Article

pubs.acs.org/IECR

Stability of Supported Amine Adsorbents to SO2 and NOx in

Postcombustion CO2 Capture. 2. Multicomponent Adsorption
Fateme Rezaei and Christopher W. Jones*
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive, Atlanta, Georgia 30332, United
States
*
S Supporting Information

ABSTRACT: Packed bed CO2 adsorption breakthrough experiments using both amine-impregnated and amine-grafted silica
adsorbent materials in the presence of SO2, NO and NO2 impurities are reported. The effects of temperature, feed concentration
and adsorbent amine loading on the dynamic adsorption capacity of the adsorbents are evaluated by performing dual component
SO2/CO2, NO/CO2 and NO2/CO2 coadsorption experiments as well as three component SO2/NO/CO2 adsorption
experiments. Although SO2 is found to significantly influence the dynamic CO2 capacity of aminosilica adsorbents, the obtained
results confirm the long-term stability of the adsorbents during SO2/CO2 coadsorption runs when the bed is not allowed to fully
saturate with SO2. On the other hand, little competitive effect of NO on CO2 adsorption is observed in any case. This is due to
the decreased affinity of amine-based adsorbents toward NO as opposed to SO2. The more reactive nitrogen oxide, NO2, is
shown to have a minimal impact on CO2 adsorption when it is present at low levels in the simulated flue gas. Among the
adsorbents investigated, the results demonstrate that secondary amine containing adsorbents are more stable to SOx and NOx
impurities in CO2 capture processes than those that contain primary amine groups.

1. INTRODUCTION As an example from the zeolite literature, recently, Deng and

The deactivation of CO2 adsorbing materials in the presence of
flue gas impurities such as SOx and NOx poses a significant
challenge to the practical application and scale-up of the
adsorption-based CO2 capture technologies. These impurities
are particularly important, as the reaction between these species
and many solid adsorbents is essentially irreversible in nature,
reducing the adsorbent lifetime and making the capture process
more costly. In that regard, recently, much effort has been put
into evaluating the stability of CO2 adsorbent materials to SOx
and NOx.1−8 The typical concentrations of SOx and NOx in
coal-fired power plants (before sulfur scrubbing and/or
selective catalytic reduction units) are approximately 0.2−0.25
and 0.15−0.2 vol %, respectively, whereas the approximate CO2
concentrations in similar power stations are 9−14 vol %.4
These elevated concentrations are often detrimental to amine
adsorbents and solutions, and for this reason, their concen-
trations are reduced by sulfur scrubbing and/or selective
catalytic reduction units to concentrations below ∼2 and ∼50
ppm, for SOx and NOx, respectively.
Because of the importance of these impurity gases, there have
been a number of investigations of the impact of SOx and NOx
on CO2 adsorption capacity of zeolites9−13 and calcium-based
adsorbents,5,14−18 as well as for solid-supported amine
materials.4,19−22 However, the majority of the work in the
literature has focused on single-component adsorption experi-
ments and the synergy in coadsorbing of the SOx or NOx and
CO2 has not been fully investigated. SOx and NOx impurities
have been shown to bind irreversibly to most amine
groups,4,19,20,23,24 therefore competitive, dynamic adsorption
of SOx/NOx on amine adsorbents merits experimental
investigation.
co-workers2 evaluated the coadsorption of SO2, NO and CO2
on a series of ion-exchanged NaX zeolites to study the
interactive effects of the gases in the simultaneous removal of
these acidic gases from flue gas. On the basis of their results, the
CO2 capacity of K-NaX dropped from 0.51 to 0.28 mmol/g in
the presence of 2000 ppm of SO2 and 1000 ppm of NO and
dropped even further to 0.13 when 5% O2 was present in the
gas mixture. In another study,25 the coadsorption of SO2 and
CO2 over tertiary amine-containing materials was performed
under humid conditions to evaluate the suitability of these
adsorbents as SO2 adsorbents. The authors reported a SO2
capacity of 2.19 mmol/g under dry conditions and a 3-fold
increase when the moisture was present.
In our previous paper,1 we evaluated the stability of
supported amine adsorbents to SO2, NO and NO2 in
postcombustion CO2 capture by performing cyclic, single-
component adsorption experiments. The degree of irreversible
binding of SO2, NO, and NO2 to four supported amine
adsorbents was evaluated to assess the SO2, NO, and NO2
adsorption capacities of the aminosilica adsorbents and their
effects on the CO2 adsorption capacities by performing
thermogravimetric studies. The materials tested in that work
consisted of one class 1 aminosilica adsorbent26 (based on
poly(ethylenimine)) and three class 2 materials26,27 made using
three different silane coupling agents (based on a propyl-
trimethoxysilane linker) with primary, secondary and tertiary
amines. The effects of temperature, concentration and amine
Received: May 17, 2014
Revised: July 3, 2014
Accepted: July 8, 2014
Published: July 8, 2014

