ARTICLE

pubs.acs.org/IECR

Suitability of a Solid Amine Sorbent for CO2 Capture by Pressure Swing

Adsorption
A. D. Ebner,† M. L. Gray,‡ N. G. Chisholm,† Q. T. Black,† D. D. Mumford,† M. A. Nicholson,† and
J. A. Ritter*,†
†
Department of Chemical Engineering, University of South Carolina, Columbia, South Carolina 29208, United States
‡
National Energy Technology Laboratory, U.S. Department of Energy, P.O. Box 10940, Pittsburgh, Pennsylvania 15236, United States

ABSTRACT: This study showed that a solid amine, composed of poly(ethylenimine) immobilized into a CARiACT G10 silica
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substrate, is a feasible sorbent for applications in a pressure swing adsorption (PSA) process for postcombustion CO2 capture. This
deduction materialized from an extensive study of the behavior of this material over a wide range of industrially relevant conditions
using thermogravimetric analysis. The temperature ranged from 40 to 100 °C, the CO2 partial pressure ranged from 1.2 to 100 vol %
with the total pressure fixed at 1 atm, the relative humidity ranged from dry conditions to 2 vol %, and the number of consecutive
adsorption and desorption cycles ranged from 4 to 76. The results revealed that this solid amine sorbent was very stable under the
conditions investigated. Water vapor at a low relative humidity exhibited only a minor and reversible effect on both the
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thermodynamics and kinetics of the CO2 uptake and release. The isothermal CO2 working capacity ranged between 0.25 and 2.8
mol/kg, increased with increasing CO2 concentration, exhibited a maximum with increasing temperature, and produced a heat of
adsorption/reaction of around 50.0 kJ/mol. It was also determined that the optimal operating temperature for a PSA process was
around 80 °C for CO2 partial pressures >10 kPa and 60
70 °C for CO2 partial pressures <10 kPa.

’ INTRODUCTION
A considerable effort is underway worldwide to reduce the
amount of CO2 emissions from coal-fired and other fossil-fuel-
based power plants because these plants are responsible for over
40% of the emissions of greenhouse gas in the USA alone.1 The
goal is to capture CO2 from a stack or flue gas (i.e., postcombus-
tion capture), concentrate it to over 95 vol %, and sequester it
somewhere in the Earth. Viable CO2 capture options include
absorption, cryogenic condensation, adsorption, and membrane
technologies.1 To date, however, none of these technologies has
been economically attractive; so, considerable research is being
done on all of them in search of a more economically feasible
process. In particular, pressure swing adsorption (PSA) offers
features that make it attractive over the other processes. These
features include its ease of retrofitting, the requirement of
nothing more than electricity from the facility, and accomplish-
ing regeneration without the need of facility and equipment-
intensive heat or steam.
To date, hydrotalcites1
8 and zeolites1,9
13 are respectively
being studied for high- (precombustion) and low-temperature
(postcombustion) capture of CO2. Hydrotalcites have one of the
highest CO2 working capacities in the 300
500 °C range,1
whereas zeolites have one of the highest CO2 working capacities
in the 30
80 °C range.1 However, a major disadvantage of
zeolites for postcombustion CO2 capture is the need to remove
water vapor from the feed stream because of its strong affinity
with zeolites, which impairs CO2 capture.
Flue gas typically contains up to 10
15 vol % H2O, which
must be removed by using either a guard bed prior to the PSA unit
or a layered adsorbent bed in the PSA unit. Both approaches add
complexity and cost. Hence, a CO2 sorbent that is water-tolerant
and exhibits a sufficient CO2 working capacity is highly desirable. A
solid amine sorbent,14
46 a relatively new type of CO2 sorbent, has
been reported to have these desirable characteristics.
Solid-supported amine sorbents are comprised of a high-
surface-area support, such as Amberlite,15,16 poly(methyl metha-
crylate),17
19 and polystyrene,19 but mostly silica,18
45 with amine
functional groups immobilized or grafted to its surface. The amine
within these sorbents behaves similarly to a liquid alkanolamine and
thus takes up appreciable amounts of CO2 reversibly, even in, or
improved by, the presence of water vapor.19,21
26 They are being
studied extensively not only for natural gas purification27 and pre-
and postcombustion CO2 capture,15
26,28
45 i.e., bulk CO2 re-
moval, but also for trace CO2 removal from air in spacecraft cabins
and submarines.15
17 Although solid amine sorbents are being
touted for bulk CO2 capture using a temperature swing adsorption
(TSA) process and although they are the first choice by NASA for
trace CO2 removal from air by PSA, they have not been considered
in detail for bulk CO2 removal from stack or flue gas by PSA, except
in the recent work by Belmabkhout and Sayari.41
Therefore, the objective of this study was to further determine
if a solid amine sorbent is suitable for the capture of bulk CO2 by
PSA. To this end, a solid amine sorbent, consisting of poly(ethyl-
enimine) (PEI) supported on a commercial silica substrate, was
investigated over a wide range of industrially relevant conditions.
The parameters of interest included temperature, CO2 partial
pressure, water vapor content, and cycling stability. The kinetic
and thermodynamic information generated from this study is
suitable for correlation with a mechanistic model, which can then
Received: January 12, 2011
Accepted: March 23, 2011
Revised: March 6, 2011
Published: April 02, 2011

