REVIEW

pubs.acs.org/IECR

Post-Combustion CO2 Capture Using Solid Sorbents: A Review

Arunkumar Samanta,† An Zhao,† George K. H. Shimizu,‡ Partha Sarkar,§ and Rajender Gupta*,†
†
Department of Chemical & Materials Engineering, University of Alberta, Edmonton, Alberta, Canada
‡
Department of Chemistry, University of Calgary, Calgary, Alberta, Canada
§
Environment & Carbon Management Division, Alberta Innovates—Technology Futures, Edmonton, Alberta, Canada

ABSTRACT: Post-combustion CO2 capture from the flue gas is one of the key technology options to reduce greenhouse gases,
because this can be potentially retrofitted to the existing fleet of coal-fired power stations. Adsorption processes using solid sorbents
capable of capturing CO2 from flue gas streams have shown many potential advantages, compared to other conventional CO2
capture using aqueous amine solvents. In view of this, in the past few years, several research groups have been involved in the
development of new solid sorbents for CO2 capture from flue gas with superior performance and desired economics. A variety of
promising sorbents such as activated carbonaceous materials, microporous/mesoporous silica or zeolites, carbonates, and polymeric
resins loaded with or without nitrogen functionality for the removal of CO2 from the flue gas streams have been reviewed. Different
methods of impregnating functional groups, including grafting techniques and modifying the support materials, have been discussed
to enhance the performance of the sorbents. The performance characteristics of the solid sorbents are assessed in terms of various
desired attributes, such as their equilibrium adsorption capacity, selectivity, regeneration, multicycle durability, and adsorption/
desorption kinetics. The potential of metal-organic frameworks (MOFs) is also recognized to determine whether these novel
materials provide better CO2 adsorption capacity under low CO2 partial pressure. A comprehensive critical review and analysis of
the literature on this subject has been carried out to update the recent progress in this arena. A comparison of different solid sorbents
at different stages is made. It also includes a brief review on techno-economic analysis and design aspects of sorbent bed contactor
configuration. Finally, a few recommendations have been proposed for further research efforts to progress post-combustion carbon
capture.

1. INTRODUCTION coal-based power plants, natural and synthesis gas processing

Growing environmental concerns in recent times for global
warming and climate change have motivated research activities
toward developing more-efficient and improved processes for
carbon dioxide (CO2) capture from large point sources of CO2.
The Intergovernmental Panel on Climate Change (IPCC)’s
fourth assessment report1 states that, as a result of anthropogenic
CO2 emission, global atmospheric concentration has increased
from a preindustrial value of ∼280 ppmv to 379 ppmv in 2005
and ∼390 ppmv currently. Global annual CO2 emissions due to
fossil-fuel use have grown by ∼80%, from ∼21 Gt in 1970 to ∼38
Gt in 2004.2 This represented 77% of the total anthropogenic
greenhouse gas (GHG) emissions in 2004, and of this, close to
60% was attributed to large (>0.1 Mt CO2 per year) stationary
emission sources, such as power plants, gas processing industries,
refineries, chemical and petrochemical industries, iron and steel
industries, and cement industries. Without the introduction of
near-term supportive and effective policy actions by govern-
ments, energy-related GHG emissions, mainly from fossil fuel
combustion, are projected to rise by over 50%, from 26 Gt CO2 in
2004 to ∼37
40 Gt CO2 by 2030, and possibly even higher.3
Therefore, mitigation has become even more challenging. The
global concern for this situation is well-reflected in the deep
global engagements that continue from the Rio Earth Summit in
1992 through the 1997 Kyoto Protocol of United Nations Frame-
work Convention on Climate Change (UNFCCC) to the recently
concluded UN Climate Change Conference in Cancun, Mexico in
December 2010. Capture of CO2 from large point sources, such as
plants, and cement plants, and its sequestration (CCS) is identified
as a major option to address the problem of global warming and
climate change. However, the main focus of CCS today is coal-
based power plants. CCS includes four primary steps: CO2
capture, compression, transport, and storage. To economically
sequester CO2, it is important to have cost-effective capture in a
relatively concentrated stream and then compressing the CO2 to
high pressures.
Three approaches are envisaged for CO2 capture from fossil-
fuel based power plants: pre-combustion, post-combustion, and
oxycombustion.4
6 Pre-combustion capture is applicable to
integrated gasification combined cycle (IGCC) plants, while
oxy-combustion and post-combustion could be applied to con-
ventional coal- or gas-fired power plants. However, in their
present development stage, these approaches are still not ready
for implementation on coal-based power plants, because of three
primary reasons: (i) they have not been demonstrated in large
scale; (ii) the required parasitic loads to supply both power and
steam to the CO2 capture plant would reduce power generation
capacity by approximately one-third; and (iii) if successfully
Special Issue: Nigam Issue
Received: April 5, 2011
Accepted: October 27, 2011
Revised: September 17, 2011
Published: October 27, 2011

r 2011 American Chemical Society 1438 dx.doi.org/10.1021/ie200686q | Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
Table 1. Typical Gas Quality in Applications to CO2 Capture
CO2 (dry)
process (vol %)4 impurities
natural gas turbine exhaust 3
4 low SOx and NOx levels, O2:
12%
15%
coal-/oil-fired boiler 11
14 high SOx and NOx levels, O2:
2%
5%
IGCC syngas turbine 4.5
6 low SOx and NOx
exhaust
blast furnace gas 27 SOx and NOx present
(after combustion)
cement kiln off-gas 14
33 SO2 and NOx, trace elements,
particulates
scaled up, they would not be cost-effective at their present phase
of process development stage.7
Amine-based regenerative chemical absorption processes using
aqueous solutions of amine, such as monoethanolamine (MEA),
diethanolamine (DEA), diglycol-amine (DGA), N-methyldietha-
nolamine (MDEA), and 2-amino-2-methyl-1-propanol (AMP)
have been widely practiced for several years for CO2 capture from
gas streams in natural gas, refinery off-gases and synthesis gas
processing.8
10 The gas streams in these processes are at a high
pressure. However, the major challenges for CO2 capture from
fossil-fueled based thermal power plants are the large volumetric
flow rates of flue gas at essentially atmospheric pressure with large
amounts of CO2 at low partial pressures and in the temperature
range of ∼100
150 °C. The presence of SOx, NOx, and
significant oxygen partial pressure in the flue gas add to additional
problems for implementation of amine absorption process for
CO2 capture from flue gas streams (see Table 1).
The state-of-the-art process uses 20
30 wt % aqueous MEA
for post-combustion capture of CO2. However, this process is
highly energy intensive, because of the high regeneration energy
requirement. In addition, thermal and oxidative degradation of
the solvents result in large solvent makeup, besides producing
products that are corrosive. A techno-economic and environ-
mental assessment study suggests an 80% increase in the cost of
electricity when CO2 capture with a 30 wt % aqueous MEA
absorption process is implemented with a coal-fired power
plant.11 The CO2 capture and compression account for 80% of
the total cost, while the balance of the cost (20%) is due to
transportation and sequestration. This high cost of CO2 capture
reduces the implementation of MEA process for CO2 capture
from the flue gas of coal-based power plants.12
Thus, the cost-effective processes for CO2 capture from the
flue gas streams of coal-based power plants are essential today in
order to mitigate the global warming problems. Among the many
process technology options used for CO2 capture from flue gases,
there is a growing interest in using adsorption processes as a
promising alternative separation technique. Adsorption pro-
cesses using novel solid sorbents capable of reversibly capturing
CO2 from flue gas streams have many potential advantages,
compared to other separation techniques for CO2 capture, such
as reduced energy for regeneration, greater capacity, selectivity,
ease of handling, etc. Adsorption on porous solid media using
pressure and/or temperature swing approaches is an emerging
alternative that seeks to reduce the costs associated with the
capture step. The regeneration energy requirement for CO2
1439
REVIEW
capture using dry solid sorbent is significantly reduced more than
that of the aqueous amine-based process, because of the absence
of large amounts of water. Moreover, the heat capacity of solid
sorbent is comparatively lower than that of an aqueous amine
solvent. The success of such an approach is also dependent on
the development of new materials with high adsorption capacity,
high CO2 selectivity, durability, and relatively fast kinetics of
sorption and desorption.
In view of the above, in the past few years, several research
groups worldwide have initiated work on the development of
new solid sorbents for CO2 capture from flue gas with superior
performance and desired economics. The impurities in flue gases
such as oxides of nitrogen and sulfur often reduce the perfor-
mance of the sorbents. Ample proof of this fact can be found in
the open literature. Characterization and understanding the
behavior of the sorbents in actual flue gas conditions is important.
This paper reviews the recent progress in CO2 capture using solid
sorbents with and without functionalized groups. A comprehen-
sive literature review and analysis on this subject has been carried
out to update the recent progress in this field. It also includes a
brief review on techno-economic analysis and design aspects of
sorbent bed contactors.
1.1. Criteria for Selecting CO2 Sorbent Material. Sorbent
selection is a complex problem.13 The sorbent materials must
satisfy some important criteria to be both economical and
operational for CO2 capture from flue gas. These criteria are
listed in this section.14
16
• Adsorption capacity for CO2: The equilibrium adsorption
capacity of a sorbent material represented by its equilibrium
adsorption isotherm is of paramount importance to the
capital cost of the capture system, because it dictates the
amount of adsorbent required, which also fixes the volume
of the adsorber vessels. That is, the high adsorption capacity
for CO2 reduces both sorbent quantity and process equip-
ment size. In practice, working capacity, defined for a short
adsorption time, is preferred to be used in place of equilib-
rium capacity. In order for solid sorbents to be competitive
with existing MEA scrubbing system, the CO2 working
capacity must be in the range of 3
4 mmol g
1 of sorbent
(hereafter shortened to mmol g
1 in this work).17
• Selectivity for CO2: The selectivity, which is defined by the
ratio of the CO2 capacity to that of another component (for
example, N2) at a given flue gas composition, has a direct
impact on the purity of CO2 captured. The purity of CO2 has
impacts on transportation and sequestration and, therefore,
plays an important role in CO2 sequestration economics. Flue
gas streams from fossil-fuel fired power plants contain N2 and
O2. Good sorbent materials should exhibit high CO2 selectivity
over these other bulk gas components. It is also important that
solid sorbents also show high capacity for CO2 in the presence
of significant amounts of water vapor in flue gas.
• Adsorption/desorption kinetics: It is essential to have fast
adsorption/desorption kinetics for CO2 under the operating
conditions. The kinetics of adsorption and desorption
controls the cycle time of a fixed-bed adsorption system.
Fast kinetics yields a sharp CO2 breakthrough curve in
which effluent CO2 concentration changes are measured as
a function of time, while slow kinetics provides a distended
breakthrough curve. Both of these impacts on the amount of
sorbent required. The overall kinetics of CO2 adsorption on
a functionalized solid sorbent is influenced by the intrinsic
reaction kinetics of CO2 with the functional group present,
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research REVIEW

Table 2. Structural Properties of the Adsorbents and be resistant to common flue gas contaminants. It is likely
that contaminants such as SOx, NOx and heavy metals18 will
pore size pore volume specific surface
also require removal from flue gas, because they unfavorably
(nm) (cm3 g
1) areaa (m2 g
1) ref affect the CO2 adsorption capacity of the sorbent materials.
• Regeneration of sorbents: The heat of adsorption, which is a
Carbonaceous Sorbents
measure of the energy required for regeneration, should be
AC 1.5
2.2 0.6
0.8 1300 33 substantially low. Heats of adsorption are generally in the
AC-hb 2.19 1.55 2829 44 range of
25 to
50 kJ mol
1 for physisorption cases and
granular AC 2 0.48 954 36
60 to
90 kJ mol
1 for chemisorptions cases. Moreover,
BPL carbon 0.7 1100 38 the sorbent should be regenerable through a suitable path-
CNT 8.9 0.91 394 36 way while maintaining efficient CO2 sorption capacity
CNT 23.54f 0.446 407 45 during repeated adsorption
desorption cycles in a power-
plant flue-gas environment. The ease of regeneration of the
Zeolites
CO2 sorbent will also help to reduce the cost of capture.
NaX 1 0.201e 508 46 • Sorbent costs: These represent perhaps the most subtle
NaY 1.54 0.46 811 47 characteristics. Tarka et al.,19 have used a baseline of
CsX 0.14e 404 48 approximately $10/kg for sorbents in their sensitivity anal-
CsY 1.58 0.21 473 47 ysis for economic performance. According to them, a cost of
Zeolite 13X 1.1 0.454 515 49 $5/kg sorbent results in a very good scenario and a cost of
chabozite 0.43 4.2 485 52 $15/kg sorbent is not economical. Therefore, to be more
clintopilec 0.44 4.1 18.4 52 economical, the cost of the CO2 capture sorbent should be
clintopiled 0.44 4.5 13.3 52
in the range of approximately $10/kg.
erionite 0.22 426 53 The above-mentioned attributes are desirable for an ideal
mordenite 0.19 266 53
adsorbent. Rarely will a single adsorbent be optimal in all these
attributes. However, useful adsorbents will be those that effec-
clinoptilolite 0.066 23 53
tively and economically capture CO2 from flue gas streams.
Silica Support
silica gel 0.94 256 50 2. PHYSICAL SORBENTS
silica gel KC 2 0.35 750 51 CO2 from flue gas may be removed using a variety of solid
MCM-41 3.6 1.03 1138 50 physisorbents materials, including porous carbonaceous materi-
PE-MCM-41 9.7 2.03 917 50 als, zeolites, alumina, silica gels, and metal-organic frameworks
SBA-15 21 200
230 54 (MOFs). For physisorption, such as adsorption of CO2 by zeolite
Polymer
or activated carbon, the mechanism for CO2 capture can be
visualized as
PMMA 17 1.2 470 55
a
BET surface area. b Activated carbon with high surface area. c Sodium CO2 þ surface S ðCO2 Þ 3 ðsurfaceÞ
aluminosilicate Type 4A zeolite. d Potassium calcium sodium aluminosili-
cate. e Microporous pore volume. f Average pore diameter of 1.7
100 nm. where the selective adsorption of CO2, in comparison with N2, is
caused by van der Walls attraction between the CO2 molecule
as well as the mass transfer or diffusional resistance of the gas and adsorbent surface, as well as by pole
ion and pole
pole
phase through the sorbent structures. The porous support interactions between the quadruple of CO2 and the ionic and
structures of functionalized solid sorbents also can be polar sites of the solid adsorbent surface.20
tailored, to minimize the diffusional resistance. The faster This section summarizes the recent progress in CO2 capture
an adsorbent can adsorb CO2 and be desorbed, the less of it using solid physisorbents, namely activated carbons, carbon
will be needed to capture a given volume of flue gas. nanotubes, carbon molecular sieves, zeolites, and MOFs.
• Mechanical strength of sorbent particles: The sorbent must 2.1. Activated-Carbon-Based Solid Sorbents. Inorganic
demonstrate microstructure and morphological stability and carbon is available in various forms, such as porous activated
carbons (ACs), graphenes, and carbon nanotubes (CNTs). ACs
retain the CO2 capture capacity during multicycling be-
are widely used as adsorbents in various industrial applications, e.
tween the absorption and regeneration steps. Microstruc-
g., gas purification, water treatment, etc., because of the low cost
ture and morphological stability of tailored regenerable of raw materials and wide availability.20,21 Sorption behavior of
sorbents in multicycle operation is critical to maintain high CO2 on commercial and synthesized ACs derived from different
kinetics. Operating conditions, such as high volumetric flow natural organic materials, as well as carbon molecular sieves, have
rate of flue gas, vibration, and temperature should not cause been widely studied experimentally and theoretically by various
appreciable disintegration of the sorbent particles. This research groups at low to very high pressure.22
43 The structural
could also happen via abrasion or crushing. Therefore, properties and adsorption capacities of carbon-based adsorbents
adequate mechanical strength of sorbent particles is critical are summarized in Tables 2 and 3, respectively.
to minimize the sorbent makeup rate and to keep CO2 Applications of the pressure swing adsorption (PSA) process
capture process cost-effective. have been reported to remove CO2 from gas streams using
• Chemical stability/tolerance to impurities: Solid CO2 capture ACs.22,23,25,37,38 Yang and co-workers23 studied the feasibility of
sorbents—in particular, amine-functionalized sorbents— the PSA process for the first time, to separate and concentrate
should be stable in an oxidizing environment of flue gas CO2 from flue gas using BPL ACs and carbon molecular sieves
1440 dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research REVIEW

Table 3. CO2 Adsorption Capacity of Carbonaceous Solid Sorbents

sorbent temperature, T (K) pressure, pCO2 (atm) capacity (mmol g
1) process ref

AC 298 1 2.07 PSA 23

AC 288 1 2.45 PSA 25
AC 298 0.2 0.75 28
AC 298 1 3.23 33
AC 298 1 2.61 PSA 37
AC 298 0.1 0.57 GC-TCD 36
ACd 298 1 2.25 43
ACe 298 1 1.53 43
AC-A35/4 293 1 2.00 flow desorption 29
AC-F30/470 288 1 2.86 volumetric analysis 51
AC-F30/470 297.3 0.16 0.65 26
AC-RB 303 1 1.22 38
AC Norit RB1 294.2 1 2.456 gravimetric analysis 32
AC Norit RB1 313.1 0.15 0.50 TPD 24
AC-Norit R1 Extra 298 0.15 0.538 30
bamboo-derived AC 275 2 3.00 volumetric analysis 35
bamboo-derived AC 275 2 0.54a volumetric analysis 35
anthracite-based ACb 303 1 1.38 TGA 42
anthracite-based ACc 303 1 1.33 TGA 42
SWNT 308 1 2.07 56
graphene 195 1 0.80 57
CMS 303 1 2.43 59
a
Wet bamboo activated carbon with water loading in the range of 1.35
2.36. Water loading refers to the weight ratio of water to dry carbon. b Activated
at 850 °C for 3 h. c Activated at 850 °C for 2 h. d Activated carbon without acid treatment. e Activated carbon with acid treatment.