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Industrial & Engineering Chemistry Research
Table 1. Amine Materials Used to Prepare Aminosilica Adsorbents
amine amine types
poly(ethylenimine) primary, secondary, tertiaryPEI
3-aminopropyltrimethoxysilane primaryAPS
(N-methylaminopropyl)trimethoxysilane secondaryMAPS
(N,N-dimethylaminopropyl)trimethoxysilane tertiaryDMAPS
loading on the adsorption capacity of aminosilica adsorbents
were then evaluated accordingly. It was shown that the
materials were stable in the presence of NO and retained
their full CO2 capacities after exposure to this gas. In contrast,
all materials treated with NO2 exhibited a dramatic decrease in
CO2 capacity as a result of deactivation of amine groups due to
the irreversible binding of NO2.
In the current study, we extend our previous work and
continue evaluating the stability of amine adsorbents to SO2
and NOx in postcombustion CO2 capture by performing
dynamic, multicomponent adsorption experiments in a fixed
bed.
2. EXPERIMENTAL SECTION
2.1. Materials Synthesis. A detailed description of
materials synthesis can be found in our previous paper.1 Here
we briefly discuss the materials used in this study. A commercial
silica support (PD09024 from PQ Corporation) was used to
synthesize four different aminosilica adsorbents; one class 1
(PEI-impregnated material) and three class 2 adsorbent
materials (aminosilane-based materials). Adsorbents with
similar amine loadings were prepared for each material type.
Table 1 summarizes the materials used to synthesize supported
amine adsorbents with their corresponding nomenclature. For
packed bed experiments, pellets were pressed under a pressure
of 3000 psi and sieved between 400 and 500 μm. The sample
codes in Table 1 start with the letters PD for the silica support,
followed by the amine type and a number indicating the
approximate amine loading for each sample.
2.2. Materials Characterization. Nitrogen physisorption
measurements were carried out on a Micromeritics TRISTAR
II at 77 K. Surface areas and pore volumes were calculated from
the collected isotherm data. Surface areas were calculated using
the Brunauer−Emmett−Teller (BET) method and pore
volumes and pore diameters were calculated using the
Frenkel−Halsey−Hill (BdB-FHH) method.36 A Netzsch
STA409PG thermogravimetric analyzer (TGA) was used to
determine the organic loading of the materials. The equilibrium
adsorption capacity of materials was also measured using a
Q500 thermogravimetric analyzer (TA Instruments).
2.3. Packed Bed Multicomponent Adsorption Meas-
urements. Coadsorption breakthrough measurements were
carried out in a packed bed column as schematically shown in
Figure 1. A 7.0 cm long Pyrex tube with the diameter of 1.0 cm
equipped with a fine-sized frit was loaded with 1.0 g of
adsorbent pellets for each experiment. A heating tape was used
to heat up the column during the desorption step and a
thermocouple was used to probe the column temperature. The
outlet gas concentrations were measured by a mass
spectrometer (Pfeiffer Vacuum Omnistar, QMG 220). The
breakthrough experiments were performed at 1 atm total
pressure.
First, nitrogen was flowed through the bed at 100 mL/min
while the bed temperature was raised to 110 °C for 30 min,
after which it was lowered back to room temperature and
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sample name
PD-PEI_2
PD-APS_2
PD-MAPS_2
PD-DMAPS_2
Figure 1. Schematic of packed bed setup for multicomponent
adsorption experiments.
allowed to equilibrate at that temperature for 30 min. The flow
was then switched from nitrogen to the CO2 and/or SO2/NOx
containing gas stream (dry) while continuously monitoring the
outlet gas concentration and bed temperature. Before the start
of the experiments, the mass spectrometer was calibrated with a
dry gas stream containing known concentrations of CO2, SO2,
NO and NO2. To assess any synergies in coadsorption of SOx
or NOx and CO2 gases, two gas mixtures comprising 200 ppm
of NO, 10% CO2 (balance nitrogen) and 200 ppm of SO2, 10%
CO2 (balance nitrogen) were used in addition to single-
component adsorption gases. The multicomponent adsorption
experiments were performed for binary (CO2/SO2 or CO2/NO
or CO2/NO2) and ternary (CO2/SO2/NO) gas components at
35, 55 and 75 °C. In this method, the materials were
simultaneously exposed to CO2 and SO2 or CO2 and NO
and thereby their CO2 uptake was measured at two different
temperatures similar to single-component tests done via TGA
in our previous study.1
The dynamic adsorption capacity (qd) of the materials was
calculated from the breakthrough profiles using the following
equation:
Q FC0tS
qd =
w (1)
In the above equation, QF is the feed molar flow rate, C0 is
the concentration of the adsorbate in the feed stream, w is the
weight of the adsorbent materials loaded in the column and tS is
the stoichiometric time, which can be estimated from
breakthrough curves using the equation below:
∞⎛ C ⎞
tS = ∫0 ⎜1 − A ⎟∂t
⎝ C0 ⎠ (2)
where CA is the adsorbate concentration at the column outlet.
dx.doi.org/10.1021/ie502024z | Ind. Eng. Chem. Res. 2014, 53, 12103−12110
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3. RESULTS AND DISCUSSION 3.2. Packed Bed Multicomponent Adsorption Meas-

