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Institute of Chemistry, Department of Inorganic Chemistry, Faculty of Science, P. J. Safarik University, Moyzesova 11, SK-041 54 Kosice, Slovak Republic
Laboratory Madirel, Centre de St. Jrme, CNRS-Universit de Provence, Marseille, France
a r t i c l e
i n f o
Article history:
Received 12 July 2007
Received in revised form 7 March 2008
Accepted 22 April 2008
Available online 27 April 2008
Keywords:
Mesoporous silica
SBA-12
Solid amine sorbents
Carbon dioxide
a b s t r a c t
SBA-12 mesoporous silica was modied by 3-aminopropyl (AP), 3-(methylamino)propyl (MAP) and
3-(phenylamino)propyl (PAP) ligands. The electronic effects in AP, MAP and PAP ligands resulted in different surface basicity of the modied silica materials. The materials were characterized by thermogravimetry, X-ray powder diffraction, nitrogen adsorption/desorption and transmission electron microscopy. The
CO2 sorption/desorption experiments performed at 25 oC by gravimetric method showed that carbon
dioxide sorption capacities were 1.04 mmol/g for the sample SBA-12/AP, 0.98 mmol/g for the sample
SBA-12/MAP and 0.68 mmol/g for the sample SBA-12/PAP. The modied silica can be regenerated by purge
with inert gas without heating. The fastest desorption was observed for the SBA-12/PAP silica containing
amine of low basicity (pKb = 8.9). The desorption process of SBA-12/AP and SBA-12/MAP samples was
accompanied by consumption of heat evolved on adsorption, while no thermal effect was recorded on
the DTA curve of SBA-12/PAP sample.
2008 Elsevier Inc. All rights reserved.
1. Introduction
Carbon dioxide is one of the greenhouse gases whose increasing
concentration in the atmosphere is proposed to have direct linkage
to global climate changes. A great deal of effort is nowadays devoted in limiting the emissions of greenhouse gases to environment. Generally, there are three steps in CO2 management:
separation, transportation and sequestration [1,2]. Various strategies have been proposed to sequester carbon dioxide including
recently invoked sequestration by injecting carbon dioxide directly
into underground geological formations, old mines or caverns
[36]. However the key point for the sequestration is the removal
of CO2 from ue gas by a gas separation process prior to its release
to the atmosphere. The separation cost constitutes about threefourths of the total cost [1,2]. Therefore it is important to nd an
efcient and economic route to capture and separate carbon dioxide produced during various industrial processes.
At present the separation of CO2 is achieved by using solvents,
cryogenic techniques, membranes and solid sorbents [710]. The
chemical absorption by liquid alkanolamines is the most widely
developed commercial technology for CO2 separation [11]. The
reaction sequences in such systems involve formation of ammonium carbamate species under anhydrous conditions and their
transformation to ammonium bicarbonate and carbonate species
* Corresponding author.
E-mail address: vladimir.zelenak@upjs.sk (V. Zelenak).
1387-1811/$ - see front matter 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2008.04.023
359
Scheme 1.
added under vigorous stirring (500 rpm) and the resulting mixture
was stirred for 1 day at 50 oC. After this time the mixture was aged
under static conditions at 80 oC. The HCl/H2O/Brij 76/TEOS molar
ratio was 26.7/910.6/1/7.3. The solid product was ltered off,
repeatedly washed with distilled water and dried at room temperature. The surfactant was removed by calcination in air ow at
500 oC for 7 h.
The surface modication of the calcined SBA-12 was carried out
by grafting. Prior to grafting the mesoporous silica was dehydrated
at 200 oC for 3 h not to remove surface hydroxyls but adsorbed
moisture. Then 1 g of SBA-12 was dispersed in 50 cm3 of toluene
dried over zeolite sieve. 3 cm3 of the respective amine (AP, MAP
or PAP) were added to toluene and suspension was kept under reux for 20 h. The solid product was ltered off, repeatedly washed
with toluene and octane and dried at 80 oC.
2.2. Characterization
The XRD patterns were measured on a Philips PW1710 diffractometer using Co Ka radiation (1.790307 ). Infrared spectra were
recorded using Avatar FT-IR spectrometer. Thermal characterization was carried out using STA Netzch 409PC apparatus under dynamic conditions with heating rate 9 oC/min in atmosphere of air
(20 cm3/min). Nitrogen adsorption/desorption experiments were
measured with a Quantachrome Autosorb Automated Gas Sorption
System at 77 K. Prior to adsorption, samples were outgassed under
vacuum for 24 h at 110 oC. The HRTEM micrographs were taken
with a Jeol 3000 microscope. Elemental analyses were performed
with FlashEA 1112 elemental analyser (ThermoFinnigan).
The CO2 sorption capacities were determined by a thermogravimetric balance Netzch 409PC using the sample sizes of 10 mg. The
10% CO2/N2 certied gas mixture, purchased from Linde gas, was
used for the sorption study. The composition of the mixture resembled the concentration of CO2 in the ue gas, where concentration
is ranging from 10% to 15% [22]. The ow rate of CO2/N2 mixture
was 20 cm3/min. Initial activation of the grafted samples was performed by heating in inert gas (Ar) to 110 oC.
