Article

Cite This: Ind. Eng. Chem. Res. 2019, 58, 5301−5313 pubs.acs.org/IECR

Amine Modification of Binder-Containing Zeolite 4A Bodies for Post-

Combustion CO2 Capture
Debashis Panda,† E. Anil Kumar,*,∥ and Sanjay Kumar Singh*,‡,§
†
Discipline of Mechanical Engineering, ‡Discipline of Chemistry, §Discipline of Metallurgy Engineering and Materials Science,
Indian Institute of Technology Indore, Simrol, Indore 453552, India
∥
Department of Mechanical Engineering, Indian Institute of Technology Tirupati, Tirupati 517506, India
*
S Supporting Information
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ABSTRACT: In the current study, a new type of composite

adsorbent was synthesized by amine modification of binder-containing
zeolite 4A bodies and its potential application in the post-combustion
CO2 capture was evaluated. A wide range of aliphatic straight chain
amines such as propylamine (PA), butylamine (BA), pentylamine
(PEA), and their respective branched chain amines, iso-propylamine
(IPA), iso-butylamine (IBA), and iso-pentylamine (IPEA), were used
in a smaller fraction to modify binder-containing zeolite 4A bodies.
The synthesized materials were characterized by various spectro-
analytical techniques to elucidate the effect of amine modification on
physicochemical properties of binder-containing zeolite 4A bodies and
its reactivity for CO2 capture. Among all of the studied hybrid
adsorbents, the iso-butylamine-modified binder-containing zeolite 4A
bodies (IBA-Z4A) exhibited excellent CO2 adsorption performance with a maximum adsorption capacity of 2.56 mmol g−1 at
25 °C and 1 bar of pressure. Notably, IBA-Z4A also demonstrated excellent purity (98%) and remarkably high CO2/N2
selectivity (335) as compared to the pristine binder-containing zeolite 4A bodies (24). Such enhanced CO2 adsorption capacity
and high CO2/N2 selectivity values for IBA-Z4A can be attributed to the symbiotic interactions between CO2 and amines
governed by the basicity, electron density at the N atom of amines, and the steric effect of adsorbing molecules (CO2 and N2) at
the adsorbent surface. Notably, IBA-Z4A also displayed a marginal isosteric heat of adsorption for CO2 (51 kJ mol−1) along
with the encouraging thermochemical cyclic stability over five consecutive CO2 adsorption−desorption cycles at 25 °C and 1
bar, believed to be the best suited for post-combustion CO2 capture.

1. INTRODUCTION expected to have a significant impact on the future energy

Emission of anthropogenic CO2 due to uncontrolled burning of
fossil fuels has become an important environmental problem,
which contributes up to 60% of the global warming effects.1,2
Therefore, different preferential carbon sequestration strategies
such as absorption, adsorption, membrane separation, wet
scrubbing, and cryogenic separation are extensively explored as
frontier processes.2−4 Among these well-established strategies
for post-combustion CO2 capture, the adsorption technique has
gained considerable interest due to its minimal energy
requirements and low capital cost investment.5 In particular,
pressure swing adsorption (PSA), vacuum swing adsorption
(VSA), and thermal swing adsorption (TSA) techniques are
being widely employed for CO2 capture from power plants.5 For
post-combustion CO2 capture, VSA and PSA techniques are
mostly used due to their easy process control and low-cost
equipment.6 Moreover, considering the importance of CO2,
which is no longer regarded as a waste product and is found to be
an essential source for the production of various value-added
chemicals,7a and fuel (such as methanol),7b the selection of an
economically viable carbon capture storage (CCS) technique is
solution.
While dealing with flue gas composition (ca. 70−90% N2, 10−
15% CO2, and remaining moisture), the choice of adsorbents
plays a vital role in efficient CO2 adsorption and separation.3,4,8
In addition to adsorption capacity, working capacity under the
required pressure window, the selectivity of CO2 over N2, facile
regenerability, adsorption/desorption kinetics, hydrophobicity,
and prolonged thermochemical stability are a few of the essential
criteria which make the materials suitable for post-combustion
CO2 capture.8 In recent years, various adsorbent materials, such
as zeolite,3,4,7 mesoporous silica,3 activated carbon (AC),4
metal−organic frameworks (MOFs),9 and covalent organic
frameworks (COFs),10 have been extensively explored for the
selective capture of CO2 from power-plant flue gas. Compared
with the other microporous adsorbents, zeolites offer most of the
features mentioned above, especially in the low-pressure regime
Received: August 17, 2018
Revised: February 1, 2019
Accepted: March 12, 2019
Published: March 12, 2019