(CMSs) as sorbents. They achieved a CO2 recovery of ∼68.4%
from a flue gas composed of 17% CO2/4%O2/79%N2, using ACs
at 298 K, while the amount of CO2 contaminant in the adsorp-
tion product was ∼6.3%. They also concluded that the equilib-
rium separation of CO2 from flue gas using ACs is better than the
kinetics separation by CMS. In another work, this group reported
that, in the case of equilibrium separation, zeolite 13X is better
than the ACs.25 The heat of adsorption (ΔHad) of activated
carbon (ΔHad=
30 kJ mol
1) is lower than that of zeolites
(ΔHad=
36 kJ mol
1), because of its weaker interaction with
CO2. Na et al.33 also demonstrated the PSA process using
commercial AC to separate CO2 from the flue gas of a power
plant. The CO2 adsorption capacities decreased significantly, e.g.,
from ca. 3.2 to ca. 1.6 mmol g
1, when temperature was increased
from 288 to 328 K at 1 atm. The maximum recovery of 34% with
a purity of 99.8% was obtained from PSA process from a flue gas
composed of 17% CO2/4% O2/79% N2 at 328 K.
In 1998, Do et al.28 presented theoretical and experimental
results on CO2 adsorption isotherm at three different tempera-
tures and at a pressure up to 20 kPa on Ajax activated carbon.
They observed that the CO2 adsorption capacity decreases
significantly as the temperature increases. The reported adsorp-
tion capacity was ca. 0.75 and 0.11 mmol g
1 at 298 and 373 K,
respectively. Siriwardane et al.37 compared the volumetric ad-
sorption isotherms of CO2 on G-32H activated carbon and
molecular sieves 13X and 14A. They established that the surface
affinity of molecular sieve 13X for CO2 was relatively better than
that of activated carbon and the CO2 adsorption capacity of three
sorbents was not adversely affected by the adsorption of other
gases such as N2, H2. From their competitive adsorption rate
studies, they concluded that it was possible to obtain excellent
1441
separation of CO2 from a gas mixture containing 14.8% CO2 and
85.2% N2 with both types of sorbents. Maroto-Valer and his
group39
42 found that anthracite coal with 2 h of activation at
890 °C achieved a CO2 adsorption capacity of 1.49 mmol g
1,
measured using a thermogravimetric analyzer (TGA) in pure
CO2. Wang et al.31 conducted a comparative study of CO2
sorption on ACs prepared from bamboo chips and coconut
shell, in the presence of water, and concluded that water
exhibited a detrimental effect on CO2 sorption at low pressure.
Recently, Radosz et al.43 proposed a low-cost low-pressure
carbon-filter process to capture CO2 from flue gas. All carbonac-
eous materials studied in this work exhibited a rapid sorption
rate and a short sorption cycle. The carbon filter process
proposed in this work could recover at least 90% of the flue
gas CO2 of 90% purity.
ACs are low cost with fast adsorption kinetics and require low
regeneration energy. However, the predominance of the porous
media of ACs still fails to offset the drawbacks of physical
adsorption processes, such as selectivity. The CO2 adsorption
capacity using porous activated carbon decreases as the tempera-
ture increases (see Figure 1).26,28 At low partial pressures of CO2,
ACs exhibit lower adsorption capacity and selectivity than
zeolites, because of their unfavorable adsorption isotherms.25
The existence of water may negatively affect the capacity of ACs,
because water gets adsorbed competitively.35 In addition, other
components or contaminants in flue gas also have a detrimental
impact on the CO2 adsorption capacity.
2.2. Carbon Molecular Sieves. Carbon molecular sieves
(CMSs), which represent a special class of microporous carbon
materials whose unique textural characteristics permit the kinetic
separation of gas mixtures, are also studied for CO2 capture. For a
CMS to be useful for gas separation, it must possess a narrow
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
Figure 1. Isotherm for adsorption of CO2 on activated carbon.26
pore size distribution (PSD), consisting of pore mouths of molec-
ular sizes and a relatively high micropore volume; these features
result in selectivity and capacity, respectively.58 A porous monolithic
carbon fiber composite molecular sieve was developed and char-
acterized by Burchell et al.59 The CO2 isotherm of this CMS showed
a CO2 uptake of >2.27 mmol g
1 at 30 °C and atmospheric pressure
but this uptake is reduced at elevated temperature. However,
analysis of the equilibrium and kinetics of batch adsorption of
CO2 with a Takeda 5A CMS indicated no molecular sieving action;
instead, micropore diffusion was shown to be rate-limiting in the
process of adsorption dynamics.60 Recently, Alca~ niz-Monge et al.61
reported that microporous carbon monoliths prepared from ni-
trated coal tar pitch showed faster CO2 kinetics than commercially
available Takeda 3A CMS.
2.3. Carbon Nanotube-Based Solid Sorbents. The use of
new generation materials, such as carbon nanotubes (CNTs) and
graphene, has also become an active area of research for separa-
tion of gas mixtures over the last several years. Considerable
theoretical modeling and experimental research efforts are being
devoted to investigate the adsorption of CO2 and N2 and their
mixtures on CNTs (see Table 3).36,45,56,62
72 By choosing the
appropriate pore size and shape and optimum conditions, CNT can
act as a suitable candidate for CO2 separation and sequestration.67,71
Cinke et al.56 reported adsorption of CO2 on purified single-walled
carbon nanotubes (SWCNT) in the temperature range of
0
200 °C (see Figure 2). SWCNTs exhibited a Brunauer

Emmett
Teller (BET) surface area of 1587 m2 g
1 and a total
pore volume of 1.55 cm3 g
1, and the micropore volume was
0.28 cm3 g
1. The CO2 adsorption capacity of SWCNTs was twice
that of AC. However, Lu and his group36,45 observed that equilib-
rium CO2 adsorption capacity of raw CNT was relatively lower than
that of granular AC at 25 °C. Skoulidas et al.66 carried out
simulations to examine the adsorption and transport diffusion of
CO2 and N2 in SWCNTs at room temperature, as a function of
nanotube diameter. They reported that transport diffusivities for
CO2 in nanotubes with diameters ranging from ∼1 nm to ∼5 nm
are roughly independent of pressure. The observed diffusion
mechanism is not Knudsen-like diffusion. Based on Monte Carlo
simulations, Huang et al.67 showed that CO2 adsorption in the range
of 4
9 mmol g
1 is an increasing function of the diameter of the
CNT, and CNTs demonstrated a higher selectivity toward CO2
than other sorbents, such as ACs, zeolite 13X, and MOFs that have
reported in the literature. Razavi et al.71 also concluded that CNTs
exhibited a higher selectivity of CO2 over nitrogen, compared to
1442
REVIEW
Figure 2. Comparison of CO2 adsorption capacities of high-pressure
CO conversion (HiPco) single-walled nanotubes (SWNTs) and acti-
vated carbon (AC) at 35 °C. (Reproduced with permission from ref 56.
Copyright Elsevier, 2003).
other carbon-based materials, for the separation of CO2/N2 mixture.
Lithoxoos et al.72 obtained Type I (Langmuir) behavior of the
adsorption isotherm for CO2 for SWCNTs.
2.4. Zeolite Sorbents. Microporous crystalline framework
materials such as synthetic and natural zeolites are widely used in
the field of gas separation and purification. Conventional zeolites
are based on silicate frameworks in which substitution of some of
the Si with Al (or other metals) leads to a negative charge on the
framework, with cations (usually Na or other alkaline or alka-
line-earth metals) within the pore structure. These cations can
be exchanged to fine-tune the pore size or the adsorption
characteristics. Because of their defined crystalline structures,
these sorbents have uniform pore sizes in the interval of 0.5 nm
to 1.2 nm,73 which is a property that allows them to separate
molecules by means of the molecular sieving effect. Separation
of gases in zeolites can also occur through the mechanism of
selective adsorption of those molecules that have a relatively
large energetic dipole and quadruple. The gases that have high
quadrupole moment, such as CO2 (
14.29  10
40 C m2),74
interact strongly with the electric field created by the structural
cations of zeolites, and this favors their adsorption. Separation of
gases by the zeolite adsorbents depends on various factors:
structure and composition of the framework, cationic form, purity,
size and shape of the molecules, and molecular polarity. The
typical physical properties of the zeolites are listed in Table 2.
Zeolites have shown promising results for separation of CO2
from gas streams. There is much published literature concerning
CO2 adsorption over different types of zeolites such as zeolite A,
X, Y, and other natural zeolites, such as chabazites, clintopiles,
ferrierites, mordenites, etc.22,37,52,53,75
96 Table 4 summarizes
the various zeolites that have been explored to date for applica-
tion of CO2 separation from gas mixtures.
Earlier, a study of adsorption of CO2 on various natural zeolites
(namely, mordenite, ferrierite, clinoptilolite, and chabazite) and
synthetic zeolites (namely, 4A, 5A, and 13X) showed chabazite
and 13X, among the natural and synthetic zeolites, respectively,
to be better adsorbents for CO2 separation from N2.79 The work
by Siriwardane et al.52 indicated that natural zeolite with the
highest sodium content and highest surface area showed the
highest CO2 adsorption capacity and highest rates of adsorption.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research REVIEW

Table 4. CO2 Adsorption Capacity of Zeolites

sorbent temperature, T (K) pressure, pCO2 (atm) adsorption capacity (mmol g
1) experimental procedure ref

Zeolite 13X 293 0.15 2.63 80

Zeolite 13X 295 1 4.61 91
Zeolite 13X 298 1 4.66 92
NaX 305 1 5.71 gravimetric analysis 83
NaY 305 1 5.5 gravimetric analysis 83
NaY 295 1 4.06 91
NaM 298 1 2.95 gravimetric analysis 83
silicalite 303 0.15 0.48 calorimeter-volumetric apparatus 104
Na-ZSM-5 303 1 0.75 GC 87
molecular sieve 13X 298 1 2.8
3.6a PSA 37
molecular sieve 4A 298 1 2.3
3.1a PSA 37
molecular sieve 13X 293 0.15 2.18 105
molecular sieve 4A 293 0.15 1.65 105
molecular sieve 13X 0.1 2.33 fluidized bed 101
molecular sieve 5A 0.1 2.35 fluidized bed 101
erionite (ZAPS) 290 1 2.8 53
mordenite (ZNT) 290 1 1.8 53
clinoptilolite (ZN-19) 290 1 1.7 53
ZSM-5b 313 0.1 0.32c GC 90
HZSM-5
30 295 1 1.9 91
HiSiv 3000 295 1 1.44 91
HY-5 295 1 1.13 91
a
Cyclic tests. b SiO2/Al2O3 ratio = 280. c Experimental data.

An extensive screening study of ∼13 synthetic zeolites, including

5A, 13X, NaY, ZSM-5, HiSiV-3000 (based on ZSM-5 structure
with a silica-to-alumina ratio (Si/Al > 1000) was conducted by
Harlick and Tezel91 for the removal of CO2 from flue gas. From
pure component isotherm data, it was observed that adsorption
capacities of the adsorbents increased in the following order (in
the pressure range of ∼0
2 atm):

13X ðSi=Al ¼ 2:2Þ > NaY ðSi=Al ¼ 5:1Þ

> H
ZSM
5
30 ðSi=Al ¼ 30Þ > HiSiv3000
> HY
5 ðSi=Al ¼ 5Þ
(see Figure 3). This might be due to a low Si/Al ratio with cations
(sodium) in the structure that show strong interactions with
CO2. Zukal et al.102 performed investigation on CO2 adsorption
on six high silica zeolites (SiO2/Al2O3 > 60), TNU-9, IM-5, SSZ-
74, ferrierite, ZSM-5, ZSM-11. The highest CO2 adsorption
capacity was found with TNU-9 and IM-5 attaining 2.61 and
2.42 mmol g
1 at the pressure of 100 kPa, respectively.
Recent studies also focused on the modification of zeolites via
the introduction of large and electropositive, polyvalent cations
to enhance the adsorption of CO2. Khelifa et al.94 demonstrated
that NaX (Si/Al = 1.21) zeolite exchanged with Ni2+ and Cr3+
had shown a decrease in CO2 adsorption capacity, compared to
that of the parent NaX zeolite, because of a weak CO2
sorbent
interaction. NaX and NaY and those resulting from ions ex-
changed with Cs, since it is the most electropositive metal of the
periodic table, were tested with regard to the adsorption of CO2
by Diaz et al.47,48 Cs-treated zeolites performed better and were
very active for adsorption at higher temperatures (100 °C).
Zhang et al.98 prepared chabazite (CHA) zeolites (Si/Al < 2.5)
and exchanged them with alkali cations (e.g., Li, Na, and K) and
1443
Figure 3. Comparison of CO2 adsorption isotherms for fresh zeolites at
295 K. (Legend: (—9—) 13X; (—b—) NaY; (—2—) HZSM-5-30;
(—(—) HiSiv 3000; and (—1—) HY-5.) (Reproduced with permis-
sion from Harlick and Tezel.91 Copyright Elsevier, Amsterdam, 2004.)
alkaline-earth cations (e.g., Mg, Ca, Ba) to assess their potential for
CO2 capture from flue gas by vacuum swing adsorption (VSA) for
temperatures below 120 °C. From the adsorption isotherm, it was
found that NaCHA and CaCHA hold comparative advantages for
high temperature (>100 °C) CO2 separation, while the NaX
zeolite shows superior performance at relatively low temperatures.
According to Katoh et al.87 the selectivity of ion-exchanged ZSM-5
zeolites, M-ZSM-5 (M = Li, Na, K, Rb, and Cs) might be due to
the fact that almost all CO2 molecules strongly adsorbed on the
cation sites, while N2 interacted with the wall of the H-ZMS-5.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
Adsorption kinetics is an important parameter to evaluate the
adsorption performance of an adsorbent. Kinetic studies of
CO2 adsorption on zeolite are rarely reported. According to the
results shown by Hernandez-Huesca et al.,53 the adsorption of
CO2 on erionite (ZAPS) occurred very fast and ∼70% of the
total capacity was achieved at both 273 and 293 K. Zhang et al.44
suggested that the adsorption kinetics could be described by the
linear driving force model and reported that the adsorption
activation energy for CO2 on 13X decreases as the pressure
increases.
Most of the research in adsorption using zeolites has focused
on PSA/VSA adsorption for separating CO2 from flue gas in
power stations that use coal as fuel.22,46,52,88,93,99 The tempera-
ture swing adsorption (TSA) process has also been suggested
by various research groups for the separation of CO2 from flue
gas using zeolites.97,100 Using the TSA process, Merel et al.97
obtained the best performance with zeolite 5A, in terms of the
CO2 capture rate (18%) and volumetric productivity (+23%),
when a simulated 10% CO2/90% N2 gas was used. Konduru
et al.100 employed the TSA process to capture CO2 from a 1.5%
CO2/98.5% N2, using zeolite 13X. Based on an average CO2
recovery of 84% after five consecutive cycles, they concluded
that zeolite 13X showed promise as an adsorbent with sub-
stantial CO2 uptake capacity. Lee et al.101 pointed out attrition
as one potential problem with the zeolite sorbents when used in
fluidized beds. Zeolites 5A and 13X presented attrition that was
2
4-fold higher than that of AC and activated alumina. This
would possibly cause high maintenance costs for a dry sorbent
and problems in the operation of the fluidized-bed process.
It has been reported that there is a detrimental effect of water
on CO2 adsorption, because it gets preferentially adsorbed from
the gas mixture.106,107 Small amounts of water could significantly
decrease the CO2 adsorption capacity, because it gets competi-
tively adsorbed on the zeolite surface and blocks the access for
CO2.106 In another study, CO2 and water vapor adsorption on
zeolite 13X has also indicated that the adsorption of CO2 is
considerably inhibited by H2O.107
In summary, zeolites have been studied extensively to deter-
mine the effect of type of ions incorporated into the structure on
the adsorption equilibrium and energetics. In general, adsorption
kinetics of CO2 on zeolites is comparatively fast and achieved
equilibrium capacity within a few minutes. However, CO2
adsorption on zeolites is strongly influenced by the temperature
and pressure. The adsorption of CO2 decreases as the tempera-
ture increases and increases as the gas-phase partial pressure of
CO2 increases. The presence of water vapor may limit the
application of zeolite sorbents by decreasing its capacity. It is
therefore obvious, that by carefully considering and optimizing
different important factors, such as basicity, pore size of zeolites,
electric field strength caused by the presence of exchangeable
cations in their cavities may significantly influence the CO2
adsorption capacities of zeolites.103
2.5. Metal-organic Frameworks. A relatively new class of
solid sorbent materials is metal-organic frameworks (MOFs).108
MOFs are network solids composed of metal ion or metal cluster
vertices linked by organic spacers. The ability to readily incorpo-
rate and vary organic linkers in these materials translates to
abundant options to control pore size, pore shape, and the
chemical potential of the adsorbing surfaces and, consequently,
their selectivity, kinetics, and capacity. Two important features of
MOF materials are, as implied by the previous statement, (i) their
syntheses can be modular (i.e., entire segments can be replaced
1444
REVIEW
by a functionalized or longer analogue) and (ii) the solids are
crystalline. The modular synthesis leads to the fact that one can
develop isoreticular families of solids (based on the same
topological net), which is a tremendous advantage for rationally
tailoring pore sizes.109 The crystalline nature of MOFs makes
them amenable to complete structural characterization via X-ray
diffraction (XRD) methods. With atomic coordinates of the
framework in hand, designing materials is greatly facilitated. With
the nature of the bonding (coordinate covalent) being weaker
than that in metal oxides, it is not a given that solvated pores
which are observed in crystal structures will necessarily persist
upon solvent removal. Indeed, this fact has led to these com-
pounds being classified into three generations: those that col-
lapse irreversibly and are not porous (first generation); those that
retain their structures and show reversible gas sorption isotherms
(second generation); and a final category where the material
behaves more like a sponge and changes structure reversibly with
guest sorption (third generation).110 While the permanently
porous solids are most akin to zeolitic solids and have the
broadest application in gas sorption (and form the bulk of the
remaining discussion), the third-generation compounds repre-
sent a unique opportunity with MOF materials and, in such
systems, gas sorption has been coupled with properties such as
magnetism,111 gate opening,112 or hydration-controlled release
under ambient conditions.113
With respect to the ability to tune pore surfaces, the most
common approach is to generate a bare-metal site lining the
pore by liberation of a coordinated solvent (typically water)
molecule. This leads to the high heat of adsorption that is
observed in MOFs such as HKUST-1,114 MIL-100/101,115 and
the MOF-74 family.116 Much effort has also been made on
amine-modified MOFs. The amine group can be selected to
interact via a physisorptive mechanism,117
119 where an aryla-
mine serves a polarizing function, or a likely chemisorptive
interaction with an alkylamine.120
MOF-210, which was synthesized by Yaghi’s group,121 currently
holds the CO2 storage record with a saturated CO2 uptake of 2400
mg g
1 at room temperature and ∼50 atm. This MOF has an
estimated bulk density of 0.25 g cm
3, a measured specific pore
volume of 3.60 cm3 g
1, and a BET surface area of 6240 m2 g
1,
which is the highest value reported for any crystalline material.
For CO2 capture, efficient sorption at low partial pressures,
such as those in post-combustion flue gas streams (∼0.1 atm),
would be required. Yazaydin et al.122 have shown that the low-
pressure sorption of CO2 in MOFs best correlates with the heat
of adsorption of CO2, rather than any structural parameter, such
as surface area or pore volume. Heats of adsorption ranging up to
90 kJ mol
1 have been observed in MOFs.120 Higher heats of
adsorption are not necessarily more favorable, because a stronger
binding of CO2 requires more energy to release the gas. Some 12
reported MOFs have heats of adsorption over 40 kJ mol
1 for
CO2 (see Table 5).
While a high heat of adsorption would favor CO2 uptake at
lower pressures, that fact alone would not necessarily translate to
good capture from flue gas in the presence of competing adsor-
bates, particularly water vapor. A prerequisite for sustainable
capture in the presence of moisture would be high moisture
stability. Increasingly, water-stable MOFs are being reported.
ZIF-8 and ZIF-69 are particularly interesting for CO2 capture in
industrial settings, because they have been demonstrated to
maintain their crystal structure in environments such as boiling
water, boiling benzene, and supercritical CO2.128,129 In 2009,
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research REVIEW

