Article

pubs.acs.org/IECR

Thermal, Oxidative, and CO2-Induced Degradation of Supported

Polyethylenimine Adsorbents
Aliakbar Heydari-Gorji and Abdelhamid Sayari*
Department of Chemistry, Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, Ontario, K1N 6N5, Canada
*
S Supporting Information

ABSTRACT: This work examines the stability of polyethylenimine(PEI)-impregnated mesoporous silica for CO2 removal over
a wide range of conditions. The support used was a SBA-15 silica with platelet morphology and short pore channels (SBA-15PL).
The effect of long-term exposure to different gaseous streams, including carbon-free air (CFair), simulated flue gas (SFG), and
different CO2/O2/N2 mixtures on the carbon dioxide adsorption capacity was investigated. Extensive CO2 adsorption−
desorption cycling using dry and humid streams at different adsorption and regeneration temperatures was also carried out.
Based on adsorption data, as well as diffuse reflectance infrared Fourier transform (DRIFT) and 13C CP MAS NMR
measurements, it was found that PEI-modified adsorbents exhibit (i) high thermal stability at moderate temperatures, (ii) highly
stable CO2 uptake in the presence of moisture, (iii) extensive degradation in the presence of dry CO2, particularly at high
temperature, (iv) fast degradation upon exposure to CFair even at moderate temperatures, (v) excellent stability in the presence
of humidified gases containing both CO2 and O2.

1. INTRODUCTION adsorbents is a multifaceted issue, which encompasses thermal

Because, carbon dioxide (CO2) is a major greenhouse gas with
significant impact on global warming, its separation and capture
received significant attention in recent years.1 In addition, the
removal of CO2 from different gas streams is an important step
for many applications such as natural gas sweetening and air
and hydrogen purification.
CO2 removal using amine-containing adsorbents has been an
increasingly active area of research.2−20 Recent literature data
provide evidence of the great variety of adsorbents produced by
supporting amine-containing species on porous materials.
Amine groups may be bound to the silica surface via such
techniques as grafting5,6 or in situ polymerization,3 or may be
impregnated.7−19 Impregnation of polyethylenimine (PEI) is a
popular strategy because this technique is simple, cheap, and
affords high loadings. PEI-containing adsorbents exhibit high
CO2 adsorption uptake and selectivity,9,10,13,16−19 tolerance to
water vapor,13,14,16,17,25 reversibility13,17 and low energy
requirements compared to aqueous amine scrubbing.20
The CO2 adsorptive properties of amine-containing materials
in the presence of a number of gaseous compounds, such as
hydrogen sulfide,9,21 sulfur oxide,22,23 and oxygen26−30 have
been investigated. Nonetheless, most literature reports were
dominated by measurements of equilibrium or near-equilibrium
adsorption capacity of materials using pure CO2 or simulated
industrial gases. However, despite its critical importance, the
stability of PEI-impregnated materials has not been thoroughly
investigated. The lifetime of adsorbents is a key property of
equal importance as adsorption capacity, selectivity, and
kinetics, with direct impact on the economics of commercial-
scale operations. As far as PEI-supported materials are
concerned, their stability was evaluated using only a limited
number of temperature swing adsorption−desorption
cycles,8−12,16,17 which may not be sufficient to draw reliable
conclusions. Moreover, the stability of amine-containing
degradation (e.g., evaporation, decomposition), mechanical
strength, and chemical degradation induced by gaseous species,
such as SO2, NO2, O2, or CO2.
Drage et al.24 carried out accelerated deactivation experi-
ments on PEI-impregnated silica in the presence of pure CO2 at
different temperatures. Beyond 135 °C, they observed a weight
gain that they attributed to the formation of urea linkages. They
also studied the thermal stability of the adsorbent in the
presence of air and nitrogen and showed that above 135 °C, the
mass of PEI (Mw = 1800)-impregnated adsorbent decreased
rapidly, particularly in air atmosphere as a result of evaporation
and/or thermal degradation. Using both grafted and impreg-
nated amine-containing adsorbents, Sayari and Belmabkhout25
found that, in the presence of dry gases, deactivation via urea
formation occurs even under mild conditions. They also
demonstrated that the formation of urea groups may be
completely inhibited in the presence of moisture.
Bollini et al.26,27 and Heydari-Gorji et al.28 studied
independently the stability of amine-functionalized CO2
adsorbents in the presence of air at different temperatures as
a function of the nature of amine groups. Although the
oxidative degradation of supported amines was not fully
delineated on a molecular scale, several interesting findings
were reported. Grafted primary monoamine was found to be
exceedingly more stable in the presence of oxygen at high
temperature than grafted secondary monoamine. In mixed
amine-containing materials, such as grafted propyldiethylenetri-
amine, the degradation was more severe than for either
monoamines, indicating the occurrence of faster oxidative
Received: February 8, 2012
Revised: April 25, 2012
Accepted: April 28, 2012
Published: April 28, 2012