r 2011 American Chemical Society 5634 dx.doi.org/10.1021/ie2000709 | Ind. Eng. Chem. Res. 2011, 50, 5634–5641
Industrial & Engineering Chemistry Research ARTICLE

syringe pump filled with water and placed in the feed line. The
speed of the syringe pump was such that it provided a feed gas
containing about 2.0 vol % water vapor continuously during both
the adsorption and desorption steps. To ensure immediate and
complete evaporation of the liquid water exiting the needle of the
syringe, a heating band and thermocouple were placed at the port
connecting the needle to the feed line to generate a temperature
of about 200 °C at the tip of the needle. Four cycles were carried
out with the syringe pump turned on, and then the same sample
was activated again and four more cycles were carried out with
the syringe pump turned off (i.e., under dry conditions). Two
sets of wet conditions were used: 80 °C with a feed containing 1.2
vol % CO2 (dry basis) and 40 °C with a feed containing 100 vol %
CO2 (dry basis).

’ EQUILIBRIUM MODEL DEVELOPMENT

Figure 1. Schematic of the adsorption
desorption cycling experimen- The mechanism envisioned to describe the kinetics of the CO2
tal apparatus, depicting a thermogravimetric analyzer, an electronic valve chemisorption reaction with the CARiACT G10 solid amine
timer, feed gases, and a water syringe pump.
sorbent was defined in the simplest terms according to the
following mass balance:
be used in a dynamic adsorption process simulator to study the
performance of a PSA process. DqCO2
¼ kf qCO2 , a ðN
qCO2 Þ
kb qCO2 ð1Þ
Dt
’ MATERIAL PREPARATION AND CYCLE TESTING where qCO2 represents the chemisorbed CO2 that has reacted
Reagent-grade methanol and PEI (MN 423) were purchased with the immobilized amine, N represents the total number of
from Aldrich Chemical Co. and used as received in the prepara- sites available for this reaction, qCO2,a represents unreacted CO2
tion of the solid amine sorbent. The substrate for the solid amine in a physisorbed state and within the vicinity of some of the
sorbent was CARiACT G10 silica from Fuji Silysia. It has a immobilized amine, and kf and kb represent kinetic constants for
surface area of 300 m2/g, a pore volume of 1.2 mL/g, and particle the forward and backward reactions.
sizes between 200 and 400 μm. The amine was dissolved in This analysis also assumed that the forward reaction depends
methanol and combined with silica at an amine/methanol/silica on qCO2,a. In other words, the immobilized amine reacts directly
weight ratio of 0.67:2.0:1.0. This slurry was placed in a rotary with physisorbed CO2 and not gaseous CO2. If qCO2,a is assumed
evaporator to remove methanol and allow amine to physically to be small and in equilibrium with the partial pressure of CO2
adsorb (i.e., become immobilized) in the silica beads. The according to Henry’s law, i.e.,
resulting solid amine sorbent contained about 40 wt % PEI.
qCO2 , a ¼ kH PCO2 ð2Þ
Further details on this synthesis method, including the use of
other solid amine sorbents, are provided elsewhere.19 then at equilibrium (i.e., ∂qCO2/∂t = 0) the chemisorbed CO2 can
A Perkin-Elmer TGA-7 thermogravimetric analyzer was used be defined in terms of a Langmuir-type expression according to
to measure the dynamic adsorption and desorption behavior of
CO2 on the solid amine sorbent. A schematic of the experimental kPCO2 N
qCO2 ¼ ð3Þ
apparatus is displayed in Figure 1. First, a sample (∼20 mg) was 1 þ kPCO2
