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Stability of a Benzyl Amine Based CO2 Capture Adsorbent in View of

Regeneration Strategies
Qian Yu,* Jorge de la P. Delgado, Rens Veneman, and Derk W. F. Brilman
Sustainable Process Technology (SPT), Faculty of Science and Technology, University of Twente, PO Box 217, 7500 AE Enschede,
The Netherlands
*
S Supporting Information

ABSTRACT: In this work, the chemical and thermal stability of a primary

amine-functionalized ion-exchange resin (Lewatit VP OC 1065) is studied in
view of the potential options of regenerating this sorbent in a CO2 removal
application. The adsorbent was treated continuously in the presence of air,
different O2/CO2/N2 mixtures, concentrated CO2, and steam, and then the
remaining CO2 adsorption capacity was measured. Elemental analysis, BET/
BJH analysis, Fourier transform infrared spectroscopy, and thermogravimetric
analysis were applied to characterize adsorbent properties. This material was
found to be thermally and hydrothermally stable at high temperatures.
However, significant oxidative degradation occurred already at moderate
temperatures (above 70 °C). Temperatures above 120 °C lead to degradation
in concentrated dry CO2. Adding moisture to the concentrated CO2 stream
improves the CO2-induced stability. Adsorbent regeneration with nitrogen
stripping is studied with various parameters, focusing on minimizing the moles of purge gas required per mole of CO2 desorbed.

1. INTRODUCTION other advantages over aqueous amine solvents such as faster

The concentration of CO2 in the atmosphere has increased by sorption kinetics, higher CO2 capacity, higher stability, and
higher resistance to contaminants, and being less corrosive and
some 100 ppm from the 1700s to 2005 and is nowadays above
more environmentally friendly.5,10,11 The development of
400 ppm.1 Electricity production and transportation were
amine based sorbents is still in its early stage compared to
estimated to contribute around 68% of total CO2 emission in
aqueous amine solvents. Until now, most studies on SASs
the U.S. in 2014, produced by burning of fossil fuel such as coal,
emphasize modifying the sorbent materials for a higher uptake
natural gas, and petroleum.2 These types of fuel cannot be
capacity of CO2.9 Since 2010, the literature shows an increasing
replaced by biofuel or carbon neutral fuel in large scale in the
number of studies on other important aspects such as
near future. Under these circumstances, carbon capture and
kinetics,12−15 process design and optimization,16−20 and
storage (CCS) becomes important to halt the CO2 emission sorbent stability.21−27 Among these, the topic of stability is
rate. In the report released by National Technology Laboratory very important since it determines the lifetime of the sorbent,
in 2010, CCS technologies would add around 83% and 44% to which is not inexpensive. The lifetime of the sorbent is closely
the cost of electricity (COE) for a new pulverized coal plant related to the number of allowable cycles for the adsorbent.
(PC) and new natural gas combined cycle power plants The higher this number of cycles, the lower the cost of the
(NGCC) respectively.3 For years, efforts have been made to adsorbent per unit of CO2 produced:
reduce the costs of carbon dioxide capture.4−7 Amine scrubbing
using aqueous amine solutions is so far the most commercial
cost of sorbent(€/ton CO2 )
and well-developed technology for postcombustion CO2
capture.8 However, it is still an expensive technology since €/ton sorbent
= tonCO2
heating up the liquid water is energy intensive. Dry sorbent
processes are seen as the possible next generation method for
no. of cycles × Δqcycle ( tonsorbent ) (1)
CO2 capture.9
Supported-amine based adsorbents (SASs) are assumed to The stability of the SASs can be affected by multiple factors
follow similar reaction pathways as aqueous phase amines but such as operating temperature and the presence of O2, CO2,
require less energy as they avoid energy required to heat up the and steam, based on previous studies.21−35 These factors relate
bulk of water. Supported-amine sorbents contain amine
functional groups (such as primary amine and secondary Received: November 30, 2016
amine) on a solid supports. The bindings of the functional Revised: February 8, 2017
groups to the support materials can be very different and is Accepted: March 2, 2017
based on their preparation methods.10 SASs are said to possess Published: March 2, 2017

© 2017 American Chemical Society 3259 DOI: 10.1021/acs.iecr.6b04645

Ind. Eng. Chem. Res. 2017, 56, 3259−3269
Industrial & Engineering Chemistry Research Article