© 2012 American Chemical Society 6887 dx.doi.org/10.1021/ie3003446 | Ind. Eng. Chem. Res. 2012, 51, 6887−6894
Industrial & Engineering Chemistry Research
pathways, possibly involving both primary and secondary
amines.28 However, whether these accelerated air-degradation
experiments are relevant to CO2 adsorption in oxygen-
containing gases is yet to be explored. The idea that, in the
presence of O2 and CO2, the amine would react faster with
CO2, leading to much more air-resistant species is worth
investigating. A similar issue has been addressed in aqueous
amine scrubbing. It was found that, in the presence of CO2,
both O2 and SO2 were much less detrimental to aqueous
monoethanolamine (MEA) solution than in the absence of
CO2, presumably because of a salting out effect; that is, due to
the higher solubility of CO2, both O2 and SO2 exhibit
diminished solubility in the MEA solution, thus less interaction
with amine molecules.31
Although there are some reports dealing with thermal
degradation of PEI-modified adsorbents, 24 as well as
oxidative26−28 and CO2-induced degradation25 of amine-grafted
materials, there are no comprehensive studies on the stability of
supported PEI under different conditions. Thus, the objective
of this work was to investigate the behavior of PEI-impregnated
adsorbents in the presence of dry CO2, oxygen, and moisture at
different temperatures and under lengthy isothermal and
nonisothermal adsorption−desorption cycling. A SBA-15
mesoporous silica with platelet morphology and short pore
channels, referred to as SBA-15PL, was used as support. In an
earlier investigation,19 this material was found to be an effective
support for PEI.
2. EXPERIMENTAL SECTION
2.1. Materials and Synthesis of Adsorbents. All
chemicals were obtained from Sigma-Aldrich. Carbon dioxide
(99.99%), nitrogen (99.999%), carbon-free air (CFair), and
carbon dioxide (5% and 15%) in nitrogen were supplied by
Linde Canada.
The preparation of SBA-15 platelets was carried out
according to Zhang et al.32 Typically, 2.4 g of Pluronic P123
was dissolved in 84 mL of HCl solution (1.07 M) and stirred at
room temperature until the solution became clear. Then, 13.9 g
of decane was added while stirring the solution at room
temperature for 1 h. Finally, 0.027 g of NH4F was added under
stirring as a hydrolysis catalyst, followed by 5.1 g of tetraethyl
orthosilicate. The mixture was stirred at 40 °C for 20 h, then
transferred into an autoclave for further treatment at 100 °C for
48 h. The material was calcined at 550 °C to remove the
template.
Regarding the preparation of CO2 adsorbents, the required
amount of branched PEI (Aldrich, average Mn ∼ 423 or Mn ∼
600) or linear PEI (Polysciences Inc., Mw ∼ 2500) was
dissolved in methanol before adding the mesoporous silica
support. The resultant slurry was stirred at room temperature
until the solvent is evaporated, then the sample was further
dried at 50 °C under reduced pressure (700 mmHg). The
adsorbents were denoted as SBA-15PL-x(y), where x is the
average molecular weight of the impregnated PEI (i.e. 400, 600,
or 2500), and y represents the weight percent of PEI in the
adsorbent. The PEI loading used in this work was 55 wt %,
which was below the maximum allowable amine loading (59 wt
%) of SBA-15PL, which can be determined based on the pore
volume of the support (1.4 cm3/g) and the density of PEI (1.05
g/cm3).
All materials were characterized by nitrogen adsorption and
desorption at −196 °C using a Micromeritics 2020 apparatus.
Scanning electron microscopy (SEM) images were collected on
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a field emission JSM-7500F FESEM (JEOL) instrument,
operated at 1 KeV.