© 2019 American Chemical Society 5301 DOI: 10.1021/acs.iecr.8b03958

Ind. Eng. Chem. Res. 2019, 58, 5301−5313
Industrial & Engineering Chemistry Research
along with superior CO2/N2 selectivity.11,12 Further, zeolites are
cost-effective and can be readily synthesized and some of the
zeolites (such as 4A and 5A) are produced from industrial
waste.13,14 Several zeolites such as zeolite 13X, Y, A, β, chabazite,
and ZSM are also used for separation of CO2 from N2.11 Due to
the high working capacities, zeolite 13X and NaY are widely
utilized in post-combustion CO2 capture, whereas zeolite NaA
offers excellent CO2-over-N2 selectivity compared to FAU due
to its narrow pore window.11,15
Further, amine modification of zeolites have also attracted
substantial scientific recognition as promising candidates for
CO2 adsorption in the low-pressure regime, presumably due to
symbiotic interaction of amine-CO2 and CO2-metal sites of
zeolites. 3,4,16−20 However, pore blockage and diffusion
hindrance of amine molecules into the zeolite pores are the
major hurdles in achieving high CO2 adsorption capaci-
ty.17b,18,19,20a This effect is more severe for small pores
containing zeolites such as zeolite 4A due to the steric hindrance
of amines with the pores of the zeolite.21 Therefore, zeolites
containing larger pores such as 13X, NaY, and β are widely used
for the amine modification, as these pores are easily accessible
for amine modification.16−19 In this context, the binder-
containing commercial zeolite 4A can be a better alternative
for enhanced CCS properties due to the presence of a
heterogeneous pore size distribution developed by the binders22
which can be utilized for amine modification. Notably, the
binder (such as kaolin or attapulgite) itself contains a network
(arteries) of mesopores which provides an additional pathway
for the diffusion of CO2 into the mouth of zeolite crystal pores.23
Since micropores of the crystals present inside the commercial
binder-containing zeolite 4A bodies cannot accommodate
amine molecules within it, the amine modification of the
additional larger pore created by the binder may advantageously
enhance the CO2 adsorption property and the CO2-over-N2
selectivity.24
Recent studies have shown the usage of various amines, such
as monoethanolamine (MEA), iso-propanolamine (IPPA),
tetraethylenepentamine (TEPA), and polyethylenimine (PEI),
to modify zeolites and other porous adsorbents for CO2 capture,
albeit in high loading, ca. 10−40 wt %.3,16−19 Although MEA is
well-known for the CO2 capture process, other aliphatic amines
(such as iso-butylamine, butylamine, iso-propylamine, and
propylamine) have also been reported for their high affinity
toward CO 2 molecules for the post-combustion CO 2
capture.25,26 Notably, the absorption capacity of iso-butylamine
(0.78 mol of CO2/mol of amine) for the post-combustion CO2
capture in amine-based CO2 absorption systems (also known as
the amine scrubbing process) is higher than the MEA (0.72 mol
of CO2/mol of amine).25a In particular, primary and secondary
amines interact favorably with CO2 to form ammonium
carbamate, where the basicity and electron density at the N
atom play a vital role in the selection of these amines for CO2
capture.26a In addition to that, a few studies have focused on
amine modification of binder-containing solid sorbents
(mesoporous silica) for CO2 capture, but they are limited to
presynthesis only (the aqueous binder solution mixed with the
amine-modified sorbent to make a pellet).27 For instance,
Klinthong et al.27a used polyallylamine and NaOH for making a
binder solution to construct a highly durable pellet from
powdered amine-functionalized mesoporous silica which is able
to achieve 90% CO2 recovery over the powder adsorbent. Thus,
these findings have helped to explore the above-mentioned
primary aliphatic amines for modification of commercial binder-
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containing zeolite 4A bodies by the post-synthesis technique
(dipping in amine solution) and investigate its applicability
toward post-combustion CO2 capture.
In this context, herein, the work presents a study on the
synthesis of amine-modified binder-containing zeolite 4A bodies
using a wide range of primary aliphatic amines, with good
adsorption performances for post-combustion CO2 capture.
The effects of steric hindrance and the carbon chain length of
amines on CO2 adsorption performance in amine-modified
binder-containing zeolite 4A bodies are investigated. The single
gas adsorption of CO2 and N2, selectivity of CO2 over N2, and
thermocyclic stability of these amine-modified binder-contain-
ing zeolite 4A bodies are critically explored. Moreover, the
effects of pore size and surface area on CO2 adsorption
properties have also been meticulously scrutinized in this work.
Several characterization techniques such as P-XRD, SAXS, BET,
FE-SEM, TGA, XPS, 15N NMR, and FTIR have been used to
investigate the proposed structural and chemical modification,
amine reactivity, and their effect on CO2 adsorption properties
for post-combustion applications.
2. EXPERIMENTAL DETAILS
2.1. Materials. Commercially available binder-containing
zeolite 4A bodies in the form of cylindrical pellets of
approximately 3.2 mm diameter were purchased from Sigma-
Aldrich (batch no. 334294). Aliphatic amines such as propyl-
amine (PA), iso-propylamine (IPA), butylamine (BA), iso-
butylamine (IBA), pentylamine (PEA), and iso-pentylamine
(IPEA) were procured from Sigma-Aldrich and used as received
without any further purification. Anhydrous ethanol was used as
solvent purchased from analytical CSS. The capacity of gas
adsorption measurement was conducted using high purity CO2
(99.99%) and N2 (99.99%) supplied by Inox Air Products Pvt
Ltd., India.
2.2. Preparation of Amine-Modified Binder-Contain-
ing Zeolite 4A Bodies. Prior to amine incorporation, 300 mg
of binder-containing zeolite 4A bodies (preheated under a
vacuum at 350 °C for 3 h) was soaked in 30 mL of anhydrous
ethanol under slight agitation for 20 min. After that, the
respective amines (linear chain amines, PA, BA, PEA, and
branched chain amines, IPA, IBA, IPEA) in a fixed concentration
(0.3 wt %) were added in the above suspension, and the resultant
suspension was vigorously stirred for 24 h at room temperature.
Finally, the solid adsorbent was filtered, repeatedly washed with
ethanol, and subsequently dried under a vacuum at 120 °C for 3
h. The obtained samples are designated as (x)-Z4A, where x
represents the respective amine. For example, butylamine-
modified binder-containing zeolite 4A bodies are represented as
BA-Z4A, whereas pristine binder-containing zeolite 4A bodies
are represented as Z4A throughout the manuscript. The
quantitative analysis of amine content on amine-modified
binder-containing zeolite bodies was calculated by the back-
titration technique.28 About 5 mg of amine-modified binder-
containing zeolite 4A bodies was dispersed in 100 mL of 1.0 mM
HCl solution under sonication for 30 min. After centrifugation
for 10 min, 20 mL of the supernatant was titrated with
standardized 1.0 mM NaOH solution, in the presence of
phenolphthalein indicator, to estimate the amine content in the
synthesized amine-modified binder-containing zeolite 4A
bodies.
2.3. Characterization. Powder X-ray diffraction (P-XRD)
patterns of the binder-containing zeolite 4A bodies and amine-
modified binder-containing zeolite 4A bodies were recorded on
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a Rigaku SmartLab advanced diffractometer with monochro-
matic Cu Kα radiation (λ = 0.154 nm) at a step size of 0.03° over
a 2θ range from 5 to 80°. The small-angle X-ray scattering
(SAXS) measurements were performed using Anton Paar
SAXSpoint 2.0 with monochromatic Cu Kα radiation (λ =
0.154 nm). The distance between the sample and the detector
was fixed at 1076 mm, and the region of the scattering vector (q
= 4π sin θ/λ) lay between 0.02 and 3 nm−1 corresponding to a 2θ
range of approximately 0−4.2°. The surface morphology and
pore structure of the synthesized amine-modified binder-
containing zeolite 4A bodies were determined by field emission
