ensure the full saturation.

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R. Seabra et al.
With the aim of discriminating correctly between the importance of
macropore or crystal diffusion, it is necessary to carry out experiments
in pellets with different sizes but with the same crystal size or pellets
with the same size with different crystals [24]. With the provided
zeolites, the first method was applied. The ZLC experimental results are
shown in the supporting information.
The determination of the diffusivity parameters can be done
through the analysis of the long time response (LTR) or by the use of
equation (7) with additional terms as explained before. Although the
initial part of the desorption curve may be affected by the washing of
the cell and by dead volume effects that may hide the real diffusivity
values, the complete solution provides a more reliable solution due to
the use of all data. On the other hand, the selection of the range of
points to be included in the LTR analysis may be difficult [28]. In this
work, a first estimate of the parameter Dap / l2 , K and was obtained
using the LTR and considering the fact that should be approximately
equal to for spherical geometry.
Afterwards, these estimated values were used as initial guess, to fit
the model to the experimental data using 32 roots of equation (7). The
model results are also shown in the Figures reported in the supporting
information.
CH4 and N2 desorption could not be analysed by this technique
because the decrease in concentration dropped from the saturation
value to zero almost instantaneously. The pellets diameter and the
apparent diffusivity of CO2 in the 4A BFK studied samples are presented
in Table 3.
The dependence of apparent diffusion with temperature is shown in
Fig. 10 for the different samples. According to the ZLC model, the
macropore and crystal mass transfer resistances occur in series. Since
the size of the macropore is much greater than the size of the pores of
the crystal, the macropore diffusion is generally much faster than the
crystal diffusion. Despite that, since the radius of the crystal is very
small compared with the pellet radius, the difference in the diffusion
length between crystal and pellet may be comparable to the difference
of diffusivities of crystal and pellet. Therefore, diffusion time constant
can be an evaluation criterion to estimate the relative importance of
macropore and crystal diffusion [14,37]. If the crystal diffusion was the
controlling step of the overall diffusion rate, the diffusion time con-
stants would not vary with the pellet size. On the other hand, if the
apparent diffusion time constant in the small pellet corresponded to
that in the large pellet multiplied by the ratio of the square of the radius
of each pellet, the dominant diffusion mechanism would be macropore
diffusion [30]. It is also known that the crystal diffusion is an activated
process with exponential dependence in temperature therefore; a linear
trend is expected when representing the logarithm of apparent diffusion
as a function of 1/T. In this way, the results obtained are presented in
the left graphics of Fig. 10 as logarithm of Dap/l vs 1/T and on the right
graphics the Dap values considering the particle radius as the re-
presentative spatial dimension (that is the values of Dap/l multiplied by
the respective pellet radius) vs T. The top graphics represent the results
for two pellet sizes of 4A BFK and the bottom ones for three pellet sizes
of 4A BFK HSD. In the case of the HSD samples, it can be seen, that for
all particle sizes, the same values of Dap/l are obtained for each tem-
perature but the Dap values diverge when the particle radius is taken in
Table 3
Diffusivity coefficients for CO2 in zeolites: 4A BFK 2.5–5.0 mm, 4A BFK
1.6–2.5 mm and 4A BFK 1.6–2.5 mm HSD at different temperatures.
4A BFK 4A BFK 4A BFK HSD 1.6–2.5 mm
2.5–5.0 mm 1.6–2.5 mm
dp (cm) 0.40 0.20 0.20 0.17 0.24
T (K) Dap/l 2 × 10 4 (s−1)
308 1.9 1.8 1.7 2.2 1.8
323 2.3 2.5 3.6 3.6 3.6
373 4.4 9.8 7.8 7.6 7.8
112
Microporous and Mesoporous Materials 277 (2019) 105–114
consideration. Furthermore, the representation of logarithm of Dap/l vs
1/T presents a linear trend. These evidences suggest that crystal dif-
fusivity is the controlling mechanism. For the 4A BFK samples, the Dap
values also diverge when the particle radius is taken in consideration
but the values of Dap/l are not equal for different pellet sizes. In this
case the controlling mass transfer resistance is not clear and it appears
that both diffusivities are important.
The small differences between the obtained diffusivity values could
be due to subtle changes in the crystal structure which are not sufficient
to cause noticeable changes in the lattice parameters and which do not
significantly alter the X-ray diffraction pattern [38].