2.2. Adsorption Measurements. CO2 adsorption and
cyclic adsorption−desorption measurements in the presence of
dry and humidified feed and purge gases were carried out using
a Rubotherm magnetic suspension balance. Details about the
experimental setup and procedure are found in the Supporting
Information. To investigate the deactivation of the adsorbent in
the presence of dry CO2, after nitrogen pretreatment at 100 °C
for 90 min, the sample was exposed to dry 5% CO2 in N2 for 10
h at different temperatures in the range 85−120 °C, then to
nitrogen at the same temperature for 1.5 h to remove gaseous
and adsorbed CO2. Subsequently, the CO2 uptake was
measured at 75 °C in order to compare with the fresh sample.
For cycling experiments, the sample was pretreated in the
same way as described above, then cooled down to the
adsorption temperature before switching to a pure CO2 or
15:85 CO2/N2 stream. After 30 min of exposure, the
regeneration took place at the desired temperature under
flowing nitrogen at atmospheric pressure. To assess the effect of
moisture, the same experiment was performed, except that the
feed and purge gases used for adsorption and desorption were
bubbled through a temperature-controlled water saturator
maintained at 20 °C. The procedure was repeated over several
cycles for both dry and humid conditions.
2.3. Long-Term Exposure to CO2- and O2-Containing
Gases. The effect of long-term exposure to CFair, simulated
flue gas (SFG), and different CO2/O2/N2 mixtures on the CO2
adsorption properties of the materials was investigated using a
Rubotherm magnetic suspension balance. In a typical run, the
adsorbent was first exposed to dry N2 at 100 °C for 90 min,
then brought to the treatment temperature (Ttre), before
switching to CFair, CO2/O2/N2 (1−20% CO2, 4.5−17% O2,
balance N2), or SFG (12% CO2, 4.5% O2, 83.5% N2). After 30
h exposure, the sample was cooled to 75 °C and then exposed
to pure dry CO2 for 30 min to measure the CO2 uptake.
Regarding the thermal stability measurements, the weight
loss of the samples upon treatment in flowing N2 (110 mL/
min) at different temperatures for 30 h was monitored using a
thermogravimetric analyzer (Q500 TA Instruments).
2.4. Diffuse Reflectance Infrared Fourier Transform
(DRIFT) Spectroscopy and Nuclear Magnetic Resonance
(NMR). A Nicolet Magna-IR 550 spectrometer equipped with a
MCT detector and a Thermo diffuse reflectance cell was used
to collect DRIFT spectra. About 15 mg of powder sample was
placed in the cell and pretreated in flowing ultrahigh purity He
at 100 °C for 2 h. The DRIFT spectra were then recorded
under He atmosphere for fresh and treated materials. The
spectrum for KBr was used as background. The 13C CP/MAS
NMR experiments were conducted on a Bruker AVANCE 500.
The spinning frequency was set to 10 kHz. The contact time
was 2 ms, with recycle delays of 2 s.
3. RESULTS AND DISCUSSION
3.1. Material Characterization. A typical SEM image for
the support material is shown in Figure 1. As seen, SBA-15PL
consisted of ca. 200 nm thick particles with ca. 1 μm diameter.
The nitrogen adsorption−desorption isotherm for SBA-15PL
support (not shown) corresponded to type IV according to the
IUPAC classification, which is characteristic of mesoporous
materials.19 The surface area of the silica support was 590 m2/g,
whereas the pore volume and diameter were 1.4 cm3/g and
13.6 nm, respectively.
dx.doi.org/10.1021/ie3003446 | Ind. Eng. Chem. Res. 2012, 51, 6887−6894
Industrial & Engineering Chemistry Research
Figure 1. SEM image of SBA-15PL.
3.2. Thermal Degradation Measurements. Table 1
shows the PEI loss for SBA-15PL-x(y) after 30 h exposure to
Table 1. PEI Weight Loss after 30 h Exposure to Dry N2a