to either the adsorption feed gas (e.g., flue gas or air) or to the adsorption and desorption is 30 h. All materials except for
regeneration stripping gas. It is crucial that for each sorbent the secondary monoamine deactivated significantly, for more than
effects of these different factors on the sorbent are identified 50% capacity decrease in these 30 h, attributed to the formation
and quantified before scaling-up the process. of urea based on two mechanisms. One is the formation of
Depending on the application, oxygen will be present in open-chain urea, which can only be formed from primary
different concentrations in the feed gas. For CO2 removal from amine. The other mechanism is to form cyclic urea. This is the
more concentrated feeds (such as biogas), air could even be only mechanism for urea formation between secondary
considered for use as stripping gas and hence be present during multiamines such as linear polyethylenimine (PEI). Didas et
regeneration. Bollini et al.30 and Heydari-Gorji et al.29 reported al.27 evaluated different pathways to form urea by DFT
in 2011 separately the long-term effect of air at high calculations and discovered that the one producing isocyanate
temperature on grafted primary, secondary, and tertiary as intermediate is the lowest-energy route. This finding
monoamines as well as on mixed-amine materials containing indicates that primary amines are more likely to form urea, in
both primary and secondary amines. Interestingly, both studies line with the finding by Sayari et al.28
found that primary and tertiary amines show superior oxidative Steam is relatively cheap and widely available and used in
stability compared to secondary amines on the studied industrial operations.36 When using steam to regenerate the
supported amines. Subsequently, Heydari-Gorji et al.23 studied adsorbent, it is simple to separate the regenerated CO2 from
supported amines based on SBA-15 impregnated with linear the product gas via condensation of water. Solid amines
polyethylenimine (PEI). It was found that the materials were obtained on silica-type support through different preparation
deactivated severely in CO2 free air. In contrast, the oxidative methods were shown to be completely regenerated through
stability of the adsorbents was improved in the presence of steam stripping under mild conditions.34 However, the
moisture and CO2. This is due to the fast reaction between supports of these adsorbents, amorphous silica, can be
CO2 and solid amines, leading to the formation of carbamate problematic during long-term steam treatment. The hydro-
and bicarbonate, which protect the material from oxygen attack. thermal stability of silica supported amine solid sorbents has
The practical implication of this finding may be limited, since been investigated by Li, Jones, et al.35 They investigated
adding CO2 to the regeneration gas will result in a reduction of different classes of amine sorbents, supported with silica
the CO2 working capacity. Based on aforementioned studies, it mesocellular foam (MCF) by flowing steam in the presence of
is clear that the oxidative stability of the studied SASs is related air or nitrogen at 106−120 °C for 24 h. The degradation of
to both the state of the amines and the gas conditions. these amine sorbents is because structural collapse, which is
Using pure CO2 in a thermal swing regeneration of the supported by a reduction in surface area and pore volume. For
adsorbents can be relevant when aiming to produce a stream of this reason, the same group switched from MCF silica to
pure CO2 without requiring downstream separation. With CO2 alumina for further research.37 Three years later, in 2013,
at elevated temperature, the formation of urea groups on SASs Hammache, Pennline, et al.32 investigated the impact of steam
was reported by Drage et al.21 based on the observation of an on sorbent of PEI impregnated with silica. After 5 h exposing to
increase in sorbent weight when the temperature was higher steam at 105 °C, a decrease of 12% in CO2 uptake was
than 140 °C under a flow of pure CO2 on a PEI impregnated measured. A reduction in the surface area and pore volume on
silica sorbent. The weight increases corresponding to a the sorbent was observed after steam treatment, which is in line
secondary product formed, which could not adsorb CO2 and with the observations from Li et al.35 One intriguing finding
was identified to contain urea linkages. Sayari et al.22 found from Hammache et al.32 is that no structural destruction was
CO2-induced deactivation in amine-containing material even at identified from SEM and BET on bare SiO2 supports. Based on
temperatures as low as 50 °C in the presence of pure CO2. The their study, they postulated that the decreases in texture
urea was confirmed to be responsible for the deactivation by properties are attributed to a reagglomeration of the amines,
13
C CP MAS NMR and DRIFT. Remarkably, they demon- resulting in a partial blockage of the pores, thereby limiting
strated that the urea can be completely inhibited and CO2 access.
regenerated by adding very little moisture. Subsequently in In summary of literature findings, the stability of amine based
2011, Sayari et al.28 published another paper on the effect of sorbents are related to the natures of amine, the types of
state of amine in urea formation. They observed that primary support, and the preparation methods. Specifically with regard
monoamine rather than secondary monoamine are deactivated to the types of support, the effect of O2, CO2, and H2O have
in pure CO2 at 55 °C for adsorption and 120 °C for been mainly explored on the materials with silica-type
regeneration in a purge flow of N2 over 60 cycles. The supports,21,22,26,30,38 alumina-type supports,33,37 or cellu-
difference in the stability of the different amines was associated lose.25,39 Recently another type of supported amine sorbents,
with isocyanate, an intermediate when forming urea. This amine functionalized ion exchange resins (and specifically
isocyanate can be produced from dehydration of carbamic acid Lewatit VP OC 1065), was investigated for CO2 removal
formed only from primary amine. Mixed amines, containing applications in our research group. This material is a
primary and secondary amines, can form isocyanate from the polystyrene based ion-exchange resin (IER), functionalized
presence of primary amine, which further reacts with primary or with a primary amine.40 It is demonstrated that this IER
secondary amine to form urea. Later, in 2012, an extended exhibits high CO2 equilibrium capacity, fast kinetics,20 and high
study on the mechanism of urea formation was published by tolerance of water.41,42 Yet there is little information on the
the same group.24 In this study, the stability of a wide variety of stability of this IER. An initial study of the stability of this IER
mesoporous silica-grafted and impregnated amine sorbents was has been done by the group of Kitchin, measuring the
investigated in the presence of CO2. Both in adsorption and in performance decay in the presence of air at 120 °C.43
desorption, the samples were exposed to a dry, pure CO2 According to their results, the CO2 adsorption capacity reduces
stream during adsorption at 50 or 100 °C and desorption at dramatically after 7 days of continuous treatment. But the
130−160 °C. The total time of CO2 exposure in both temperature as high as 120 °C would not be necessary for the
3260 DOI: 10.1021/acs.iecr.6b04645
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Industrial & Engineering Chemistry Research Article