The use of 100% active adsorption matter (zeolite) does not only
lead to an increase in adsorption capacity but also to transport en-
hancement, which is in accordance with data already reported in the
open literature [4]. The preparation method of shaped binderless mo-
lecular sieves allows for more open macropore space, with reduced
transport resistance, than the one found in a binder containing shaping
[4]. In the literature, an apparent diffusion of 1.1 × 10−4 s−1 for CO2
diffusion at 303 K in zeolite 4A provided by UOP Co. was found [30],
this value is in good agreement with the one found in the present study
with a binderless 4A.
5. Conclusions
In this work, the adsorption of CO2, CH4 and N2 in binderless zeolite
4A spheres with different sizes (4A BFK 2.5–5.0 mm, 4A BFK
1.6–2.5 mm) as well as different (higher) bulk density (4A BFK
1.6–2.5 mm HSD) was studied. In order to characterize the materials,
and therefore obtain useful information for adsorption equilibrium and
adsorption kinetics properties, several techniques were employed: CO2
physisorption isotherms measured at 273 K, mercury intrusion,
Scanning Electron Micrograph (SEM), Energy Dispersive X-ray, and X-
ray Diffraction (XRD).
The adsorption equilibrium isotherms were measured using a
gravimetric method at 303, 343 and 373 K. The results show that the
adsorption equilibrium of all zeolites 4A samples were equally well
described by the same model when the adsorption capacity is given in
terms of mass of adsorbent which was expected since the three samples
have the same type of crystals. Yet, all three samples present higher
capacity than other 4A samples reported in the literature, due to the
fact of being binderless materials. The experimental data was fitted
using the Dual site Langmuir for the adsorption of CO2 and One site
Langmuir for the adsorption of CH4 and N2. The isosteric heats of ad-
sorption of this material, when comparing with the values reported in
literature, are slightly lower in the case of CO2 and N2 and slightly
higher for CH4. However, when the adsorption capacity is described by
volume of adsorbent, the high bulk density sample presents a significant
higher value. For example, from the results at 1.0 bar and 303 K an
adsorbed concentration of CO2 of 5776 mol m−3 was found for 4A BFK
HSD 1.6–2.5 mm showing a gain of 29% in comparison with the
4556 mol m−3 found for 4A BFK 1.6–2.5 mm zeolite. The adsorption
capacity described by weight is similar for all three samples. The ad-
vantages of the denser material in terms of adsorption capacity are
evident, significantly smaller equipment can be used.
The kinetic study was done by the Zero Length Column technique.
The results indicate that the crystal diffusion controls the mass transfer
of CO2 in 4A BFK 1.6–2.5 mm HSD and that for 4A BFK 2.5–5.0 mm and
4A BFK 1.6–2.5 mm both mechanisms, crystal and macropore diffusion,
are important. At 1 bar and 308 K an average apparent diffusion of
1.88 × 10−4 s−1 was found.
Declarations of interest
None.
R. Seabra et al. Microporous and Mesoporous Materials 277 (2019) 105–114

Fig. 10. Dependence of the apparent diffusivity coefficient for CO2 in zeolites 4A with temperature.

Acknowledgements qm, i maximum adsorption capacity of component i in the ad-

sorbent mol kg−1
This work was financially supported by: Project POCI-01-0145- Qp purge flowrate m3 s−1
FEDER-006984 – Associate Laboratory LSRE-LCM funded by FEDER rc crystal representative spatial dimension m
through COMPETE2020 Programa Operacional Competitividade e Rg universal gas constant J mol−1 K−1
Internacionalização (POCI) – and by national funds through FCT – T temperature K
Fundação para a Ciência e Tecnologia and Project NORTE-01-0145- Tb boiling temperature K
FEDER-000006, supported by Norte Portugal Regional Operational Tc critical temperature K
Programme (NORTE 2020), under the Portugal 2020 Partnership v molar volume of the substance in the adsorbed state m3
Agreement, through the European Regional Development Fund. mol−1
vb molar volume at the boiling temperature m3 mol−1
Notation and Glossary Vc volume of the permanent magnet, of the sample basket and
the glass wool used to hold the sample m3
b Van der Waal's volume m3 mol−1 Vs volume of the solid adsorbent m3
C instantaneous concentration mol m−3 Greek letters
C0 initial gas phase concentration mol m−3
Dap apparent diffusivity cm2 s−1 j roots of the transcendental equation
Dc crystal diffusivity cm2 s−1 ( H) heat of adsorption kJ mol−1
Dm molecular diffusivity m2 s−1 ( isosteric heat of adsorption of component i kJ mol−1
H )i
Dp pore diffusivity cm2 s−1 m difference in weight between two measurements kg
dp pellet diameter cm p porosity of the pellet
DK Knudsen diffusivity m2 s−1 ap apparent density kg m−3
H Henry's constant mol kg−1 Pa−1 g density of the gas phase at the measuring conditions (T,P) kg
J0 J1 Bessel functions m−3
K eq dimensionless equilibrium constant ads density of the adsorbed phase kg m−3
Ki adsorption constant or Langmuir constant of component i s, Hg density of the solid measured by mercury intrusion kg m−3
bar−1 sk, He skeleton solid density measured by helium pycnometry kg
K i0 adsorption constant at infinite temperature bar−1 m−3
l representative spatial dimension of the pellet m p tortuosity
L zero length column parameter List of Acronyms
ms adsorbent mass kg
Mw adsorbate molecular weight kg mol−1 BFK Binder-Free molecular sieves
n ZLC geometrical factor of the adsorbent EDS Energy Dispersive X-Ray
P pressure bar FID Flame Ionization Detector
qi adsorbed concentration of component i mol kg−1 GC Gas Chromatographer

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MFC Mass Flow Controller
SEM Scanning Electron Micrograph
PT Pressure Transducer
TCD Thermal Conductivity Detector
TT Temperature Transducer
XRD X-Ray Diffraction
ZLC Zero Length Column
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.micromeso.2018.10.024.