activated at 100 °C for 80 min in N2 (UHP grade, Airgas) flowing
at around 60 cm3/min and 1 atm. At the end of the activation with
step, the temperature was adjusted to a predetermined value  
kf kH ΔH
between 40 and 100 °C using a 20 °C/min ramping rate. When k¼ ¼ k0 exp
ð4Þ
the temperature was reached, the test gas was switched from N2 kb RT
to a N2/CO2 gas mixture (also flowing at around 60 cm3/min and
and 1 atm) to initiate adsorption and begin the first half of an
adsorption
desorption cycle. The concentration of CO2 ΔH ¼ Ef þ ΔHa
Eb ð5Þ
(Coleman grade, Airgas) in the mixture was varied between 1
and 100 vol %. The adsorption step was continued for 40 min, k is the affinity coefficient between CO2 and the sorbent, ΔH is
and then the gas was switched back to N2 to initiate desorption the effective heat of adsorption/reaction, Ef and Eb are the
and finish the second half of the adsorption
desorption cycle. activation energies for the forward and backward reactions, and
Unless otherwise indicated, four adsorption
desorption cycles ΔHa is the heat of adsorption associated with physisorbed CO2.
were carried to elucidate the CO2 loading and dynamic behavior To obtain ΔH and k0 from experimental data, eq 3 can be
of the amine-doped CARiACT G10. To study the stability of the expressed in the linear form
material, 78 cycles were carried out continuously with a sample at PCO2 1 1
80 °C using 100 vol % CO2 during the adsorption step. ¼ þ PCO2 ð6Þ
qCO2 kN N
The role of humidity on the adsorption
desorption behavior
of CO2 on the CARiACT G10 solid amine sorbent was evaluated where 1/kN and 1/N can be resolved respectively from the y
in a similar fashion but with the aid of a Cole Parmer 74900 series intercept and slope of a plot of PCO2/qCO2 versus PCO2.
5635 dx.doi.org/10.1021/ie2000709 |Ind. Eng. Chem. Res. 2011, 50, 5634–5641
Industrial & Engineering Chemistry Research
Figure 2. CO2 loading in a CARiACT G10 solid amine sorbent at 80 °C
for 78 adsorption (CO2) and desorption (N2) cycles with a 40 min half-
cycle time. The gas flow rate was set at 60 cm3/min and 1 atm. Cycles
18
61 were removed for clarity.
’ RESULTS AND DISCUSSION
The stability of the CARiACT G10 solid amine sorbent is
displayed in Figure 2. It shows the adsorption and desorption
behavior during 78 continuous cycles. Cycles 18
61 were
removed for clarity. This run was carried out at 80 °C under
dry conditions using 100 vol % CO2 during the adsorption step.
The performance of this sorbent did not show any signs of
deterioration during the 78 cycles, as noted by there being no
apparent difference between the behavior of cycle 17 and cycle 62
and the working capacity (i.e., the difference between the CO2
loading at the end of the adsorption step and the CO2 loading at
the end of the desorption step) being constant at around 2.75
mol/kg (∼12 wt %). The stability of this particular solid amine
sorbent is thus suitable for use in a PSA process.
As an aside, it is worth noting that this result is in stark contrast
to that recently reported by Sayari’s group.21 They showed a
significant decrease in the working capacity while cycling a
similar PEI-based solid amine sorbent at 105 °C under dry
conditions. They attributed the loss of capacity to the possible
formation of urea. However, Drage et al.46 reported that urea
formation takes place only at temperatures above 135 °C, which
is well above the temperatures run in this work and that by