regeneration using air as sweep gas. So far, there is no experiment, the IER was first heated up to 100 °C for 1 h in
comprehensive study on the stability of this IER. N2 to desorb any preadsorbed CO2 and H2O. A separate test
The objective of this paper is to study the stability of this IER showed that by this pretreatment the sorbent capacity was not
over variable conditions during long-term exposure, thereby affected negatively. After this desorption step, the conditions in
varying specifically the O2, CO2, and H2O partial pressure in the test tube were adjusted to the measurement temperature,
the feed gas and operating over a wide temperature range. The before switching to the gas to be tested; dry air, CO2-free (CF)
deactivation results can be used to extrapolate the sorbent air, CO2/O2 (0−42% CO2, 12% or 21% O2, both as dry and as
lifetime. Furthermore, regeneration experiments in inert gas humidified gas), N2, or CO2/N2 (80% or 100% CO2). The
under varying flow rate, and temperature will be studied using a oxidative stability was tested at different temperatures in the
lab-scale fixed bed reactor. range of 50−120 °C up to 72 h of exposure. Particularly, an
extensively long measurement of 18 days dry air exposure was
2. EXPERIMENTAL SECTION carried out at 80 °C for inquiring more information on the
2.1. Material. The sorbent material used in this study was effect of oxygen after 72 h. Apart from the effect of oxygen, the
obtained from Lanxess. It is a commercial adsorbent contains CO2-induced stability was measured under the flow of 80 vol %
polystyrene−divinylbenzene copolymer functionalized with and 100% CO2/N2 at 120 and 150 °C up to 7 days.
aminomethylene groups.44 The external morphology was Additionally, the thermal effect was measured in pure nitrogen
measured by scanning electron microscopy (SEM) named at 150 °C for 72 h. After the long-term exposure treatment, the
JEOL JSM 6010LA; the result is shown in Figure 1 displaying material was then cooled at lab temperature under flowing N2
and then collected for further analysis of the remaining CO2
adsorption capacity. Steam stability was studied in small
assembled lab-scale setup, where 1 g of the adsorbent was
loaded in a Büchner funnel with filter paper underneath. Under
the funnel, a three neck flask filled with deionized water was
applied as steam generator. The other two mouths of the
boiling flask were connected to the supply of water and the
thermometer. The supply of water compensates the loss of
steam but did not affect the water boiling. A watch glass was
used to cover the funnel. The thermocouple was connected to a
hot plate below the boiling flask. By regulation of the power of
the hot plate, intensive boiling water can be generated. In this
way, the setup produced a continuous flow of saturated water
vapor at ambient pressure, passing the adsorbent particles. In
advance to the steam exposure, the IER has been treated in N2
at 100 °C for 60 min then moved to the setup for treating in
steam continuously for 48 h. Subsequently, the CO2 adsorption
capacity was measured and compared with that of the fresh
Figure 1. SEM graph of Lewatit VP OC 1065.
adsorbent.
2.3. Adsorbent Characterization after the Degrada-
the porous structure of the sample. The averaged pore volume, tion Experiments. A NETZSCH STA 449 F3 Jupiter
surface area, and pore radius of the IER are 0.2 cm3/g, 25 m2/g, thermogravimetric analyzer (TGA) was used to evaluate the
and 38 nm, respectively. The adsorbent is spherical-bead like CO2 adsorption uptake of the IER before and after the
with diameter between 0.3 and 1 mm. The molar concentration degradation experiments. The CO2 uptake was measured twice
of N is 7.5 mol/kg, measured by Alesi et al.45 via energy- for each sample, then the average value was shown in the
dispersive X-ray spectroscopy (EDS). Results and Discussion section. A typical run in TGA consists
2.2. Continuous Exposure to O2-, CO2-, N2- and H2O- of preheating the sample in flowing N2 at 100 °C for 1 h to
Containing Gases. The stability of the IER under the remove the preadsorbed CO2 and moisture, then cooling to 40
conditions of continuous exposure to O2-, CO2-, N2-, and °C before switching to a gas mixture of 15% CO2/N2 for 3 h of
steam-containing gas was examined in a continuous flow setup, adsorption. Elemental analysis (Carlo Erba EA 1100 CHNS,
presented in Figure S1 in the Supporting Information (SI). A EA) was used to determine any change in chemical
test tube DURAN GL 14 (13 mm diameter and a 100 mm composition of the IER after continuous exposure treatment.
height) was loaded with 1 g of the adsorbent. The test tube was Prior to the elemental analysis, the sample was again pretreated
put into a heating block with temperature controller. in flowing nitrogen at 100 °C for 1 h to obtain a CO2-unloaded
Degradation experiments were performed at the temperature sample. Approximately 20 mg of ground sample was placed into
range of 50−200 °C with different gas compositions, obtained the machine for one measurement, which takes 6 min. Surface
by mixing technical-air, pure N2, and pure CO2. To exclude a areas and total pore volumes of the sample were measured to
possible impact of CO2 during the oxidative degradation tests, a identify the changes in the morphology of the IER after
larger “guard bed” filled with the same IER was connected continuous exposure in O2-containing gas. The results were
upstream of the test tube to obtain CO2 free air. A bubbling estimated from N2 physisorption data obtained by measure-
humidifier filled with deionized water was connected prior to ments performed on a Micromeritics Tristar apparatus at 77 K.
the test tube and mixed with dry air and dry concentrated CO2 Prior to physisorption analysis, the sample was degassed at 150
to investigate the moisture effect. Two three-way valves were °C for at least 10 h. Surface areas were estimated by the
connected to let the gas mixture either bypass or pass through Brunauer−Emmett−Teller (BET) equation. The pore size
the “guard bed” and/or the humidifier. Prior to each distribution and the pore volume were determined from the
3261 DOI: 10.1021/acs.iecr.6b04645
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nitrogen desorption branch using the Barrett−Joyner−Halenda displayed in Figure 2 are straight and overlapping, indicating
(BJH) method. Fourier transform infrared (FTIR) spectrosco- that there is no degradation after 50 h at both temperatures. Yet
py analysis was used to determine the changes in the nature of the sorbent is degraded severely when temperature is ramped
amine of the IER as a result of exposure to O2- and CO2- up further to 200 °C. It is found that 39% of the CO2 uptake
containing gases. Measurements were taken on a Bruker IR capacity is lost after continuous exposure in N2 at 200 °C for a
Tensor 27 at an optical cell temperature of 200 °C, and spectra time span of 50 h. However, for this IER a regeneration
were recorded in the range of 400−4000 cm−1. temperature of 150 °C seems sufficiently high to allow for
2.4. Thermal Swing Desorption of CO2. The regener- complete regeneration, and there is no clear need to increase
ation of the sorbent material was measured in separate fixed- the temperature beyond this level. Furthermore, this result can
bed (16 mm ID, 500 mm long) setup. A schematic is shown in be regarded as blank test to compare with the results in the
Figure S2 in the SI. The setup was equipped with other succeeding sections.
apparatuses such as three mass flow controllers, a water bath, To evaluate the impact of oxygen during adsorption or
and an infrared CO2 gas analyzer. The CO2 concentration in regeneration, experiments were done in the setup described in
the inlet gas was controlled by mixing a flow of high purity the section 2.2. The experiments were carried out using a
(grade 5.0) N2 and high purity (grade 5.0) CO2. The flow rates continuous flow of dry air in the temperature range of 50 to
were controlled using two BROOKS mass flow controllers. The 120 °C, which was deemed as practical thermal swing operating
CO2 analyzer (LI-COR LI840A) was used to monitor the CO2 window. Figure 3 shows the CO2 adsorption capacity of the
concentration in the outlet gas of the fixed-bed reactor