scanning electron microscopy (FE-SEM) using a Carl ZEISS
Supra-55 instrument. Thermogravimetric study (TGA) was
performed to analyze the thermal stability and dehydration
characteristics of the studied adsorbents using a Mettler-Toledo
TGA/SDTA851 thermal analyzer. The nitrogen sorption
isotherm and the physicochemical properties (surface area,
pore volume, pore size) of the adsorbent materials were
measured at −196 °C using a Quantachrome Autosorb iQ2
TPX automated gas sorption system. Samples were degassed at
120 °C for 3 h under a high vacuum (10−4−10−5 bar) before
analysis. The surface area of the adsorbents was calculated using
the Brunauer−Emmett−Teller (BET) equation applied to
adsorption data in the relative pressure (P/P0) range of 0.05−
0.30. The micropore surface area of binder-containing zeolite 4A
bodies was calculated by subtracting the Langmuir surface area
[obtained from the CO2 adsorption isotherm at 0 °C in the
relative pressure (P/P0) range of 0.0002−0.008] and the BET
surface area as reported by Akhtar et al.11 The total pore volume
was calculated from the amount of adsorbed N2 at P/P0 = 0.99
using the single point adsorption method and the nonlocal
density functional (NLDFT) algorithm (considering spherical
pores kernel), respectively.29 Similarly, the mesopore volume
(Vmeso) and mesopore diameter (Dp) were calculated from the
BJH method using desorption data. The above physicochemical
properties were evaluated using Quantachrome ASiQwin data
processing software. Fourier transform infrared spectra (FTIR)
of the studied adsorbents were recorded using a spectrometer
equipped with an attenuated total reflectance (FTIR/ATR
model FTIR-STD-10, PerkinElmer, MA, U.S.A) in the wave-
number range 4000−500 cm−1. 15N NMR spectra [retrieved
from heteronuclear multiple bond correlation (HMBC) experi-
ments] were recorded in CDCl3 using a Bruker Avance 400 (400
MHz) spectrometer. The detailed experimental procedure of
15
N NMR and SAXS is given in the Supporting Information.
2.4. Adsorption Measurements. The gas sorption
measurements were carried out in a Quantachrome Autosorb
iQ2 TPX automated gas sorption system equipped with highly
accurate pressure transducers and a thermostatic bath. The static
volumetric mechanism measured the amount of gas adsorbed in
the adsorbents. Before adsorption experiments, the samples
were degassed at 120 °C for 8 h under a turbomolecular vacuum
pump using a customized heating program, allowing slow
removal of moisture at low temperature, without structural
changes to samples. The CO2 and N2 adsorption capacities of
binder-containing zeolite 4A bodies and amine-modified binder-
containing zeolite 4A bodies were evaluated at 1 bar and 25 °C,
respectively. Further, an additional CO2 adsorption experiment
was carried out for binder-containing zeolite 4A bodies and the
best performing amine-modified binder-containing zeolite 4A
bodies at 1 bar and 25 °C with high degassing conditions (350
°C for 12 h).
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2.5. Adsorption Isotherm Modeling. To evaluate the
adsorption affinity between the adsorbate and the adsorbent in
the pressure range (0−1 bar), the CO2 and N2 adsorption data
were modeled by fitting them to the Toth and Sips equations
(eqs 1 and 2), respectively. The Toth isotherm is an empirical
modification of the Langmuir equation, whereas the Sips
isotherm is the combined form of the Langmuir and Freundlich
equations developed to reduce the error between experimental
data and the predicted value of equilibrium data. These models
are used to describe the heterogeneous adsorption systems,
subjected to low and high adsorbate concentration10,30
qtbtP
q=
(1 + (btP)t )1/ t (1)
qs(bsP)1/ s
q=
1 + (bsP)1/ s (2)
where P is the equilibrium adsorbate pressure (bar), q is the
adsorption capacity (mmol g−1), and qt and qs are the saturated
CO2 adsorption capacities (mmol g−1) and bt and bs are the
affinity constants for both the Toth and Sips models,
respectively. The parameters t and s are usually less than unity
and characterize the heterogeneity of the adsorption system.30
The values of the parameters of the Toth and Sips models can be
evaluated by nonlinear curve fitting of the respective isotherm
data. Henry constant (Kh) calculations were based on the virial
plots of the CO2 and N2 adsorption isotherms at 1 bar and 25 °C,
respectively, as mentioned in eq 331
q
P= exp(A1q + A 2q2 + ...)
KH (3)
where A1 and A2 are the virial coefficients and q is the adsorption
capacity (mmol g−1). A plot of ln(P/q) versus q should approach
the axis linearly as q → 0 with the intercept −ln(KH). The Henry
constant depicted the quantitative information about the
interaction strength of the adsorbate with the adsorbent at
very low coverage.31
2.6. Adsorption Thermodynamics. The thermodynamic
property such as the isosteric heat of adsorption at a given CO2
adsorption capacity (q) under isothermal condition was
calculated from the isotherm data at two different temperatures
(0 and 25 °C) by applying the Clausius−Clapeyron equation, as
represented in eq 432
ij ∂(ln P) yz
jj z
j ∂(1/T ) zz = R
qst
k {q
(4)
where qst and R are the isosteric heat of adsorption and the
universal gas constant, respectively. The difference between the
activation energy for adsorption and desorption is called the
isosteric heat of adsorption. It depends on the temperature and
surface coverage signifying the interacting binding strength
between adsorbate and adsorbent.32
2.7. Adsorbent Evaluation Parameters for CO 2
Capture. As flue gas streams emitting from coal-fired power
plants contain relatively low CO2 and high N2 concentrations,
the adsorbent must be capable of selectively adsorbing the CO2
component from the gas mixture. Further, the purity of CO2 is
also desired for developing a suitable transport and storage
infrastructure.33 Thus, in this study, adsorbents were evaluated
regarding a few essential parameters, such as selectivity of CO2
over N231 and purity of CO2 captured,33 retrieved from their
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adsorption data. The evaluation of the adsorption performance Table 1. Physicochemical Properties of the Amine-Modified
of an adsorbent from the adsorption isotherm data points for Binder-Containing Zeolite 4A Bodies
studied gas is a well-established methodology and has been used
pore volume
by various groups. 12,31−33 Pure component adsorption
selectivity (KhCO2/KhN2) was estimated as the ratio of the SBETa Dpc Vtotald Vmesoe amine content
material (m2 g−1) (nm) (cc g−1) (cc g−1) (mmol g−1)
Henry constants for respective CO2 and N2 at 25 °C (eq 5),
Z4A 37, 337b 3.4 0.140 0.138
whereas the CO2/N2 selectivity and purity of CO2 under
PA-Z4A 36 3.4 0.135 0.132 0.89
adsorption conditions were calculated at 25 °C using the IPA-Z4A 33 3.4 0.133 0.130 0.90
following equations (eqs 6 and 7)12,31,33 BA-Z4A 35 3.9 0.139 0.136 0.96
K hCO2 IBA-Z4A 32, 255b 3.8 0.125 0.123 0.98
Pure component adsorption selectivity = PEA-Z4A 35 3.4 0.135 0.132 0.94
K hN2 (5) IPEA-Z4A 32 3.4 0.127 0.118 0.91
a
BET surface area. bMicropore surface area. cMesopore diameter.
qCO /qN d
Total pore volume. eMesopore volume.
2 2
Selectivity (αCO2 /N2) =
PCO2 /PN2 (6)
The P-XRD and FESEM results suggest the intactness of
qCO structural and morphological integrity for binder-containing
Purity = 2
× 100 (%) Z4A bodies after amine modification (Figure 1 and Figure S1).
qCO + qN (7) The effect of amine(s) on the physicochemical properties of
2 2
binder-containing zeolite 4A bodies is also evaluated and listed
where qCO2 and qN2 are the amounts of CO2 and N2 adsorbed at in Table 1.
their respective equilibrium partial pressures (PCO2 and PN2).
KhCO2 and KhN2 are the corresponding Henry constants for CO2
and N2 at 25 °C. It was assumed that the flue gas was generated
at a total pressure of approximately 1 bar having a CO2
concentration of 15% and a N2 concentration of 75%. Therefore,
under these conditions, the corresponding partial pressure was
found to be 0.15 bar for CO2 and 0.75 bar for N2.33
2.8. CO2 Adsorption Capacity over Prolonged Cyclic
Testing. For the post-combustion CO2 capture, adsorbents