Sayari’s group.21 The stability of the CARiACT G10 solid amine
sorbent under dry conditions might be due to the presence of a
trace amount of water (∼50 ppm) that leaked in during the
thermogravimetric analysis (TGA) runs that protected the
sample or due to differences in the preparation procedures.
The effect of water vapor on the adsorption and desorption
behavior of CO2 on the CARiACT G10 solid amine sorbent
under low humidity conditions is displayed in Figure 3. It shows
four continuous cycles that were operated under humid condi-
tions during both the adsorption and desorption steps by
injecting 2 vol % H2O vapor into the flowing gas stream. The
corresponding relative humidities at 80 and 40 °C are 4.27% and
27.45%, respectively. For comparison, the figure also includes
four cycles carried out under identical but dry conditions on the
same sorbent after it was reactivated and four cycles carried out
under dry conditions on a completely different sorbent. Figure 3a
shows a run carried out at 80 °C using a feed containing 1.2 vol %
CO2 (dry basis) in N2 during the adsorption step, while Figure 3b
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Figure 3. CO2 loading in a CARiACT G10 solid amine sorbent at (a)
80 °C for four adsorption (CO2 at 1.2 vol % in N2, dry basis) and
desorption (N2, dry basis) cycles with a 40 min half-cycle time and (b)
40 °C for four adsorption (CO2, dry basis) and desorption (N2, dry
basis) cycles with a 40 min half-cycle time while continuously exposing
the sample to 2 vol % H2O vapor in the flowing gas stream, the same
sample under dry conditions after reactivation, and a completely
different sample under dry conditions. The gas flow rate was set at
60 cm3/min and 1 atm.
shows a run carried out at 40 °C using a feed containing 100 vol %
CO2 (dry basis) during the adsorption step.
The presence of H2O vapor had a slight effect on both the
kinetics and thermodynamics associated with the uptake and
release of CO2 by the sorbent. This was particularly true when
the relative humidity was higher at 40 °C. However, the perfor-
mance of the sorbent returned to that exhibited under dry
conditions when the sorbent was subsequently reactivated and
run under dry conditions. Moreover, the curves for the two
different samples of sorbent run under dry conditions nearly
overlapped, suggesting that the effect of H2O vapor on the
behavior of the sorbent was completely reversible, as reported
elsewhere with other solid amine sorbents.19,21
26 This material
is thus far superior to zeolites with respect to processing a water-
saturated feed stream because it obviates the use of a guard bed or
a layered bed in a PSA process.
The effects of the temperature and CO2 concentration on the
adsorption and desorption behavior of CO2 on the CARiACT
G10 solid amine sorbent are shown in Figures 4 and 5. They each
display four cycles at 40, 60, 80, and 100 °C and at different CO2
concentrations (in N2) during the adsorption step of 1.2, 4.8,
14.5, and 32.8 vol % (Figure 4) and 56.1, 69.8, 88.6, and 100 vol
% (Figure 5). The panels on the left show the behavior of the
sorbent throughout all four cycles, while the panels on the right
show the behavior of the samples during the first 4 min of the
adsorption step of the first cycle. All runs were carried under dry
conditions.
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Industrial & Engineering Chemistry Research ARTICLE

