Microporous and Mesoporous Materials 145 (2011) 146–149

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Microporous and Mesoporous Materials

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

Degradation of amine-supported CO2 adsorbents in the presence of

oxygen-containing gases
Aliakbar Heydari-Gorji, Youssef Belmabkhout, Abdelhamid Sayari ⇑
Department of Chemistry, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5

a r t i c l e i n f o a b s t r a c t

Article history: Three samples containing grafted primary, secondary and tertiary monoamines (pMono, sMono and
Received 16 March 2011 tMono) as well as a triamine-grafted material (TRI) with both primary and secondary amines were
Received in revised form 6 May 2011 exposed to flowing air at 120 °C for 30–40 h. It was found that pMono and tMono were stable as evi-
Accepted 7 May 2011
denced by CO2 adsorption measurements as well as infrared and NMR data, whereas sMono and TRI
Available online 13 May 2011
adsorbents exhibited extensive deactivation. Infrared data showed the development of an absorption
band at 1665–1680 cm 1 whose intensity increased with the degree of oxidative degradation. However,
Keywords:
only minor changes occurred in the corresponding 13C CP/MAS NMR spectra. The findings were discussed,
Oxidative degradation
CO2 adsorption
and a tentative explanation was provided.
Amine-functionalized silicas Ó 2011 Elsevier Inc. All rights reserved.
Stability

1. Introduction key step in many current and potential gas separations. This in-
cludes air purification prior to cryogenic separation of nitrogen
Because of their high CO2 adsorption uptake at low pressure [1], and oxygen, and CO2 removal in closed-circuit breathing systems.
high selectivity toward CO2 in a wide range of concentration [2], Several industrial gases such as flue gas and biogas that could be
their tolerance to water vapour [3,4], and their low energy require- treated via CO2 adsorption may also contain different amounts of
ments [5], supported amines are among the most promising mate- oxygen. Moreover, using air as a low cost purge gas during CO2
rials for CO2 removal in industrial gases, especially for low desorption in a cyclic operation may also be contemplated. It is
temperature and low pressure applications [6,7]. Most work re- thus important to investigate the effect of oxygen on supported
ported to date was dominated by measurements of equilibrium amines under appropriate conditions.
or near-equilibrium adsorption data using pure CO2 or simulated Our group developed a CO2 adsorbent based on triamine grafted
gas mixtures. However, despite its critical importance, the stability on pore-expanded MCM-41 silica (TRI-PE-MCM-41) [16,17]. Earlier
of the materials has been mostly ignored. The term ‘‘stability’’ may contributions dealt with the effect of water vapour [8], SO2 [10],
include the behavior of the material during long-term operation and H2S [9] on the CO2 adsorptive properties of TRI-PE-MCM-41.
under specific conditions, or its tolerance to a number of gaseous In particular, we reported on the beneficial effect of water vapour
compounds, such as water vapour [8], hydrogen sulfide [9], sulfur not only on the CO2 adsorption capacity, but also on the stability of
oxide [10], oxygen [1,4] and CO2 [8]. the material as it was found to inhibit the formation of CO2-
Although oxidative degradation of amines has been studied induced amine coupling into urea [8]. Sulfur dioxide had a delete-
in depth in association with CO2 absorption in amine solutions rious effect on CO2 adsorption [10], whereas H2S was found to
[11–15], there are no studies on the stability of supported amines compete with CO2, but without any lasting effect [9]. Oxygen
in the presence of oxygen at high temperature. The adverse effect was used only in binary and ternary mixtures to evaluate the selec-
of oxygen observed in gas–liquid systems (CO2 absorption) may tivity vis-à-vis CO2 [1,18,19] or the removal of CO2 from air [1], but
also occur for gas–solid processes (CO2 adsorption), although there no attempt was made to look into the effect of oxygen upon
are fundamental differences in the nature of typically alkanolam- lengthy exposure at relatively high temperature on the adsorption
ines used in absorption and mostly (poly)alkylamines used for of CO2. Thus, the objective of this contribution was to investigate
adsorption. Removal of CO2 in oxygen-containing mixtures is a the stability of amine-supported CO2 adsorbents in the presence
of air at different temperatures as a function of the type of amine
⇑ Corresponding author. Tel.: +1 613 562 5483; fax: +1 613 562 5170. groups. In addition to TRI-PE-MCM-41 mentioned above, this study
E-mail addresses: [email protected], [email protected] included materials containing single primary, secondary and ter-
(A. Sayari). tiary amines.