should not only possess a high adsorption capacity but also
display a stable cyclic adsorption performance to avoid their
frequent replacement during long-term cyclic operation. There-
fore, cyclic CO2 adsorption and desorption experiments were
conducted for the best performing adsorbent at 25 °C. After
attaining the adsorption equilibrium, the sample was degassed
under two different conditions: (i) via vacuum desorption at
different pressures (0.01 and 0.1 bar) and combination of
vacuum and thermal desorption (0.01 bar at 120 °C) for 30
min.34 The results were illustrated in the form of the adsorption
index (abbreviated as AI, %), which is defined as a percentage
ratio of the adsorption capacity of the regenerated samples to Figure 1. (a−c) FE-SEM images and (d) P-XRD patterns of Z4A, BA-
fresh samples.34 Thus, 100% AI implies that the adsorbent has Z4A, and IBA-Z4A.
not deteriorated at all during these cyclic adsorption−
desorption studies. It has been well established that, for the binder-containing
zeolite bodies, the BET surface area represents the total surface
3. RESULTS AND DISCUSSION area including the internal surface (pore) and the external
3.1. Synthesis and Characterization of Amine-Modi- surface (crystal, binder).35 On the other hand, for binder-free
fied Binder-Containing Zeolite 4A Bodies. Amine- microporous zeolites such as 4A, the surface area represents the
modified binder-containing zeolite 4A bodies are synthesized external surface area only, which is accessible for the N2
by treating a suspension of binder-containing zeolite 4A bodies molecule.35 In this context, the studied binder-containing
in ethanol with a fixed concentration of 0.3 wt % of respective zeolite 4A bodies exhibit quite a different physicochemical
amines (linear chain amines, PA, BA, PEA, and branched chain behavior than the conventional binder-free microporous zeolite
amines, IPA, IBA, IPEA), as elaborated in the Experimental 4A due to the presence of the binder. As shown in Figure 2a and
Details. The schematic diagram of amine modification and the Figure S2, all of the individual isotherms of binder-containing
molecular structure of the amines used are illustrated in Schemes zeolite 4A bodies before and after amine modification are
S1 and S2, respectively. The amine content in the synthesized classified as type IV having a well-defined plateau with modest
amine-modified binder-containing zeolite 4A bodies (Table 1) hysteresis, whereas binder-free microporous LTA type zeolite
is estimated by the titration technique, and it is inferred that the (4A, 5A) generally displays a type I isotherm.36 Moreover, it has
amine loading is equivalent in all cases (using a different been observed that the binder-containing zeolite 4A bodies
concentration of HCl), as listed in Table 1. display a higher BET surface area (37 m2 g−1) and DFT total
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Figure 2. (a) N2 adsorption−desorption isotherm, (b) BJH pore size distribution curves, (c) small-angle X-ray scattering patterns, and (d) pore-size
distribution curve obtained from small-angle X-ray scattering of Z4A, BA-Z4A, and IBA-Z4A (solid and open symbols represent adsorption and
desorption isotherms, respectively).
pore volume (0.074 cc g−1) as compared to the other binder-free
microporous zeolite 4A (typically ∼5−32 m2 g−1 11,37a−d and
DFT total pore volume ∼0.029 cc g−1),37a reported in the
literature. The binder also increases the total pore volume of the
system.37e Since the kinetic diameter of the nitrogen molecule
(0.36 nm) is comparable to the effective pore opening of zeolite
4A (about 0.4 nm), it is unable to enter into a pore (as
shrinkages of eight-membered ring (8-MR) pore window) at a
temperature of −196 °C, and consequently, it exhibits a low
BET surface area and pore volume.37a−d Therefore, the obtained
surface area of the binder-containing zeolite 4A bodies is not the
true surface area of microporous zeolite 4A powder (crystal);
rather, it is the surface area of the binder itself. Alternatively,
CO2, having a kinetic diameter (0.33 nm) less than N2, will more
easily enter into the pore opening of zeolite 4A; thus, the
Langmuir surface area is calculated for the binder-containing
zeolite 4A bodies from the CO2 adsorption isotherm at 0 °C and
found to be 374 m2/g. In addition to that, the micropore surface
area is calculated as 337 m2 g−1, which is comparable to the
findings of other research groups on microporous zeolite 4A
powder.11 It is further noted that all of the samples that display a
closed hysteresis loop (Figure 2a) in the relative pressure region
of 0.45−1.0 could be related to the capillary condensation in
mesopores.38 The presence of mesopores is probably due to the
binder (existence of nonrigid aggregates of plate-like particles),
which is in accordance with some existing reports.22a,23 It is clear
from Table 1 that the textural properties of binder-containing
zeolite 4A bodies seemed to be heterogeneous and decreased
after incorporation of amines. The reduction of surface area and
pore volume (for IBA-Z4A: total pore volume from 0.140 to
0.125 cc g−1 and mesopore volume from 0.138 to 0.123 cc g−1 in
comparison to Z4A bodies) is supposed to fill the external pores
(as generated by the binder) during the amine modification
process. Due to the difference in critical diameters between the
amine and the window aperture, it is assumed that amine
molecules fail to insert themselves into the small micropores of
the zeolite 4A units inside the binder and thus fill or clog the
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interparticle mesopores present in the binder or zeolite pore
space.20a It is anticipated that, in zeolite systems, the amine will
first clog onto pore walls rather than filling the pores, as
suggested by Cogswell et al.20a and Holewinski et al.39 Since
most of the amine molecules can be preferentially accom-
modated into the large mesopore network available in the binder
of the zeolite bodies, the mesopore volume is proportionately
decreased (Figure 2b).
It is evident that the pores which are smaller than the size of
N2 will not be detected and therefore a conventional micropore
model such as the Horvath−Kawazoe (HK) model may
underestimate the size accuracy of the micropores smaller
than 0.36 nm.37d Consequently, the Kelvin equation is not
appropriately applicable for small pores less than 1 nm.40a In this
context, a small-angle X-ray scattering (SAXS) is quite fruitful in
overlapping the range of 1−2 nm and can provide a reasonable
estimate of the pore size distribution of binder-containing
zeolite 4A bodies after amine modification (bearing both micro-
and mesopores).40b In the SAXS technique, Guinier’s law is used
to calculate the mean pore radius (referred to as structural sizes)
of the particle by applying the method of tangents (Figure
S3a).37c The Guinier equation describes the mean intensity of
the radiation scattered by a particle of any shape, averaged
through all of its possible orientations in space. As shown in
Table S1, the values of surface fractal dimension (pore diameter)
of binder-containing zeolite 4A bodies expressed as the radius of
gyration are in the mesoporous or slightly macroporous range
(51 nm), which indicates the primary particle of the sample has a
rough pore−solid interface, presumably due to the presence of
binder.37c It means that the binder circumscribed the micro-
porous particles within it. The observed and calculated SAXS
patterns (I(q) vs q) and the resultant broad pore size
distributions are shown in Figure 2c,d. The broad pore size
distribution obtained by SAXS indicates the region between
micro and meso and includes a contribution from every pore size
within the entire range.41 The observation is in good agreement
with the finding of commercial zeolite 4A reported by Du et
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Figure 3. (a, b) CO2 and N2 adsorption isotherms for binder-containing zeolite 4A bodies and amine-modified binder-containing zeolite 4A bodies at
25 °C in the pressure range: (a) CO2 adsorption isotherms in 0−1 bar; (b) N2 adsorption isotherms in 0−1 bar.