(detection range 0−2 mol %). In the adsorption process, a
JULABO F32 water bath was used to control the temperature
of the reactor. In the regeneration process, an electric heating
spiral, which was wound around the column, was used to
control the temperature to reach the maximum temperature of
150 °C. Typically, around 5 g of dried IER was loaded in the
reactor during the fixed bed desorption tests. Prior to the
adsorption, the reactor was first heated up to 100 °C for 60 min
to completely desorb the preadsorbed CO2 and water. Then,
1.5 vol % CO2/N2 gas stream passed through the column at 40
°C until the concentration of CO2 in the outlet equaled the
concentration in the inlet. Subsequently, temperature swing
desorption by N2 stripping was conducted by using N2 as sweep
gas to the reactor at flow rates in the range of 0.50 to 2.50 L/
min at different temperatures in the range of 80 to 120 °C. The
product gas of the regeneration was brought to a nondispersive Figure 3. Effect of temperature in dry air exposure on the CO2
infrared (NDIR) CO2 analyzer for quantification. adsorption capacity (evaluated at 15 vol % CO2, 40 °C) as a function
of treatment time.
3. RESULTS AND DISCUSSION
adsorbent after treatment, normalized by their adsorption
3.1. Thermal Effect and the Effect of Oxygen on the capacity before treatment, and plotted as a function of the
Sorbent. The thermal and oxidative stability of the IER was treatment duration. According to the results, the CO2 capacity
measured in pure N2 and O2 containing gases at different of the IER is affected by the oxygen when the temperature is
temperatures. The adsorbent material displays thermal stability high. The IER displays a dramatic decrease in CO2 uptake
when the temperature is below 150 °C, as shown in Figure 2. capacity when the temperature is above 80 °C, whereas it seems
The sorbent has been tested at 100 and 150 °C; the curves stable (for the time span evaluated) at 50 °C. The CO2 uptake
reduces by as much as 30.2%, 46.7%, and 80.5% of its original
capacity, when treated at temperatures of 80, 100 and 120 °C,
respectively, for 72 h. On the other hand, the adsorbent
material does not seem to be progressively degraded by the
oxygen-containing gas by the continuous exposure at the lower
temperature conditions (50−70 °C). The CO2 adsorption
capacity decreases less than 10% at 70 °C after 72 h air
exposure. It is noteworthy that the rate of losing capacity from
80 to 120 °C is faster at the beginning and decreases with
progressing time. The degradation rate increases with temper-
ature; it seems that a kinetic effect is a dominant factor in the
degradation mechanism. To examine the effect of air in a
prolonged condition (more than 72 h), a longer measurement
was done at 80 °C for 432 h, resulting in an additional 31% of
CO2 capacity losses (hence, to a total capacity loss of 61% in
432 h). To study the thermal effect separately from that of
Figure 2. Normalized CO2 adsorption uptake capacity (evaluated at 15 oxygen, the IER was also treated at elevated temperature in the
vol % CO2, 40 °C) of the IER after long-term exposure to N2 at presence of pure N2. A minor 5% decrease in CO2 adsorption
temperatures of 100, 150, and 200 °C. capacity was found in the IER after being treated in pure N2 for
3262 DOI: 10.1021/acs.iecr.6b04645
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72 h at 150 °C, ruling out the thermal effect as main therefore essential to avoid as much as possible the presence of
contributor to capacity loss. It was therefore concluded that the oxygen during the regeneration process.
main reason for the capacity decrease observed was oxidative Subsequently, the effect of CO2 on oxidative degradation of
degradation. Earlier studies demonstrated that primary amines the IER was studied. From the work by Heydari-Gorji et al.23 it
are, among the amines, the most stable ones to oxidative appears that the oxidative stability of supported amines is
degradation.29,30 The amine sorbents in both cited studies are significantly improved in the case of humid gases containing
supported with silica-type material. Our results are in line with both O2 and CO2. Experiments were carried out using
an earlier publication of Hallenbeck et al., who found 79% CO2 12%:42%:46% O2/CO2/N2 at 100 °C and atmospheric
capacity loss after continuous exposure in air at 120 °C for 7 pressure for both dry and humidified purge gases, with a
days using the same material.43 partial pressure of water of 2847 Pa. As shown in Figure 4, this
In a further experiment, the effect of the oxygen IER exhibits 30% and 24% uptake capacity losses after exposure
concentration on the degradation rate was investigated. The to dry and wet CO2 containing gases at 100 °C after 72 h. This
experimental work was carried out by mixing the air with is significantly less compared to 42% CO2 capacity losses at the
nitrogen to a gas mixture with a reduced oxygen concentration same oxygen concentration without CO2. Hence, indeed, the
of 12 vol %, as verified by micro-GC analysis. A series of oxidative stability increases in the presence of humidified gases
experiments was carried out by treating the sorbent in 12% O2 containing both CO2 and O2 under mild conditions, probably
at 80, 100, and 120 °C for 72 h. According to the results in because of their rapid conversion to carbamate and bicarbonate
Figure 4, the reduction of oxygen concentration slows down the that protect the amine group from degradation by oxygen.23
However, we found that the reduction in O2 degradation is not
as large as in the cited study. When oxygen is present during
regeneration at elevated temperatures, some degradation seems
unavoidable.
Apart from the study of oxidative stability of the IER at high
temperatures, also the sorbent oxidative stability at relative low
temperature was studied. In this test, 2 g of the sample was
exposed to ambient (indoor) air at 20−25 °C, at 30−60%
relative humidity for three months. The sample was then
collected and its remaining capacity for CO2 was measured
every month. The results (Figure S3 in SI) show there is no
significant capacity loss after three months of exposure. The
oxygen only has detrimental effect on the IER at high
temperature (above 70 °C in this study), but exposure to
oxygen at ambient conditions (e.g., during CO2 air capture or
Figure 4. Normalized CO2 adsorption capacity (evaluated at 15 vol %
in flue gas) is not leading to significant degradation rates. Since
CO2, 40 °C), normalized by fresh sorbent capacity under the same only continuous exposure is tested here, additional work with
conditions, after treating the sample with 12% and 21% O2 (balance multiple adsorption/desorption cycles is recommended for
N2) at the temperature of 80, 100, and 120 °C. At 100 °C, the IER was confirmation and for evaluation of sorbent lifetime during cyclic
treated under two additional conditions: (a) 12% O2 and 42% CO2; operation.
(b) 12% O2, 42% CO2 and 2847 Pa water. 3.2. Sorbent Characterization before and after
Oxidative Degradation. On the basis of the results in the
section 3.1, the loss of CO2 capacity during regeneration is
degradation rate for the sorbent in all cases. After 72 h, the CO2 found to be more related to oxidative degradation rather than
capacity during treatment with 12% O2 decreases by 9%, 42%, to thermal degradation effects. Several chemical reaction
and 72% at 80, 100, and 120 °C, respectively, versus 30.2%, pathways involved in oxidative degradation of amines have
46.7%, and 80.5% reduction in air at the same temperatures. been proposed in literature. In these proposed reactions, the
Decreasing the concentration of oxygen to 12% reduced the reaction products can be categorized as in either gas31 or solid
degradation most significantly at 80 °C. At higher temperatures phase.38 If the loss of amine functionality leads to gaseous
the differences between runs with air and the gas with 12% O2 degradation products, there would be a corresponding change
is much smaller. The results show that oxidative degradation at in the nitrogen content of the sorbent. For this reason,
high temperature is difficult to avoid if oxygen is present. It is elemental analysis (EA) and sorbent structure characterization