Table 5. Heat of Adsorptions of Selected MOFs

heat of adsorption
MOF (kJ mol
1) ref

Cu-BTTri (en) 90 120

Zn2([4-(carboxyphenyl)oxamethyl] 84 123
methane)(4,40 -bipyridine)
MIL-100 62 115
USO-1-Al-A 50 124
[Cu(PF6)2(bpetha)2] 50 125
MOF-74 (Mg) 47 116
bio-MOF-11 45 117
MIL-101 44 115
[Pd(m-H-pymo)2 3 (H2O)x] 44 126
MOF-74 (Ni) 41 116
Zn2(Ox)(Atz)2 3 (H2O)0.5 40.8 127
[Pd(m-F-pymo)2 3 (H2O)x] 40 126
Snurr et al.130 reported that, HKUST-1, which is a MOF, exhibited
enhanced CO2 uptake in the presence of 4% water. It was
recognized that this did not translate to better uptake of CO2 in
the presence of higher degrees of hydration. Work by LeVan et al.131
in 2010 examined the Ni-analogue of MOF74 and HKUST-1 for
CO2 sorption in humid atmospheres. For the Ni-MOF74
material, high CO2 capacities (3.28 mmol g
1) were found at a
point of interest for flue gas application (25 °C, 0.1 atm CO2
partial pressure). Ni-MOF74 has a higher CO2 capacity than
benchmark zeolites (5A and NaX) under these conditions. Adsorbed
water vapor impacted CO2 adsorption in the MOFs, but not
nearly as greatly on 5A and NaX zeolites. Importantly, adsorbed
water was more easily removed from the MOFs by regeneration
than in the zeolites, not surprising given the less-hydrophilic
nature of the MOFs. Most importantly, Ni-MOF74 was found
to retain substantial CO2 capacity with moderate H2O loadings.
This team also studied the effect of hydration on the stability of
the MOF. The HKUST-1 sample showed increasing degradation
over 7 runs; however, the Ni-MOF74 material showed higher
stability over 10 runs. The authors concluded that “Consider-
ing the less intensive regeneration processes compared with
benchmark zeolites and its hydrothermal stability, Ni-MOF74
may have a promising future for capturing CO2 from flue
gases.” Certainly for low-moisture coals or natural gas, there is
potential. This report131 represents the first thorough study of
CO2 capture by MOFs with water as a coadsorbent, and it
appeared in late 2010. Studies on other MOFs performed in
the absence of moisture have reported selectivities for CO2
over CH4 and N2 as high as 30132 and ∼80,117 respectively, under
ambient conditions.
Given that the field of MOFs is still emerging, a general
statement on the prospects for MOF materials is still largely
based on their potential. A search for publications on “CO2
adsorption and/or separation in MOFs” per year, on the ISI
Web of Knowledge, shows as few as 10 publications in 2006,
increasing to 42 in 2008 and 90 in 2010. MOFs have very high
capacity at high pressures, however, at atmospheric pressures
their capacity is lower as compared to other physical sorbents.
Further research is needed to develop MOFs targeting key
material properties such as stability, multicycle applicability and
competitive sorption.
1445
Figure 4. Effect of temperature on the efficiency of CO2 capture by
alkali-metal carbonates. Feed gas composition: 13.8% CO2, 10% H2O,
and balance He.134
3. CHEMISORBENTS
Most of the conventional physisorbents described above (such
as zeolites, ACs, CMSs, and CNTs) suffer from low CO2 adsorp-
tion capacities at relatively low CO2 partial pressure and lower
selectivity toward CO2. Recently, modifications in the surface
chemistry of the porous materials by incorporating basic sites
capable of interacting strongly with acidic CO2 in order to increase
CO2 adsorption capacity and to keep high selectivity for CO2 are
considered very promising. The common modifying functional
groups include alkaline carbonates and various amine groups.
3.1. Regenerable Alkali-Metal Carbonate-Based Sorbents.
Chemical adsorption of CO2 with a dry regenerable alkali-metal
carbonate-based solid sorbent (M2CO3, where M = K, Na, Li) is
being considered for a period of time for CO2 capture from flue gas,
since its operating temperature could be below 200 °C. This class of
sorbents has been investigated for their commercial feasibility by
Hoffman et al.133 In the adsorption process (carbonation, reaction 1),
CO2 and moisture react with the carbonate sorbent at 60
110 °C
and form alkali-metal bicarbonate. Heat treatment of the bicarbonate
at 100
200 °C regenerates alkali-metal carbonate, releasing the CO2
(this process in known as decarbonation; see reaction 2). The
maximum theoretical capacity of Na2CO3 is 9.43 mmol g
1.
Carbonation:
M2 CO3 þ H2 O þ CO2 ¼ 2MHCO3 ð1Þ
(

135 kJ mol
1 when M ¼ Na
ΔH ¼

141 kJ mol
1 when M ¼ K
Decarbonation:
2MHCO3 ¼ M2 CO3 þ H2 O þ CO2 ð2Þ
Hayashi et al.134 developed a TSA process and a regeneration cyclic
process for CO2 capture using potassium carbonate (K2CO3)
supported on AC. For regeneration, pure steam was utilized. As
shown in Figure 4, K2CO3 performs the best out of the three
carbonates. It has a wide carbonation temperature range where the
sorbent efficiency is 100%. They have shown that there was an
optimum loading of K2CO3 on AC support and suggest that above
the optimum loading, excess K2CO3 blocks micropores of AC,
restricting CO2 supply at the active reaction sites, resulting in
reduction of adsorption kinetics and working CO2 capture capacity.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research REVIEW

Table 6. Alkali Carbonate Sorbents for CO2 Capture

active temperature of wt % active gas capacity method of
phase support operation (°C) phase composition (mmol g
1) testing ref

K2CO3 AC, activated coke, Ads.: 100 ∼35 wt % in AC simulated flue gas ∼2.1 (Ads. fixed-bed labscale 134
and silica Reg.: 150 and actual flue efficiency ∼80%) and benchscale
gas in slip stream
Na2CO3 ceramic supported Ads.: 60
70 10
40 wt % simulated flue ∼0.5
3.2 TGA, fixed-bed, 151
153
sorbents Reg.: 120
140 gas and actual entrained-bed reactor,
flue gas field testing by cocurrent
moving bed, limited no.
of cycles
Na2CO3 ceramic supported Ads.: 50
70 35 wt % 10% CO2, ∼2.6 (∼80% bubbling bed 137
sorbents Reg.: >135 (in N2) 12.2% H2O, efficiency with
and 77.8% N2 a 35% active
phase)
Na2CO3 ceramic supported Ads.: 50
70 20
50 wt % simulated flue gas: ∼2.3 (>80% sorbent TGA 138
sorbents Reg.: 120 (in N2) 14.4% CO2, 5.4% efficiency with a
O2, 10% H2O, 30% active phase)
and 70.2% N2
K2CO3 AC, TiO2, Al2O3, Ads.: 60
100 30 wt % 1% CO2, 0
11% H2O, ∼1.1
2.7 fixed-bed, multiple cycle 142
145
MgO, ZrO2, Reg.: 130
400 and N2 balance
CaO, SiO2, and (moisture up to 9%
zeolites and balance N2)
K2CO3 “Sorb KX35” Ads.:60
100 35 wt % simulated flue gas: dry ∼2.1 (∼96% coupled fluidized bed 154
(proprietary Reg.:120
220 basis-12% CO2 and sorbent efficiency) reactor: adsorber- fast
recipe) (in N2) 88% N2; 7
30% fluidized bed and
moisture regenerator- bubbling
fluidized bed, multiple cycle
K2CO3 “Sorb A” Ads.: 70
90 35 wt % slip stream-coal-fired CO2 >85% (capacity coupled fluidized bed 155, 156
(proprietary Reg.: g150 (in N2) flue gas: 7
9% not available) reactor: adsorber- fast
recipe) CO2 (dry basis), fluidized bed and
10
19% H2O regenerator- bubbling
fluidized bed, multiple cycle
K2CO3 AC, silica gel, Ads.: 60 ∼25 wt % 15% CO2, 15% H2O, ∼0.34
1.7 TGA and bubbling 149
activated Al2O3 Reg.: 200 (in N2) and N2 balance fluidized bed
K2CO3 modified Al2O3 Ads.: 70
90 ∼28
48 wt % 1% CO2, 9% H2O, ∼2.9 (∼48 wt % TGA and fixed-bed, 146
support- Reg.: 130 (in N2) and N2 balance K2CO3 loading) multiple cycle
KAl(CO3)(OH)2

Liang et al.135 suggested that the active sodium compound
must be dispersed on a ceramic support such as Al2O3 to satisfy
the durability and needs of high kinetics. Research Triangle
Institute (RTI, Research Triangle Park, NC) also identified136
that fixed-bed and dense-phase fluidized-bed systems were not
optimal reactor schemes for the dry carbonate process, because
of its exothermic nature of chemical reaction. In field testing of
RTI’s prototype cocurrent downflow gas
solid contactor sys-
tem was operated for a total of 235 h, using a fossil fuel-derived
flue gas. The system has been demonstrated to run continuously
for extended periods of time and has achieved >90% capture of
CO2 under various process conditions.
Seo et al.,137,138 a Korean group, studied the effect of water
vapor pretreatment on Na2CO3-based sorbent system in a
bubbling fluidized-bed reactor and found that, out of six types
of spray-dried sorbent systems, three samples had better CO2
1446
sorption capacity than MEA (33.3 wt % MEA solution was used
as the reference and its CO2 absorption capacity was 6 wt %).
Okunev et al.139
141 investigated the influence of a porous
support matrix on the CO2 sorption of K2CO3. For support,
both hydrophilic (silica gel, alumina, vermiculite) and hydro-
phobic (AC) materials were used. This study found that, initially,
the porous alumina/K2CO3 sorbent system possesses the highest
dynamic capacity but it decreases immediately after the first
cycle. A completely reversible regeneration was observed in case
of an AC-impregnated sorbent system. The sorbent system
dynamic capacity decreases in the following sequence:
alumina > activated carbon ðACÞ > vermiculite > silica gel
To identify the best sorbent support system, some Korean re-
searchers142,143 have prepared several K2CO3-based sorbents by
impregnating it on various supports, such as AC, TiO2, Al2O3,
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
Table 7. Structure of Widely Used Amines for Sorbents Functionalization
MgO, SiO2, and di zeolites. CO2 capture capacities of K2CO3/
AC, K2CO3/TiO2, K2CO3/MgO, and K2CO3/Al2O3 (with an
active phase loading of ∼30 wt %) were ∼2.0, 1.9, 2.7, and
1.9 mmol g
1, respectively. However, the CO2 capture capacities of
K2CO3/Al2O3 and K2CO3/MgO, after regeneration at e200 °C,
decreased, because of the formation of KAl(CO3)2(OH)2,
K2Mg(CO3)2, and K2Mg(CO3)2 3 4(H2O) phases during carbo-
nation, which were not completely converted to the original
K2CO3 phase. However, regeneration was not a problem in the
temperature range of 130°
150 °C in the case of K2CO3/AC
and K2CO3/TiO2 sorbent systems. In 2009, a new dry sorbent-
system, called “KZrI30” (30 wt % K2CO3/ZrO2 sorbent system)
was developed. The CO2 capture capacity of the sorbent was
∼96% of the theoretical value in the presence of 1% CO2 and 9%
H2O at 50 °C, and the capacity was almost same in multicycle
operation.144 It is reported that the enhanced CO2 capture
capacity can be obtained by converting the entire K2CO3 3 1.5
H2O phase to the KHCO3 phase if the sorbents are fully activated
with excess water.145 Recently, Lee et al.146 reported a new
regenerable modified-Al2O3 support for K2CO3 sorbent system
for CO2 capture below 200 °C. The CO2 capture capacity of the
1447
REVIEW
48 wt % K2CO3 loaded sorbent was ∼2.9 mmol g
1. In addition,
it was confirmed that the CO2 capture capacities of new sorbents
did not decrease over 5 cycles.
Zhao et al.147,148 found that K2CO3 with hexagonal crystals has
superior carbonation kinetics over monoclinic K2CO3, because of
the crystal structure similarities between K2CO3(hexagonal) and
KHCO3. After identifying the crystal structure and carbonation
kinetics relationship, the research has focused on studying K2CO3-
impregnated composite sorbent systems (where the support materi-
als are coconut AC, coal AC, silica gel, activated alumina) and
dolomite.149 In 2010, Zhao et al.150 have focused their attention on
the effect of carbonation temperature, CO2 concentration, and H2O
concentration and operation pressure on carbonation conversion
rate and reaction rate of K2CO3 calcined from KHCO3. These basic
operational parameters were collected by the group for designing and
operating a large-scale CO2 capture process. Table 6 summarizes the
literature data on alkali carbonate sorbents for CO2 capture.
In summary, the high CO2 capture capacity of Na2CO3
(9.43 mmol g
1) and K2CO3 (7.23 mmol g
1) and favorable
carbonation/regeneration temperature between 60 °C and 200 °C
suggest them as potential sorbents for post-combustion CO2
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
capture. Besides, dry regenerable alkali-metal-based sorbents have
the added advantage of being relatively inexpensive. However, to
be commercially viable, the long-term stability and persistence
performance of these sorbents under real flue gas conditions of
post-combustion applications have yet to be established.
3.2. Amine-Functionalized Solid Sorbents. A variety of
microporous/mesoporous materials loaded with basic nitrogen
functionality, more specifically, organic amine functionality has
been synthesized and characterized to chemisorb CO2 from flue
gas streams. Supported amine sorbents have been classified into
three classes:157,158
• Class 1: This class of supported sorbents is prepared by
physically loading monomeric or polymeric amine species
into or onto the porous support (typically, the porous silica
by impregnation technique).
• Class 2: This class of supported adsorbents is that in which
the amine, mainly amine-containing silane, is covalently
tethered to a solid support, such as porous silica. This is
accomplished by binding amines to oxides via the use of
silane chemistry or via preparation of polymeric supports
with amine-containing side chains. This provides covalently
tethered amine sorbents with the potential to be completely
regenerable through multicycle adsorption/desorption uses.
• Class 3: These supported adsorbents are based on porous
supports upon which amino-polymers are polymerized
in situ. This category of supported sorbents can be con-
sidered a hybrid of the other two classes.157
The structure of widely used amines for sorbent functionaliza-
tion is given in Table 7.
3.2.1. Reaction Scheme of CO2 with Amines. Adsorption of
CO2 using amine-functionalized sorbents involves chemical reac-
tion and, therefore, it is necessary to know how the nature of amine
influences the rate of adsorption and kinetics, in terms of amine
efficiency, defined as the number of CO2 molecules adsorbed for
each nitrogen atom in the amine functional group present. The
zwitterion mechanism originally proposed by Caplow159 and
reintroduced by Danckwerts,160 is generally accepted mechanism
for the reaction of primary and secondary amines CO2. The
mechanism involves two steps: formation of zwitterion (not
shown by reaction here), followed by base catalyzed deprotona-
tion of zwitterion. However, overall reaction can be written as
where R2 = H for the primary amine.
If we consider only the amine as a base, the equilibrium CO2
loading capacities of primary and secondary amines are limited by
the overall stoichiometry of reaction 3 to 0.5 mol (mol of amine)
1.
The only reaction of importance between CO2 and the
sterically hindered primary or secondary amine161 would be the
formation of bicarbonate, as shown by reaction 4, similar to the
case of tertiary amines. Therefore, the stoichiometry of reaction 4
allows a CO2 loading of up to 1 mol (mol of amine)
1 for
hindered primary or secondary amine.
The reaction of CO2 with moderately hindered amines includes
the formation of a carbamate, as in the case of nonhindered amines
1448
REVIEW
(see reaction 3), the stoichiometry of which allows a CO2 loading
of up to 0.5 mol (mol of amine)
1. Tertiary amines do not react
directly with CO2; the primary and secondary amines do react
directly with CO2. They lack the free proton needed in the
deprotonation step. Instead, the reaction produces protonated
amine and bicarbonate ion in the presence of moisture, resulting in
a higher capacity for CO2 up to 1.0 mol (mol of amine)
1. The
mechanism of this reaction is suggested to be base-catalyzed
hydration of CO2, as shown previously in reaction 4.162 Generally,
the formation of bicarbonate allows a high equilibrium capacity.
However, the kinetics is very slow.
3.2.2. Amine-Functionalized Activated Carbonaceous Mate-
rials. It has been shown that, by incorporating certain functional
groups into its porous structure, thus enhancing the CO2
adsor-
bent interactions, the adsorption capacity of carbonaceous
materials could be significantly improved. This section involves
activated carbonaceous materials such as ACs, biochar, fly ash
containing unburnt carbon, CNTs, and solid resins impreg-
nated/grafted with amine functional groups.
3.2.2.1. Amine-Functionalized Activated Carbon Sorbents.
Przepiorski et al.163 found significant enhancement in CO2
adsorption in commercial AC treated with ammonia at high
temperatures (>200 °C). The sorbent treated with ammonia at
400 °C had shown the adsorption capacity of 1.73 mmol g
1.
This enhancement was attributed to the introduction of nitro-
gen-containing groups to carbon structure. Pevida and his
group164 concluded that the CO2 capture capacity is not directly
related to the total nitrogen content of sorbents but rather to
specific nitrogen functionalities that are responsible for increas-
ing the CO2-adsorbent affinity. Plaza et al.165 reported that
amine-treated sorbents prepared from biomass residue and
almond shell preactivated with CO2 exhibited significant differ-
ences in texture and surface chemistry and, therefore, showed
significantly higher capacities than the starting char.
Several amine-impregnated solid sorbents were developed by
chemical treatment of carbon-enriched fly ash concentrates with
various amine groups by Gray et al.,166,167 Maroto-Valer and
others,40,168 and Arenillas et al.169 A typical comparison of CO2
adsorption capacities of activated fly ash carbon and its alkano-
lamine-modified counterparts at various temperatures is shown
in Figure 5, based on the maximum possible adsorption capacity
data reported by Maroto-Valer and others.168 It was found that
activation by steam before impregnation could successfully
increase the surface area and pore volume of carbon-enriched
fly ash, consequently resulting in increased CO2 capture
capacity.40,168 Maroto-Valer et al.40 showed that the impregna-
tion with polyethyleneimine (PEI) could significantly improve
the adsorption capacity of this class of sorbents up to 2.13 mmol g
1
at 75 °C, which is much more than that without impregnation (0.22
mmol g
1 at 75 °C). Arenillas and others169 achieved the highest
CO2 adsorption capacity of ∼1.02 mmol g
1 at 75 °C using
activated fly-ash-derived sorbents impregnated with PEI.40,169 This
group169 also impregnated AC derived from fly ash with PEI and its
blend with poly(ethylene glycol) (PEG). They confirmed that the
addition of PEG into the PEI-loaded sorbents improves the CO2
adsorption capacity and kinetics. This might be due to the
bicarbonate formation reaction in the presence of PEG, which
attracts more water.
The feasibility of a high-surface-area sorbent from low-cost
anthracites was also investigated by Maroto-Valer and his
group.41,42 They reported adsorption capacity of PEI-impreg-
nated deashed anthracite sorbent was ∼2.13 mmol g
1 at
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
Figure 5. CO2 adsorption capacity of activated fly ash carbon and
impregnated fly ash at different temperatures, based on the data reported
by Maroto-Valer et al.168
75 °C.41 In another study, a decrease in adsorption capacity of
activated anthracites impregnated with PEI was observed with
increasing adsorption temperature.42 In 2007, Plaza et al.170 also
reported similar negative effects on capture capacities of com-
mercial AC (Norit CGP super) impregnated with different
alkylamines, such as diethylenetriamine (DETA), pentaethylene
hexamine (PEHA), and PEI.
More recently, Alesi et al.171 studied CO2 capture and
regeneration conditions of tertiary amidine derivatives (N-
methyltetrahydropyrimidine (MTHP)) supported on AC in
the temperatures ranging from 29 °C to 50 °C. It was found
that CO2 capture on the amidines only occurred in the presence
of moisture. Adsorption of moisture on the hydrophilic AC
support places a limit on the CO2 capture capacities. The capture
capacity of 1,5-diazo-bicyclo[4.3.0]non-5-ene (DBN) impreg-
nated AC was shown to have a higher value up to 0.8 mmol g
1 at
an adsorption temperature of 29 °C, compared to those im-
pregnated with 1,8-diazobicyclo[5.4.0]-undec-7-ene (DBU).
3.2.2.2. Amine-Functionalized Carbon Nanotube Sorbents.
The potential application of CNT as the support for amine-
impregnated sorbents has been studied by Fifield and others.63
Pyrene methyl picolinimide (PMP) was introduced as anchors to
increase the affinity of the carbon structure. In 2008, Lu and
others36 reported a comparative study of CO2 capture by CNT,
granulated AC (GAC), and zeolite modified by 3-aminopropyl-
triethoxysilane (APTES) (see Table 7). Figure 6 shows the CO2
adsorption capacities of raw and modified adsorbents. After
functionalization, CNT showed a significant enhancement in
CO2 adsorption capacity, followed by the zeolite. Dillon et al.70
synthesized and characterized PEI-functionalized SWNTs. A
maximum absorption of 2.1 mmol g
1 was reported for PEI
(25000)-SWNT at 27 °C. CNTs modified by APTES were also
tested for their CO2 adsorption potential at multiple tempera-
tures by Su et al.45 The adsorption capacities of CO2 of CNTs
and CNTs (APTES) decreased with temperature, indicating the
exothermic nature of adsorption process, and increased with
water content. They observed that CO2 adsorption capacity of
CNT (APTES) was ∼2.59 mmol g
1 at 20 °C and suggested that
the CNT (APTES) could be a promising low-temperature
adsorbent for CO2 capture. Recently, Hsu et al.68 suggested that
a combination of thermal and vacuum desorption of CNT
1449
REVIEW
Figure 6. CO2 adsorption capacities of raw and modified adsorbents at
25 °C with a [CO2,in] = 50%.36
(APTES) at 120 °C could reduce the regeneration time. The
adsorption capacities and other physicochemical properties were
preserved for 20 cycles of adsorption/regeneration.
3.2.2.3. Amine-Functionalized Solid Resin Sorbents. Amine-
functionalized solid resins are also being studied for use as
sorbents for CO2 capture. Drage et al.172 observed that CO2
adsorption capacity was dependent on both nitrogen func-
tionality and textural properties of precursors of the resins.
The best-performing adsorbent in this class was capable of
capturing ∼1.86 mmol g
1 at 25 °C under pure CO2. Besides,
both categories sorbents showed rapid adsorption halftimes.
However, they found a substantial decrease in capacity
(∼56%) with increasing the adsorption temperature from
25 °C to 75 °C.
In summary, the nitrogen enrichment of carbonaceous mate-
rials is found to be effective in enhancing the specific
CO2
adsorbate interactions. However, the impregnation of
amines resulted in a significant decrease of the surface areas, as
well as mesopore or micropore volume.168,170 This is probably
due to the pore filling or blockage, because the amine incorpora-
tion is assumed to be affected by the molecular size and shape of
alkanolamines used, although the mechanism of pore filling is still
not well-understood.168
3.2.3. Functionalized Zeolite-Based Sorbents. Zeolites with
significant surface area and pore volume present a potential option
for CO2 capture. However, it is reported that CO2 adsorption on
zeolite sorbents decreases significantly as the temperature increases,
and it also shows very low capacity in the presence of moisture in the
flue gas. Therefore, there have been a few investigations (Table 8) to
synthesize aminated zeolites as alternative sorbents.
Zeolite 13X was modified with MEA by Jadhav et al.187 via the
impregnation method. The aminated zeolites showed improve-
ment in CO2 adsorption capacity by a factor of ca. 1.6 at 30 °C. A
higher capacity at the temperature of 120 °C was obtained with
MEA loading of 50 wt %, compared with unmodified zeolite or
modified zeolite with low loading level. Unlike at room tempera-
ture, where physisorption is dominant, the chemical interaction
between CO2 and amine may be playing a significant role in
sorption of CO2 at 120 °C, despite reduced pore volume and
lower surface area resulted from impregnation. The similar
conclusion was also reached by Su et al.188 They dispersed TEPA
into commercially available Y-type zeolite (Si/Al = 60). The CO2
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Industrial & Engineering Chemistry Research REVIEW