Table 2. CO2 and N2 Adsorption Capacities of Amine-Modified Binder-Containing Zeolite 4A Bodies at 25 °C

CO2 adsorption capacity N2 adsorption capacity
0.15 bar 1 bar 0.75 bar 1 bar chemical shift
−1 −1 −1 −1
adsorbent (mmol g ) (mmol g ) wt % (mmol g ) (mmol g ) 15
N δ (ppm)
Z4A 0.97 2.20 9.69 0.20 0.25
PA-Z4A 0.89 2.33 10.27 0.04 0.05 21.58
IPA-Z4A 0.96 2.43 10.68 0.07 0.09 43.74
BA-Z4A 1.14 2.48 10.89 0.04 0.06 21.95
IBA-Z4A 1.34 2.56 11.26 0.02 0.02 17.14
PEA-Z4A 0.37 1.90 8.38 0.10 0.13 20.97
IPEA-Z4A 0.68 1.91 8.39 0.09 0.12 22.06

al.37c From Figure 2c, it is quite clear that IBA-Z4A displays a
higher scattering intensity compared to Z4A, which is attributed
to its high porosity.40a,42 The development of new and smaller
pores (<2 nm) after amine modification can be observed in the
pore size distribution (Figure 2d). The new pore space
generation is apparently due to the decrease in pore number
density observed for the same pore sizes by the filling of amine,41
which is in line with the reported results.20
Further, to verify the prejudicial impact of amine modification
on textural properties, FTIR and TGA analyses are also
performed for these amine-modified Z4A bodies (Figures S4
and S5, respectively). As compared to Z4A, FTIR spectra of BA-
Z4A and IBA-Z4A display increasing intensity and broadness of
bands ranging from 3600 to 2800 cm−1, which could be due to
the overlapping of several bands including 3270 cm−1 (N−H
stretching) and 1470 cm−1 (NH2 bending) in the single region
(Figure S4b).19,43 Z4A, BA-Z4A, and IBA-Z4A exhibit
analogous thermograms with a significant weight loss (∼17%)
in the temperature range 100−160 °C, which is attributed to the
removal of moisture17a,24 and the elimination of amine. With a
further increase in temperature, the weight loss becomes
insignificant, and no weight loss is observed for the remaining
weight of 83% up to 650 °C, indicating the high thermal stability
of Z4A/amine-modified binder-containing zeolites bodies
(Figure S5).
3.2. CO2 and N2 Adsorption Studies of Amine-
Modified Binder-Containing Zeolite 4A Bodies. The
efficacy of the amine-modified zeolite bodies for post-
combustion CO2 capture applications is extensively investigated
through quantifying the CO2 and N2 adsorption capacities at the
low-pressure regime (up to 1 bar), pertaining to flue-gas-like
conditions (Figure 3). The results related to CO2 and N2
adsorption capacities of amine-modified binder-containing
zeolite 4A bodies along with the parent binder-containing
zeolite 4A bodies are listed in Table 2.
5306
The CO2 and N2 adsorption capacity of Z4A bodies is found
to be comparably lesser than the reported binder-free micro-
porous zeolite 4A (100% active material), presumably due to
lower volumetric efficiency.11 Analogously, a lower CO2
adsorption capacity was also observed by other researchers,
while dealing with the binder-containing zeolite bodies.44 In
general, the zeolite 4A based adsorbents are being degassed at a
higher temperature (300−350 °C) to get rid of the moisture.12
However, enduring such high degassing temperature after each
adsorption cycle is highly energy intensive. On the other hand,
the low-temperature exhaust gases (70−230 °C) exiting from
recovery devices in gas-fired boilers and ethylene furnaces
remain largely unutilized for electricity generation due to their
low Carnot efficiency.45 Hence, these unused low-temperature
exhaust gases can be utilized to regenerate the adsorbents. In this
context, a lower degassing temperature (120 °C) for binder-
containing zeolite 4A bodies is selected for investigating the CO2
adsorption performance to utilize the waste heat generated from
recovery devices.
On the other hand, it is observed that the studied amine-
modified Z4A bodies display enhanced CO2 adsorption
properties at 0.15 and 1 bar, respectively, at 25 °C. From Figure
3 and Table 2, it is evident that, among several amines utilized
for modification of binder-containing zeolite 4A bodies, the
branched chain amines display superior CO2 adsorption
capacities as compared to the straight chain amine-modified
binder-containing zeolite 4A bodies. Notably, among a wide
range of utilized branched chain amines, the iso-butylamine-
modified binder-containing zeolite 4A bodies (IBA-Z4A)
display the steepest increase in CO2 adsorption capacity at
0.15 bar (1.34 mmol g−1, 5.89 wt %), which further increases to
2.56 mmol g−1 (11.26 wt %) at 1 bar. Notably, IBA-Z4A also
exhibits the lowest N2 adsorption capacity (0.02 mmol g−1)
among all of the studied absorbents at 1 bar. In contrast to IBA-
Z4A, pentylamine- and iso-pentylamine-modified binder-con-
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Industrial & Engineering Chemistry Research
Figure 4. (a) CO2 adsorption isotherms for Z4A and IBA-Z4A at 0 and 25 °C. (b) Isosteric heat of adsorption of CO2 for Z4A and IBA-Z4A. (c)
Comparative chart for the isosteric heat of adsorption of CO2 of other amine-modified adsorbents.
taining Z4A bodies display a lower CO2 adsorption capacity,
presumably due to the bulky nature of pentylamine and iso-
pentylamine25a and/or narrower adsorption energy distribution,
which means amines are not able to modify the binder-
containing zeolite 4A bodies properly.46a With this under-
standing, the loading of iso-butylamine in binder-containing
zeolite 4A bodies is further varied (0.1, 0.3, and 1 wt %) to study
the effect of amine loading on CO2 adsorption capacity at 25 °C
and 1 bar (Figure S6a). Results showed that at minimal loading
(0.1 and 0.3 wt %) the CO2 adsorption capacity is better in
comparison to the higher amine loading of 1 wt %. These
findings are consistent with the earlier report of Bezerra et al.17a
At optimal minimum loading (0.3 wt %), the CO2 adsorption
capacity is found to be high in comparison to the loading of 0.1
and 1 wt % in IBA-Z4A. Further study revealed the effect of
loading (0.1, 0.3, and 1 wt %) of another amine, iso-pentylamine
(IPEA), which is closest to iso-butylamine (IBA) in terms of its
basicity, on the CO2 adsorption properties. Contrary to IBA-
Z4A, results infer no significant enhancement in CO2 adsorption
capacity for IPEA-Z4A with varying amine loading. Even with a
higher loading of 1 wt % IPEA, the CO2 adsorption is analogous
to that of 0.3 wt % IPEA (Figure S6b). These results are
consistent with the assumption that, due to the sterically bulky
nature of IPEA and its narrow adsorption energy distribution,
the pores of the binder-containing zeolite 4A bodies may be
unable to be properly modified by the amine.25a,46a It is believed
that the basicity of straight chain amines increases with the
increase in chain length (to a certain limit) due to the increase in
electron donating alkyl groups and decreases due to the steric
hindrance effect, which adversely affects the interaction of the
amines with CO2 molecules. This complexity occurs due to
5307
Article
partial coverage of the nitrogen atom by long organic chains,
owing to the lower accessibility of the lone pair of electrons,
resulting in decreased interaction with CO2.16a,46b,c On the basis
of these findings, 0.3 wt % amine loading in binder-containing
zeolite 4A bodies is believed to be optimal to achieve high CO2
adsorption capacity in binder-containing zeolite 4A bodies.
In order to further investigate the adsorbate−adsorbent
interaction, the measured pure component adsorption isotherm
data for CO2 and N2 on the studied adsorbents are fitted with the
Toth and Sips models, respectively (Figure 3 and Figure S7). All
of the fitted parameters with the normalized standard deviation
(NSD) are summarized in Table S2. The goodness-of-fit value
(R2 ∼ 0.99) for the Toth model over the entire pressure and
temperature range in amine-modified binder-containing zeolite
4A bodies indicates that CO2 molecules are efficiently adsorbed
on amine-modified Z4A bodies in multimolecular layers due to a