Table 1. Mass-Based Elemental Composition and CO2 Capacity of Lewatit VP OC 1065 before and after Degradation
Experiments in Dry Air at 120°C for 72 h
Adsorbent %C %H %N %O N loading (mol/kg) CO2 uptakea (mol CO2/kg IER)
fresh_01 81.04 8.38 9.53 1.05 6.81 2.15
fresh_02 80.48 8.23 9.46 1.83 6.76 2.15
fresh_03 80.57 8.29 9.64 1.50 6.89 2.15
degraded_01 79.06 7.01 7.24 6.68 5.17 0.42
degraded_02 80.00 6.99 7.44 5.57 5.31 0.42
degraded_03 79.53 7.01 7.36 6.10 5.26 0.42

a
CO2 capacity was measured at 40 °C for 15 vol % CO2 in N2 at atmospheric pressure

3263 DOI: 10.1021/acs.iecr.6b04645

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techniques (BET and BJH, SEM) were applied to characterize

the material. Besides, FTIR analysis was applied to identify
possible newly formed species in the solid state. The degraded
sample used in this section was obtained after treatment in dry
air at 120 °C for 72 h.
The elemental composition of the IER before and after
oxidative degradation is shown in Table 1. The experiments
were repeated three times resulting in nitrogen loadings of 6.82
mol/kg for the fresh sample and 5.25 mol/kg for the degraded
sample, a reduction of 23%. Meanwhile, the (dry) CO2
adsorption uptake drops from 2.15 to 0.42 mol/kg, hence a
reduction of more than 80%. Since in the absence of water two
moles of amine bind to one mole of CO2 in dry conditions
theoretically, the decrease in CO2 adsorption capacity is much
larger than the decrease in N-content. Therefore, the decrease
of the N-content is not the main reason (nor the main
characteristic in analysis) for the reduction of CO2 uptake. Figure 5. IR absorbance spectra before and after exposure to dry air at
Oxidative degraded species still present in the solid sorbent 120 °C for 72 h.
may lead to CO2 adsorption capacity decreases for two reasons.
First, the newly formed species may accumulate in the pores, stretching range can be observed in studies with other
potentially leading to pore blocking, which should be reflected supported amine sorbents, such as AEAPDMS-NFC25 and
by morphology changes in the degraded material. To analyze TP600S,38 treated for 15 h in humid air at 90 °C and for 12 h at
this, the surface area, pore volume, and pore radius were 100 °C in air, respectively. Furthermore, a new peak in the
measured as shown in Table 2. The results show the surface range of 1660−1680 cm−1 was observed after oxidative
degradation, which is consistent with the findings of other
Table 2. N2 Physisorption Characterization of Lewatit VP studies in the field of oxidative degradation.29,38 However,
OC 1065 before and after Oxidative Degradation in Dry Air different types of species were related to this range according to
at 120°C for 72 h different papers. Calleja et al.47 found an additional peak at
fresh IER degraded IER 1667 cm−1 on their amine grafted SBA-15 after drying in air at
110 °C for 85 h and associated this with CN species.
BET surface area (m2/g) 24.8 23.4
Meanwhile, Srikanth et al.38 tested one type of SAS with SiO2
BJH pore volume (cm3/g) 0.20 0.16
supported on TEPA, which lost 55% of its original CO2
BJH pore diameter (nm) 38 32
adsorption capacity after exposure in air at 100 °C for 12 h,
exhibiting an extra peak at 1670 cm−1 upon degradation. It was
area of the fresh and degraded sample to be similar. The pore proposed in Srikanth’s study that there are two species
volume decreases somewhat from 0.20 to 0.16 cm3/g corresponding to this peak. One is nitrite (NO) formed by
accompanied by a reduction of pore diameter from 38 to 32 oxidation of the primary amine. The other is carbonyl CO
nm. However, the CO2 uptake losses, as large as 80%, exceed resulting from amide species, of which the band is overlapping
the 20% reduction in the pore volume and the minor change in with the nitrites NO band. In the present work, both the
area. The minor change in morphology is further confirmed by NH2 and the CH2 spectra decline, which may point to the
SEM. The surface pore volume of the degraded adsorbent formation of species in line with Srikanth’s study. The
declines somewhat but cannot completely explain the extreme formation of nitrite and amide is in agreement with the
reduction in the capacity for CO2. The results of SEM can be increased oxygen content, see Table 1. In summary, the
found in Figure S4 in the Supporting Information. Thus, the decrease of intensity in the ranges of 1350−1480, 1600, 2850−
structural morphology changes only contribute slightly, if at all, 3000, and 3300−3400 cm−1 together with the increase in the
to the losses of the CO2 uptake. Second, the amine functional range of 1660−1680 cm−1 clearly shows the change on the
group is altered, forming new species that are incapable of surface groups in the degraded sorbent.
capturing CO2. For this purpose, it is important to examine the 3.3. CO2-Induced Degradation. Using CO2 as purge gas
functional groups present in the sorbent after oxidative for regeneration can be a relevant condition when pure CO2 is
degradation. targeted as product. Due to the adsorption equilibrium, the
Figure 5 shows the FTIR spectra of IER before and after required regeneration temperature when using pure CO2 to
exposure to 120 °C for 72 h in dry air. All the samples have desorb the sorbent is much higher than for nitrogen stripping.
been desorbed in a flow of N2 at 100 °C for 1 h in advance to According to the result of Alessi and Kitchin,45 the resin used in
measuring the FTIR spectra, in order to eliminate the CO this study can regenerate completely under 1 atm of CO2 at 200
signal due to carbamate. After treatment in oxidizing °C. However, the thermal stability turns out to be a problem at
conditions, it was found that the intensity of the bands in the this temperature for the IER studied here. Based on the results
ranges of 1350−1480, 1600, 2850−3000, and 3300−3400 on thermal stability, as shown in Figure 2, the maximum
cm−1, which belong to the alkane C−H bending, amide N−H temperature of continuous CO2 exposure was found to be
deformation of primary amine, C−H stretching, and N−H around 150 °C. We therefore evaluated the sorbent stability
stretching, decrease.38,46 After oxidative degradation, the under 0.8 atm CO2 at 120 °C and at 1 atm of CO2 at 150 °C, as
decrease of the intensity of C−H band is more pronounced can be seen in Figure 6. By comparing of the results at 120 and
than that of the N−H stretching bond. Similar changes of a 150 °C, we found that sorbent degradation increases with
reduction of FTIR peak intensity of the band in C−H temperature and with the partial pressure of CO2. The loss of
3264 DOI: 10.1021/acs.iecr.6b04645
Ind. Eng. Chem. Res. 2017, 56, 3259−3269
Industrial & Engineering Chemistry Research Article

in this study. This distinguished stability in concentrated CO2

of the IER studied here may originate from the manufacturing
method and, hence, is probably more related to the amine−
support interaction than to the type of amine. This is illustrated
by an earlier study,22 where the adsorption capacity loss of PEI-
MCM-41 prepared by impregnation decreased by 41% after
CO2 exposure at 105 °C for 22 cycles while the capacity loss
was as high as 45% for MONO-MCM-41, a grafting material,
treating under the same conditions but for 40 cycles.
The sorbent was also tested for degradation under CO2
exposure after humidifying the gas at the dew point of water at
23 °C. The experiments were conducted under a flow of 80%
CO2/N2 at 120 and 150 °C for 72 h in both dry and wet
conditions. Based on the results shown in Table 3, the sorbent
Figure 6. CO2 adsorption capacity after treatment in dry 80% CO2/N2 Table 3. CO2 Uptake for IER after Exposure to Dry
at 120 °C and 100% dry CO2 at 150 °C, normalized by the fresh
Concentrated CO2, Wet Concentrated CO2, and Post-
sorbent capacity.
Processing in Humidified N2
CO2 capacity is around 9% at 120 °C under continuous 80% q_CO2a adsorption uptake (mol/kgIER)
CO2 exposure for 72 h. The degradation for (repeated) short condition dry wet
periods of exposure was not tested, but this is probably best
120 °C, 72 h, 80%b 1.97 2.10 (2 vol % H2O)
tested in a multicycle duration test. The samples after the 72 h
150 °C, 72 h, 80%b 1.69 1.81 (1.8 vol % H2O)
continuous treatment were analyzed by FTIR, see Figure 7. The
150 °C, 72 h, 100%c 1.66 1.80 (1.8 vol % H2O)
a
q_CO2 = 2.15 for the undegraded IER, measured at 40 °C under
15% CO2/N2. bConcentrated CO2 streams were humidified using a
water column controlled at 23 °C. cDegraded sample was collected,
then treated in a flow of N2 at 150 °C containing 0.6% RH for 24 h.