References
[1] D. Saha, Z.B. Bao, F. Jia, S.G. Deng, Adsorption of CO2, CH4, N2O, and N-2 on
MOF-5, MOF-177, and zeolite 5A, Environ. Sci. Technol. 44 (2010) 1820–1826.
[2] S. Cavenati, C.A. Grande, A.E. Rodrigues, Adsorption equilibrium of methane,
carbon dioxide, and nitrogen on zeolite 13X at high pressures, J. Chem. Eng. Data
49 (2004) 1095–1101.
[3] D.Y.C. Leung, G. Caramanna, M.M. Maroto-Valer, An overview of current status of
carbon dioxide capture and storage technologies, Renew. Sustain. Energy Rev. 39
(2014) 426–443.
[4] D. Mehlhorn, R. Valiullin, J. Kärger, K. Schumann, A. Brandt, B. Unger, Transport
enhancement in binderless zeolite X- and A-type molecular sieves revealed by PFG
NMR diffusometry, Microporous Mesoporous Mater. 188 (2014) 126–132.
[5] J.A. Silva, K. Schumann, A.E. Rodrigues, Sorption and kinetics of CO2 and CH4 in
binderless beads of 13X zeolite, Microporous Mesoporous Mater. 158 (2012)
219–228.
[6] J.D. Domaine, R.L. Swain, O.A. Hougen, Cation-exchange water softening rates, Ind.
Eng. Chem. 35 (1943) 546–553.
[7] G.E. Boyd, A.W. Adamson, L.S. Myers, The exchange adsorption of ions from aqu-
eous solutions by organic zeolites. II. Kinetics 1, J. Am. Chem. Soc. 69 (1947)
2836–2848.
[8] H.F. Walton, Strong Ion Exchange, F. G. Helfferich McGraw-Hill, New York, 1962 ix
+ 624 pp. Illus. $16, Science, 138 (1962) 133-133.
[9] R. Bujalski, F.F. Cantwell, Continuous desorption rate measurement from a shallow-
bed of poly(styrene–divinylbenzene) particles with correction for experimental
artifacts, J. Chromatogr. A 1048 (2004) 173–181.
[10] D. Gowanlock, R. Bailey, F.F. Cantwell, Intra-particle sorption rate and liquid
chromatographic bandbroadening in porous polymer packings I. Methodology and
validation of the model, J. Chromatogr. A 726 (1996) 1–23.
[11] S. Saunders Malcolm, B. Vierow John, G. Carta, Uptake of phenylalanine and tyr-
osine by a strong-acid cation exchanger, AIChE J. 35 (1989) 53–68.
[12] C. Costa, A. Rodrigues, Design of cyclic fixed-bed adsorption processes. Part I:
phenol adsorption on polymeric adsorbents, AIChE J. 31 (1985) 1645–1654.
[13] M. Eic, D.M. Ruthven, A new experimental technique for measurement of in-
tracrystalline diffusivity, Zeolites 8 (1988) 40–45.
[14] D.M. Ruthven, Z. Xu, Diffusion of oxygen and nitrogen in 5A zeolite crystals and
114
Microporous and Mesoporous Materials 277 (2019) 105–114
commercial 5A pellets, Chem. Eng. Sci. 48 (1993) 3307–3312.
[15] S. Brandani, Analytical solution for ZLC desorption curves with bi-porous adsorbent
particles, Chem. Eng. Sci. 51 (1996) 3283–3288.