Figure 4. CO2 loading in a CARiACT G10 solid amine sorbent at 40, 60, 80, and 100 °C for four adsorption [CO2 at (a) 1.2, (b) 4.8, (c) 14.5, and (d)
32.8 vol % in N2] and desorption (N2) cycles with a 40 min half-cycle time during (1) all four cycles and (2) the first 4 min of the adsorption step during
the first cycle. The gas flow rate was set at 60 cm3/min and 1 atm.

This solid amine sorbent exhibited significant, but widely vary-
ing, working capacities that ranged between 0.25 (Figure 4a.1,
100 °C) and 2.8 mol/kg (Figure 5d.1, 80 °C) for a broad range of
temperatures and CO2 partial pressures. There were two plausible
reasons why the working capacity of this material was limited under
certain conditions. One reason was associated with kinetics, and the
other reason was associated with thermodynamics.
The kinetic limitation arises because the CO2 desorption
kinetics were strongly dependent on and thus limited by the
temperature. Only the runs carried out at 80 and 100 °C achieved
complete regeneration during the 40 min desorption step in N2.
5637
In contrast, the very slow desorption rates at 40 °C limited the
working capacity to about 0.4
0.6 mol/kg for all CO2 partial
pressures. The thermodynamic limitation arises because the
reaction between CO2 and the amine is exothermic, which
decreased the chemisorbed CO2 conversion with increasing tem-
perature. Notice that the maximum CO2 loadings achieved by the
samples were consistently smaller at 100 °C than at 80 °C, with the
effect being significantly more pronounced at lower CO2 partial
pressures (Figure 4a.1). This compromise between the kinetic
limitation at lower temperatures and the thermodynamic limitation
at higher temperatures revealed a range of temperatures between
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Industrial & Engineering Chemistry Research ARTICLE

Figure 5. CO2 loading in a CARiACT G10 solid amine sorbent at 40, 60, 80, and 100 °C for four adsorption [CO2 at (a) 56.1, (b) 69.8, (c) 88.6, and (d)
100.0 vol % in N2] and desorption (N2) cycles with a 40 min half-cycle time during (1) all four cycles and (2) the first 4 min of the adsorption step during
the first cycle. The gas flow rate was set at 60 cm3/min and 1 atm.