1387-1811/$ - see front matter Ó 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2011.05.010
 A. Heydari-Gorji et al. / Microporous and Mesoporous Materials 145 (2011) 146–149 147

2. Experimental 3. Results and discussion

2.1. Materials and synthesis The main structural characteristics of the prepared materials
are listed in Table 1. Table 2 shows the CO2 uptake on fresh mate-
All chemicals were obtained from Sigma–Aldrich. Carbon diox- rials and the corresponding capacity loss after 30 h exposure to
ide (99.99%), nitrogen (99.999%) and carbon-free air (CFair) were CFair at different temperatures. The primary monoamine-contain-
supplied by Linde Canada. ing sample did not suffer any loss in CO2 uptake upon air-treat-
The detailed preparation procedure for amine-grafted PE-MCM- ment below 120 °C, with limited loss (7.5%) at this temperature.
41 may be found elsewhere [3,16]. Briefly, samples referred to as As for sMono, the CO2 uptake decreased by 5.3% upon CFair expo-
pMono, sMono, tMono and TRI were prepared by surface grafting sure for 30 h at 90 °C, and 32% at 120 °C. Upon CFair treatment in a
of 3-(aminopropyl)trimethoxysilane, trimethoxy[3-(methyl- fixed-bed at 140 °C for 40 h, sMono lost as much as 86% of its CO2
amino)propyl]silane, (N,N-dimethylaminopropyl)trimethoxysilane adsorption capacity. The TRI sample was even more sensitive to air
and N1-(3-trimethoxysilylpropyl) diethylenetriamine. After drying treatment, with CO2 uptake losses of 5%, 47%, and 94% upon expo-
PE-MCM-41 in a vacuum oven at 120 °C, the support material was sure to CFair for 30 h at 70, 90, and 120 °C.
loaded into a multi-neck glass flask containing 150 mL of toluene. DRIFT spectra for samples treated in a fixed-bed reactor under
Once a homogeneous mixture was produced, 0.4 mL of distilled flowing CFair for ca. 40 h at 120 °C are shown in Fig. 1. As seen,
deionized water per gram of PE-MCM-41 was added and left stir- the spectra associated with pMono and tMono did not undergo
ring for 30 min. The glass flask equipped with condenser was then any significant change, although a low intensity peak appeared at
submerged in a silicon oil bath set at 85 °C using a temperature- 1665 and 1677 cm 1, respectively. This is consistent with the fact
controlled stirring hotplate with an external temperature probe. that the two materials were air-stable under these treatment
Mono-aminosilanes (2 mL per gram of silica) or triamine-silane conditions. In contrast, upon exposure to CFair for 30 h at 120 °C,
(3 mL per gram of silica) was subsequently added to the mixture sMono exhibited a new IR band at 1668 cm 1. Moreover with
and left stirring for 16 h, and then the product was filtered and increasing the air-treatment temperature to 140 °C, the intensity
washed with toluene and pentane. The recovered solid was dried of this band increased sharply. As for the TRI sample, it developed
at room temperature overnight. a similar IR band at 1674 cm 1, in addition to the disappearance of
All materials were characterized by nitrogen adsorption and a band at 2826 cm 1 accompanied by a decrease in the resolution
desorption at 196 °C using a Micromeritics 2020 apparatus. of N–H stretching bands at 3300–3400 cm 1. Thus, it is clear that
Nitrogen content was determined by elemental analysis using a the occurrence and intensity of the ca. 1670 cm 1 IR band is asso-
Carlo Erba EA1100 CHNS elemental analyzer. ciated with the material oxidative degradation upon exposure to
air at high temperature.
In situ DRIFT data shown in Figures S1, S2, and S3 (Supporting
2.2. Long-term exposure to carbon free-air
information) are in general agreement with Fig. 1. Consistent with
the high air-stability of pMono, its DRIFT did not show any signif-
The effect of long-term exposure to CFair on the CO2 adsorption
icant change upon air treatment. In contrast, sMono exhibited a
capacity of the materials was investigated using a Rubotherm mag-
gradual development of an absorption band at ca. 1668 cm 1, sim-
netic suspension balance, described elsewhere [17]. In a typical run,
ilar to Fig. 1. Moreover, in situ FTIR data for TRI were comparable to
a sample adsorbent was first pretreated in dry nitrogen at 120 °C for
those of the sample treated in a fixed-bed reactor, i.e., formation of
2 h, cooled to 55 °C and then exposed to pure dry CO2 for 30 min to
a band at 1674 cm 1 whose intensity increased as a function of air-
measure the CO2 uptake for the fresh materials before exposure to
treatment temperature. Note that as the degree of deactivation
CFair. The temperature was then increased under flowing CFair up
to a temperature (Tox) in the range of 70–120 °C for 30 h. Subse-
quently, it was treated again in dry nitrogen at 120 °C for 2 h, cooled
to 55 °C, and exposed to pure CO2 for 30 min. The materials were
Table 1
designated as TRI or xMono with x = p, s or t depending on the nat- Structural properties of materials.
ure of the monoamine, followed by ‘‘Fresh’’ or ‘‘Tox’’ for samples ex-
Materials SBET (m2/g) Vp (cm3/g) Dp (nm)
posed to nitrogen at 120 °C for 2 h, then to CFair at Tox for 30 h,
respectively. Alternatively, samples were treated in a fixed-bed PE-MCM-41 1153 2.81 11
reactor under flowing CFair for ca. 40 h at different temperatures TRI 367 0.87 9.4
pMono 420 0.65 7.2
before DRIFT, 13C CP/MAS NMR and CO2 adsorption measurements. sMono 471 0.72 6.3
tMono 519 1.05 7.5