Table 8. CO2 Adsorption Capacity of Amine-Impregnated Solid Sorbents

Experimental Conditions

adsorption capacity
support amine amine content (wt %) (humid) (mmol g
1) pCO2 (atm) T (°C) No. of cycles ref

MCM-41 PEI 75 3.02 1 75 173

MCM-41 PEI 50 2.05 0.1 75 173
PE-MCM-41 DEA 77 2.93 0.05 25 50
PE-MCM-41 DEA 73 2.81 (2.89) 0.05 25 50
MCM-41 PEI 50 (3.08) 0.13 75 10 174
MCM-41 TEPA 50 4.54 0.05 75 6 175
SBA-15 TEPA 50 3.23 0.05 75 6 183
SBA-15 DEA + TEPA 50 (30% TEPA, 3.61 0.05 75 6 184
20% DEA)
SBA-15 PEI 50 3.18 0.15 75 185
SBA-15 PEI 50 1.36 0.12 75 186
SBA-15 APTES (2.01) 0.10 25 54
KIT-6 PEI 50 1.95 0.05 75 176
monolith PEI 65 3.75 0.05 75 5 177
mesoporous silica PEI 40 2.4 1 75 178
MC400/10 TEPA 83 5.57 (7.93) 0.1 75 50 179
precipitated silica PEIa 67 4.55 1 100 180
b
R-IAS E-100c (4.19) 0.10 25 54
PMMA TEPA 41 (14.03) 0.15 70 181
PMMA DBU 29 (3.0) 0.10 25 1 17
PMMA DBU 29 (2.34) 0.10 65 6 17
PMMA (Diaion) PEI 40 2.40 (3.53) 0.10 45 182
SiO2 (CARiACT) PEI 40 2.55 (3.65) 0.10 45 182
Zeolite 13X MEA 10 1.0 0.15 30 187
Zeolite Y60 TEPA 50 (4.27) 0.15 60 20 188
β-zeolite TEPA 38 2.08 0.10 30 189
a
Low-molecular-weight PEI (MW ∼ca. 800). b Reformulated immobilized amine sorbent.14 c E-100: ethyleneamine.