40 and 100 °C that exhibit an optimal CO2 working capacity for a
PSA process.
Another interesting aspect shown in Figures 4 and 5 was the
relatively fast initial rate of CO2 adsorption compared to that
observed during desorption, which was then followed by a very
slow uptake of CO2 that was more apparent in the runs carried out at
40 and 60 °C. Except for the 1.2 vol % CO2 case, all of the runs
exhibited this very fast dynamic in the first 5 min of the adsorption
step (panels on the right). These characteristically different rates of
adsorption alluded to the presence of a multistep adsorption/
reaction mechanism taking place during CO2 uptake.
5638
These figures also show that the rate of CO2 adsorption
increased with decreasing temperature, giving rise to an apparent
negative activation energy. This intriguing result can be explained
by the presence of physisorbed CO2 that not only was in
thermodynamic equilibrium with CO2 in the gas phase but also
participated directly in the reaction with the immobilized amine,
as indicated by the mass balance expression in eq 1. According to
eq 2, which represents the equilibrium state of the physisorbed
CO2, the rate of the forward reaction in eq 1 becomes controlled
by an activation energy given by Ef þ ΔHa that may take on
negative values. Because Ef is always a positive number and ΔHa
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Industrial & Engineering Chemistry Research
Figure 6. (a) Adsorption rates of CO2 in a CARiACT G10 solid amine
sorbent at different temperatures and CO2 partial pressures during the
adsorption step of the first cycle. (b) Desorption rates of CO2 in the
amine-doped CARiACT G10 at different temperatures and CO2 partial
pressures during the desorption step of the first cycle. (c) CO2 working
capacity in a CARiACT G10 solid amine sorbent at different tempera-
tures and CO2 partial pressures during the last (fourth) cycle.
is always a negative number, it is entirely possible that the
absolute magnitude of ΔHa can be greater than that of Ef, giving
rise to this apparent negative activation energy.47
A clearer depiction of the trend between the adsorption rate
and temperature is shown in Figure 6. It displays the maximum
adsorption (Figure 6a) and desorption (Figure 6b) rates during
the first cycle of the runs shown in Figures 4 and 5 and the CO2
working capacity of the last (fourth) cycle of those same runs
(Figure 6c). In addition to a strong dependence of the CO2
adsorption rate on PCO2, the CO2 adsorption rates were generally
faster at lower temperatures. This was again consistent with
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Figure 7. Model predictions versus experimental data: (a) equilibrium
CO2 loading in a CARiACT G10 solid amine sorbent at 80 and 100 °C
according to eq 6 (linearized version of eq 3); R2 = 0.9989; (b)
equilibrium CO2 loading in a CARiACT G10 solid amine sorbent at
80 and 100 °C according to eq 3 and equilibrium CO2 loading predicted
from eq 3 at 40 and 60 °C by extrapolation. All experimental CO2
loadings correspond to those from the last (fourth) cycle shown in
Figures 4 and 5. An apparent equilibrium state is reached in the CO2
loading at 80 and 100 °C but not at 40 and 60 °C (refer to the text).
physisorbed CO2 in equilibrium with PCO2 that participated
directly in the reaction with the immobilized amine. In contrast,
the CO2 desorption rates were much smaller, strongly decreased
with decreasing temperature, and exhibited only a weak depen-
dence on PCO2, particularly at the lower temperatures, i.e., at 40
and 60 °C. This apparent dependence of the desorption rate on
PCO2 was actually manifested through its dependence on the
initial CO2 loading at the onset of the desorption step. As a result
of the thermodynamic restriction described earlier, those initial
CO2 loadings generally decreased with increasing temperature
and decreasing PCO2, giving rise to this apparent dependence of
the desorption rate on PCO2.
It was mentioned earlier that it would be possible to operate a
PSA process in the 40
100 °C range, based on the CO2 working
capacities observed in Figures 4 and 5. Figure 6c further shows that
the optimal operating temperature for a PSA process depended on
PCO2. For situations where the CO2 partial pressure in the feed is
larger than about 10 kPa, around 80 °C would be optimal. However,
for situations where the CO2 partial pressure in the feed is below
about 5 kPa, between 60 and 80 °C would be optimal.
It was also very clear from the runs carried out at 80 and
100 °C (Figures 4 and 5) that an equilibrium state was achieved
by the end of the adsorption step at all of the CO2 partial
pressures. It was also very clear from the runs carried out at 40
and 60 °C that this was not the case at those lower temperatures
because of the very slow kinetic process that took place after the
initial rapid uptake of CO2 in the first 5 min. Figure 7 shows the
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Industrial & Engineering Chemistry Research
correlation of eq 3 or 6 to the experimental equilibrium CO2
loadings extracted from the runs carried out at just 80 and