2.3. Diffuse Reflectance Infrared Fourier Transform (DRIFT) and

Nuclear Magnetic Resonance (NMR)

Table 2
A Nicolet Magna-IR 550 spectrometer equipped with a MCT
CO2 uptake loss after 30 h exposure to dry CFair at 120 °C.
detector and a Thermo diffuse reflectance cell was used to record
DRIFT spectra. About 15 mg of powder sample was placed into Materials CO2 uptake at 55 °C (wt.%) Uptake loss (%)
the cell and pretreated in flowing ultrahigh purity He at 120 °C pMono-Fresh 9.3 –
for 2 h. The DRIFT spectra were then collected under He atmosphere pMono-120 8.6 7.5
sMono-Fresh 5.6 –
for fresh materials. Subsequently, in situ oxidative treatment was
sMono-90 5.3 5.4
performed using CFair (30 mL/min) and the temperature was in- sMono-120 3.8 32
creased stepwise for n hours up to 120 °C and DRIFT spectra were sMono-140a 0.75 86
recorded. The spectrum for KBr was used as background. The 13C TRI-Fresh 10.1 –
CP/MAS NMR experiments were conducted on a Bruker AVANCE TRI-70 9.6 5.0
TRI-90 5.4 47
500. The spinning frequency was set to 10 kHz. The contact time
TRI-120 0.6 94
was 2 Ms, with recycle delays of 2 s. The time for data collection
a
ranged from 7 to 16 h. This sample was exposed to CFair in a fixed-bed reactor at 140 °C for 40 h.
148 A. Heydari-Gorji et al. / Microporous and Mesoporous Materials 145 (2011) 146–149

27.5
10.5
44.8
1677
3 2
4
tMono-120
Absorbance (a.u.)

164.6
tMono-Fresh
2933

pMono-120
2864

1600
1665
3295
3363

pMono-120

22.7
pMono-Fresh
pMono-Fresh
3500 3000 2500 2000 1500 1000
-1
Wavenumber (cm ) 200 150 100 50 0 -50
Chemical shift (ppm)
b
1600
1674

1462
2935
2880
2826

Fig. 2. 13C CP MAS NMR spectra of pMono before and after exposure to CFair at
3320
3370

120 °C for 40 h.

TRI-120 no before and after exposure to CFair for 40 h at 120 °C, shown in
Absorbance (a.u.)

Fig. 3 exhibit three peaks at ca. 11, 24, and 54 ppm assigned to pro-
TRI-Fresh
pyl chain carbon atoms as indicated, and a peak at ca. 34 ppm
1668
2933