adsorption capacity reported was 4.27 mmol g
1 at 60 °C in the
presence of 15% CO2 and 7% water vapor in gas stream.
Besides, Fisher et al.189 employed β-zeolite as a solid support
for TEPA impregnation and compared it with TEPA-impreg-
nated silica and alumina. The TEPA-modified β-zeolite exhibited
the CO2 adsorption capacity up to 2.08 mmol g
1 at 30 °C under
the 10% CO2/90% argon flow, outperforming TEPA/SiO2 and
TEPA/Al2O3 sorbents. It was suggested that the higher capacity
of TEPA/β-zeolite could be related to zeolite’s high surface area.
TEPA/β-zeolite maintained its CO2 capture capacity for more
than 10 adsorption/regeneration cycles.
3.2.4. Functionalized Polymer-Based Sorbents. Polymeric
amine sorbents have been used for years in closed environments,
such as aircraft, submarine, and space shuttles, to capture CO2 for
CO2 concentrations of <1%.190,191 However, the cost of these
sorbents is too high for large-scale applications in the industry,
such as CO2 capture from flue gas. There are two ways to make
polymeric amine sorbents: (i) impregnation method or covalent
functionalization by chemical reaction of polymers/oligomers
with high amine content into polymer support, and (ii) synthesis
of copolymers with amine-containing monomers or monomers
that can be subsequently aminated easily through the reaction of
functional groups such as chloride, etc.124
Satyapal et al.191 reported on a proprietary adsorbent, HSC+
(consisting of PEI bonded to a high-surface-area, solid polymethyl
1450
methacrylate (PMMA) polymeric support coated with PEG).
PEG was used to improve the cyclic capacity of the sorbent
material. The heat of adsorption of the HSC+ sorbent was
estimated to be
94 ( 8 kJ (mol CO2)
1, and its CO2 adsorption
capacity was ∼0.91 mmol g
1 at ambient pressure and 40 °C. A
range of ethanolamines and their mixtures were impregnated
within the pores of PMMA beads with high surface areas by
Filburn et al.55 The results demonstrated the advantage of
secondary amines over other amine types in removing low levels
of CO2, using a pressure swing adsorption process.55 In further
studies, they used MEA, modified TEPA (referenced hereafter as
TEPAN), and a mixture of ethyleneimine (E-100), reaction-
modified ethyleneimine with acrylonitrile (E-100AN), etc. to
functionalize PMMA.181 TEPAN and E-100AN demonstrated
remarkably higher cyclic CO2 capacities and reproducibility. For
example, PMMA-supported TEPAN exhibited cyclic capacities as
high as 10.21 mmol g
1 at 40 °C.
In 2005, Gray et al.192 immobilized Michael addition reaction
products of ethylenediamine and TEPA with acrylonitrile within the
pores of PMMA beads. They evaluated the performance of the
sorbents in a temperature swing system using (10% CO2 + 2%
H2O) in helium gas over the temperature range of 20
65 °C. The
average CO2 capture capacities for the sorbent over four adsorp-
tion/desorption cycles was in the range of 3.4
6.6 mmol g
1. The
thermal stability of the sorbent was also investigated over a 10-cycle
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Industrial & Engineering Chemistry Research
study, and the results suggested that these sorbents could be one of
the potential sorbents for the capture of CO2 from flue gas streams.
Furthermore, in an effort to achieve the higher CO2 capture
capacity, Gray et al.17 immobilized DBU in PMMA beads. With a
DBU loading of ca. 29 wt %, the modified sorbent showed an
adsorption capacity of 3.43 mmol g
1 at room temperature under
the simulated flue gas containing 10% CO2 and 2% H2O. However,
the CO2 capacity decreased considerably to 2.34 mmol g
1 as the
temperature increased to 65 °C, which is contrary to that observed
for amine-impregnated mesoporous inorganic sorbents.
Besides PMMA (diaion), other supports such silicon dioxide
(CARiACT) and polystyrene (Macronet) were also compared.182
The heat of reaction (ΔHr) was also determined as key criteria for
sorbent screening. It was found that both CARiACT- and PMMA-
supported PEI sorbents with ΔHr values of 26.7 and 24.6 kJ (mol
CO2)
1, respectively were within the acceptable value of ∼30.66 kJ
(mol CO2)
1. Moreover, the sorbents exhibited acceptable CO2
capture capacities of 2.5
3.5 mmol g
1 under humid conditions
and stable over the temperature range of 25
105 °C for 10 cycles.
Li et al.193,194 reported development of fibrous sorbents for
CO2 capture by coating PEI onto commercial glass fiber matrix
with high surface area, using epoxy resin (EP)193 and epichlor-
ohydrin (ECH)194 as a cross-linking agent. The CO2 adsorption
capacities obtained were 6.30 mmol g
1 for PEI cross-linked with
EP-coated fiber and 4.12 mmol g
1 for PEI cross-linked with
ECH-coated fiber at 30 °C, 1 atm and under humid conditions.
Both modified fibrous adsorbents could be completely regener-
ated at 120 °C. However, these modified glass fibrous adsorbents
were most efficient at room temperature. At a higher temperature
of 50 °C, the adsorption capacity decreases drastically. Recently,
Yang et al.195 synthesized and characterized an amine-containing
fibrous adsorbent (PAN-AF) by grafting copolymerization of
allylamine onto polyacrylonitrile (PAN) fiber. They reported a
CO2 adsorption capacity of 6.22 mmol g
1 with a grafting degree
of 60.0 wt %. However, regeneration of PAN-AF is proposed to
be carried out by heating PAN-AF in boiled water. Table 8 shows
the CO2 adsorption capacity of few impregnated polymer-based
solid sorbents.
This class of polymer-based functionalized sorbents has exhibited
high equilibrium capacity. However, there is not adequate informa-
tion, regarding other selection criteria.
3.2.5. Functionalized Silica-Supported Sorbents. 3.2.5.1. Im-
pregnated Silica-Supported Sorbents. The first amine-impreg-
nated silica used to capture CO2 was reported by Song and others
in 2002.173 They used wet impregnation of hydrothermally
synthesized MCM-41, a high-surface-area mesoporous silica with
cylindrical pores of relatively small diameter (2.8 nm), with PEI to
create an adsorbent, termed as a “molecular basket”.173,174,196
198
In 2003, Xu et al.196 reported the highest CO2 adsorption capacity
of 3.02 mmol g
1 with MCM-41-PEI at a PEI loading of 75 wt %
under a pure CO2 atmosphere and at 75 °C. The adsorbent
prepared by a one-step wet impregnation method showed a higher
CO2 adsorption capacity than that prepared by a two-step
impregnation method and mechanical mixing method.
Increased PEI loadings resulted in higher adsorption of CO2,
as expected. The physical adsorption on the unmodified pore
wall of MCM-41 (and the capillary condensation in the
mesopore) is negligible, in comparison with the chemical ad-
sorption for higher loadings. In addition, it has been hypothe-
sized that there is a synergetic effect of MCM-41on the PEI for
the adsorption of CO2.196 The highest synergetic adsorption gain
1451
REVIEW
was obtained when the mesoporous pores were loaded with
∼50 wt % PEI.
Compared with conventional adsorbents (ACs and zeolites),
PEI-impregnated MCM-41 showed an increase in adsorption
capacity with increasing temperature. Xu et al.196 assumed that
the low adsorption capacity at low temperature could be a result
of low adsorption rate caused by kinetic limitations, and the
overall process is kinetically controlled. They also verified that
the adsorption capacity at low temperature will be even larger
than that high temperature if the adsorption time is sufficiently
long to overcome the diffusion limitation.
A series of performance and stability studies using a MCM-41-
PEI sorbent was also carried out by Song and his groups174,197,198
to separate CO2 from simulated flue gas, flue gas from a natural-
gas-fired boiler, and simulated humid flue gas using a packed-bed
adsorption column. The adsorbent was tested with simulated flue
gas (14.9% CO2/4.25% O2/80.85% N2) at the temperature
range of 25
100 °C by Xu et al.197 The adsorbent showed a
separation selectivity of >1000 for CO2/N2 and ∼180 for CO2/
O2. The cyclic adsorption/desorption operation indicated that
the adsorbent was stable at 75 °C after 10 cycles of operation.
However, it was not stable when the operation temperature
was >100 °C. NOx was observed to be adsorbed simultaneously
with CO2, indicating the need for preremoval of NOx from flue
gas.174,198 In addition, the presence of moisture in the simulated
flue gas and flue gas from a natural-gas-fired boiler was shown to
enhance the adsorption capacity when the moisture concentra-
tion in the feed is lower than that of the CO2. The possible
reasons could be the formation of bicarbonate ion (eq 4) during
the chemical interaction between PEI and CO2 in the presence of
moisture.
More recently, a nanoporous SBA-15-supported sorbent with
50 wt % PEI loading was developed by Ma et al.185 This sorbent
showed a sorption capacity of 3.18 mmol g
1 at 75 °C under a
CO2 partial pressure of 15 kPa. The reported CO2 adsorption
capacity was ∼50% higher than that of their previously devel-
oped MCM-41-PEI sorbent, possibly due to the higher pore
diameter and pore volume of SBA-15. This allows the PEI-
modified sample prepared from SBA-15 to have a higher surface
area for the same PEI loading (50 wt %). A two-stage sorption
approach was also proposed by Ma et al.185 to remove CO2 and
H2S from gas streams using this sorbent. The sorbent and
process has been shown to be capable of removing H2S to a
level of <60 ppbv.
Franchi et al.50 impregnated DEA, which is a secondary
alkanolamine, on a pore-expanded MCM-41 (PE-MCM-41,
dp = 9.7). PE-MCM-41, which has a larger pore diameter and
greater volume, allowed for a higher loading level of amine agents
and exhibited better CO2 adsorption performance, which shows
a good agreement with the observations of Ahn’s group.176,177
The effect of moisture on the uptake capacity of DEA-loaded PE-
MCM-41 appeared to be insignificant. Moreover, DEA-impreg-
nated PE-MCM-41 showed good cyclic stability, in comparison
to other impregnated sorbents, such as DEA-impregnated zeo-
lites 13X (see Figure 7).50
Gargiulo et al.199 compared PEI-functionalized mesoporous
MCM-48 and SBA-15. PEI-loaded SBA-15 constantly showed a
slightly higher CO2 adsorption capacity than that of PEI-loaded
MCM-48, because of the pore size effect. The significant role of
the distribution of the amine groups impregnated in the porous
materials has been demonstrated by Zhu and his group.183 They
used as-prepared mesoporous SBA-15 occluded with an organic
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Industrial & Engineering Chemistry Research
Figure 7. CO2 adsorption capacity, as a function of adsorption cycle for
6.98 DEA/PE-MCM-41 and other CO2 adsorbents.50 Amine content of
6.98 DEA/PE-MCM-41 = 6.98 mmol DEA g
1.50
template (Pluronic P123), to impregnate TEPA. The reported
that the CO2 adsorption capacity of the modified SBA-15 with a
TEPA loading of 50 wt % was higher than that for calcined SBA-
15. The presence of the template optimized the accessibility of
TEPA to CO2, via a better dispersion and distribution of amines.
Furthermore, Yue et al.184 also fabricated as-prepared SBA-15
supported sorbents through dispersing amine blends of TEPA
and DEA. The hydroxyl group in DEA is found to significantly
promote the adsorption. Hydroxyl group facilitates the formation
of the carbamate zwitterion, and, therefore, equilibrium CO2
loadings of amine can reach 2 mol CO2 (mol amine)
1.
As a new strategy to further improve efficiency for CO2 capture,
Yue et al.175 impregnated TEPA into as-prepared MCM-41 that
had been prepared with the ionic surfactant cetyltrimethylammo-
nium bromide (CTAB). The as-prepared MCM-41 with 50 wt %
TEPA exhibited a CO2 adsorption capacity of 4.16 mmol g
1 in
5% CO2, probably due to better amine distribution, resulting from
the use of ionic surfactant templates.175 They concluded that the
amount, type, and distribution of the surfactant in the pores of the
silica support all have significant influence on the CO2 adsorption
capacities. However, their studies showed that TEPA-impregnated
as-prepared MCM-41 required only 1.5 min to reach the adsorp-
tion halftime but 140 min to reach close to equilibrium adsorption
capacities. Therefore, Choi et al.124 suggested that the adsorption
halftime or working capacities defined for short adsorption
time should be used instead of equilibrium capacities in real
application cases.
In 2008, Ahn and co-workers176 synthesized and studied a
series of PEI-loaded (50 wt %) ordered mesoporous silica
supports, namely, MCM-41, MCM-48, SBA-15, SBA-16, and
KIT-6 to assess their CO2 adsorption performance. All impreg-
nated sorbents showed faster adsorption kinetics, as well as
substantially higher CO2 sorption capacities and stability, than
that of pure PEI. The CO2 adsorption capacities were found to be
in the following order:
KIT
6 ðdp ¼ 6:5Þ > SBA
15 ðdp ¼ 5:5Þ≈SBA
16 ðdp ¼ 4:1Þ
> MCM
48 ðdp ¼ 3:1Þ > MCM
41 ðdp ¼ 2:1Þ
where dp is the average pore diameter (given in nanometers).
The performance was proposed to be influenced by the pore
1452
REVIEW
diameter and pore arrangement of mesoporous silica materi-
als. Bulky PEI is assumed to be introduced to the pore easily as
the pore size in the support increases. The same research group177
also developed PEI-impregnated silica monoliths showing a hier-
archical pore structure as a support. For 5% diluted CO2 sorption
tests, the amine-impregnated monolith with 65% PEI loading
exhibited a maximum adsorption capacity of 3.75 mmol g
1 at
75 °C, outperforming the KIT-6
PEI-50, which has been reported
to have an adsorption capacity of 1.95 mmol g
1 under the same
conditions.176
Recently, Goeppert et al.180 impregnated nanostructured fumed
silica using various organoamines, namely PEI, MEA, DEA, TEPA,
and PEHA, as well as 2-amino-2-methyl-1-3-propanediol(AMPD),
2-(2-amino-ethylamino)ethanol (AEAE), etc. They observed that
simple amines such as MEA, DEA, AEAE, etc. are not suitable,
because of amine leaching problems at higher temperature.
More recently, Qi et al.179 proposed a novel high-efficiency CO2
capture platform obtained using PEI and TEPA supported on
specially designed mesoporous capsules. The novel composite
sorbent showed excellent CO2 capture capacity of 6.6 mmol g
1
under 1 atm of moisture-free CO2 at 75 °C and exceptional CO2
capture capacity of 7.9 mmol g
1 under simulated humid flue gas
with 10% CO2 at 75 °C. The CO2 capture kinetics was found to be
relatively fast and attained 90% of the total capacity within the first
few minutes (see Figure 8). Besides, sorbents could be regenerated
below 100 °C and exhibited good cyclic stability over repetitive
adsorption/regeneration cycle (∼50 cycles).
Further studies took into consideration the mode of regenera-
tion and the lifetime of adsorbents during the evaluations of
amine-impregnated adsorbents. Drage et al.178 demonstrated
thermal swing desorption for PEI-functionalized proprietary
mesoporous silica, using pure CO2, and reported good cyclic
regeneration capacities (2 mmol g
1). A successive loss of
adsorption capacity of the sorbent—and, therefore, lifetime of
sorbents—was observed over numerous regeneration cycles. It
was probably due to the secondary reaction between CO2 and
PEI above 135 °C to form a stable product (e.g., urea), which
leads to the irreversible degradation of the adsorbents. The use of
steam as a stripping gas instead of CO2 was suggested in
overcoming the problems. In addition to the TSA process,
Dasgupta et al.186 investigated a single column five-step PSA
option using PEI-impregnated SBA-15 as an adsorbent. A strong
adsorptive rinse cycle was suggested for CO2 recovery during
PSA process. Pirngruber et al.200 concluded that neither the
conventional TSA or VSA modes seem to be a viable option for
their amine-immobilized sorbents.
In summary, novel amine-impregnated silica supports, as
shown in Table 8, are promising and can effectively adsorb
CO2 with relatively higher working capacity; even some cases
of >4 mmol g
1 stipulated industrial requirements for solid
sorbents. The modification of pore size of silica support is shown
to enhance the adsorption capacity. Moreover, their adsorption
capacities are not impaired by the presence of moisture (in many
cases, moisture helps to obtain higher capacity). However, the
durability and regeneration kinetics of the amine-impregnated
solid sorbents have not been tested adequately under real flue gas
conditions. Their desorption kinetics is still slower. Considerable
leaching of the amines may be a major drawback for the use of
impregnated amine-functionalized sorbents for CO2.
3.2.5.2. Grafted Silica-Supported Sorbents. Many groups
have reported the synthesis and characterization of amine-grafted
ordered mesoporous silica sorbents (Class 2 category) for CO2
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Industrial & Engineering Chemistry Research
Figure 8. CO2 capture kinetics of mesoporous silica sorbents with
different amine loadings. (Reprinted with permission from ref 179.
Copyright The Royal Society of Chemistry, 2011.)
capture. Here amine—mainly, amino-silane—is covalently teth-
ered to the silica support.124 Three methods can be used for the
grafting of amine onto a silica support: post-synthesis grafting,
direct synthesis by co-condensation, and anionic template synth-
esis with help of the interaction between the cation head in
aminosilane and anionic surfactants.201 The mesoporous nature
of the support permits good diffusivity of organic amine into the
pore space and, following functionalization, good mass diffusion
of CO2 gas molecules into and out of the structure (except when
the pores are blocked). In addition, a wide variety of aminosilanes
(see Table 2) are being grafted onto the surface of porous silica to
investigate the impact of amine type and amine loadings on the
CO2 adsorption capacity of resulting sorbent composites.
Leal et al.202 first described the chemisorption of CO2 on a
APTES grafted surface of silica gel. They confirmed that each
molecule of CO2 uses two surface amino groups to form an
ammonium carbamate species in the absence of H2O and ammo-
nium bicarbonate surface species in the presence of H2O. However,
their sorbent capacity was far below the requirement for industrial
application of the sorbents. Afterward, a series of aminopropyl-
functionalized (grafted) hexagonal mesoporous silica (HMS) com-
pounds was prepared and characterized by Chaffee’s group203
207
to enhance CO2 adsorption, because of their high porosity. The
grafted HMS materials, as shown in Figure 9 were developed by
Delaney et al.203 using 3-aminopropyltrimethoxysilane (APTS), ami-
noethyl-aminopropyl-trimethoxysilane (AEAPTS), and N-[3-(tri-
methoxysilyl)propyl) diethylenetriamine (DAEAPTS), ethylhy-
droxyl-aminopropyl-trimethoxysilane (EHAPTS) and diethylhy-
droxyl-aminopropyl-trimethoxysilane (DEHAPTS) (see Table 7).
The modified silica supports have shown very high surface area
with varied concentrations of surface bound amine and hydroxyl
functional groups. The modified HMS sorbents have also been
shown to reversibly adsorb substantially more CO2 than modified
silica gel, as reported by Leal et al.202 Another observation reveals
that, for HMS-APTS, HMS-AEAPTS, and HMS-DEAPTS, the
ratio of CO2 molecules adsorbed per available N atom was ∼0.5.
This is consistent with the carbamate formation mechanism, as
presented by eq 3. With HMS-DEHAPTS, the ratio was ∼1.
Because tertiary amines cannot form stable carbamates (see
section 3.2.1), it has been proposed that the hydroxyl groups
may serve to stabilize carbamate-type zwitterions.
1453
REVIEW
Figure 9. Modified hexagonal mesoporous silica (HMS) materials.
Based on a systematic investigation on CO2 adsorption on
different mesoporous silica substrates and their amine-function-
alized hybrid product, Knowles et al.204
207 also pointed out that
the extent of surface functionalization is found to be dependent
on substrate morphology (e.g., available surface area, pore
geometry, and pore volume), diffusion of reagents to the surface,
as well as the silanol concentration on the substrate surface. Their
results showed that the higher nitrogen content of the tether
leads to a higher CO2 capacity on the adsorbent surface. The
CO2 adsorption performance of hybrid materials exhibited good
adsorption kinetics, reaching equilibrium within 4 min for each
sample, and highest CO2 capacity of ∼1.66 mmol g
1 at 20 °C in
dry 90% CO2/10% argon mixture.204
As an extension of their previous work on APTS- and
AEAPTS-functionalized HMS, and to explore the potential of
the longer side chain and greater number of N atoms/tether to
achieve still higher CO2 capacities, Knowles et al.207 assessed
DAEAPTS-functionalized HMS. The sample with the best CO2
adzsorption performance was determined to have a CO2 adsorp-
tion capacity of 1.2 mmol g
1 at 20 °C, which was less than the
previously observed capacity for the analogous APTS- and
AEAPTS-functionalized silica (1.66 mmol g
1).205 In compar-
ison with APTS- and AEAPTS-functionalized silica sorbents, the
DAEAPTS-functionalized sorbents had a greater CO2 adsorp-
tion capacity but lower amine efficiencies. It was thought to be
due to reduced accessibility of CO2 to the surface-bound amine
groups brought about by entanglement (reduced mobility) of the
longer hydrocarbon chains within the mesoporous domain and
the relative proximity of amine pairs. All functionalized HMS
sorbents were found to be thermally stable up to 170 °C in both
pure N2 and mildly oxygenated (2%) N2 atmosphere and showed
no affinity for N2 and O2. However, DAEAPTS-functionalized
sorbents were found to degrade in a highly oxygenated
atmosphere.
Liang et al.208 synthesized a series of functionalized SBA-15
with melamine-based dendrimers, using the similar stepwise
polymerization reaction scheme proposed by Acosta et al.209 It
was found that the CO2 adsorption capacities of the dendrimer-
functionalized SBA-15 did not show any improvement over that
of the aminopropyl-modified SBA-15.
Hiyoshi et al.210,211 demonstrated the potential application of
aminosilane-modified mesoporous silica for the separation of
CO2 from gas streams containing moisture (see Table 9). The
characterization of the adsorbents showed the significant de-
crease in the surface area or pore volume after grafting, which was
close to the predicted values for each adsorbent. In their
subsequent research,211 they found that the DAEAPTS
SBA-15
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research REVIEW

Table 9. CO2 Adsorption Capacity of Amine Grafted Solid Sorbents

Experimental Conditions

adsorption capacity
support amine amine content (mmol g
1) (humida) (mmol. g
1) pCO2 (atm) T (°C) ref

SBA-15 APTES 2.7 0.52 (0.5) 0.15 60 210

SBA-15 AEAPSf 4.2 0.87 (0.9) 0.15 60 210
SBA-15 DAEAPTS 5.1 1.1 (1.21) 0.15 60 210
SBA-15b APTES 2.61 0.66 (0.65) 0.15 60 211
SBA-15b AEAPSf 4.61 1.36 (1.51) 0.15 60 211
b
SBA-15 DAEAPTS 5.8 1.58 (1.80) 0.15 60 211
SBA-15 AEAPTS 0.45 0.15 25 218
SBA-15 AEAPTS 1.95 1 22 218
SBA-15c AEAPTS 0.91 0.15 25 217
SBA-15 APTES 0.4 0.04 25 213
SBA-15 APTES 2.72 1.53 0.1 25 232
SBA-15 aziridine polymer 9.78 (5.55) 0.1 25 230
SBA-15 aziridine polymer 9.78 (4) 0.1 75 230
SBA-15 aziridine polymer 7 (1.98) 0.1 75 229
SBA-15 aziridine polymer 7 (3.11) 0.1 25 229
SBA-16 AEAPTS 0.76 1.4 1 27 231
SBA-12 APTES 2.76 1.04 0.1 25 232
MCM-41 APTES 3 0.57 0.1 25 232
PE-MCM-41 DAEAPTS 7.95 2.65 0.05 25 220
PE-MCM-41 DAEAPTS 7.8 2.28 0.05 70 223
MCM-48 APTES 2.3 2.05 1 25 212
MCM-48 APTES 2.3 1.14 0.05 25 212
HMSd APTS 2.29 1.59 0.9 20 205
HMSd DAEAPTS 4.57 1.34 0.9 20 207
MSPe AEAPTS 0.73 0.1 60 234
silica gel APTES 1.26 0.89 1 50 202
CNTs APTES 1.32 0.15 20 68
CNTs AEAPTS 2.59 0.5 20 45
a
CO2 adsorption capacity within parentheses indicates humid condition result. b SBA-15 support is boiled in water for 2 h followed by grafting of
aminosilanes. c EDA-SBA-15 enhanced by backfilling with propylsilane (C3) in supercritical fluid propane. d Hexagonal mesoporous silica. e Mesoporous
spherical-silica particles. f N-(2-aminoethyl)-3-aminopropyltriethoxysilane.

showed improved CO2 adsorption capacity after SBA-15 was
boiled in water for 2 h, followed by the grafting of aminosilanes.
The amount of CO2 adsorbed reached 1.58 and 1.80 mmol g
1
in the absence and presence of water vapor, respectively, under
the same experimental conditions. The efficiencies of the ami-
nosilanes at identical amine surface density, were found to be in
the following order:
APTES > AEAPTS > DAEAPTS
In an effort to develop selective sorbents for the removal of
CO2 and H2S from natural gas mixtures, 3-aminopropyl-func-
tionalized silica xerogel and MCM-48 silica sorbents were also
synthesized and studied by Huang et al.212 The CO2 uptake
capacity of amine-grafted MCM-48 sorbent was always higher
than that of amine-grafted xerogel. With the respect to pure CO2,
the amount of CO2 adsorbed reached 2.05 mmol g
1 at 25 °C. In
the presence of water, the CO2 adsorption capacity was doubled
as the adsorption mechanism changed from carbamate formation
to bicarbonate formation.
Gray and co-workers54,213
216 prepared a series of amine-
grafted SBA-15 sorbents for CO2 adsorption. They reported that
1454
APTES-grafted SBA-15 could adsorb up to 0.4 mmol g
1,
whereas SBA-15 grafted with AEAPTS215 could adsorb 0.79
mmol g
1 at 25 °C.213 CO2 was found to adsorb on the amine
sites in the form of bicarbonate and carbonates. Therefore,
enhanced CO2 adsorption capacity was reported in the presence
of H2O, because it helps to form carbonate and bicarbonate,213
which was confirmed by Khatri et al.216 Khatri et al.216 and Zheng
et al.217,218 investigated the thermal stability of several grafted
SBA-15 and found these to be stable up to 250 °C. In addition,
the SO2 adsorption on APTES-SBA-15 resulted in a negligible
CO2 adsorption capacity, indicating the necessity of SO2 removal
before amine-based CO2 adsorption.216
As a continuous effort to develop high-capacity, water-tolerant
amine-grafted silica-based sorbents with large amine loadings, as
well as with large pore volume and pore size, Sayari and co-
workers219
228 developed pore-expanded MCM-41 mesoporous
silica (PE-MCM-41) grafted with amine, such as DAEAPTS. The
sorbent was prepared through a post-synthesis hydrothermal
treatment of the as-synthesized MCM-41.221 The DAEAPTS-
grafted PE-MCM-41 support showed an adsorption capacity of
2.05 mmol g
1 at 25 °C and 1.0 atm for a dry 5% CO2 in N2 feed
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research REVIEW