3.1. Physical Properties of Materials. The physical urements. 3.2.1. SO2/CO2 Coadsorption. In our previous
characteristics of the bare silica support and amine-function- paper,1 we measured and compared the CO2 capacity of
alized silica adsorbent pellets used in this study are summarized aminosilica materials before and after exposure to SO2 with
in Table 2 along with the amine loading of the materials, as various concentrations (i.e., 20, 100 and 200 ppm) at different
temperatures (i.e., 35, 55 and 75 °C). In this investigation, the
Table 2. Physical Properties of Amine-Functionalized Silica adsorbent materials were exposed to CO2 and SO2 simulta-
Adsorbent Pellets neously to assess the synergetic effects in coadsorption of SO2
and CO2. Figure 2a shows the CO2 and SO2 breakthrough
amine average profiles for the PD-MAPS_2 material when exposed to a gas
loading SBET Vpore pore size
material abbreviation (mmolN/g) (m2/g) (cm3/g) (nm) mixture containing 200 ppm of SO2 and 10% CO2 at 35 °C. As
silica-bare PD 294 1.04 10
can be observed, the CO2 breaks through the bed very quickly,
silica with PEI, PD−PEI_2 1.9 213 0.54 7 whereas it takes much longer for SO2 to break through, mainly
low loading due to the low concentration of SO2 relative to that of CO2.
silica with PD-APS_2 1.8 188 0.37 9 The corresponding breakthrough times for CO2 and SO2 are 2
APS, and 90 min, respectively. Figure 2b displays the SO 2
medium
loading concentration curves for aminosilica adsorbents with similar
silica with PD-MAPS_2 2.0 138 0.35 7 amine loadings. Furthermore, the working capacities, calculated
MAPS, high from eq 1, and breakthrough times corresponding to each
loading
silica with PD-DMAPS_2 1.8 163 0.33 6
material are listed in Table S1 (Supporting Information).
DMAPS, In agreement with the single-component adsorption experi-
high loading ments,1 PD-MAPS_2, containing secondary amine moieties,
exhibits the highest SO2 adsorption capacity, characterized by
determined by combustion in a TGA. To make direct the longest breakthrough time, whereas PD-DMAPS_2 shows
comparisons between adsorption characteristics of the samples, the fastest SO2 breakthrough, indicating that this adsorbent has
materials were synthesized with similar amine loadings. As can the lowest adsorption capacity compared to other materials.
be seen in the table, incorporating amines into the pores of the To investigate the impact of the presence of SO2 on CO2
silica supports reduces the surface areas as well pore volumes adsorption capacities, two approaches were employed. In the
and diameters, as expected. The amine loadings of the as- first approach, the coadsorption experiments were carried out
synthesized materials are also listed in Table 2. until the CO2 appeared in the bed outlet gas stream and the
It should also be noted here that upon pelletizing the powder runs were stopped right after the bed was saturated with CO2,
samples, porosity decreased and therefore the pellets exhibited akin to a real adsorption cycle; whereas in the second approach,
less porosity than the virgin powders. This was most likely a the adsorption runs were continued until the bed was saturated
result of pore collapse that occurred under pressure. As a result, with SO2. Analyzing the experimental results shown in Figure
all pellet samples showed decreased CO2 uptake as compared 3a−c, it can be inferred that for all materials, the CO2 capacity
to their powder counterparts. Comparing the data in Table 2 decreased significantly after five cycles when the bed was
and those published in our previous paper1 confirms the drop allowed to become saturated with SO2 during each cycle,
in porosity. For example, the surface area and pore volume whereas capacities remained almost unchanged (only slightly
dropped from 150 m2/g and 0.5 cm3/g to 138 m2/g and 0.35 decreased) when the SO2 saturation did not occur in the bed
cm3/g, respectively, in the case of the PD-MAPS_2 material. during each cycle. Thus, the deactivation by SO2 can be
Although this change is a minor one, it is consistent across all suppressed by using short adsorption−desorption cycles during
samples and is significant enough to warrant noting. CO2 capture. The trend of the breakthrough curves in Figure 2