treated with humidified gas degraded less compared with the

IER treated under dry conditions. In an additional experiment,
the material was treated first in a flow of pure dry CO2 at 150
°C for 72 h, then under a flow of N2 containing 0.6% RH for 24
h without altering the temperature. The CO2 uptake of the
fresh sample, the sample treated in dry CO2, and the sample
post-treated in wet N2 is 2.15, 1.66, and 1.80 mol/kg,
respectively. Hence, there is a recovery of 7% of the CO2
capacity of the fresh IER due to post-treatment in wet N2.
These findings demonstrate that the CO2-induced deactivation
of sorbent is reduced but not completely recovered by either
Figure 7. IR spectra for IER after treatment in dry 80% CO2 at 120 °C using humidification of the feed or postprocessing hydrolysis.
and 100% dry CO2 at 150 °C for 72 h conditions, as well as for fresh As opposed to the findings in this study, Sayari et al. indicated
urea and undegraded IER sample. Samples of IER were pretreated at
that the formed urea from grafted propyl amine can be
100 °C in flowing N2 for 1 h then cooled.
completely recovered under a stream of N2 containing 0.15%
RH and 200 °C.22 For this SAS, however, it is difficult to
results of FTIR show that the deactivated sample develops a reproduce the condition since thermal degradation occurs at
peak at 1670 cm−1 and the intensity of this peak increases with 200 °C. In other studies, urea formed was recovered in SBA-
the increased extent of degradation. The developed peak lays in 15PL-60023 and MONO-MCM-4122 by adding moisture at a
the same range with the FTIR result of fresh urea, which points dew point of 20 °C to the CO2 stream at 75 °C (6% RH) and
toward the formation of urea after treatment in concentrated 105 °C (2% RH). The experiments in this study were carried
CO2. out at lower RH, which may have contributed to the
From the literature, it was found that primary amines are incomplete prevention of urea formation or recovery by
more likely to form urea than secondary and tertiary amines in hydrolysis. In an attempt to improve the prevention of urea
the presence of CO2 since the intermediate species in urea formation, the temperature of the water column saturator was
formation, isocyanate, is only produced from primary amines.28 increased from 23 to 60 °C, but the resulting increase in RH
Surprisingly, this IER shows less tendency to be deactivated by did not improve the results. In conclusion, it seems advisable to
CO2 to form urea in comparison with other SASs, reported in control the temperature below 120 °C to avoid CO2-induced
literature: the CO2 uptake loss of PEI-423/600/1800-MM,21 degradation, which is important in view of sorbent regener-
PEI-SBA-15,23 and MCM-41-s-pMono22 after exposure in pure ation.
CO2 for 1 h at 130 °C, for 10 h in 5% CO2 at 105 °C, and at 55 When using pure CO2 at ambient pressure as the purge
°C in pure CO2 for 30 h, respectively, are all above 20%. The medium at this temperature, thermodynamics limits the
treatment conditions for the amine based sorbents mentioned working capacity of CO2. The proposed mode of application
above were significantly less severe compared to the conditions is to reduce the CO2 partial pressure during regeneration by
3265 DOI: 10.1021/acs.iecr.6b04645
Ind. Eng. Chem. Res. 2017, 56, 3259−3269
Industrial & Engineering Chemistry Research Article