PEI weight loss (wt %)
temp.
(°C) SBA-15PL-400(55) SBA-15PL-600(55) SBA-15PL-2500(55)
75 2.6 0.3 0.0
105 n.d.b 1.0 n.d.
120 22.5 4.0 1.3
150 n.d. 10.0 5.0
a
Losses (wt %) are based on total PEI content. bn.d.: not determined.
flowing nitrogen at different temperatures for PEI with three
different molecular weights (Mn ∼ 400, 600 and Mw ∼ 2500).
As seen, the heavier PEI showed limited weight loss due to
evaporation. At 75 °C, the PEI(600 and 2500)-containing
samples did not suffer any loss, whereas SBA-15PL-600(55)
and SBA-15PL-2500(55) underwent 10 wt % and 5 wt % loss at
150 °C, respectively. As for PEI(400)-containing material, the
weight losses were 2.6% and 22.5% upon heating in nitrogen
for 30 h at 75 and 120 °C, respectively. This is mostly due to
the evaporation of tetraethylenepentamine, which represents ca.
20% of PEI-400, as indicated by the supplier (Aldrich).
Therefore, the PEI-modified adsorbents are thermally stable
under mild conditions. Higher molecular weight PEIs are
understandably more thermally stable, but they may lead to
higher diffusion resistance because of higher viscosity.
3.3. CO2-Induced Degradation. 3.3.1. Cyclic Adsorp-
tion−Desorption Measurements. Using SBA-15PL-600(55),
extensive adsorption−desorption measurements were carried
out in the presence of pure CO2 and 15:85 CO2/N2 mixture at
different temperatures in both dry and humid conditions.
Figure 2 presents the temperature swing adsorption data in the
presence of pure CO2 at two different desorption temperatures
under dry and humid conditions. As seen, after 66 cycles, using
dry feed and purge gases, the adsorbent lost ca. 40% and 52% of
CO2 uptake for regeneration under dry condition at 105 and
120 °C, respectively, which was mainly due to loss of amine
groups via urea formation (vide inf ra).25 In contrast, using
prehumidified gases (with 6%, 2%, and 1.2% relative humidity
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Figure 2. CO2 uptake during nonisothermal CO2 adsorption−
desorption cycling over SBA-15PL-600(55) in both dry and humid
conditions (adsorption at 75 °C and 1 bar using pure CO2 for 30 min
and desorption at (a) 105 °C and (b) 120 °C using pure N2 for 30
min, dew point for humid condition was 20 °C).
(RH) at 75, 105, and 120 °C, respectively) under otherwise the
same conditions, the adsorbent was stable, confirming the
effective role of water vapor in preventing the loss of amine
groups via the formation of urea. The small amount of uptake
loss (ca. 2 and 3.5%) in humid condition was consistent with
PEI evaporation loss at 105 and 120 °C, respectively.
Most CO2-containing industrial gases are dilute. For
instance, flue gas is a water-saturated mixture with typically
10−15% CO2. Therefore, the performance of SBA-15PL-
600(55) was investigated in the presence of humidified 15%
CO2 in N2 at two typical flue gas temperatures (i.e., 50 and 75
°C), and the results are shown in Figure 3 (temperature swing
adsorption at 50 °C for adsorption and 85 °C for desorption)
and Figure 4 (concentration swing process at 75 °C for both
adsorption and desorption). As seen in Figure 3, the adsorbent
was stable over 66 cycles. Moreover, because of the favorable
properties of the support, the obtained CO2 working capacity
(ca. 13.8 wt %) was one of the highest uptakes reported for
15% CO2 at 50 °C.4,12,17−19 Figure 4 provides evidence that,
under mild and humid conditions, PEI (Mn ∼ 600)-containing
adsorbents are stable over hundreds of cycles. Upon 300 cycles
totalling approximately 350 h of CO2 exposure with both
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Industrial & Engineering Chemistry Research Article