1614
2884

attributable to –NH–CH3. The carbamate peak at ca. 165 ppm is

2795
3308

understandably small. Even sMono-140, which was exposed to

CFair in a fixed bed reactor for 40 h at 140 °C, and lost ca 86% of
sMono-140*
CO2 uptake, not only showed similar 13C NMR spectrum (not
sMono-120 shown), but similar weight loss as the fresh sample upon thermal
decomposition in a thermogravimetric analyzer. Owing to the
sMono-Fresh extensive loss in adsorption capacity, it was rather surprising that
the 13C NMR spectrum did not undergo any significant changes.
With regard to TRI, Fig. 4 shows the 13C CP/MAS NMR spectra
3500 3000 2500 2000 1500 1000 for the sample before and after exposure to CFair for 30 h at differ-
-1
Wavenumber (cm ) ent temperatures. The signals below 70 ppm were assigned to the
different carbon atoms of the triamine-silane as indicated. Except
Fig. 1. DRIFT spectra for (a) pMono, tMono and (b) sMono and TRI before and after for the line-broadening at ca. 50 ppm, no major changes occurred
exposure to CFair at 120 °C for 40 h. (⁄) sMono treated in a fixed-bed reactor at
even upon extensive air-degradation. Nevertheless, as the degree
140 °C for 40 h.
of deactivation increased, the carbamate peak at ca. 165 ppm
broadened and a new peak at ca. 158 ppm appeared. This peak
increased, sMono and TRI adsorbents changed colour from white to could be associated with different C@O or C@N species such as car-
brownish-yellow. boxylic acids and imines [20].
Nitrogen content data for all samples before and after exposure
to CFair are shown in Table 3. As seen, there is little variation, if
23.6
11

any, in nitrogen content despite the significant loss of CO2 uptake.

34

Although air-treated TRI showed some decrease in nitrogen con-

54

tent, it was significantly lower than the decrease in CO2 uptake. 3 2

5
Fig. 2 shows the 13C CP/MAS NMR spectra for pMONO before 4
and after CFair exposure at 120 °C for 40 h. In addition to the three
signals corresponding to the propyl chain, there was a small signal
164.6

at ca. 165 ppm corresponding to carbamate, due to CO2 adsorption

sMono-120
from ambient air [8]. Consistent with the stable CO2 uptake, there
was no change in the NMR spectrum. The 13C NMR spectra for sMo-

Table 3
Elemental analysis of the materials before and after exposure to dry CFair at 120 °C.

Materials Elemental analysis

sMono-Fresh
N (mmol/g) C (mmol/g)
pMono-Fresh 4.3 13.6
pMono-120 4.2 13.7 200 150 100 50 0 -50
sMono-Fresh 3.8 14.9
sMono-120 3.5 14.4
Chemical shift (ppm)
TRI-Fresh 7.1 17.1
TRI-120 5.8 16.5 Fig. 3. 13C CP MAS NMR spectra of sMono before and after exposure to CFair at
120 °C for 40 h.
 A. Heydari-Gorji et al. / Microporous and Mesoporous Materials 145 (2011) 146–149 149

indicates that the backbone of the grafted species is most likely

62
50
42

22
10
preserved even at very high deactivation. Although, we are at a loss
1, 5, 6, 7 2 to delineate the dramatically different behaviours of primary and
164.6 3 secondary amines upon exposure to air at high temperature, the
158
occurrence of species such as imine (1), carbamic acid (2) and pos-
4
sibly nitrone (3) cannot be ruled out. This will require further
TRI-120 investigation.
8

TRI-90

TRI-70

TRI-Fresh
In conclusion we demonstrated that primary monoamine is
exceedingly more stable than secondary amine and also mixed
200 150 100 50 0 -50 amine-containing materials in the presence of oxygen at high tem-
Chemical shift (ppm) perature. The oxidative degradation of mixed amine-containing
compounds such as TRI, may involve both primary and secondary
Fig. 4. 13C CP MAS NMR spectra of TRI before and after exposure to CFair for 30 h at
different temperatures. amines. However, interpretation of such findings at the molecular
scale has so far been elusive.
As stated earlier, oxidative degradation of alkanolamines in
solution has been investigated extensively [11–15]. Lepaumier Acknowledgments
et al. [12] treated a number of ethanolamines and ethylenediam-
ines in the presence of air under severe conditions (2 MPa, The financial support of the Natural Science and Engineering
140 °C, 15 days). In all cases, the degree of deactivation was less Council of Canada (NSERC) is acknowledged. A.S. thanks the Fed-
than 22%, indicating that the oxidative degradation of amines in eral Government for the Canada Research Chair in Nanostructured
solution at a typical concentration of 4 mol/kg is a much slower Materials for Catalysis and Separation (2001-2015).
process than the degradation of amine-supported materials. This
is most likely related to the limited solubility of oxygen in amine
Appendix A. Supplementary data
solutions. Many different processes, often triggered by the hydro-
xyl group have been identified [11–15]. Moreover, in a separate
Supplementary data associated with this article can be found, in
study, Lepaumier et al. [21] investigated the oxidative degradation
the online version, at doi:10.1016/j.micromeso.2011.05.010.
of several tertiary polyalkylamines with 2–4 carbon chains be-
tween the amine groups. Interestingly, they found that triamine
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