Figure 2. (a) Coadsorption breakthrough profiles for CO2 and SO2 on PD-MAPS_2 at 75 °C and (b) SO2 breakthrough profiles during
coadsorption experiments on PEI, APS, MAPS and DMAPS adsorbents at 35 °C after exposure to 200 ppm of SO2/10% CO2.

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Industrial & Engineering Chemistry Research Article

Figure 3. CO2 working capacity with and without SO2 breakthrough on (a) PEI, (b) APS and (c) MAPS adsorbents after exposure to 200 ppm of
SO2/10% CO2 at 35 °C.

Figure 4. SO2 concentration profiles (a) at different temperatures and (b) SO2 feed concentrations.

and the analysis of the adsorption capacities in Figure 3 show
that the cyclic adsorption capacity decreases on passing from
the first to the second adsorption cycle, whereas it remains
almost constant throughout successive adsorption−desorption
cycles. This sharp capacity loss can be attributed to the strong
12106
and irreversible binding of SO2 on some amine sites and as a
result, only a small fraction of adsorbed SO2 is desorbed while
regenerating the adsorbent and therefore SO2 has a negative
effect on CO2 adsorption. The plateau capacity after successive
cycles might be explained by considering the weak interaction
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Industrial & Engineering Chemistry Research Article

between CO2 and the remaining surface amine sites after ppm of NO and 10% CO2 at 35 °C, and the corresponding NO
degradation. Chuang and co-workers28 explained this plateau and CO2 concentration profiles over PD-MAPS_2 are
capacity as being associated with isolated amine sites that arise displayed in Figure 5. On the basis of our single-component
after a majority of surface amine sites irreversibly bind SO2. It
was suggested that these isolated amine sites are thermally
reversible and exhibit very weak interactions with CO2. The
effect may also be due to the interaction of CO2 with the free
silanol groups (Si−OH) on the surface of the silica support,
leading to the physisorption of CO2 via hydrogen bonding.
Furthermore, capacity loss is lower in the case of PD-MAPS_2,
containing secondary amine moieties, relative to the other
adsorbents, suggesting that this material is more stable upon
exposure to SO2 than primary and tertiary containing amine
adsorbents. It should be pointed out that because all
measurements were carried out under dry conditions and
tertiary amines do not appreciably chemisorb CO2 under dry
conditions, a similar analysis was not performed for the PD-
DMAPS_2 sample.
These results clearly indicate that supported amine
adsorbents are reasonably stable to flue gas impurities during
cyclic adsorption operation, even at high SO2 concentrations, Figure 5. Coadsorption breakthrough profiles for CO2 and NO on
especially in fast cycles. It should also be noted that actual PD-MAPS_2 after exposure to 200 ppm of NO/10% CO2 at 35 °C.
concentration of SO2 in flue gas streams after sulfur treatment
is much lower than the concentration considered in this study
(i.e., ∼2 ppm versus 200 ppm), suggesting that rapid cycling adsorption measurements, NO is not expected to adversely
affect CO2 capture by competitive adsorption on the amine-
with low SO2 concentrations will allow for long-term, stable
based adsorbents. Comparing the breakthrough curves in
cycling.
Figure 5, it follows that NO breaks through the bed almost
Next, we evaluated the effect of temperature and SO2
immediately, indicating very little affinity of the amines toward
concentration on the dynamic adsorption profiles of the
NO and very trivial capacity. As a result, the CO2 capacity was
aminosilica adsorbents. Figure 4a shows the breakthrough
not influenced when NO was present in the gas mixture. The
profiles at 35, 55 and 75 °C for PD-MAPS_2 when exposed to
same trend was observed for other materials (i.e., PEI, APS and
200 ppm of SO2/10% CO2. It is clear that performing
DMAPS; breakthrough data not shown).
coadsorption experiments at higher temperatures results in an
Table S2 (Supporting Information) summarizes the dynamic
earlier SO2 breakthrough time and a drop in the SO2
CO2 and NO coadsorption characteristics obtained from
adsorption capacity. As shown in our previous paper, the
breakthrough profiles for amine-functionalized materials with
single-component adsorption runs showed a decrease in
similar amine loadings. Our data show that for all materials, the
equilibrium capacities with temperature, as expected for class
CO2 capacity can be retained in the presence of NO.
2 materials, due to the exothermic nature of adsorption.
For a more realistic analysis of the effect of NO on CO2
Depending on the source of fuel, the concentration of SO2 in
adsorption performance of the aminosilica adsorbents,
flue gas varies to some extent and therefore, it is worth
consecutive adsorption/desorption cycle experiments were
investigating its influence on adsorption capacity of amine-
performed and the corresponding CO2 working capacities
based materials. A comparison between SO2 breakthrough
before and after NO/CO2 exposure are displayed in Figure 6.
adsorption curves corresponding to 20 and 200 ppm feed gas
As evident from this figure, no significant capacity loss was
concentrations at 35 °C over the PD-MAPS_2 is depicted in
Figure 4b. As can be derived from the data shown, the decrease
in SO2 concentration leads to a displacement of the SO2
breakthrough curve to longer adsorption times and also results
in a reduction of the capacity of the adsorbent from about 1.6
to almost 0.6 mmol SO2/g in the simultaneous presence of SO2
and CO2. Correspondingly, adsorption breakthrough times are
dramatically lengthened from about 5 to 18 h when
concentration increases from 20 to 200 ppm. Assuming that
SO2 diffusion in the adsorbent bed remains the same, this
decrease in breakthrough time with concentration is expected,
which could be attributed to the increase in SO2 capacity with
concentration, as mentioned above.
3.3.2. NO/CO2 Coadsorption. For the solid CO2 adsorbent
materials to be stable under real flue gas conditions, it is not
only important to evaluate their stability in the presence of SO2
but also to NOx, as flue gas contains NOx impurities as well. We
therefore performed NO/CO2 coadsorption experiments in a
similar way as the SO2/CO2 runs, namely, the aminosilica Figure 6. CO2 working capacity of amine-functionalized materials
adsorbents were exposed to a mixture of gas containing 200 before and after exposure to 200 ppm of NO/10% CO2 at 35 °C.