100 °C. Figure 7a displays the very good fit (R2 = 0.9989) that
resulted by fitting simultaneously all of those loadings to the
linearized form of eq 3, i.e., eq 6, over the entire range of CO2
partial pressures. The resulting linear behavior suggested that the
underlying thermodynamic mechanism described by eq 1 was
quite plausible.
The corresponding fitting parameters from eq 6 were N =
2.891 mol/kg, k0 = 1.069  10
8 kPa
1, and ΔH = 5.003  101
kJ/mol. These values were consistent with those previously
reported for this material.19 They were also used in eq 3 to
generate the curves in Figure 7b, which displays a comparison of
the experimental data with the Langmuir-type model at 80 and
100 °C. The agreement was again quite good. However, when
eq 3 was used to extrapolate the equilibrium behavior to the two
lower temperatures (40 and 60 °C), the predictions did not agree
with the experimental CO2 loadings extracted from the corre-
sponding runs at 40 and 60 °C at the end of the adsorption step of
the fourth cycle (Figures 4 and 5). This was not surprising and
further confirmed that equilibrium was not attained at those
lower temperatures because of the very slow kinetic process that
was taking place. These results suggested very strongly that the
optimal temperature for operating a PSA process would be in the
80 °C range, where both the kinetics (adsorption and desorption
rates) and thermodynamics (CO2 loading) would be most
favorable.
’ CONCLUSIONS
A solid amine sorbent consisting of PEI immobilized into a
CARiACT G10 silica substrate was investigated over a wide
range of conditions using TGA to evaluate its potential for CO2
capture by PSA. Each TGA run consisted of an initial activation
step at 100 °C for 80 min in N2, followed by four consecutive
cycles of 40 min adsorption in CO2/N2 and 40 min desorption in
N2. The role of the CO2 concentration in the adsorption step
(1.2, 4.8, 14.5, 32.8, 56.1, 69.8, 88.6, and 100 vol %) at four
temperatures (40, 60, 80, and 100 °C) under dry conditions was
investigated, along with the role of water vapor at two conditions
(2 vol % H2O and 1.2 vol % CO2 at 80 °C and 2 vol % H2O and
100 vol % CO2 at 40 °C). The sorbent stability was also
investigated by carrying out 78 consecutive adsorption (100 vol %
CO2) and desorption (100 vol % N2) cycles at 80 °C under dry
conditions.
The results revealed that CARiACT G10 solid amine sorbent
was very stable over 78 adsorption
desorption cycles under the
conditions investigated. Water vapor at a low relative humidity
exhibited only a minor and reversible effect on both the thermo-
dynamics and kinetics of CO2 uptake and release. The isothermal
CO2 working capacity ranged between 0.25 and 2.8 mol/kg,
increased with increasing CO2 concentration, exhibited a max-
imum with increasing temperature, and produced a heat of
adsorption/reaction of around 50.0 kJ/mol.
Overall, these results suggested that CARiACT G10 solid
amine sorbent is suitable for use in a PSA process for post-
combustion CO2 capture, based on its attractive kinetic and
thermodynamic properties. Because it was very stable with
respect to isothermal cycling and in the presence of water vapor
and because it exhibited reasonable CO2 uptake and release rates
and working capacities over a broad range of temperatures, the
performance of this material in a PSA process should prove to be
5640
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far superior to zeolites. An optimal PSA operating temperature
was determined to be around 80 °C for CO2 partial pressures >10
kPa and between 60 and 70 °C for CO2 partial pressures <10 kPa.
These temperature ranges are ideally suited for postcombustion
CO2 capture.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: ritter@cec.sc.edu.
’ ACKNOWLEDGMENT
The authors gratefully acknowledge financial support pro-
vided, in part, by the NSF Research Experience for Under-
graduates (REU) Site in Chemical Engineering at the
University of South Carolina under Grant EEC-0851997 and,
in part, by the Center for Strategic Approaches to the Generation
of Electricity at the University of South Carolina.
’ NOMENCLATURE
Eb = backward activation energy for the CO2 chemisorption
reaction (J/mol)
Ef = forward activation energy for the CO2 chemisorption
reaction (J/mol)
k = affinity coefficient between CO2 and the sorbent (1/kPa)
k0 = preexponential constant for the affinity coefficient (1/kPa)
kb = backward rate constant for the CO2 chemisorption reaction (1/s)
kf = forward rate constant for the CO2 chemisorption reaction
(kg/mol/s)
kH = Henry’s law constant for physisorbed CO2 (kg/mol/kPa)
N = total number of sites for chemisorbed CO2 (mol of CO2/kg of
sorbent)
PCO2 = partial pressure of CO2 in the gas phase (kPa)
qCO2 = loading of chemisorbed CO2 (mol of CO2/kg of sorbent)
qCO2,a = loading of physisorbed CO2 (mol of CO2/kg of sorbent)
R = universal gas constant (J/mol/K)
T = temperature (K)
Greek Symbols
ΔHa = heat of adsorption for physisorbed CO2 (J/mol)
ΔH = effective heat of adsorption/reaction (J/mol)
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