Figure 10. Relationship between amine, CO2, carbamate, and urea

species during CO2 adsorption
desorption under dry and humid
conditions.228

mixture with amino-silane loading of 5.98 mmol (N) g
1.219

They showed that the effect of amine surface density of the
sorbent has a strong impact on the adsorption efficiency. How-
ever, the presence of moisture did not significantly enhance the
performance of the amine-impregnated PE-MCM-41 sorbents as
expected toward the bicarbonate formation pathway.
Subsequently, Harlick and Sayari220 also focused on optimiz-
ing the grafting conditions and concluded that, in comparison to
the dry grafting procedure, wet grafting via the co-addition of
water at 85 °C showed an increase in the total amine content,
resulting in a 90% overall improvement. They found that,
through regeneration under a vacuum at 70 °C, the sorbent
showed good stability over 100 cycles with an average working
adsorption capacity of 2.28 mmol g
1 for pure CO2,223 while the
temperature swing regeneration process was suitable only above
120 °C.224 In addition to thermal stability, it also showed
infinitely high selectivity for CO2 over N2 and O2.224
227 It
was also confirmed by Belmabkhout and Sayari227 that SO2 has
an adverse effect on CO2 removal, which has also been demon-
strated by Khatri et al.216 Recently, they228 reported that the
deactivation of the amine-grafted MCM-41 silica sorbents took
place through the urea formation reaction under dry conditions
(Figure 10), even under mild conditions of 20 °C, and deactiva-
tion was dependent on the adsorption
desorption conditions
and the nature of the adsorbent. Moreover, this research group
noted that their sorbent underwent over 700 cycles without any
loss of sorption capacity when adsorption and regeneration was
carried out using a humid gas with ∼7.5% relative humidity at
70 °C. Therefore, they suggested that the stability of sorbent
could be enhanced significantly by inhibiting the formation of
urea, using moisture-containing gases.
A novel covalently tethered hyperbranched aminosilica (HAS)
sorbent (Figure 11) with high amine content capable of capturing
CO2 reversibly from flue gas was developed and compared with
other covalently supported solid sorbents by Jones and his research
group.229,230 HAS was synthesized via a one-step surface polymer-
ization reaction of aziridine monomer inside SBA-15 pores230 The
HAS sorbent had an amine loading of 7.0 mmol N g
1 and CO2
adsorption capacity of 3.08 mmol g
1 when tested in a packed-bed
reactor under a flow of 10% CO2/90% argon saturated with water
at 25 °C. It was stable over 12 cycles with regeneration at 130 °C.
Following their early research work, Drese et al.230 proposed
modification of the HAS synthesis conditions, such as the azir-
idine-to-silica ratio and the solvent to further tune the sorbent’s
composition, adsobent capacity, and kintetics. They found that
higher amine loadings—and, therefore, higher potential active
adsorption sites—contributed to a better adsorption capacity.
Knofel et al.231 functionalized SBA-16 silica with AEAPTS.
The functionalization of SBA-16, which has a three-dimensional
(3D) cubic pore matrix with interconnected pores, allows good
accessibility for the grafting species, as well as the gas molecules
during adsorption. The sorbent capacity was not found to be
1455
Figure 11. Hyperbranched amino silica.
higher than ∼1.4 mmol g
1 at 27 °C with high enthalpies for
adsorption for CO2 (
100 kJ/mol).
The comparison of three APTES-grafted mesoporous silica
materials—MCM-41 (dp = 3.3), SBA-12 (dp = 3.8), and SBA-15
(dp = 7.1)—was made by Zelenak et al.232 The sorbent capacity
was in accordance with the order of pore size as well as amine
surface density, similar to that observed in the amine-impreg-
nated mesoporous silica sorbents. Kim et al.233 developed and
tested a series of amine-functionalized mesoporous silica sor-
bents via anionic surfactant-mediated synthesis method for CO2
adsorption at room temperature. Higher amine loading on the
mesoporous structure was determined to be the governing factor
to achieve high CO2 adsorption, as expected.
Table 9 summarized the CO2 adsorption capacity of amine-
grafted adsorbents. Although the functionalization of mesopor-
ous silicas with amine functional groups significantly improves
the CO2 adsorption capacity of silica substrate, the reported
equilibrium CO2 adsorption capacities are not as high as those
reported with amine-impregnated mesoporous silicas. More-
over, the low thermal stability of mesoporous silicas, in the
presence of water vapor at elevated temperature, is still one of
the major concerns.
3.2.6. Impregnated Alumina-Supported Sorbents. Because of its
high resistance to steam and good mechanical and thermal stability
properties, porous alumina was also considered for impregnation.235
Plaza et al.236 synthesized and tested a series of solid sorbents by
impregnating six different amines (DETA, DIPA, TEA, AMPD,
PEHA, and PEI) on the surface of a mesoporous alumina. Alumina
sorbent impregnated with 40 wt % DETA (A-DETA) presented the
highest CO2 adsorption capacities throughout the temperature
range of 298
373 K (ca. 1.82 mmol g
1 at 373 K). A-DETA
sorbent doubled the CO2 capture capacity of the raw alumina at
298 K (i.e., 1.36 mmol g
1 vs 0.68 mmol g
1). It is also worth noting
that alkanolamine-impregnated samples (A-TEA, A-AMPD, and
A-DIPA) showed a gradual decrease in CO2 adsorption with
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Industrial & Engineering Chemistry Research
increasing temperature, whereas the alkylamine-impregnated
samples (A-DETA, A-PEHA, and A-PEI) presented a gradual
increase in CO2 capture capacity. The probable reason for this
could be an improvement of CO2 mass diffusivity through the
amine film with temperature, because this would allow more
amine groups to react.173
The above discussion clearly indicates that chemisorbents
hold great potential to overcome the energy penalty in the base
case: the MEA process. Several chemisorbents, such as amine-
functionalized sorbent (both impregnated and grafted), have
shown promise to meet the desired working capacity target in
simulated flue gas conditions. Mostly, chemisorbents are found
to have higher CO2 selectivity. Amine-functionalized polymer-
based sorbents showed very high adsorption capacity, but there
is not adequate information regarding other selection criteria.
Impregnated mesoporous silica sorbents showed improved
capacity in the presence of water vapor, whereas grafted silica
showed good thermal stability at high temperature (<200 °C).
However, a considerable amount of time is required to regen-
erate these sorbents via thermal swing cycling and it is found
that SO2 has an adverse effect on CO2 removal and its removal
is required prior to CO2 adsorption.227 Moreover, all of the
identified sorbents are in the early development stage and
require further investigation.
4. TECHNO-ECONOMIC ANALYSIS AND DESIGN
ASPECTS OF CONTACTORS FOR SORBENT-BASED
SYSTEMS
An efficient and cost-effective novel sorption technique using a
solid sorbent could produce certain technical and economic
advantages, compared to conventional aqueous amine absorp-
tion/regeneration processes. On the basis of the ongoing theo-
retical and experimental research activities conducted so far, it
appears that there are some potential candidate sorbent materials
that exhibit better CO2 capture capacities and lower regeneration
energy than conventional amine-based sorbents. However, the
efficient use of the solid sorbent in a particular contactor type is a
key and will ultimately determine whether the sorbent-based
technology can indeed be economical for CO2 capture from flue
gas. The knowledge of key engineering data such as equilibrium
CO2 loading capacity under given conditions of pressure,
temperature and concentration, kinetic data for adsorption
and desorption, mass transfer and diffusional effects, effects of
moisture, effects of flue gas contaminant, etc. are important for
candidate sorbents being developed and for the design of CO2
removal system. Other than those data, information such as the
heat of desorption, specific heats, mass-transfer and diffusional
effects, and particle/bed characteristics of solid sorbents are
also essential. At this stage, all of these characteristics are not
available. Because of the lack of sufficient data on solid sorbent
performance in various contactor configurations, limited pro-
cess design and economics analysis exist.
A techno-economic process evaluation on CO2 capture con-
ducted by Tarka et al.19 for 30% aqueous MEA absorption showed
that amine-functionalized solid sorbents will require less regenera-
tion energy (∼1442 kJ (kg CO2)
1 versus 4498 kJ (kg CO2)
1)
and parasitic load. Sjostrom and Krutka237 compared ∼24 differ-
ent sorbent materials in a cyclic TSA/regeneration CO2 capture
process using simulated coal combustion flue gas. The comparison
showed that supported amines exhibited the highest working CO2
capacities and several of the sorbents tested have theoretical
1456
REVIEW
regeneration energies that are significantly lower than that of
the industry benchmark. Ten of these sorbents were amine-
functionalized.
The process technologies frequently explored for a continuous
CO2 capture process are the cyclic processes, such as pressure
swing adsorption (PSA), VSA, and TSA. In PSA, flue gas flows
through the bed of sorbent at elevated pressure until the bed
adsorption of CO2 reaches equilibrium with the solid sorbent.
The bed is then desorbed, reducing the pressure. Ho et al.238
examined the economic feasibility of PSA for capturing CO2
from power-plant flue gas, using zeolite 13X with a working
capacity of 2.2 mmol g
1 and a CO2/N2 selectivity of 54. They
reported that the use of vacuum desorption reduces the capture
cost from $57 US to $51 US per ton of CO2 captured. This cost
of CO2 capture is comparable to the cost of MEA absorption.239
The sensitivity analysis shows that a hypothetical solid sorbent
with a working capacity of 4.3 mmol g
1 and a CO2/N2
selectivity of 150 can reduce the capital cost for the adsorption
system and CO2 compression, thereby reducing the capture cost
to $30 US per ton of CO2 captured. On the basis of experimental
data and economic analysis on VSA process for CO2 capture
from flue gas, Zhang et al.46 found that the operating capture
costs vary significantly with process configuration and operating
parameters, such as feed gas temperature, feed concentration and
evacuation pressure, have significant influence on power con-
sumption and CO2 capture cost. For example, the estimated
operating capture costs for a six-step VSA cycle without purge is
$12
$35 US per ton CO2 captured and the costs for a nine-step
VSA cycle with purge are $18
$32 US per ton CO2 captured,
each for CO2 capture from a 500 MW coal-fired power-plant flue
gas stream using zeolite 13X sorbents.
Techno-economic analysis is also strongly influenced by the
bed configuration for sorbent system. The possible configura-
tions for contacting CO2-laden flue gas streams with solid
sorbents are fixed-bed, fluidized-bed, and moving-bed. Because
of some inherent advantages of the fluidized-bed contactors, such
as (i) excellent gas
solid contact due to vigorous agitation of
sorbent particles, (ii) minimum diffusional resistance, (iii) uni-
formity of temperature, and (iv) faster overall kinetics, etc. over
fixed-bed contactors, fluidized-bed contactors is likely to be
superior to the fixed-bed adsorber.
Tarka et al.19 compared design parameters, plant performance,
and economics for amine-functionalized SBA-15 sorbent used in
fixed beds, fluidized beds, and novel radial-flow fixed beds to
capture CO2 from a 500 MW supercritical PC plant. For the
imposed designed constraints of 90% CO2 removal efficiency
and a pressure drop of <0.42 bar (6 psi), a fixed-bed contactor
cannot meet the constraints, given the required very large
footprint. Fluidized-bed and proposed radial-flow fixed-bed
systems with specific configurations met the constraints with a
relatively small footprint, but the fluidized-bed contactor sig-
nificantly increases the rate of sorbent attrition and, thereby, the
cost of sorbent replacement. Fluidized-bed and proposed radial-
flow fixed-bed systems reduce the cost of electricity by 8%
9%
with CO2 capture over MEA by reducing the parasitic load.
Preliminary design analysis was carried out recently by Yang
and Hoffman for a fluidized bed as a CO2 adsorber and a counter-
current moving bed as a CO2 regenerator.240 They found that
using a moving-bed contactor as a regenerator is not effective,
because of poor heat transfer and a very high pressure drop when
small sorbent particles are used. For slow kinetics, a significantly
larger bed height is required. They proposed an assisted
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
self-fluidization bed with an embedded heat-transfer surface
instead of a moving-bed system.
In summary, one important focus of the research, therefore, is
to develop cost-effective process equipment designs that are
tailored to the sorbent characteristics. If suitable sorbents that
can withstand fluidized-bed conditions can be developed, many
drawbacks that fixed beds introduce can be overcome. Circulating-
bed and fast-fluidized-bed, transport-bed, and other innova-
tive contactor configurations will be the subject of future search
for an optimal contactor configuration to meet the design
constraints of CO2 capture from flue gas.240 Moreover, there is
considerable scope for process optimization, because of the
variety of cycle configurations, process conditions, and adsorbent
types available.46
5. CONCLUSIONS
Improved cost-effective processes for post-combustion CO2
capture from flue gas streams from power plants running on fossil
fuels are essential in order to mitigate the global warming
problem. Among several different process technologies, solid
sorbents are promising alternatives in CO2 capture from flue gas
today and have a great potential in the future. On the basis of the
ongoing research activities conducted so far, this review article
summarizes the present state of knowledge on the solid sorbents
with and without nitrogen functionality.
Activated carbon and zeolite-based sorbents without any
nitrogen functionality are low cost with fast adsorption kinetics
and require low regeneration energy. However, this review
identifies that CO2 adsorption on these sorbents is strongly
influenced by the temperature, pressure, and presence of mois-
ture. The CO2 adsorption capacities of these physisorbents
decrease significantly at high temperatures. The presence of
water vapor, which is an inevitable component in flue gas, may
negatively affect the capacity of these sorbents and reduces the
availability of the active surface area. In addition, other con-
taminants in flue gas, such as SOx and NOx, also have a
detrimental impact on the CO2 adsorption capacity. Metal-
organic frameworks (MOFs) as sorbents for post-combustion
CO2 capture are expected to have very high adsorption capacity
but require substantial research efforts to be suitable under flue
gas conditions. Use of these sorbents for CO2 adsorption is
further limited by the CO2/N2 selectivity.
In contrast to sorbents based on physisorption, chemisorbents
hold great potential for CO2 capture from flue gas. Alkali
carbonates such as sodium and potassium carbonates have
reached pilot-scale trials with simulated and coal combustion
flue gas. However, these sorbents-based systems still have
challenges, such as high heat of reaction and long-term stability.
Research on functionalizing solid supports with amine functional
groups for CO2 capture has reached various stages of develop-
ment. A variety of supports, functional groups, and functionaliza-
tion techniques have been studied, and the outcomes have been
quite promising. The comparison based on available literature
data indicate that many amine-functionalized sorbents—in
particular, amine-impregnated and grafted silica and amine-
functionalized polymer sorbents—have shown promise to meet
the desired working capture capacity of 3
4 mmol g
1 in
simulated flue gas conditions and are stable over multiple cycles.
Several of the sorbents tested have theoretical regeneration
energies that are significantly lower than that of the industry
benchmark. However, additional work is needed to determine
1457
REVIEW
the long-term stability, regenerability, and consistent perfor-
mance of these sorbents under flue gas conditions over hundreds
of cycles through bench-scale and pilot-scale studies before
commercialization.
At this stage, from a design point of view, several important
key characteristics, such as kinetic data for adsorption and
desorption, mass transfer and diffusional effects, effects of flue
gas contaminant, particle characteristics, and other physicochem-
ical properties of candidate sorbents are not available. Limited
process design and economics analysis exists because of the lack
of adequate data on solid sorbent performance in various
contactor configurations. It has also been identified that sorbents
alone are not enough to provide the solution: the adsorption
reactor, regeneration process, and overall process integration of
the capture system (mainly thermal integration with the power
plant) is vital for the success of a solid sorbent capture system.
Finally, as more scientific data on these sorbents become
available, the system modeling, optimization, and techno-economic
analysis needed to estimate the potential improvement in solid
sorbents capture technologies will be more precise and reliable.
6. RECOMMENDATIONS FOR FUTURE WORKS
The potential of solid sorbents to remove CO2 from flue gas is
huge, compared to conventional liquid amine processes, in terms
of regeneration energy and significant cost reduction. However,
as discussed previously, solid sorbents also have limitations and
challenges to be addressed and solved before these can be
employed commercially in post-combustion CO2 capture.
Hence, based on the this review and discussion, the following
recommendations are proposed for further research on the topic:
• Synthesis and microstructural modification of the potential
sorbents to improve the performance, in terms of working
capacity, cycle time, and multicycle durability;
• Performance study of the potential sorbents under actual
flue gas conditions, using various bed configurations, such as
structured bed, require attention;
• A comparison of some of the most-promising sorbents,
based on techno-economic assessment of the system in-
cluding thermal integration.
’ AUTHOR INFORMATION
Corresponding Author
*Tel.: +1 780-492-6861. Fax: +1 780-492-2881. E-mail address:
Rajender.gupta@ualberta.ca.
’ ACKNOWLEDGMENT
The financial support of the Canadian Centre for Clean Coal/
Carbon and Mineral Processing Technology, Carbon Manage-
ment Canada and Alberta Innovates
Energy and Environment
Solutions is acknowledged.
’ REFERENCES
(1) Rogner, H.-H.; Zhou, D.; Bradley, R.; Crabbe, P.; Edenhofer, O.;
Hare, B., Kuijpers, L.; Yamaguchi, M. Introduction. In Climate Change
2007: Mitigation. Contribution of Working Group III to the Fourth
Assessment Report of the Intergovernmental Panel on Climate Change;
Metz, B., Davidson, O.R., Bosch, P. R., Dave, R., Meyer, L. A., Eds.;
Cambridge University Press: Cambridge, U.K. and New York, 2007.
(2) Climate Change 2007: Synthesis Report. Core Writing Team,
Pachauri, R. K., Reisinger, A., Eds.; IPCC, Geneva, Switzerland.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
(3) Sims, R. E. H.; Schock, R. N.; Adegbululgbe, A.; Fenhann, J.;
Konstantinaviciute, I.; Moomaw, W.; Nimir, H. B.; Schlamadinger, B.;
Torres-Martínez, J.; Turner, C.; Uchiyama, Y.; Vuori, S. J. V.; Wamu-
konya, N.; Zhang, X. Energy Supply. In Climate Change 2007: Mitigation.
Contribution of Working Group III to the Fourth Assessment Report of the
Intergovernmental Panel on Climate Change; Metz, B., Davidson, O.R.,
Bosch, P. R., Dave, R., Meyer, L. A., Eds.; Cambridge University Press:
Cambridge, U.K. and New York, 2007.
(4) Working Group III of the Intergovernmental Panel on the
Climate Change (IPCC). Carbon Dioxide Capture and Storage, Inter-
governmental Panel on the Climate Change (IPCC); Cambridge Univer-
sity Press: Cambridge, U.K. and New York, 2005.
(5) Herzog, H. J. What future for carbon capture and sequestration?
Environ. Sci. Technol. 2001, 35, 148A–153A.
(6) Yang, H.; Xu, Z.; Fan, M.; Gupta, R.; Slimane, R. B.; Bland, A. E.
Progress in carbon dioxide separation and capture: A review. J. Environ.
Sci. 2008, 20, 14–27.
(7) DOE/NETL. Carbon Dioxide Capture and Storage RD&D Road-
map, U.S. Department of Energy, December 2010.
(8) Astarita, G.; Savage, D. W.; Bisio, A. Gas Treating with Chemical
Solvents; John Wiley and Sons: New York, 1983.
(9) Kohl, A. L.; Nielsen, R. B. Gas Purification, 5th ed.; Gulf
Publishing Company: Houston, TX, 1997.
(10) Maddox, R. N.; Morgan, D. J. Gas Conditioning and Processing,
Vol. 4: Gas Treating and Liquid Sweetening, 4th Ed.; Campbell Petroleum
Series: Norman, OK, 1998.
(11) Rao, A. B.; Rubin, E. S. A Technical, Economic, and Environ-
mental Assessment of Amine-Based CO2 Capture Technology for
Power Plant Greenhouse Gas Control. Environ. Sci. Technol. 2002, 36,
4467–4475.
(12) Gabrielsen, J.; Svendsen, H. F.; Michelsen, M. L.; Stenby, E. H.;
Kontogeorgis, G. M. Experimental validation of a rate-based model for