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Industrial & Engineering Chemistry Research
observed, indicating that the presence of NO did not influence
the CO2 capacity of the adsorbents, in close agreement with
previous findings.1,19 These results clearly suggest that there is
no negative synergy in the coadsorption of NO and CO2.
3.2.3. NO2/CO2 Coadsorption. Aminosilica adsorbents are
reported to have some preferred affinity toward NO2.1,8,19,20,22
In our earlier investigation, we used a 200 ppm of NO2 gas
concentration for single-adsorption experiments and inves-
tigated the impact of this concentration on the adsorbent’s CO2
adsorption capacity. This concentration is, however, far higher
than the actual concentration of NO2 in flue gas streams
coming from NOx removal units. Therefore, to have a more
realistic analysis, we used a feed gas stream with 20 ppm of
NO2/10% CO2 composition for coadsorption experiments. As
can be observed from the data in Figure 7, for the PD-MAPS_2
Figure 7. Coadsorption breakthrough profiles for CO2 and NO2 on
PD-MAPS_2 after exposure to 20 ppm of NO2/10% CO2 at 35 °C.
adsorbent, the NO2 breakthrough occurs at the same time as
the CO2 breakthrough and the material exhibits a working
capacity of 0.30 mmol NO2/g (at 20 ppm of NO2 in 10% CO2
at 35 °C). It should be noted that the other materials show
similar behavior, also exhibiting nearly the same breakthrough
time for CO2 and NO2. The high affinity of the adsorbent
toward very low concentrations of NO2 can be attributed to the
higher polarity and adsorption strength of NO2 than NO and
CO2, and as a result, this gas will have a more adverse effect on
CO2 adsorption than NO. It will also have a more adverse effect
than SO2 on CO2 adsorption when its concentration is
comparable to SO2, as our previous results demonstrated.1
The corresponding CO2 working capacities for each material
were estimated from breakthrough curves and the results are
listed in Table S3 (Supporting Information) along with the
breakthrough times for both NO2 and CO2. From these data, it
can be observed that for all amine-based adsorbents, the NO2
capacities are relatively high compared to those for NO under
the experimental conditions studied here, even though its
concentration was lower than that of NO in the breakthrough
experiments. This is consistent with our past work focusing on
single component measurements.1 Of the two gases that are
more harmful to the CO2 capacity, NO2 and SO2, it is
noteworthy that their relative impact on CO2 capacity depends
on the exposure level. At identical 20 ppm feed concentrations,
which might be in the range expected after flue gas
desulfurization and NOx removal treatments, the NO2 working
capacity is lower than the SO2 working capacity, and thus NO2
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has a less detrimental impact on the CO2 adsorption capacity
under these conditions. However, in our previous study1 that
used 200 ppm exposure levels, NO2 led to a more significant
capacity loss than SO2. Thus, the relative importance of each
gas in impacting CO2 capacities will depend on the exposure
level, though both gases should be viewed as harmful to amine
sites.
To further address the long-term stability of the aminosilica
adsorbents for CO2 capture, cyclic adsorption/desorption
experiments were carried out at 35 °C. Figure 8 illustrates
Figure 8. CO2 working capacity of amine-functionalized materials
before and after exposure to 20 ppm of NO2/10% CO2 at 35 °C.
the CO2 working capacities of PD-MAPS_2 before and after
NO2/CO2 exposure for five consecutive cycles. According to
this figure, the presence of a low concentration of NO2 does
not impact the stability of the adsorbents significantly, and the