material. Assuming that this is due to the formation of urea, the

weight increase would correspond to the consumption of 7
mmol of amine groups per gram PEI. Based on 13C NMR data
(vide inf ra), the PEI has about 30% of primary amine and 40%
of secondary amines, for a total amine content of 23.2 mmol/g
PEI. Thus, the 7 mmol of amine consumed per gram PEI would
correspond to about 43% of the 16.2 mmol of primary and
secondary amines, assuming that tertiary amines (30%) are not
involved in urea formation. Yet, the CO2 uptake loss compared
to the fresh material was 68%, possibly because of the decrease
in the surface density of the remaining free amines. Similarly, at
105 °C, the amount of amines involved in urea formation was
ca. 3.5 mmol/g PEI, representing about 21% of the original
number of primary and secondary amines, yet the decrease in
CO2 uptake was 25%. Earlier work33 on CO2-deactivation of
grafted propylamine also showed that the deactivated material
Figure 3. CO2 uptake during CO2 adsorption−desorption cycling over exhibited a lower CO2/N ratio than expected based on its
SBA-15PL-600(55) in humid condition (adsorption at 50 °C and 1 bar average surface density of amine groups, indicating the
using 15:85 CO2/N2 for 30 min with 19% RH and desorption at 85 °C importance of local vs average surface density.34
using pure N2 for 30 min with 4% RH). 3.3.3. DRIFT Spectroscopy and Solid State NMR Studies.
As reported earlier, the CO2-induced degradation of the
adsorbent is associated with the formation of urea.25 In a
recent report,33 we demonstrated that contrary to grafted
propylamine (primary amine), grafted N-methyl propylamine
(secondary amine) did not undergo any adverse effect in the
presence of dry CO2, even at 200 °C. The CO2-induced
degradation of the primary amine was interpreted on the basis
of urea formation via both carbamate dehydration and, most
likely, isocyanate-amine coupling. The deactivation of mixed-
amine adsorbents such as grafted propyldiethylenetriamine was
higher than expected based on complete transformation of the
primary amine groups into the corresponding urea. To explain
this behavior, it was proposed that the primary amine-derived
isocyanate reacts with either primary or secondary amines,
leading to di- or tri-substituted ureas, respectively. Such ureas
could be cyclic or linear, depending on whether or not the two
amine groups involved belonged to the same polymer branch
Figure 4. Isothermal adsorption−desorption cycling over SBA-15PL- or not. Interestingly, in a recent report, Wu et al.35 reported
600(55) at 75 °C and 1 bar in humid condition (adsorption using that, under high temperature and CO2 pressure (180 °C, 10
15:85 CO2/N2 for 30 min and desorption using pure N2 for 40 min MPa), primary amines afford the corresponding disubstituted
with 6% RH). ureas in moderate to high yields without any catalyst. Using
mixtures of primary and secondary amines, they obtained
adsorption and desorption at 75 °C, the uptake loss was only 2 significant yields of primary amine-derived disubstituted ureas
wt %. and mixed amine-derived trisubstituted ureas, but no tetra-
3.3.2. Continuous Exposure to Dry CO2. Table 2 shows the substituted ureas from secondary amines only. It was inferred
CO2 uptake on fresh SBA-15PL-600(55) and the correspond- that the isocyanate route, which requires the presence of
primary amines, is the dominant mechanism toward the
Table 2. CO2 Uptake Loss for SBA-15PL-600(55) after 10 h formation of ureas. These findings are fully consistent with
Exposure to Dry 5% CO2 in N2 the surface chemistry we reported elsewhere.33
Moreover, using a series of ethanolamines and ethylenedi-
5% CO2/N2 adsorption at 75 °C amines (R1R2N−CH2−CH2−NR3R4), Lepaumier at al.36
exposure temp. (°C) CO2 uptake (wt %) uptake loss (%) investigated the mechanisms of amine degradation in the
fresh 12.8 presence of CO2 under the following conditions: amine, 4−5
85 12.5 2 mol/kg; CO2 pressure, 2 MPa; temperature, 140 °C; time, 15
105 9.5 25 days, stirring, 250 rpm. They reported that one of the main
120 4.1 68 degradation pathways of ethylenediamines was the formation of
imidazolidinones, which was particularly fast for diamines with
the general formula R1NH−CH2−CH2−NHR2. It is thus
ing capacity loss after 10 h exposure to dry 5% CO2/N2 at inferred that, in the presence of dry CO2, PEI-containing
different temperatures. As seen, the degree of deactivation adsorbents may deactivate through the formation of open chain
increases with increasing temperature. The weight gain for and/or cyclic ureas.
SBA-15PL-600(55) treated at 120 °C was approximately 5%, DRIFT and 13C NMR data for CO2-deactivated SBA-15PL-
corresponding to 9.1% of PEI, which represents 55 wt % of the 600(55) provide strong support to the formation of different
6890 dx.doi.org/10.1021/ie3003446 | Ind. Eng. Chem. Res. 2012, 51, 6887−6894
Industrial & Engineering Chemistry Research Article

urea linkages. The DRIFT spectrum for fresh adsorbent (Figure

5, trace a) showed absorption bands at 3360, 3285, and 1600

Figure 6. 13C CP MAS NMR spectra of fresh and CO2-degraded SBA-

15PL-600(55) at 120 °C for 10 h.