[16] J.C. Silva, A.E. Rodrigues, Analysis of ZLC technique for diffusivity measurements
in bidisperse porous adsorbent pellets, Gas Separ. Purif. 10 (1996) 207–224.
[17] M.L. Pavlov, O.S. Travkina, B.I. Kutepov, Grained binder-free zeolites: synthesis and
properties, Catal. Ind. 4 (2012) 11–18.
[18] M.M. Dubinin, Theory of the physical adsorption of gases and vapors and adsorp-
tion properties of adsorbents of various natures and porous structures, Bull. Acad.
Sci. USSR Div. Chem. Sci. 9 (1960) 1072–1078.
[19] N.A. Al-Baghli, K.F. Loughlin, Adsorption of methane, ethane, and ethylene on ti-
tanosilicate ETS-10 zeolite, J. Chem. Eng. Data 50 (2005) 843–848.
[20] D.D. Do, Adsorption Analysis: Equilibria and Kinetics, Imperial college press,
London, 1998.
[21] D. Graham, The characterization of physical adsorption systems. I. The equilibrium
function and standard free energy of adsorption, J. Phys. Chem. 57 (1953) 665–669.
[22] N.P. Stadie, Synthesis and Thermodynamic Studies of Physisorptive Energy Storage
Materials, California Institute of Technology, 2013.
[23] F.O. Mertens, Determination of absolute adsorption in highly ordered porous
media, Surf. Sci. 603 (2009) 1979–1984.
[24] J.A.C. Silva, Separation of N/iso-Paraffins by Adsorption Processes, Universidade
do Porto, 1998.
[25] S. Brandani, C. Cavalcante, A. Guimarães, D. Ruthven, Heat effects in ZLC experi-
ments, Adsorption 4 (1998) 275–285.
[26] J.-B.W.P. Loos, P.J.T. Verheijen, J.A. Moulijn, Improved estimation of zeolite dif-
fusion coefficients from zero–length column experiments, Chem. Eng. Sci. 55
(2000) 51–65.
[27] S. Brandani, D.M. Ruthven, Analysis of ZLC desorption curves for gaseous systems,
Adsorption 2 (1996) 133–143.
[28] C.A. Grande, Propane/propylene Separation by Adsorption Processes, Department
of Chemical Engineering, University of Porto, 2004.
[29] S.C.o.t.I.Z. Association, Database of Zeolite Structures, (2017).
[30] H. Ahn, J.-H. Moon, S.-H. Hyun, C.-H. Lee, Diffusion mechanism of carbon dioxide
in zeolite 4A and CaX pellets, Adsorption 10 (2004) 111–128.
[31] Q. Liu, A. Mace, Z. Bacsik, J. Sun, A. Laaksonen, N. Hedin, NaKA sorbents with high
CO 2-over-N 2 selectivity and high capacity to adsorb CO 2, Chem. Commun. 46
(2010) 4502–4504.
[32] S. Sircar, R. Mohr, C. Ristic, M. Rao, Isosteric heat of adsorption: theory and ex-
periment, J. Phys. Chem. B 103 (1999) 6539–6546.
[33] A. Romero-Pérez, G. Aguilar-Armenta, Adsorption kinetics and equilibria of carbon
dioxide, ethylene, and ethane on 4A (CECA) zeolite, J. Chem. Eng. Data 55 (2010)
3625–3630.
[34] R. Harper, G. Stifel, R. Anderson, Adsorption of gases on 4A synthetic zeolite, Can.
J. Chem. 47 (1969) 4661–4670.
[35] X. Hu, S. Brandani, A.I. Benin, R.R. Willis, Development of a semiautomated zero
length column technique for carbon capture applications: study of diffusion beha-
vior of CO2in MOFs, Ind. Eng. Chem. Res. 54 (2015) 5777–5783.
[36] C.A. Grande, V.M.T.M. Silva, C. Gigola, A.r.E. Rodrigues, Adsorption of propane and
propylene onto carbon molecular sieve, Carbon 41 (2003) 2533–2545.
[37] H. Ahn, H.-K. Yoo, Y. Shul, S. Hyun, C.-H. Lee, Diffusion mechanism of N2 and CH4
in pelletized zeolite 4A, 5A and CaX, J. Chem. Eng. Jpn. 35 (2002) 334–345.
[38] H. Yucel, D.M. Ruthven, Diffusion in 4A zeolite. Study of the effect of crystal size, J.
Chem. Soc., Faraday Trans. 1: Phys. Chem. Condens. Phases 76 (1980) 60–70.