using steam or reducing the system pressure. Steam can be leaching of the functional amine group, and hence a much
simply separated by condensation and has the accompanying better hydrothermal stability than Si−O−C bonds.48
advantage that it inhibits partly the formation of urea. For such 3.5. Regeneration Studies Using Nitrogen Stripping.
a steam-assisted regeneration approach, it is necessary to check Regeneration of CO2 loaded sorbent by nitrogen stripping does
the effect of steam itself on sorbent stability, which is presented not degrade the IER when the temperature is below 150 °C and
in the following section. is in that sense cost-efficient. For optimizing cost efficiency, the
3.4. The Influence of Water Vapor on Sorbent amount of (inert) stripping gas during regeneration should be
Degradation. The effect of continuous exposure to steam minimized. In this study, the amount of inert stripping gas
on the uptake of CO2 in the IER, in comparison to other required during regeneration will be investigated using
supported amine sorbents, in shown in Figure 8. As illustrated nitrogen, but results will hold for other inert gases, most likely
including water vapor. The economy of nitrogen stripping is
affected by the choice of temperature and flow. To assess the
effect of temperature and flow on the IER, experiments were
done at 100 °C with flow rates of 0.50−2.50 L min−1. At a fixed
flow rate of 1.00 L min−1, the temperature was varied between
80 and 120 °C. The results of varying the flow rate are shown
in Figure S5 in the SI, showing that the rate of regeneration
increases with increasing flow rate of the stripping gas. Among
the flows studied, the lowest flow rate of 0.50 L min−1 results in
the most time-consuming regeneration process, requiring
double the amount of time than for the flow rate of 1.00 L
min−1 to regenerate 80% of CO2 from the IER. The reason for
this is probably that the adsorption equilibrium limits the
regeneration rate of CO2 at low flow rates, due to the higher
concentration of CO2 inside the reactor during regeneration.
Therefore, next to a temperature swing, it is important to
maintain a certain flow to flush out the regenerated CO2
Figure 8. Impact of continuous steam exposure on the normalized
CO2 capacity for the studied IER and for other supported amine
(partial pressure swing). To measure the effect of temperature
sorbents.32,33,35,37 on the nitrogen stripping at constant flow rate, the experiments
were carried out at a flow rate of 1.00 L min−1 at temperatures
in the range of 80−120 °C. The results are shown in Figure S6
in the figure, no significant capacity loss for this IER was in the SI. The results show that the regeneration rate of CO2
observed after 48 h of exposure. For nearly all other studies on increases with increasing temperature. The regeneration takes
steam stability of supported amines, a significant CO2 capacity much longer time at 80 °C than at the other four temperatures.
decrease was observed. The differences are related to both the This is because the adsorption equilibrium capacity noticeably
choice of the amine and the choice of supports, which are silica- limits the desorption rate at 80 °C. At higher temperatures the
based or γ-alumina based in the cited studies. When comparing position of the adsorption equilibrium is much more favorable
the performances of these latter two supports, γ-alumina for desorption. Hence, for a given flow rate a certain minimum
displays better stability toward steam exposure than meso- temperature is necessary to maintain a fast regeneration rate of
porous silica SBA-15.37 The poor steam stability of the CO2.
mesoporous silica is owing to structure collapse and hydrolysis, Operating at various flows and temperatures leads to
which dramatically decrease the final CO2 capacity. On the different costs related to nitrogen use and to energy
other hand, the hydrolysis of γ-alumina forming boehmite does consumption for raising the temperature. The cost of purge
not result in significant loss of CO2 uptake.33 The formation of (N2) for sorbent regeneration is related to the amount of purge
boehmite occurs within 12 h of steam exposure and resulted in (N2) required per amount of CO2 desorbed. The ratio of the
merely 12% CO2 uptake loss, while amine leaching decreases amount of N2 required to desorb per amount of CO2 (factor F,
50% of sorbent CO2 loading capacity when the exposure to in mol of N2/mol of CO2) is calculated using eq 2.
steam continued from 12 to 24 h. Apart from the choice of φN
2
support, steam stability can also be affected by the preparation t
Vm a
method of the sorbent. A sorbent MCF-HAS, which was F=
na (2)
prepared by in situ polymerization, lost 6% of capacity after N2/
steam exposure at 106 °C for 24 h, whereas 19% of the capacity In this equation, n (mol) represents the total amount of CO2
was lost for a sorbent MCF-PEI, which was synthesized by that can be desorbed, while a and ta (s) represent the fraction of
physical impregnation.35 The instability of these mesocellular CO2 actually desorbed and the time required to reach that
foam (MCF) silica supported amines in steam is ascribed to fraction. The fractional CO2 desorbed is defined by the ratio of
both structure destruction of the supports and amine CO2 desorbed at time ta (s) to the maximum total amount of
degradation. To sum up, both the choice of the support and CO2 desorbed during the regeneration. Symbols ϕN2 (L/s) and
the preparation method of the sorbent have significant Vm (L/mol) represent flow of the nitrogen and the standard
influence on the steam stability of the solid amine sorbents. volume of 1 mol of gas at the desorption temperature. Figure 9
The good steam stability of the IER studied in this work is shows the relation between the fractional CO2 desorbed and
therefore enabled by the good hydrothermal stability of the the value of F. From this figure, it is clear that regeneration of
sorbent structure and the C−C chemical bonding of the amine the sorbent beyond 95% requires enormous amounts of purge
groups to the polymeric backbone of the sorbent, avoiding gas. Furthermore, when the fractional CO2 desorbed is less
3266 DOI: 10.1021/acs.iecr.6b04645
Ind. Eng. Chem. Res. 2017, 56, 3259−3269
Industrial & Engineering Chemistry Research Article

Figure 9. Effect of the flow on nitrogen required vs fractional CO2 Figure 10. Effect of the temperature on nitrogen required vs fractional
desorbed at 100 °C in the range of 0.50−2.50 L min−1. CO2 desorbed under 1.00 L min−1 in the temperature range of 80−
120 °C.
than 90%, there is a decrease in the value of factor F as the flow
is decreased. Although the regeneration time is maximal under estimated based on the energy consumption of heating the IER,
0.50 L min−1, it consumes the least amount of nitrogen to nitrogen, and heat of reaction. The results are shown in Table
regenerate the same amount of CO2 in the first 90% 5. The heat capacity of the IER and the N2 are assumed to be
regeneration. 1.5 and 1.04 kJ/(kg·K).20 The calculation of the sensible heat
The choice of fractional regeneration of CO2 is also does not consider any heat integration. At an increased
important as it determines the working capacity of the process. regeneration temperature, the increment of the sensible energy
Working capacity also determines the energy consumption for required for the sorbent is compensated by a reduction in the
regeneration in the form of sensible heat per unit of CO2. We energy consumed by the purge, since less purge gas is required.
estimated the purchase cost of the sorbent and cost of the Both the value of F and the temperature affect the energy
nitrogen required at and 13 €/kg and 2 €/ton, respectively. The consumption of the purge. The energy consumption of the
time of adsorption, 100% working capacity, and lifetime of the purge is always larger than either the energy of the sorbent or
sorbent are assumed to be 1 h, 1.5 mol/kg,41 and 3 years, the reaction energy. Fortunately, this energy is also easier to
respectively. The results of the calculation of the costs related recover if heat integration is implemented.
to sorbent and nitrogen use for regeneration at 100 °C and at In summary, a first indication of the required amount of
95% fractional CO2 desorbed are shown in Table 4 for the stripping gas to regenerate the sorbent and per ton of CO2
regenerated is now obtained. When using a stripping gas, the
Table 4. Moles of Nitrogen, Time Required to Desorb 95% cost of the purge medium is essential for determining the
of the adsorbed CO2, and the Corresponding Cost of process economics. Even at a low, fictive price of 2 €/ton N2,
Nitrogen and Sorbent per Amount of CO2 Captured over a the cost of nitrogen as stripping gas is much more than the cost
Range of Flows at 100 °C of the thermal energy required. A cheaper purge medium and
further process optimization is required to regenerate the
flow rate F95 (N2/ cost of
(L CO2) purge cost of IER total cost sorbent. Steam stripping may be a better option in this regard
min−1) (mol/mol) t95 (s) (€/tonCO2) (€/tonCO2) (€/tonCO2) as it enables sorbent regeneration and (pure) CO2 production.
0.50 125 2442 159 13.9 173 However, the presence of water in the process may have an
1.00 110 1071 140 10.8 151 influence on desorption kinetics for some types of supported
1.50 118 768 150 10.2 160 amine sorbents.32,49 Further study on the effect of steam in
2.00 119 583 152 9.7 162 terms of desorption kinetics is required and ongoing.
2.50 130 530 166 9.7 176
4. CONCLUSION
In this work, we have evaluated the thermal and chemical
experimental flow rates studied. The results show that the cost stability of Lewatit VP OC 1065 in view of the potential
of the purge overweighs the cost of the IER. The minimum cost strategies of regenerating this sorbent in CO2 removal
of considering both the nitrogen and the sorbent occurs at application. The effect of long-term continuous exposure to
minimum value of F. The idea is to decrease F by increasing the air, different O2/CO2/N2 mixtures, concentrated CO2, and
temperature, as this is favorable for reversing the adsorption steam on the CO2 adsorption uptake is investigated at different
equilibrium. The value of F needs to decrease to 65 to reach a temperatures and exposure time for both dry and wet
total price less than 100 €/tonCO2. conditions. In view of the degradation observed, sorbent
The influence of temperature on the F factor is shown in regeneration should be carried out in absence of oxygen when
Figure 10. The results show that the value of F decreases with operating above 70 °C and at temperatures below 150 °C to
increase of the temperature. The increase of temperature will avoid thermal degradation. If the partial pressure of CO2
result in a higher cost for the thermal energy to the increase the approaches 1 bar, the maximum temperature should not be
temperature from adsorption conditions (here taken at 40 °C) higher than 120 °C to avoid urea formation. Humidity was
to the regeneration temperature. The economic analysis is unable to completely prevent urea formation nor to reverse it.
3267 DOI: 10.1021/acs.iecr.6b04645
Ind. Eng. Chem. Res. 2017, 56, 3259−3269
Industrial & Engineering Chemistry Research Article