Figure 5. DRIFT spectra for SBA-15PL-600(55) before and after peaks at 160 and 163.5 ppm appeared, which may be assigned
exposure to dry 5% CO2/N2 at 120 °C for 10 h. to CO in different open chain or cyclic ureas with different
degrees of substitution. More detailed studies of urea formation
cm−1, which were assigned to asymmetric NH2 stretch, and associated mechanisms for different types of amines will be
symmetric NH2 stretch (or NH stretch of secondary amine), the topic of future work.
and NH2 deformation of hydrogen bonded amino group, 3.4. Oxidative Degradation. Table 3 shows the CO2
respectively.37 A weak shoulder at 1662 cm−1 may be assigned uptake loss on SBA-15PL-600(55) after 30 h exposure to dry
to NH3+ deformation of ammonium carbamate species
associated with CO2 adsorption from air or the protonated Table 3. CO2 Uptake Loss for SBA-15PL-600(55) after 30 h
amino group with silica surface hydroxyls.37 CH2 stretch Exposure to Dry CFair, Humidified SFG, and CO2/O2/N2
showed absorption bands at 2939, 2883, and 2816 cm−1, and Mixturesa
the band at 1458 cm−1 was assigned to CH2 deformation.37 pure CO2 uptake loss (%) at 75 °C
The material obtained after 10 h exposure to dry 5% CO2/N2
CO2/O2/N2
at 120 °C (68% deactivated, Table 2) was analyzed using
DRIFT (Figure 5, trace b). As seen, the disappearance of the treatment
1600 cm−1 band and the appearance of four new bands at 1498, temp. CFair SFG 1:17:82 5:14:81 7.5:10.5:82 20:17:63
1560, 1660, and 1702 cm−1 provide evidence for urea formation
b
50 n.d. 0.0 n.d. n.d. n.d. 0.0
in dry condition and high temperature. It is believed that all 75 6 0.1 n.d. n.d. 0.1c n.d.
these bands are attributable to different types of ureas. The 90 22 1.8 n.d. n.d. n.d. 1.8
bands centered at 1560 and 1660 cm−1 can be assigned to 100 70 n.d. 70 37 3.0d 2.6
open-chain ureas,25 whereas the bands at 1498 and 1702 cm−1 120 100e n.d. n.d. n.d. n.d. n.d.
are tentatively associated with cyclic ureas38 formed by two a
All streams except CFair were humidified using a water saturator
consecutive amine groups in a single polymer branch. controlled at 20 °C. bn.d.: not determined cAfter 120 h exposure.
d
Figure 6 shows the 13C CP/MAS NMR spectra for fresh and 50% uptake loss in the presence of 10.5:89.5 O2/N2 stream, under
CO2-degraded SBA-15PL-600(55) at 120 °C for 10 h (68% otherwise the same conditions eAfter 20 h exposure.
deactivated, Table 2). For fresh PEI, the peaks between 39 and
58 ppm are associated with the methylene groups adjacent to CFair, humidified SFG, and CO2/O2/N2 mixtures, including
primary (39−41 ppm), secondary (49−52 ppm), and tertiary CFair (0% CO2) at different temperatures. Except CFair, all
(52−58 ppm) amine groups.39 In addition, there was a small other feed gases were humidified in order to prevent the urea
signal at ca. 164.1 ppm corresponding to carbamate, due to formation, thus discriminating between CO2- and O2-induced
CO2 adsorption from ambient air. Upon CO2-deactivation, the degradations. As seen, the CO2 uptake decreased by 6% upon
13
C NMR spectrum underwent significant changes. In the CFair exposure for 30 h at 75 °C, and by 22 and 70% at 90 and
aliphatic region, signals associated with carbon atoms adjacent 100 °C, respectively. The sample was even more sensitive to air
to primary and secondary amines at 41 and 49.5 ppm, treatment at 120 °C, as it was completely deactivated upon 20 h
respectively disappeared; whereas signals at 39.3 and 46 ppm exposure to CFair. It was also observed that the adsorbent lost
developed. Using the ACD/C+H NMR Predictors software, it 16 and 25% of the loaded PEI at 100 and 120 °C, respectively,
is proposed to assign the peak centered at 39.3 to methylene compared to 1 and 4% upon N2 exposure, under otherwise the
groups adjacent to primary amines participating in the urea same conditions. In addition to temperature, the stability of
formation, while the peak at 46 is assigned to methylene groups SBA-15PL-600(55) depends on the oxygen partial pressure.
adjacent to secondary amines involved in the formation of urea. For example using 10.5:89.5 O2/N2 at 100 °C for 30 h led to
Notice that the carbons adjacent to tertiary amines at 52 ppm only 50% CO2 uptake loss. It should be noted that as the
remained unchanged, suggesting that such amines may not take degree of deactivation increased, the adsorbent turned from
part in the deactivation mechanisms. Moreover, upon CO2 white to brownish-yellow. Drage et al.24 also reported that the
degradation, the carbamate signal at 164.1 vanished, and two weight loss of PEI-1800 at about 135 °C was lower in the
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Industrial & Engineering Chemistry Research Article