CO2 capacity only slightly dropped after a few cycles. In our
previous paper,1 we showed that NO2 could have a significant
negative impact on the stability of aminosilica adsorbents when
it is present at very high concentrations, whereas, as these
results indicate, the materials retain their CO2 capacities in the
presence of lower levels of NO2.
3.2.4. SO2/NO/CO2 Multiadsorption. Finally, to investigate
any synergetic effect during the simultaneous adsorption of SOx
and NO, a simulated flue gas stream with 200 ppm of SO2/200
ppm of NO/10% CO2 (balance nitrogen) was used for
adsorption experiments. Figure 9 shows the comparison of the
CO2, SO2 and NO breakthrough profiles for the PD-MAPS_2
adsorbent. Comparing the concentration profiles in this figure,
it can be observed that NO and CO2 quickly breakthrough the
fixed bed while SO2 is trapped in the bed. NO exhibits the
fastest breakthrough, which can be attributed to its minimal
dynamic adsorption capacity.
The cyclic adsorption capacities obtained from the multi-
adsorption fixed bed runs suggest that the CO2 adsorption is
influenced primarily by SO2 coadsorption and the CO2 capacity
loss was dictated by SO2 and not NO, as would be inferred
from the dual component adsorption experiments. Additionally,
the presence of NO changes neither the CO2 nor SO2
adsorption characteristics, suggesting no synergistic interactions
of NO and SO2.
4. CONCLUSIONS
Multicomponent adsorption experiments were carried out to
investigate the impact of SOx/NOx impurities on the CO2
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Industrial & Engineering Chemistry Research
Figure 9. Multiadsorption breakthrough profiles for CO2, SO2 and
NO2 on PD-MAPS_2 after exposure to 200 ppm of SO2/200 ppm of
NO/10% CO2 at 35 °C.
adsorption capacity of an array of aminosilica adsorbents. The
coadsorption breakthrough profiles of SO2, NO and NO2 were
evaluated in conjunction with CO2 concentration profiles. On
the basis of our experimental results, it was found that the
presence of NOx impurities at low concentrations do not
significantly influence the CO2 adsorption capacity of amino-
silica materials, with NO having no significant impact even at
high concentrations of 200 ppm and NO2 having a minimal
impact at more typical concentrations of 20 ppm. In addition,
although high concentrations of SO2 in the simulated flue gas
stream would result in CO2 capacity loss over many cycles, the
adsorbents retained their CO2 capacities over many cycles
when exposed to a low-concentration SO2 gas stream,
suggesting that amine-based solid adsorbents are reasonably
stable under dry flue gas conditions with realistic concen-
trations of impurity gases.
■
ASSOCIATED CONTENT
*
S Supporting Information
Tables S1−S3 show, respectively, SO2/CO2, NO/CO2 and
NO2/CO2 coadsorption characteristics over aminosilica
adsorbents at 35 °C using 200 ppm of SO2 or 200 ppm of
NO or 20 ppm of NO2/10% CO2. This material is available free
of charge via the Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*C. W. Jones. E-mail: cjones@chbe.gatech.edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by DOE-NETL through
grant number DE-FE0007804. However, any opinions,
findings, conclusions or recommendations expressed herein
are those of the author(s) and do not necessarily reflect the
views of the DOE.
■
REFERENCES
(1) Rezaei, F.; Jones, C. W. Stability of Supported Amine Adsorbents
to SO2 and NOx in Post-Combustion CO2 Capture. 1. Single
Component Adsorption. Ind. Eng. Chem. Res. 2013, 52, 12192−12201.
12109
Article
(2) Deng, H.; Yi, H.; Tang, X.; Liu, H.; Zhou, X. Interactive Effect for
Simultaneous Removal of SO2, NO, and CO2 in Flue Gas on Ion
Exchanged Zeolites. Ind. Eng. Chem. Res. 2013, 52, 6778−6784.
(3) Zhou, X.; Yi, H.; Tang, X.; Deng, H.; Liu, H. Thermodynamics