high degree of adsorbent surface heterogeneity.32a,33 Partic-
ularly, CO2 interacts with the lattice oxygen present inside the
zeolite framework (Lewis basic site) which acts as an adsorption
center. Since the framework of the zeolite 4A crystal lies inside
the binder, these broad ranges of pores present inside the binder
act as microreactors for the capture of CO2. Therefore, when the
amine modifies these pores, they exhibit superior CO 2
adsorption performance, due to the symbiotic interaction
between CO2 and amines.
After amine modification, the basicity of binder-containing
zeolite 4A bodies increases due to the formation of extra
adsorption centers by the presence of free −NH2 groups (Table
2). The mechanism of CO2 adsorption on amine-modified
adsorbents has been described in recent literature report-
s.16a,26,47 Recently, Yaghi et al.47b investigated the interaction
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between CO2 and the −NH2 group using solid-state NMR and Table 3. Adsorbent Evaluation Parameters for CO2 Capture
identified the formation of ammonium carbamate and carbamic
Henry constant
acid as an important species. Perinu et al.26 also established a Kh (mmol
relationship between the reactivity of a series of primary straight g−1 bar−1) selectivity
chain alkyl amines (propylamine, butylamine) and branched adsorbents CO2 N2 (KhCO2/KhN2)a αCO2/N2b purity (%)
chain alkyl amines (iso-propylamine, iso-butylamine) using 15N
Z4A 11 0.30 37 24 83
NMR spectroscopy for CO2, where the formation of carbamate
PA-Z4A 12 0.07 171 111 96
at equilibrium depends upon the basicity of the interacting
IPA-Z4A 17 0.17 100 69 93
amine. Therefore, the higher CO2 adsorption capacity observed
BA-Z4A 18 0.04 450 143 97
for IBA-Z4A bodies is in accordance with the lowest 15N NMR
IBA-Z4A 18 0.03 600 335 98
chemical shift of IBA (Table 2 and Figure S8) which may
PEA-Z4A 3 0.12 25 19 79
facilitate the efficient amine interaction with CO2.
IPEA-Z4A 6 0.15 40 38 88
3.3. Adsorption Thermodynamics and Evaluation a
Parameter of Amine-Modified Binder-Containing Zeo- Pure component adsorption selectivity. bSelectivity based on the
lite 4A Bodies for CO2 Capture. Further, to study the energy adsorption conditions (qCO2 at 0.15 bar, qN2 at 0.75 bar).
penalty associated with the regeneration of the studied
adsorbents, the isosteric heat of adsorption (Qst) is estimated
adsorbent (Figure 5a). As a result, IBA-Z4A displays excellent
for Z4A and IBA-Z4A. Figure 4a shows that there is a 10.2%
pure component adsorption selectivity of CO2/N2 measured
increase in CO2 adsorption capacity, when the temperature rises from the value of the Henry constant ratio at 25 °C (Table 3).
from 0 to 25 °C for IBA-Z4A, due to the effect of chemisorption The observed higher CO2/N2 selectivity in IBA-Z4A could be a
(forming covalent C−N bonds), which is often seen in amine- consequence of the exceptionally larger polarizability and
modified adsorbents.16b,18a,19 Concurrently, the CO2 adsorption quadrupole moment of CO2 (29.11 × 10−25 cm−3 and 4.30 ×
capacity decreases in Z4A with an increase in temperature 10−26 esu−1 cm−1, respectively) than those of N2 (17.40 × 10−25
because of the exothermic nature of physisorption (Figure 4a). cm−3 and 1.52 × 10−26 esu−1 cm−1, respectively) and the steric
Notably, the derived Qst value of Z4A bodies (38 kJ mol−1) is in effect of adsorbing molecules (CO2, N2) at the adsorbent
line with the zeolite 4A series (ca. 35−50 kJ mol−1) reported in surface.11,33 Furthermore, IBA-Z4A exhibits excellent flue gas
the literature.32b,c Furthermore, upon amine modification, IBA- normalized selectivity (αCO2/N2 = 335) along with the high VCO2/
Z4A displays a significantly higher value of Qst (51 kJ mol−1).
The large Qst value of IBA-Z4A indicates the heterogeneity and VN2 selectivity (128 at 1 bar), suggesting that high purity CO2
higher affinity of IBA-Z4A for CO2 adsorption (Figure 4b). In (98%) could be recovered from the dry flue gas (Figure 5b). It is
fact, it has been observed that there is a reasonable increment in quite obvious that generating pure CO2 would support the
Qst (13 kJ mol−1) with a little rise in CO2 adsorption capacity in reduction of high capital investment for compression, trans-
IBA-Z4A as compared to Z4A bodies, which is presumably due portation, and storage/utilization of CO2 in power plants.33
to the high carbamate formation tendency of iso-butylamine For further investigations, additional CO2 and N2 adsorption
during the chemical reaction with CO2.26b experiments were conducted for the studied binder-containing
Figure 4b displays an initial decreasing and then almost zeolite 4A bodies and IBA-Z4A at 1 bar and 25 °C with higher
stabilizing trend in Qst value with CO2 loading (indicating the degassing conditions (350 °C for 12 h). The effect of degassing
preferential occupancy of high energy sites) followed by a temperature on CO2 adsorption performance (Figure S10 and
plateau (saturation level). The Qst value (51 kJ mol−1) obtained Tables S3) is estimated. From the results, an obvious
for IBA-Z4A is lying in the very narrow range of weak enhancement in the CO2 and N2 adsorption capacity for both
chemisorption, which is at par with or even smaller than the Z4A and IBA-Z4A is observed, due to the elimination of amine
established amine-modified adsorbents as reported in the and water molecules from these adsorbents at the higher
literature (Figure 4c).48 The obtained lower Qst value of IBA- degassing temperature.12 Additionally, the higher degassing
Z4A suggests that regeneration of the adsorbents will consume temperature for adsorbents may also adversely affect the CO2/
less energy.48c N2 selectivity, due to the unhindered mobility of the adsorbing
The above results are encouraging enough to calculate the gases (CO2 and N2) in the pores of the binder-containing zeolite
Henry constant (Kh), CO2-over-N2 selectivity, and purity of the bodies. Results infer that the CO2/N2 selectivity of IBA-Z4A
amine-modified binder-containing zeolite 4A bodies to study decreases significantly to 58 under degassing at 350 °C for 12 h,
their further applicability in selective CO2 capture under flue gas in comparison to the higher CO2/N2 selectivity of 335 observed
conditions (Figure S9 as an example). under degassing at 120 °C for 8 h. Hence, the preferential
As listed in Table 3, it is found that the pure component adsorption of CO2 over N2 on IBA-Z4A makes it a suitable
candidate for selective CO2 capture from flue gas with low
adsorption selectivity of Z4A bodies (KhCO2/KhN2 = 37) is higher
energy penalty.
than the reported microporous powder zeolite 4A (ca. KhCO2/ Besides high CO2/N2 selectivity, IBA-Z4A also exhibits a
KhN2 = 19) at 25 °C (gas composition: 94.9% N2, 5.1% CO2).32b better adsorption performance during the cyclic CO 2
The reason may be due to the selection of different gas phase adsorption−desorption experiment at 25 °C and 1 bar (Figure
compositions while calculating the pure component selectivity 5c,d). While operating the experiment at moderate desorption
at low pressure. The calculated Henry constant (KhCO2) of Z4A pressure (0.1 bar), the respective CO2 adsorption capacity and
adsorption index of the spent IBA-Z4A are significantly reduced
is in accordance with the reported literature.44c It is worth to 0.62 mmol g−1 (AI = 24%) after 10 cycles of CO2 adsorption−
noticing that the observed higher KhCO2 for IBA-ZA as compared desorption (Figure S11). However, when the experiment was
to the other amine-modified Z4A and parent Z4A bodies is conducted at low desorption pressure (0.01 bar), after the initial
presumably due to the strong interaction of CO2 with the drop, the respective CO2 adsorption capacity and adsorption
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Industrial & Engineering Chemistry Research Article