presence of nitrogen than air. It is thus inferred that the loss of

CO2 uptake upon air exposure is due to a combination of
material loss and oxidative reactions. Moreover, since the
material loss under air treatment was significantly higher than
under nitrogen, it cannot be associated solely with PEI
evaporation. Rather, some oxidative decomposition must take
place. Lepaumier et al.40 reported that, under air (2 MPa, 140
°C, 15 days), ethylenediamines (similar to the repetitive units
in PEI) undergo significant “dealkylation” (N−C bond
splitting), leading to volatile compounds. Although no attempt
was made to identify such species, it is inferred that, in the
presence of air, even at moderate temperature, supported PEI
undergoes significant weight loss due to the formation of low
molecular weight amine-containing species.
To study the effect of oxygen in CO2-containing mixtures,
the material was treated with prehumidified SFG and different Figure 7. DRIFT spectra for SBA-15PL-600(55) before and after
CO2/O2/N2 mixtures with O2 concentrations ranging from exposure to dry CFair at 90 and 120 °C for 30 h.
4.5% (in SFG) to 17%. Prehumidification of the mixed gases
was carried out to prevent the CO2-induced degradation in species was observed. Moreover, with increasing the air-
order to discriminate between the effect of O2 (oxidative treatment temperature to 120 °C, the intensity of this band
degradation) and the effect of CO2 (urea formation). SBA- increased sharply. Besides, the resolution of N−H stretching
15PL-600(55) treated with humidified 1:17:82 CO2/O2/N2 bands at 3300−3400 cm−1 and NH2 deformation at 1600 cm−1
mixture at 100 °C for 30 h showed the same behavior as the decreased significantly with increasing temperature. Earlier
CFair-treated material (i.e., ca. 70% uptake loss). In contrast, work28 on the interaction of oxygen with different grafted
the material did not suffer any loss in CO2 uptake upon amines showed that single primary amine (propylamine) was
treatment with humidified SFG (12% CO2, 4.5% O2) below 75 highly resistant to oxidative degradation, whereas single
°C; however, at 90 °C, a limited loss (1.8%) was observed, secondary amine (N-methylpropylamine) and propyldiethyle-
mostly because of PEI evaporation at this temperature (Table netriamine deactivated readily and showed a similar prominent
1). SBA-15PL-600(55) also exhibited 3% uptake loss after IR band at ca. 1670 cm−1. Similarly, Calleja et al.41 monitored
exposure to humidified 7.5:10.5:82 CO2/O2/N2 for 30 h at 100 the behavior of SBA-15 grafted propylamine, propylethylenedi-
°C due to PEI evaporation loss, compared to as high as 50% amine, and propyldiethylenetriamine by DRIFT spectroscopy
loss in the presence of the same partial pressure of O2, but upon drying in air at 110 °C for different periods of time, up to
without CO2 (10.5:89.5 O2/N2), under otherwise the same 85 h. The DRIFT spectrum for the propylamine-containing
conditions. The adsorbent was also stable even in the presence material, as well as its CO2 adsorption capacity, did not show
of higher O2 content (20:17:63 CO2/O2/N2) as only 1.8 and any significant change. On the contrary, the other two materials
2.6% CO2 uptake losses were observed at 90 and 100 °C, exhibited decreasing CO2 adsorption uptakes, paralleled by the
respectively, which are associated mostly with PEI evaporation. development of an absorption band at 1667 cm−1, which was
The foregoing discussion provides evidence that, in the associated to CN species in oxime or imine groups.
presence of carbon dioxide, the material is much more stable Figure 8 shows the 13C CP/MAS NMR spectra for SBA-
toward oxygen and does not deactivate by oxidative 15PL-600(55) before and after CFair exposure at 90 and 120
degradation. It is inferred that the amine reacts faster with °C for 30 h. Parallel to the CO2 uptake loss (Table 3), the
CO2 than with O2, leading to species such as carbamate and intensity of the peaks associated with aliphatic carbons at 39−
bicarbonate, with enhanced oxygen stability. Thus, the extent of 41 ppm and 49−58 ppm decreased, and instead, a new peak at
oxidative degradation based solely on the effect of CO2-free air,
as reported earlier,26−28 does not reflect the actual limited effect
of O2 in the presence of CO2. Notice that Uyanga and Idem31
investigated the effect of O2 and SO2 on aqueous MEA in the
presence and absence of CO2. In both cases, they found that
CO2 inhibited the otherwise deleterious effect of O2 and SO2.
They explained this behavior based on the salting out effect,
whereby CO2 dissolves into the MEA solution in preference to
the other gases, thus preventing the interaction of MEA with
SO2 and O2. Although the explanation is different, the general
phenomenon is similar for CO2 absorption in amine solutions,
or adsorption on supported amine. The main practical
implication of this finding is the inference that during CO2
removal from flue gas, the amine groups convert rapidly into
carbamate (and bicarbonate) and, therefore, are preserved
against O2 attack.
DRIFT spectra for SBA-15PL-600(55) treated in dry CFair
at 90 and 120 °C for 30 h are shown in Figure 7 (traces b and
c). As seen, upon exposure to CFair for 30 h at 90 °C, a new IR Figure 8. 13C CP MAS NMR spectra of SBA-15PL-600(55) before
band at 1679 cm−1 consistent with the occurrence of a CO and after exposure to CFair for 30 h at different temperatures.