3. Results and discussion
3.1. Characterization of SBA-12 mesoporous matrix
Fig. 1 shows the XRD pattern of calcined SBA-12 mesoporous
silica. A strong peak with d-spacing of 49.8 , typical of SBA-12
material [23], was observed in the XRD pattern. The pattern avoids
an unequivocal assignment of the symmetry due to the presence of
only one peak. The HRTEM micrographs showed predominantly
hexagonal phase, with small fraction of cubic phase (upper right
part of Fig. 2a), showing intergrowth of hexagonal (hcp) and cubic
(ccp) phases, typical for SBA-12 material [23,24]. Fig. 2 shows that
the prepared material has an excellent periodicity of mesopores
with mean pore size approximately 3.5 nm.
Nitrogen adsorption/desorption isotherms of SBA-12 sample
(Fig. 3) are of type IV without hysteresis. The initial part of the
adsorption isotherm corresponds to adsorption in the micropores
and formation of the multilayer lm on the pore walls. The
360
isotherm shows a well dened adsorption/desorption step between partial pressures P/P0 of 0.20.4, indicative of the lling of
mesopores. The prepared SBA-12 has well-dened uniform pore
dimensions, with an average pore size of 38 and a pore volume
0.842 cm3/g. BET surface area was 1347 m2/g.
3.2. Characterization of amine-modied materials
The XRD measurements of the modied materials showed that
long-range order of the materials was retained after the modication (see Fig. 4). The diffraction peaks of grafted materials occur at
similar angle in comparison with pure SBA-12, indicating no substantive change in the mesoporous matrix after silanization treatments. The decrease of intensity of diffraction peak in grafted
materials was observed due to partial lling of the mesopores by
the amines [2,21].
The modication of the SBA-12 silica signicantly affected the
N2 uptake and BET surface area in the modied materials (Fig. 5).
The sorption experiments yielded BET surface area of 416 m2/g
for SBA-12/AP sample, 317 m2/g for SBA-12/MAP and 381 m2/g
for SBA-12/PAP sample. The pore radius in the grafted samples
was about 1.2 nm.
The thermal stability of the samples was characterized by thermogravimetric analysis. Fig. 6 shows TG/DTA curves of SBA-12/AP,
SBA-12/MAP and SBA-12/PAP samples during heating in air. The
mass loss between room temperature and 200 oC corresponds to
liberation of adsorbed moisture. It is to note, that mass loss in this
361
Fig. 5. Nitrogen adsorption isotherms of AP, MAP and PAP modied SBA-12 silica.
Table 1
Results of elemental analysis and calculated amine surface densities in the prepared
amine-modied SBA-12 silica samples
Sample
Fig. 6. TG/DTA curves of SBA-12/AP (solid line), SBA-12/MAP (dashed line) and SBA12/PAP (dot-dashed line) during heating in air.
SBA-12/AP
SBA-12/MAP
SBA-12/PAP
Element content
C%
H%
N%
9.79
12.17
18.82
2.59
2.87
2.52
2.98
3.02
2.19
Amine
concentration
(mmol/g)
2.13
2.16
1.56
0.94
0.97
0.70
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Fig. 8. Carbon dioxide sorption and carbon dioxide sorption rate on SBA-12/AP
(solid line), SBA-12/MAP (dashed line) and SBA-12/PAP (dot-dashed line).
Fig. 7. FT-IR spectra of the samples (a) SBA-12/AP, (b) SBA-12/MAP, and (c) SBA-12/
PAP.
R1 R2 NH
CO
2
R1 R2 NH !
R1 R2 NH
2
R1 R2 NCO
2
PAP is a weaker base (pKb = 8.9) [28]. This property agrees with
the lower sorption capacity of carbon dioxide observed for PAP
modied material.
On the other hand, the electron donating methyl group is supposed to make MAP a stronger base than the primary amine
(AP). However the real situation is more complicated involving a
steric hindrance effect. The overall net result of the combination
of the electron donating and steric effects is that the secondary
amines are not in general stronger bases than primary amines
and therefore AP and MAP are of approximately equal basicity
pKb 4. Thus the small difference in carbon dioxide sorption
capacity observed for AP and MAP modied samples may be a consequence of steric hindrance and the lower accessibility of lone
electron pair of MAP, which may result in lower experimental carbon dioxide uptake observed by MAP modied silica in comparison
with AP modied silica.
These results were also conrmed in our recent work dealing
with measurement of isosteric adsorption heats of carbon dioxide
sorption on SBA-15 modied by AP, MAP and PAP [29]. With the
silica samples containing AP and MAP ligands (pKb 4) the enhanced values of qst at low surface coverage proved the strength
of the bond formed between CO2 molecule and amine group. On
the other hand, low values of qst observed for pure silica sample
and the sample containing PAP ligand indicated week interaction
of CO2 molecule with PAP or with pure silica surface [29].
It is to note, that we have performed the experiments in dry
conditions due to experimental set-up of our commercial apparatus. However the presence of water can further increase the sorption capacity since carbamate formed during the reaction of
primary and secondary amines with carbon dioxide can further react with CO2 and H2O to form bicarbonate
R1 R2 NCO
2 2H2 O CO2 ! R 1 R 2 NH2 2HCO3
impregnated MCM-41, on the other hand the moisture did not hinder it as was observed with zeolite 13X [18]. Moreover the DEA
impregnated MCM-41 showed good cyclic stability and maintained
its capacity for CO2 better than zeolite 13X tested at the same con-
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