Figure 5. (a) Semi-log plot of CO2 adsorption isotherm on amine-modified adsorbents at 25 °C. (b) CO2 over N2 selectivity (αCO2/N2) of studied
adsorbents. (c, d) Cyclic CO2 adsorption−desorption experiment for IBA-Z4A under different desorption conditions: (c) vacuum desorption at 0.01
bar and (d) combined vacuum and thermal desorption at 0.01 bar and 120 °C. (e) P-XRD patterns of spent IBA-Z4A before (i) and after five
consecutive CO2 adsorption−desorption cycles under desorption conditions (ii) 0.01 bar and (iii) 0.01 bar at 120 °C.

index show better values and remain stable after the 5th cycle
(1.4 mmol g−1 and 55%) with only a marginal loss in CO2
adsorption capacity even up to the 10th cycle (Figure S11). The
decrease in CO2 adsorption capacity and adsorption index in
both prior cases could be attributed to the chemical interaction
of CO2 and IBA-Z4A, where the adsorbed CO2 is unable to
desorb completely from IBA-Z4A only by decreasing the
desorption pressure. Hence, a fresh cyclic experiment (five
cycles) was conducted at 0.01 bar desorption pressure with
thermal treatment (120 °C). It is worth noticing that, at
combined vacuum and thermal desorption, the cyclic CO2
adsorption capacity is found to be almost unchanged (2.4
mmol g−1) with 96% adsorption index (Figure 5d). The stable
adsorption capacity during the following five cycles is
comparable with the other well-established amine-modified
adsorbents.49 Notably, P-XRD analysis of the spent IBA-Z4A
after cyclic adsorption−desorption displays no significant
change in the characteristic diffraction patterns, confirming the
excellent physico- and thermochemical stability of IBA-Z4A
(Figure 5e). Hence, the study suggests that the combined
vacuum and thermal treatment (0.01 bar at 120 °C) is the most
suitable desorption condition to regenerate the spent IBA-Z4A
during CO2 adsorption experiments.
3.4. Comparison of Adsorption Performance of IBA-
Z4A and Other Amine-Modified Adsorbents. In the
current study, it has been observed that, after successful amine
5309
modification of the binder-containing zeolite 4A bodies, it is
possible to achieve superior CO2/N2 selectivity under the flue
gas conditions. Further, the low utilization of amine is able to
address the conventional limitations like corrosion and high
regeneration cost for solid amine-based adsorption systems. The
upgradation of CO2/N2 selectivity and purity of adsorbents
upon amine modifications are in line with the previous literature
reports (Table S4).24,46b,50 Several studies have been conducted
by various researchers on amine-modified adsorbents to increase
the CO2/N2 selectivity. For instance, Xu et al.24 reported the
enhancement of CO2/N2 selectivity from 12.19 (parent zeolite
β) to 25.67 upon 40 wt % MEA loading in zeolite β,
predominantly due to the steric effect of adsorbate by reduction
of the adsorbent’s pore diameter and chemical adsorbate−
adsorbent interaction. Especially in the flue gas, due to
competitive adsorption, CO2 is preferentially adsorbed on
amine-modified adsorbents by displacing the preadsorbed N2
over time, which increases the CO2/N2 selectivity. This is in
agreement with the results obtained by Jadhav et al.50a and
Demessence et al.50b They evaluated the CO2/N2 selectivity for
triazolate-bridged MOF (Cu-BTTri) before and after ethyl-
enediamine modification (Cu-BTTri-en) under post-combus-
tion CO2 capture conditions and observed an enhancement in
CO2/N2 selectivity of 21−25 after amine impregnation. Unlike
amine impregnation, grafting of amine onto the surface of silica
also helps in increasing CO2/N2 selectivity. Wang et al.50c
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Table 4. Comparison of Adsorption Capacities of Various Amine-Modified Adsorbentsa