6892 dx.doi.org/10.1021/ie3003446 | Ind. Eng. Chem. Res. 2012, 51, 6887−6894

Industrial & Engineering Chemistry Research
45 ppm developed. Moreover, two peaks attributable to
different CO species at 158 and 164.1 ppm developed.
Notice that 164.1 ppm peak in the air-deactivated material at
120 °C for 30 h is very close to the peak corresponding to
carbamate species in the fresh sample. However, this signal
cannot be attributed to carbamate because the sample does not
adsorb any CO2 (Table 3).These species are similar to those
observed in air-deactivated grafted propyldiethylenetriamine.28
Lepaumier et al.40,42 reported that, in the presence of air,
ethylenediamines afford different piperazinones through deal-
kylation/oxidation followed by cyclization. Based on our
DRIFT and NMR data, there are strong indications that
species containing different CO groups such as carboxylic
acids and/or amides were formed upon oxygen deactivation of
supported PEI. However, accurate identification of these
species requires further investigation.
4. CONCLUSION
This work provides key data regarding the stability of PEI-
impregnated adsorbents for CO2 removal applications. The
effect of long-term exposure to carbon-free air, simulated flue
gas (SFG), and different CO2/O2/N2 mixtures on the CO2
adsorption capacity as well as extensive CO2 adsorption−
desorption cycling were investigated at different temperatures
in both dry and humid conditions.
It was revealed that PEI (Mn ≥ 600)-containing materials are
thermally stable at mild temperatures. Long-term exposure to
dry CO2 or extensive adsorption−desorption cycling using dry
CO2-containing gases showed that the material deactivates,
even under mild conditions. The dry CO2−induced degrada-
tion was attributed to the formation of different urea groups as
revealed by NMR and DRIFT measurements. In contrast, in
the presence of moisture, the formation of urea was strongly
inhibited and the adsorbent showed high stability. Analysis of
the adsorbents after exposure to CFair at 100−120 °C using
13
C CP MAS NMR, DRIFT spectroscopy and CO2 adsorption
measurements showed that the PEI-impregnated materials
degraded in the presence of CO2-free oxygen. On the contrary,
the adsorbent was stable after long-term exposure to wet CO2
and O2-containing gas mixtures, indicating that, in the presence
of CO2, amine groups are protected from oxygen attack,
presumably because of their rapid conversion to carbamate and
bicarbonate. These findings will play a significant role in the
design of CO2 removal processes based on adsorption over
amine-containing materials.
■
ASSOCIATED CONTENT
*
S Supporting Information
Experimental setup and procedures. This material is available
free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: abdel.sayari@uottawa.ca.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The financial support of the Canada Carbon Management
(CMC-NCE) and the Natural Science and Engineering
Council of Canada (NSERC) is acknowledged. A.S. thanks
the Federal Government for the Canada Research Chair in
6893
Article
Nanostructured Materials for Catalysis and Separation (2001−
2015).
■
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