CO2 capture using an AMP solution. Chem. Eng. Sci. 2007, 62,
2397–2413.
(13) Yang, R. T. Adsorbents: Fundamentals and Applications;
Wiley
Interscience: Hoboken, NJ, 2003.
(14) Yong, Z.; Mata, V.; Rodrigues, A. E. Adsorption of carbon
dioxide at high temperature—A review. Sep. Purifi. Technol. 2002, 26,
195–205.
(15) Zheng, F.; Addleman, R. S.; Aardahl, C. L.; Fryxell, G. E.;
Brown, D. R.; Zemanian, T. S. Amine functionalized nanoporous
materials for carbon dioxide (CO2) capture. Environmental Applications
of Nanomaterials: Synthesis, Sorbents and Sensors; Fryxell, G. E., Cao, G.,
Eds.; Imperial College Press: Singapore, 2007; pp 285
311.
(16) Sayari, A.; Belmabkhout, Y.; Serna-Guerrero, R. Flue gas
treatment via CO2 adsorption. Chem. Eng. J. 2011, 171, 760–774.
(17) Gray, M. L.; Champagne, K. J.; Fauth, D.; Baltrus, J. P.; Pennline,
H. Performance of immobilized tertiary amine solid sorbents for the
capture of carbon dioxide. Int. J. Greenhouse Gas Control 2008, 2, 3–8.
(18) Adams, D. Flue Gas Treatment for CO2 Capture; IEA Clean Coal
Centre: London, 2010.
(19) Tarka, T. J.; Ciferno, J. P.; Gray, M. L.; Fauth, D. CO2 capture
systems using amine enhanced solid sorbents. Presented at the Fifth
Annual Conference on Carbon Capture & Sequestration, Alexandria, VA,
USA, May 8
11, 2006; Paper No. 152, 30 pp. (Available via the Internet
at http://www.netl.doe.gov/publications/proceedings/06/carbon-seq/
Tech%20Session%20152.pdf.)
(20) Ruthven, D. M. Principles of Adsorption and Adsorption Processes;
Wiley
Interscience: New York, 1984.
(21) Thomas, W. J.; Crittenden, B. D. Adsorption Technology and
Design; Butterworth
Heinemann: Oxford, U.K., 1998.
(22) Dong, F.; Lou, H.; Goto, M.; Hirose, T. The Petlyuk PSA
process for separation of ternary gas mixtures: Exemplification by
separating a mixture of CO2
CH4
N2. Sep. Purif. Technol. 1990, 15,
31–40.
(23) Kikkinides, E. S.; Yang, R. T. Concentration and recovery of
CO2 from flue gas by pressure swing adsorption. Ind. Eng. Chem. Res.
1993, 32, 2714–2720.
1458
REVIEW
(24) Foeth, F.; Andersson, M.; Bosch, H.; Aly, G.; Reith, T.
Separation of dilute CO2
CH4 mixtures by adsorption on activated
carbon. Sep. Sci. Technol. 1994, 29, 93–118.
(25) Chue, K. T.; Kim, J. N.; Yoo, Y. J.; Cho, S. H.; Yang, R. T.
Comparison of activated carbon and zeolite 13X for CO2 recovery from
flue gas by pressure swing adsorption. Ind. Eng. Chem. Res. 1995, 34,
591–598.
(26) Berlier, K.; Frere, M. Adsorption of CO2 on activated carbon:
Simultaneous determination of integral heat and isotherm of adsorption.
J. Chem. Eng. Data 1996, 41, 1144–1148.
(27) Chen, J. H.; Wong, D. S. H.; Tan, C. S.; Subramanian, R.; Lira,
C. T.; Orth, M. Adsorption and desorption of carbon dioxide onto and
from activated carbon at high pressures. Ind. Eng. Chem. Res. 1997, 36,
2805–2815.
(28) Do, D. D.; Wang, K. A new model for the description of
adsorption kinetics in heterogeneous activated carbon. Carbon 1998,
36, 1539–1554.
(29) Heuchel, M.; Davies, G. M.; Buss, E.; Seaton, N. A. Adsorption
of carbon dioxide and methane and their mixtures on an activated
carbon: simulation and experiment. Langmuir 1999, 15, 8695–8705.
(30) Dreisbach, F.; Staudt, R.; Keller, J. U. High pressure adsorption
data of methane, nitrogen, carbon dioxide and their binary and ternary
mixtures on activated carbon. Adsorption 1999, 5, 215–227.
(31) Mugge J.; Bosch, H.; Reith, T. Gas Adsorption kinetics in
activated carbon. In Adsorption Science and Technology: Proceedings of the
Second Pacific Basin on Adsorption Science and Technology, 2nd, Brisbane,
Australia, May 14
18, 2000; pp 451
455.
(32) Vaart, R.; van der; Huiskes, C.; Bosch, H.; Reith, T. Single and
mixed gas adsorption equilibria of carbon dioxide/methane on activated
carbon. Adsorption 2000, 6, 311–323.
(33) Na, B. K.; Koo, K. K.; Eum, H. M.; Lee, H.; Song, H. K. CO2
recovery from flue gas by PSA process using activated carbon. Korean
J. Chem. Eng. 2001, 18, 220–227.
(34) Davini, P. Flue gas treatment by activated carbon obtained from
oil-fired fly ash. Carbon 2002, 40, 1973–1979.
(35) Wang, Y.; Zhou, Y.; Liu, C.; Zhou, L. Comparative studies of
CO2 and CH4 sorption on activated carbon in presence of water. Colloids
Surf. A 2008, 322, 14–18.
(36) Lu, C.; Bai, H.; Wu, B.; Su, F.; Hwang, J. F. Comparative study
of CO2 capture by carbon nanotubes, activated carbons, and zeolites.
Energy Fuels 2008, 22, 3050–3056.
(37) Siriwardane, R. V.; Shen, M.-S.; Fisher, E. P.; Poston, J, A.
Adsorption of CO2 on molecular sieves and activated carbon. Energy
Fuels 2001, 15, 279–284.
(38) Sircar, S.; Golden, T. C. Isothermal and isobaric desorption of
carbon dioxide by purge. Ind. Eng. Chem. Res. 1995, 34, 2881–2888.
(39) Tang, Z.; Maroto-Valer, M. M.; Zhang, Y. CO2 capture using
anthracite based sorbents. Div. Fuel Chem., Am. Chem. Soc.
Prepr. Symp.
2004, 49, 298
299.
(40) Zhang, Y.; Maroto-Valer, M. M.; Tang, Z. Microporous acti-
vated carbons produced from unburned carbon fly ash and their
application for CO2 capture. Div. Fuel Chem., Am. Chem. Soc.
Prepr.
Symp. 2004, 49, 304
305.
(41) Tang, Z.; Zhang, Y.; Maroto-Valer, M. M. Study of the CO2
adsorption capacities of modified activated anthracites. Div. Fuel Chem.,
Am. Chem. Soc.
Prepr. Symp. 2004, 49, 308
309.
(42) Maroto-Valer, M. M.; Tang, Z.; Zhang, Y. CO2 capture by
activated and impregnated anthracites. Fuel Process. Technol. 2005, 86,
1487–1502.
(43) Radosz, M.; Hu, X.; Krutkrarnelis, K.; Shen, Y. Flue-gas carbon
capture on carbonaceous sorbents: toward a low-cost multifunctional carbon
filter for “green” energy producers. Ind. Eng. Chem. Res. 2008, 47, 3783–3794.
(44) Zhang, Z.; Zhang, W.; Chen, X.; Xia, Q.; Li, Z. Adsorption of
CO2 on zeolite 13X and activated carbon with high surface area. Sep. Sci.
Technol. 2010, 45, 710–719.
(45) Su, F.; Lu, C.; Chen, W.; Bai, H.; Hwang, J. F. Capture of CO2
from flue gas via multiwalled carbon nanotubes. Sci. Total Environ. 2009,
407, 3017–3023.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
(46) Zhang, J.; Webley, P. A.; Xiao, P. Effect of process parameters
on power requirements of vacuum swing adsorption technology for CO2
capture from flue gas. Energy Convers. Manage. 2008, 49, 346–356.
(47) Diaz, E.; Munoz, E.; Vega, A.; Ordonez, S. Enhancement of the
CO2 retention capacity of Y zeolites by Na and Cs treatment: Effect of
adsorption temperature and water treatment. Ind. Eng. Chem. Res. 2008,
47, 412–418.
(48) Diaz, E.; Munoz, E.; Vega, A.; Ordonez, S. Enhancement of the
CO2 retention capacity of X zeolites by Na- and Cs- treatment. Chemo-
sphere 2008, 70, 1375–1382.
(49) Bezerra, D. P.; Oliveira, R. S.; Vieira, R. S.; Cavalcante, C. L.;
Azevedo, D. C. S. Adsorption of CO2 on nitrogen-enriched activated
carbon and zeolite 13X. Adsorption 2011, 17, 235–246.
(50) Franchi, R. S.; Harlick, P. J. E.; Sayari, A. Applications of pore-
expanded mesoporous silica. 2. Development of a high-capacity, water-
tolerant adsorbent for CO2. Ind. Eng. Chem. Res. 2005, 44, 8007–8013.
(51) Berlier, K.; Frere, M. Adsorption of CO2 on microprous. 1. On
activated carbon and silica gel. J. Chem. Eng. Data 1997, 42, 533–537.
(52) Siriwardane, R. V.; Shen, M.-S.; Fisher, E. P. Adsorption of
CO2, N2, and O2 on natural zeolites. Energy Fuels 2003, 17, 571–576.
(53) Hernandez-Huesca, R.; Diaz, L.; Aguilar-Armenta, G. Adsorp-
tion equilibria and kinetics of CO2, CH4, and N2 in natural zeolites. Sep.
Purif. Technol. 1999, 15, 163–173.
(54) Gray, M. L.; Soong, Y.; Champagne, K. J.; Pennline, H.; Baltrus,
J. P.; Stevens, R. W.; Khatri, R.; Chuang, S. S. C.; Filburn, T. Improved
immobilized carbon dioxide capture sorbents. Fuel Process. Technol.
2005, 86, 1449–1455.
(55) Filburn, T.; Helble, J. J.; Weiss, R. A. Development of supported
ethanolamines and modified ethanolamines for CO2 capture. Ind. Eng.
Chem. Res. 2005, 44, 1542–1546.
(56) Cinke, M.; Li, J.; Bauschlicher, C. W.; Ricca, A.; Meyyappan, M.
CO2 adsorption in single-walled carbon nanotubes. Chem. Phys. Lett.
2003, 376, 761–766.
(57) Ghosh, A.; Subrahmanyam, K. S.; Krishana, K. S.; Datta, S.;
Govindaraj, A.; Pati, S. K.; Rao, C. N. R. Uptake of H2 and CO2 by
graphene. J. Phys. Chem. C 2008, 112, 15704–15707.
(58) Foley, H. C. Carbogenic molecular sieves: synthesis, properties
and applications. Microporous Mater. 1995, 4, 407–433.
(59) Burchell, T. D.; Judkins, R. R.; Rogers, M. M.; Williams, A. M. A
novel process and material for the separation of carbon dioxide and
hydrogen sulfide gas mixtures. Carbon 1997, 35, 1279–1294.
(60) Rutherford, S. W.; Do, D. D. Adsorption dynamics of carbon
dioxide on a carbon molecular sieve 5A. Carbon 2000, 38, 1339–1350.
(61) Alca~niz-Monge, J.; Marco-Lozar, J. P.; Lillo-Rodenas, M. A.
CO2 separation by carbon molecular sieve monoliths prepared from
nitrated coal tar pitch. Fuel Process. Technol. 2011, 92, 915–919.
(62) Zhao, J.; Buldum, A.; Han, J.; Lu, J. P. Gas molecule adsorption
in carbon nanotubes and nanotube bundles. Nanotechnology 2002, 13,
195–200.
(63) Fifield, L. S.; Fryxell, G. E.; Addleman, R. S.; Aardahl, C. L.
Carbon dioxide capture using amine-based molecular anchors on multi
wall carbon nanotubes. Div. Fuel Chem., Am. Chem. Soc.
Prepr. Symp.
2004, 49, 296
297.
(64) Bienfait, M.; Zeppenfeld, P.; Dupont-Pavlovsky, N.; Muris, M.;
Johnson, M. R.; Wilson, T.; De Pies, M.; Vilches, O. E. Thermodynamics
and structure of hydrogen, methane, argon, oxygen, and carbon dioxide
adsorbed on single-wall carbon nanotube bundles. Phys. Rev. B 2004,
350, 423–426.
(65) Matranga, C.; Bockrath, B. Controlled confinement and release
of gases in single-walled carbon nanotube bundles. J. Phys. Chem. B 2005,
109, 9209–9215.
(66) Skoulidas, A. I.; Sholl, D. S.; Johnson, J. K. Adsorption and
diffusion of carbon dioxide and nitrogen through single-walled carbon
nanotube membranes. J. Chem. Phys. 2006, 124, 054708.
(67) Huang, L.; Zhang, L.; Shao, Q.; Lu, L.; Lu, X.; Jiang, S.; Shen, W.
Simulations of binary mixture adsorption of carbon dioxide and methane
in carbon nanotubes: Temperature, pressure, and pore size effects.
J. Phys. Chem. C 2007, 111, 11912–11920.
1459
REVIEW
(68) Hsu, S.-C.; Lu, C.; Su, F.; Zeng, W.; Chen, W. Thermodynamics
and regeneration studies of CO2 adsorption on multiwalled carbon
nanotubes. Chem. Eng. Sci. 2010, 65, 1354–1361.
(69) Kishimoto, Y.; Hata, K. Behaviors of single CO2 molecule on
pentagon at carbon nanotube tip observed by field emission microscopy.
Surf. Interface Anal. 2008, 40, 1669–1672.
(70) Dillon, E. P.; Crouse, C. A.; Barron, A. R. Synthesis, character-
ization, and carbon dioxide adsorption of covalently attached polyethy-
leneimine-functionalized single-wall carbon nanotubes. ACS Nano 2008,
2, 156–164.
(71) Razavi, S. S.; Hashemianzadeh, S. M.; Karimi, H. Modeling the
adsorptive selectivity of carbon nanotubes for effective separation of
CO2/N2 mixtures. J. Mol. Model. 2011, 17, 1163–1172.
(72) Lithoxoos, G. P.; Labropoulos, A.; Peristeras, L. D.; Kanellopoulos,
N.; Samios, J.; Economou, I. G. Adsorption of N2, CH4, CO and CO2
gases in single walled carbon nanotubes: A combined experimental and
Monte Carlo molecular simulation study. J. Supercrit. Fluids 2010,
55, 510–523.
(73) Chester, A. W., Derouane, E. G., Eds. Zeolite Characterization
and Catalysis: A Tutorial; Springer: New York, 2009.
(74) Coriani, S.; Halkier, A.; Rizzo, A.; Ruud, K. On the
molecular electric quadrupole moment and the electric-field-gradient-
induced birefringence of CO2 and CS2. Chem. Phys. Lett. 2000, 326,
269–276.
(75) Haq, N.; Ruthven, D. M. A chromatographic study of sorption
and diffusion in 5A zeolite. J. Colloid Interface Sci. 1986, 112, 164–169.
(76) Haq, N.; Ruthven, D. M. Chromatographic study of sorption
and diffusion in 4A zeolite. J. Colloid Interface Sci. 1986, 112, 154–163.
(77) Ma, Y. H.; Mancel, C. Diffusion studies of CO2, NO, NO2 and
SO2 on molecular sieve zeolites by gas chromatography. AIChE J. 1972,
18, 1148–1153.
(78) Hayhurst, D. T. Gas adsorption by some natural zeolites. Chem.
Eng. Commun. 1980, 4, 729–735.
(79) Inui, T.; Okugawa, Y.; Yasuda, M. Relationship between
properties of various zeolites and their CO2-adsorption behaviours in
pressure swing adsorption operation. Ind. Eng. Chem. Res. 1988,
27, 1103–1109.
(80) Calleja, G.; Jimenez, A.; Pau, J.; Dominguez, L.; Pbrez, P.
Multicomponent adsorption equilibrium of ethylene, propane, propy-
lene and CO2 on 13X zeolites. Gas. Sep. Purif. 1994, 8, 247–256.
(81) Triebe, R. W.; Tezel, F. H. Adsorption of nitrogen, carbon
monoxide, carbon dioxide and nitric oxide on molecular sieves. Gas. Sep.
Purif. 1995, 9, 223–230.
(82) Khodakov, A. Y.; Rees, L. V. C. Effect of propane on the kinetics
of carbon dioxide adsorption in NaA zeolites. Gas. Sep. Purif. 1995,
9, 253–257.
(83) Choudhary, V. R.; Mayadevi, S.; Singh, A. P. Sorption isotherms
of methane, ethane, ethene and carbon dioxide on NaX, NaY and Na-
mordenite zeolites. J. Chem. Soc., Faraday Trans. 1995, 91, 2935–2944.
(84) Duanne, J A.; Rao, M.; Sircar, S.; Gorte, R. J.; Myers, A. L.
Calorimetric heats of adsorption and adsorption isotherms. 2. O2, N2,
Ar, CO2, CH4, C2H6 and SF6 on NaX, H-ZSM-5, and Na-ZSM-5
zeolites. Langmuir 1996, 12, 5896–5904.
(85) Wang, Z. M.; Kumagai, M.; Tamura, T.; Takashima, Y. Char-
acterization and CO2 adsorptivity of acid-washed and cation-exchanged
natural mordenites. J. Colloid Interface Sci. 1997, 193, 300–306.
(86) Suzuki, T.; Skoda, A.; Suzuki, M.; Izumi, J. Adsorption of
carbon dioxide onto hydrophobic zeolite under high moisture. J. Chem.
Eng. Jpn. 1997, 30, 954–958.
(87) Katoh, M.; Yoshikawa, T.; Tomonari, T.; Katayama, K; Tomida,
T. Adsorption characteristics of ion-exchanged ZSM-5 zeolites for
CO2/N2 mixtures. J. Colloid Interface Sci. 2000, 226, 145–150.
(88) Takamura, Y.; Narita, S.; Aoki, J.; Hironaka, S.; Uchida, S.
Evaluation of dual-bed pressure swing adsorption for CO2 recovery from
boiler exhaust gas. Sep. Purif. Technol. 2001, 24, 519–528.
(89) Rege, S. U.; Yang, R. T.; Qian, K.; Buzanowski, M. A. Air-
prepurification by pressure swing adsorption using single/layered beds.
Chem. Eng. Sci. 2001, 56, 4827–4838.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
(90) Harlick, P. J. E.; Tezel, F. H. Adsorption of carbon dioxide,
methane and nitrogen: pure and binary mixture adsorption for ZSM-5
with SiO2/Al2O3 ratio of 280. Sep. Purif. Technol. 2003, 33, 199–210.
(91) Harlick, P. J. E.; Tezel, F. H. An experimental adsorbent
screening study for CO2 removal from N2. Microporous Mesoporous
Mater. 2004, 76, 71–79.
(92) Cavenati, S.; Grande, C. A.; Rodrigues, A. E. Adsorption
equilibrium of methane, carbon dioxide, and nitrogen on zeolite 13X
at high pressures. J. Chem. Eng. Data 2004, 49, 1095–1101.
(93) Ko, D.; Siriwardane, R.; Biegler, L. T. Optimization of a
pressure swing adsorption process using zeolite 13X for CO2 sequestra-
tion. Ind. Eng. Chem. Res. 2003, 42, 339–348.
(94) Khelifa, A.; Benchechida, L.; Derriche, Z. Adsorption of carbon
dioxide by X zeolites exchanged with Ni2+ and Cr3+: isotherms and
isosteric heat. J. Colloid Interface Sci. 2004, 278, 9–17.
(95) Maurin, G.; Llewellyn, P. L.; Bell, R. G. Adsorption mechanism
of carbon dioxide in Faujasites: Grand Canonical Monte Carlo simula-
tions and microcalorimetry measurements. J. Phys. Chem. B 2005, 109,
16084–16091.
(96) Delgado, J. A.; Uguina, M. A.; Sotelo, J. L.; Ruíz, B. Fixed-bed
adsorption of carbon dioxide
helium, nitrogen
helium and carbon
dioxide
nitrogen mixtures onto silicalite pellets. Sep. Purif. Technol.
2006, 49, 91–100.
(97) Merel, J.; Clausse, M.; Meunier, F. Experimental investigation
on CO2 post-combustion capture by indirect thermal swing adsorption
using 13X and 5A zeolites. Ind. Eng. Chem. Res. 2008, 47, 209–215.
(98) Zhang, J.; Singh, R.; Webley, P. A. Alkali and alkaline earth
cation exchanged chabazite zeolites for adsorption based CO2 capture.
Microporous Mesoporous Mater. 2008, 111, 478–487.
(99) Gomes, V. G.; Yee, K. W. K. Pressure swing adsorption for
carbon dioxide sequestration from exhaust gases. Sep. Purif. Technol.
2002, 28, 161–171.
(100) Konduru, N.; Lindner, P.; Assaf-Anid, N. M. Curbing the
greenhouse effect by carbon dioxide adsorption with zeolite 13X. AlChE
J. 2007, 53, 3137–3143.
(101) Lee, S.-S.; Yoo, J.-S.; Moon, G.-H.; Park, S.-W.; Park, D.-
W.; Oh, K.-J. CO2 adsorption with attrition of dry sorbents in a
fluidized bed. Div. Fuel Chem., Am. Chem. Soc.
Prepr. Symp. 2004,
49, 314
315.
(102) Zukal, A.; Mayerova, J.; Kubu, M. Adsorption of carbon
dioxide on high-silica zeolites with different framework topology. Top.
Catal. 2010, 53, 1361–1366.
(103) Bonenfant, D.; Kharoune, M.; Niquette, P.; Mimeault, M.;
Hausler, R. Advances in principal factors influencing carbon
dioxide adsorption on zeolites. Sci. Technol. Adv. Mater. 2008, 9
(012007), 7.
(104) Dunne, J. A.; Mariwala, R.; Rao, M.; Sircar, S.; Gorte, R. J.;
Myers, A. L. Calorimetric heats of adsorption and adsorption isotherms.
1. O2, N2, Ar, CO2, CH4, C2H6, and SF6 on silicalite. Langmuir 1996, 12,
5888–5895.
(105) Kamiuto, K.; Abe, S.; Ermalina Effect of desorption tempera-
ture on CO2 adsorption equilibria of the honeycomb zeolite beds. Appl.
Energy 2002, 72, 555–564.
(106) Brandani, F.; Ruthven, D. M. The effect of water on the
adsorption of CO2 and C3H8 on type X zeolites. Ind. Eng. Chem. Res.
2004, 43, 8339–8344.
(107) Li, G.; Xiao, P.; Webley, P.; Zhang, J.; Singh, R.; Marshall, M.
Capture of CO2 from high humidity flue gas by vacuum swing adsorp-
tion with zeolite 13X. Adsorption 2008, 14, 415–422.
(108) Li, J. R.; Kuppler, R. J.; Zhou, H. C. Selective gas adsorption
and separation in metal-organic frameworks. Chem. Soc. Rev. 2009, 38,
1477–1504.
(109) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.;
O’Keeffe, M.; Yaghi, O. M. Systematic design of pore size and function-
ality in isoreticular MOFs and their application in methane storage.
Science 2002, 295, 469–472.
(110) Kitagawa, S.; Kitaura, R.; Noro, S. Functional porous coordi-
nation polymers. Angew. Chem., Int. Ed. 2004, 43, 2334–2375.
1460
REVIEW
(111) Halder, G. J.; Kepert, C. J.; Moubaraki, B.; Murray, K. S.;
Cashion, J. D. Guest-dependent spin crossover in a nanoporous
molecular framework material. Science 2002, 298, 1762–1765.
(112) Seo, J.; Matsuda, R.; Sakamoto, H.; Bonneau, C.; Kitagawa, S.
A pillared-layer coordination polymer with a rotatable pillar acting as a
molecular gate for guest molecules. J. Am. Chem. Soc. 2009,
131, 12792–12800.
(113) Chandler, B. D.; Enright, G. D.; Udachin, K. A.; Pawsey, S.;
Ripmeester, J. A.; Cramb, D. T.; Shimizu, G. K. H. Mechanical gas
capture and release in a network solid via multiple single-crystalline
transformations. Nat. Mater. 2008, 7, 229–235.
(114) Plant, D. F.; Maurin, G.; Deroche, I.; Llewellyn, P. L. In-
vestigation of CO2 adsorption in Faujasite systems: Grand Canonical
Monte Carlo and molecular dynamics simulations based on a new
derived Na+
CO2 force field. Microporous Mesoporous Mater. 2007,
99, 70–78.
(115) Llewellyn, P. L.; Bourrelly, S.; Serre, C.; Vimont, A.; Daturi,
M.; Hamon, L.; De Weireld, G.; Chang, J. S.; Hong, D. Y.; Hwang, Y. K.;
Jhung, S. H.; Ferey, G. High uptakes of CO2 and CH4 in mesoporous
metal orgnanic frameworks MIL-100 and MIL-101. Langmuir 2008, 24,
7245–7250.
(116) Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. Dramatic
tuning of carbon dioxide uptake via metal substitution in a coordination
polymer with cylindrical pores. J. Am. Chem. Soc. 2008, 130,
10870–10871.
(117) An, J.; Geib, S. J.; Rosi, N. L. N
CN bond cleavage of
cyanamides by a transition-metal complex. J. Am. Chem. Soc. 2009, 131,
38–39.
(118) Arstad, B.; Fjellvag, H.; Kongshaug, K. O.; Swang, O.; Blom, R.
Amine functionalised metal organic frameworks (MOFs) as adsorbents
for carbon dioxide. Adsorption 2008, 14, 755–762.
(119) Vaidhyanathan, R.; Iremonger, S. S.; Dawson, K. W.; Shimizu,
G. K. H. An amine functionalized metal organic framework for prefer-
ential CO2 adsorption at low pressures. Chem. Commun. 2009, 35,
5230–5232.
(120) Demessence, A.; D’Alessandro, D. M.; Foo, M. L.; Long, J. R.
Strong CO2 binding in a water-stable, triazolate-bridged metal-organic
framework functionalized with ethylenediamine. J. Am. Chem. Soc. 2009,
131, 8784–8786.
(121) Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi,
E.; Yazaydin, A. O.; Snurr, R. Q.; O’Keeffe, M.; Kim, J.; Yaghi, O. M.
Ultrahigh porosity in metal-organic frameworks. Science 2010, 329,
424–428.
(122) Yazaydın, A. O.; Snurr, R. Q.; Park, T. H.; Koh, K.; Liu, J.;
LeVan, M. D.; Benin, A. I.; Jakubczak, P.; Lanuza, M.; Galloway, D. B.;
Low, J. J.; Willis, R. R. Screening of metal
organic frameworks for
carbon dioxide capture from flue gas using a combined experimental and
modeling approach. J. Am. Chem. Soc. 2009, 131, 18198–18199.
(123) Thallapally, P. K.; Tian, J.; Kishan, M. R.; Fernandez, C. A.;
Dalgarno, S. J.; McGrail, P. B.; Warren, J. E.; Atwood, J. L. Flexible
(breathing) interpenetrated metal
organic frameworks for CO2 separa-
tion applications. J. Am. Chem. Soc. 2008, 130, 16842–16843.
(124) Choi, S.; Drese, J. H.; Jones, C. W. Adsorbent materials for
carbon dioxide capture from large anthropogenic point sources. Chem-
SusChem 2009, 2, 796–854.
(125) Noro, S.; Tanaka, D.; Sakamoto, H.; Shimomura, S.; Kitagawa,
S.; Takeda, S.; Uemura, K.; Kita, H.; Akutagawa, T.; Nakamura, T.
Selective gas adsorption in one-dimensional, flexible CuII coordination
polymers with polar units. Chem. Mater. 2009, 21, 3346–3355.
(126) Navarro, J. A. R.; Barea, E.; Salas, J. M.; Masciocchi, N.; Galli,
S.; Sironi, A.; Ania, C. O.; Parra, J. B. Borderline Microporous