for the Adsorption of SO2, NO and CO2 from Flue Gas on Activated
Carbon Fiber. Chem. Eng. J. 2012, 200−202, 399−404.
(4) Khatri, R. A.; Chuang, S. S. C.; Soong, Y.; Gray, M. Thermal and
Chemical Stability of Regenerable Solid Amine Sorbent for CO2
Capture. Energy Fuels 2006, 20, 1514−1520.
(5) Ridha, F. N.; Manovic, V.; Macchi, A.; Anthony, E. J. The Effect
of SO2 on CO2 Capture by CaO-Based Pellets Prepared with a Kaolin
Derived Al(OH)3 Binder. Appl. Energy 2012, 92, 415−420.
(6) Lu, H.; Smirniotis, P. G. Calcium Oxide Doped Sorbents for CO2
Uptake in the Presence of SO2 at High Temperatures. Ind. Eng. Chem.
Res. 2009, 48, 5454−5459.
(7) Levasseur, B.; Ebrahim, A. M.; Bandosz, T. J. Interactions of NO2
with Amine-Functionalized SBA-15: Effects of Synthesis Route.
Langmuir 2012, 28, 5703−5714.
(8) Xu, X.; Song, C.; Miller, B. G.; Scaroni, A. W. Adsorption
Separation of Carbon Dioxide from Flue Gas of Natural Gas-Fired
Boiler by a Novel Nanoporous “Molecular Basket” Adsorbent. Fuel
Process. Technol. 2005, 86, 1457−1472.
(9) Zhang, J.; Xiao, P.; Li, G.; Webley, P. A. Effect of Flue Gas
Impurities on CO2 Capture Performance from Flue Gas at Coal-Fired
Power Stations by Vacuum Swing Adsorption. Energy Procedia 2009, 1,
1115−1122.
(10) Adeyemo, A.; Kumar, R.; Linga, P.; Ripmeester, J.; Englezos, P.
Capture of Carbon Dioxide from Flue or Fuel Gas Mixtures by
Clathrate Crystallization in a Silica Gel Column. Int. J. Greenhouse Gas
Control 2010, 4, 478−485.
(11) Beeskow-Strauch, B.; Schicks, J. M.; Spangenberg, E.; Erzinger,
J. The Influence of SO2 and NO2 Impurities on CO2 Gas Hydrate
Formation and Stability. Chemistry 2011, 17, 4376−4384.
(12) Daraboina, N.; Ripmeester, J.; Englezos, P. The Impact of SO2
on Post Combustion Carbon Dioxide Capture in Bed of Silica sand
through Hydrate Formation. Int. J. Greenhouse Gas Control 2013, 15,
97−103.
(13) Yi, H.; Deng, H.; Tang, X.; Yu, Q.; Zhou, X.; Liu, H. Adsorption
Equilibrium and Kinetics for SO2, NO, CO2 on Zeolites FAU and
LTA. J. Hazard. Mater. 2012, 203−204, 111−117.
(14) Reddy, M. K. R.; Xu, Z. P.; Lu, G. Q. M.; Costa, J. C. D. Effect
of SOx Adsorption on Layered Double Hydroxides for CO2 Capture.
Ind. Eng. Chem. Res. 2008, 47, 7357−7360.
(15) Czyżewski, A.; Kapica, J.; Moszyński, D.; Pietrzak, R.;
Przepiórski, J. On Competitive Uptake of SO2 and CO2 from Air by
Porous Carbon Containing CaO and MgO. Chem. Eng. J. 2013, 226,
348−356.
(16) Li, Y.; Buchi, S.; Grace, J. R.; Lim, C. J. SO2 Removal and CO2
Capture by Limestone Resulting from Calcination/Sulfation/Carbo-
nation Cycles. Energy Fuels 2005, 19, 1927−1934.
(17) Arias, B.; Cordero, J. M.; Alonso, M.; Diego, M. E.; Abanades, J.
C. Investigation of SO2 Capture in a Circulating Fluidized Bed
Carbonator of a Ca Looping Cycle. Ind. Eng. Chem. Res. 2013, 52,
2700−2706.
(18) Manovic, V.; Anthony, E. J. Sequential SO2/CO2 Capture
Enhanced by Steam Reactivation of a CaO-Based Sorbent. Fuel 2008,
87, 1564−1573.
(19) Diaf, A.; Garcia, J. L.; Beckman, E. J. Thermally Reversible
Polymeric Sorbents for Acid Gases: CO2, SO2, and NOx. J. Appl.
Polym. Sci. 1994, 53, 857−875.
(20) Diaf, A.; Beckman, E. J. Thermally Reversible Polymeric
Sorbents for Acid Gases, IV. Affinity Tuning for the Selective Dry
Sorption of NOx. React. polym. 1995, 25, 89−96.
(21) Belmabkhout, Y.; Sayari, A. Isothermal versus Non-isothermal
Adsorption-Desorption Cycling of Triamine-Grafted Pore-Expanded
MCM-41 Mesoporous Silica for CO2 Capture from Flue Gas. Energy
Fuels 2010, 24, 5273−5280.
(22) Liu, Y.; Ye, Q.; Shen, M.; Shi, J.; Chen, J.; Pan, H.; Shi, Y.
Carbon Dioxide Capture by Functionalized Solid Amine Sorbents with
dx.doi.org/10.1021/ie502024z | Ind. Eng. Chem. Res. 2014, 53, 12103−12110
Industrial & Engineering Chemistry Research Article