equilibrium CO2 adsorption
operating conditions capacity

support amine loading (vol/wt %) PCO2 (bar) T (°C) (mmol g−1) (wt %) ref
zeolite β MEA 40 (w) 1 30 0.77 3.38 24
zeolite Y MEA 20 (w) 1 25 1.15 5.06 18b
zeolite Y TEPA 20 (w) 1 25 1.90 7.08 18b
zeolite Y MEA 40 (w) 1 25 1.97 8.66 18b
zeolite Y IPPA 40 (w) 1 25 1.61 8.36 18b
zeolite 13X MEA 0.2 (v) 0.1 25 1.68 7.39 17a
zeolite 13X MEA 0.5 (w) 1 30 1.25 5.50 50a
zeolite 13X MEA 10 (v) 1 25 0.56 2.46 50a
zeolite 13X MEA 25 (w) 1 30 0.78 3.43 50a
AC PEHA 40 (w) 1 25 1.10 4.80 51a
Si-MCM-41 PEI 50 (w) 1 25 0.74 3.29 51b
Z4A bodies BA 0.3 (w) 1 25 2.47 10.89 this work
Z4A bodies IBA 0.3 (w) 1 25 2.56 11.26 this work
a
MEA, monoethanol amine; TEPA, tetraethylenepentamine; IPPA, iso-propanol amine; PEHA, pentaethylenehexamine; PEI, polyethylenimine;
BA, butylamine; IBA, iso-butylamine; Z4A bodies, binder-containing zeolite 4A bodies.

reported a CO2/N2 selectivity enhancement from 46 (parent
SBA-15) to 131 for (3-aminopropyl) trimethoxysilane grafted
SBA-15 under flue gas conditions (0.15 bar of CO2 and 0.85 bar
of N2). Besides, adsorbents with high N-donor molecules are
also useful to achieve high CO2/N2 selectivity. Recently, Tekin
et al.50d found an enriched CO2/N2 selectivity of 473 at 23 °C in
the microporous metal dicyanamide cluster [Co(hmt)(dca)2
(hmt, hexamethylenetetramine; dca, dicyanamide)] because of
diffusion hindrance of N2 to the small pore cavity of the
adsorbent.
Notably, apart from excellent CO2/N2 selectivity, we also
observe a much higher CO2 adsorption capacity of 2.56 mmol
g−1 (11.26 wt %) even with ∼10 times less amine loading (0.3 wt
%) in binder-containing zeolite 4A bodies as compared to
previously reported results (Table 4).17a,18b,24,48a,51 Earlier
reports revealed that amine-modified zeolite Y exhibited
enhanced CO2 adsorption capacities with high amine loading
(20−40 wt %) of MEA, IPA, or TEPA.18b Further, with other
adsorbents such as activated carbon or ordered MCM-41, at 25
°C, even with the high surface area and with high amine loading,
the observed CO2 adsorption capacities are much lower than
those obtained with IBA-Z4A in the present work (Table S5).
Moreover, the adsorbent binder-containing zeolite 4A bodies
and the respective modifying agent iso-butylamine (code
I14150) are of lower cost than the commonly used microporous
zeolite 13 X powder (or bodies) and MEA (code 398136).
Interestingly, the CO2 uptake behavior of amine-modified
binder-containing zeolite 4A bodies is found to be substantially
affected by the carbon chain length, straight/branched nature,
and electronic behavior of the aliphatic amines. The findings
have inferred that amine-modified binder-containing zeolite 4A
bodies, with iso-butylamine (IBA-Z4A), demonstrate superior
CO2 adsorption capacity (2.56 mmol g−1), high purity (98), and
excellent CO2/N2 selectivity (335) as compared to various other
amine-modified Z4A bodies. The high CO2/N2 selectivity
values can be attributed to the steric effect and strong chemical
adsorbate−adsorbent interaction. Notably, IBA-Z4A exhibits a
marginal isosteric heat of adsorption (51 kJ mol−1) at 1 bar,
suggesting the facile regenerability of IBA-Z4A and prolonged
thermocyclic stability over five consecutive cycles of CO2
adsorption−desorption. To the best of our knowledge, the
obtained pure component CO2/N2 selectivity (600) and the
CO2/N2 selectivity (335) derived from the adsorption condition
for IBA-Z4A is comparable with the best values reported for
other microporous materials. Thus, the study of amine
modification of binder-containing zeolite 4A bodies to achieve
superior CO2 adsorption capacity has demonstrated a better way
to utilize the cost-effective material binder-containing zeolite 4A
bodies as a promising adsorbent for the carbon capture storage
(CCS) process.

Hence, IBA-modified binder-containing zeolite 4A bodies (IBA-
Z4A) can be considered as a promising adsorbent for efficient
CO2 capture.
4. CONCLUSIONS
Efficient CO2 adsorption capacity over binder-containing zeolite
4A bodies is achieved by modification of a wide range of aliphatic
amines (straight and branched chain amines) in binder-
containing zeolite 4A bodies. In this study, various character-
ization techniques such as BET, SAXS, and FESEM have
confirmed the presence of a heterogeneous pore size distribution
in binder-containing zeolite 4A bodies, which are utilized for
amine modification. It is anticipated that amines are located in
the bigger pore of zeolite bodies created by the binder or filler of
zeolite crystals owing to a decrease in mesopore volume, and
therefore, it facilitates enhanced interaction with CO2.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.8b03958.
The physicochemical characterization (P-XRD, BET,
FTIR, TGA, 15 N NMR, and SAXS) for studied
adsorbents, fitting parameters for CO2 and N2 adsorption
isotherms from respective Toth and Sips models, effect of
amine loading on CO2 adsorption properties, CO2 and N2
adsorption properties for Z4A and IBA-Z4A at high
degassing temperature, and comparison of pure gas
adsorption selectivity of CO2/N2 and adsorption capacity
for IBA-Z4A with other porous materials (PDF)

5310 DOI: 10.1021/acs.iecr.8b03958

Ind. Eng. Chem. Res. 2019, 58, 5301−5313
Industrial & Engineering Chemistry Research
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: anil@iittp.ac.in.
*E-mail: sksingh@iiti.ac.in.
ORCID
Sanjay Kumar Singh: 0000-0002-8070-7350
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors thank IIT Indore, CSIR-HRDG, New Delhi, and
SERB-DST, New Delhi, for the financial support. SIC National
facility of IIT Indore is acknowledged for instrumentation
facilities. The authors thank Ms. Navjot Saini and Mr. Shyama
Prasad Pal (Anton Paar Gurgaon, Delhi) for their valuable
support in SAXS and BET characterization. The authors would
also like to thank Dr. Pratibha Sharma from DAVV Indore and
ACMS, IIT Kanpur, for providing the FTIR and XPS facility,
respectively. D.P. thanks IIT Indore for the fellowship. Dr. Rohit
Kumar Rai, Dr. Kavita Gupta, and Ms. Chinky Binnani (IIT
Indore) are acknowledged for their valuable suggestions to
understand the chemical reaction mechanism. Dr. Lakshmi
Iyengar (former visiting faculty, School of Humanities and
Social Science, IIT Indore) is highly acknowledged for her
valuable support in proof correction.
■
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5313 DOI: 10.1021/acs.iecr.8b03958

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