Table 5. Moles of Nitrogen, Time Required to Desorb 95% of the Adsorbed CO2, and the Corresponding Energy in the
Regeneration at the Temperature of 80−120 °C under the Flow of 1.00 L min−1
temp (°C) F95 (N2/CO2) (mol/mol) t95 (s) energy for IER (GJ/tonCO2) energy for N2 (GJ/tonCO2) reaction energy41 (GJ/tonCO2) total (GJ/tonCO2)
80 267 2603 1.0 7.1 1.7 9.8
90 121 1174 1.2 4.0 1.7 6.9
100 110 1071 1.4 4.4 1.7 7.5
110 92 897 1.7 4.3 1.7 7.7
120 69 669 1.9 3.7 1.7 7.3

The application of steam or water vapor, however, did not (6) D’Alessandro, D. M.; Smit, B.; Long, J. R. Carbon Dioxide
negatively affect the sorbent capacity. Regeneration of IER by Capture: Prospects for New Materials. Angew. Chem., Int. Ed. 2010, 49,
nitrogen stripping, as inert gas, has been evaluated in terms of 6058−6082.
required amount of purge gas at different flow rates and (7) Kenarsari, S. D.; Yang, D.; Jiang, G.; Zhang, S.; Wang, J.; Russell,
temperatures and for different degrees of sorbent regeneration. A. G.; Wei, Q.; Fan, M. Review of recent advances in carbon dioxide
separation and capture. RSC Adv. 2013, 3, 22739−22773.
Nitrogen stripping is not an attractive option in practical (8) Mazari, S. A.; Si Ali, B.; Jan, B. M.; Saeed, I. M.; Nizamuddin, S.
application since it is too expensive. Considering the stability of An overview of solvent management and emissions of amine-based
the sorbent and the low cost of steam makes steam stripping a CO2 capture technology. Int. J. Greenhouse Gas Control 2015, 34, 129−
promising method for sorbent regeneration. Still, optimization 140.
of regeneration is required taking into account actual prices for (9) Dutcher, B.; Fan, M.; Russell, A. G. Amine-Based CO2 Capture
utilities and sorbent costs, as well as heat integration. Technology Development from the Beginning of 2013-A Review. ACS

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*
ASSOCIATED CONTENT
S Supporting Information
Appl. Mater. Interfaces 2015, 7, 2137−2148.
(10) Samanta, A.; Zhao, A.; Shimizu, G. K. H.; Sarkar, P.; Gupta, R.
Post-Combustion CO2 Capture Using Solid Sorbents: A Review. Ind.
Eng. Chem. Res. 2012, 51, 1438−1463.
The Supporting Information is available free of charge on the (11) Goto, K.; Yogo, K.; Higashii, T. A review of efficiency penalty in
ACS Publications website at DOI: 10.1021/acs.iecr.6b04645. a coal-fired power plant with post-combustion CO2 capture. Appl.
Schematic of the adsorbent treatment setup, schematic of Energy 2013, 111, 710−720.
the adsorbent adsorption and regeneration setup, long- (12) Bollini, P.; Brunelli, N. A.; Didas, S. A.; Jones, C. W. Dynamics
term oxidative degradation at ambient condition, SEM of of CO2 Adsorption on Amine Adsorbents. 1. Impact of Heat Effects.
Ind. Eng. Chem. Res. 2012, 51, 15145−15152.
fresh and degraded IER, effect of flow and temperature (13) Bollini, P.; Brunelli, N. A.; Didas, S. A.; Jones, C. W. Dynamics
on adsorbent regeneration kinetics (PDF) of CO2 Adsorption on Amine Adsorbents. 2. Insights Into Adsorbent

■ AUTHOR INFORMATION
Corresponding Author
Design. Ind. Eng. Chem. Res. 2012, 51, 15153−15162.
(14) Monazam, E. R.; Shadle, L. J.; Siriwardane, R. Equilibrium and
absorption kinetics of carbon dioxide by solid supported amine
sorbent. AIChE J. 2011, 57, 3153−3159.
*E-mail: [email protected]. (15) Serna-Guerrero, R.; Sayari, A. Modeling adsorption of CO2 on
ORCID amine-functionalized mesoporous silica. 2: Kinetics and breakthrough
Qian Yu: 0000-0001-9576-2021 curves. Chem. Eng. J. 2010, 161, 182−190.
(16) Zhao, W.; Zhang, Z.; Li, Z.; Cai, N. Continuous CO2 Capture in
Notes Dual Fluidized Beds Using Silica Supported Amine. Energy Procedia
The authors declare no competing financial interest.

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2013, 37, 89−98.
(17) Hoffman, J. S.; Hammache, S.; Gray, M. L.; Fauth, D. J.;
ACKNOWLEDGMENTS Pennline, H. W. Parametric study for an immobilized amine sorbent in
This research was carried out within the EU MIRACLES a regenerative carbon dioxide capture process. Fuel Process. Technol.
project (www.miraclesproject.eu) and has received funding 2014, 126, 173−187.
(18) Zhang, W.; Liu, H.; Sun, C.; Drage, T. C.; Snape, C. E.
from the European Union’s Seventh Framework Program for
Capturing CO2 from ambient air using a polyethyleneimine−silica
research; technological development and demonstration under adsorbent in fluidized beds. Chem. Eng. Sci. 2014, 116, 306−316.
Grant Agreement No. 613588.

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(19) Schöny, G.; Zehetner, E.; Fuchs, J.; Pröll, T.; Sprachmann, G.;
Hofbauer, H. Design of a bench scale unit for continuous CO2 capture
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3269 DOI: 10.1021/acs.iecr.6b04645

Ind. Eng. Chem. Res. 2017, 56, 3259−3269