Simulated Flue Gas Conditions. Environ. Sci. Technol. 2011, 45, 5710−
5716.
(23) Uyanga, I. J.; Idem, R. O. Studies of SO2- and O2-Induced
Degradation of Aqueous MEA during CO2 Capture from Power Plant
Flue Gas Streams. Ind. Eng. Chem. Res. 2007, 46, 2558−2566.
(24) Aaron, D.; Tsouris, C. Separation of CO2 from Flue Gas: A
Review. Sep. Sci. Technol. (Philadelphia, PA, U. S.) 2005, 40, 321−348.
(25) Tailor, R.; Ahmadalinezhad, A.; Sayari, A. Selective Removal of
SO2 over Tertiary Amine-Containing Materials. Chem. Eng. J. 2014,
240, 462−468.
(26) Bollini, P.; Didas, S. A.; Jones, C. W. Amine-Oxide Hybrid
Materials for Acid Gas Separations. J. Mater. Chem. 2011, 21, 15100−
15120.
(27) Harlick, P. J. E.; Sayari, A. Applications of Pore-Expanded
Mesoporous Silica. 5. Triamine Grafted Material with Exceptional CO2
Dynamic and Equilibrium Adsorption Performance. Ind. Eng. Chem.
Res. 2007, 46, 446−458.
(28) Srikanth, C. S.; Chuang, S. S. C. Infrared Study of Strongly and
Weakly Adsorbed CO2 on Fresh and Oxidatively Degraded Amine
Sorbents. J. Phys. Chem. C 2013, 117, 9196−9205.

12110 dx.doi.org/10.1021/ie502024z | Ind. Eng. Chem. Res. 2014, 53, 12103−12110