ultramicroporous palladium(II) coordination polymer networks. Effect
of pore functionalisation on gas adsorption properties. J. Mater. Chem.
2007, 17, 1939–1946.
(127) Vaidhyanathan, R.; Iremonger, S. S.; Shimizu, G. K. H.; Boyd,
P. G.; Alavi, S.; Woo, T. K. Direct observation and quantification of CO2
binding within an amine-functionalized nanoporous solid. Science 2010,
330, 650–653.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
(128) Liu, Y.; Hu, E.; Khan, E. A.; Lai, Z. Synthesis and characteriza-
tion of ZIF-69 membranes and separation for CO2/CO mixture.
J. Membr. Sci. 2010, 353, 36–40.
(129) Park, K. S.; Ni, Z.; Cote, A. P.; Choi, J. Y.; Huang, R. D.;
Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M. Exceptional
chemical and thermal stability of zeolitic imidazolate frameworks. Proc.
Natl. Acad. Sci. U.S.A. 2006, 103, 10186–10191.
(130) Yazaydın, A. O.; Benin, A. I.; Faheem, S. A.; Jakubczak, P.;
Low, J. J.; Willis, R. R.; Snurr, R. Q. Enhanced CO2 adsorption in metal-
organic frameworks via occupation of open-metal sites by coordinated
water molecules. Chem. Mater. 2009, 21, 1425–1430.
(131) Liu, J.; Wang, Y.; Benin, A. I.; Jakubczak, P.; Willis, R. R.;
LeVan, M. D. CO2/H2O adsorption equilibrium and rates on metal-
organic frameworks: HKUST-1 and Ni/DOBDC. Langmuir 2010, 26,
14301–14307.
(132) Bae, Y. S.; Mulfort, K. L.; Frost, H.; Ryan, P.; Punnathanam, S.;
Broadbelt, L. J.; Hupp, J. T.; Snurr, R. Q. Separation of CO2 from CH4
using mixed-ligand metal-organic frameworks. Langmuir 2008, 24,
8592–8598.
(133) Hoffman, J. S.; Pennline, H. W. Study of regenerable sorbents
for CO2 capture. In Proceedings of First National Conference on Carbon
Sequestration, Washington, DC, May 2001.
(134) Hayashi, H.; Taniuchi, J.; Furuyashiki, N.; Sugiyama, S.; Hirano,
S.; Shigemoto, N.; Nonaka, T. Efficient recovery of carbon dioxide from
flue gases of coal-fired power plants by cyclic fixed-bed operations over
K2CO3-on-carbon. Ind. Eng. Chem. Res. 1998, 37, 185–191.
(135) Liang, Y.; Harrison, D. P.; Gupta, R. P.; Green, D. A.;
McMichael, W. J. Carbon dioxide capture using dry sodium-based
sorbents. Energy Fuels 2004, 18, 569–575.
(136) Nelson, T. O.; Coleman, L. T. J.; Green, D. A.; Gupta, R. P.
The Dry Carbonate Process: Carbon dioxide recovery from power plant
flue gas. Energy Procedia 2009, 1, 1305–1311.
(137) Seo, Y.; Jo, S. H.; Ryu, C. K.; Yi, C. K. Effects of water vapor
pretreatment time and reaction temperature on CO2 capture character-
istics of a sodium-based solid sorbent in a bubbling fluidized-bed reactor.
Chemosphere 2007, 69, 712–718.
(138) Lee, J. B.; Ryu, C. K.; Baek, J. I.; Lee, J. H.; Eom, T. H.; Kim,
S. H. Sodium-based dry regenerable sorbent for carbon dioxide capture
from power plant flue gas. Ind. Eng. Chem. Res. 2008, 47, 4465–4472.
(139) Okunev, A. G.; Sharonov, V. E.; Aristov, Y. I.; Parmon, V. N.
Sorption of carbon dioxide from wet gases by K2CO3-in-porous matrix:
Influence of the Matrix Nature. React. Kinet. Catal. Lett. 2000,
71, 355–362.
(140) Okunev, A. G.; Sharonov, V. E.; Gubar, A. V.; Danilova, I. G.;
Paukshtis, E. A.; Moroz, E. M.; Kriger, T. A.; Malakhov, V. V.; Aristov,
Y. I. Sorption of carbon dioxide by the composite sorbent 00 potassium
carbonate in porous matrix. Russ. Chem. Bull., Int. Ed. 2003, 52, 359–363.
(141) Sharonov, V. E.; Okunev, A. G.; Aristov, Y. I. Kinetics of
carbon dioxide sorption by the composite materials K2CO3 in Al2O3.
Kinet. Catal. Lett. 2004, 82, 363–369.
(142) Lee, S. C.; Choi, B. Y.; Lee, T. J.; Ryu, C. K.; Ahn, Y. S.; Kim,
J. C. CO2 absorption and regeneration of alkali metal-based solid
sorbents. Catal. Today 2006, 111, 385–390.
(143) Lee, S. C.; Kim, J. C. Dry potassium-based sorbents for CO2
capture. Catal. Surv. Asia 2007, 11, 171–185.
(144) Lee, S. C.; Chae, H. J.; Lee, S. J.; Parka, Y. H.; Ryu, C. K.; Yi,
C. K.; Kim, J. C. Novel regenerable potassium-based dry sorbents for
CO2 capture at low temperatures. J. Mol. Catal. B 2009, 56, 179–184.
(145) Lee, S. C.; Choi, B. Y.; Ryu, C. K.; Ahn, Y. S.; Lee, T. J.; Kim,
J. C. The effect of water on the activation and the CO2 capture capacities
of alkali metal-based sorbents. Korean J. Chem. Eng. 2006, 23, 374–379.
(146) Lee, S. C.; Kwon, Y. M.; Ryu, C. Y.; Chae, H. J.; Ragupathy, D.;
Jung, S. Y.; Lee, J. B.; Ryu, C. K.; Kim, J. C. Development of new
alumina-modified sorbents for CO2 sorption and regeneration at
temperatures below 200 °C. Fuel 2011, 60, 1465–1470.
(147) Zhao, C.; Chen, X.; Zhao, C.; Liu, Y. Carbonation and
hydration characteristics of dry potassium-based sorbents for CO2
capture. Energy Fuels 2009, 23, 1766–1769.
1461
REVIEW
(148) Zhao, C.; Chen, X.; Zhao, C. Effect of crystal structure on CO2
capture characteristics of dry potassium-based sorbents. Chemosphere
2009, 75, 1401–1404.
(149) Zhao, C.; Chen, X.; Zhao, C. CO2 absorption using dry
potassium-based sorbents with different supports. Energy Fuels 2009, 23,
4683–4687.
(150) Zhao, C.; Chen, X.; Zhao, C. Study on CO2 capture using dry
potassium-based sorbents through orthogonal test method. Int. J. Green-
house Gas Control 2010, 4, 655–658.
(151) Green, D. A.; Nelson, T. O.; Turk, B. S.; Box, P. D.; Gupta,
R. P. Carbon dioxide capture from flue gas using dry regenerable
sorbents. DOE Cooperative Agreement No. DE-FC26-00NT40923,
2006.
(152) Nelson, T. O.; Green, D. A.; Box, P. D.; Weber, A.; Gupta,
R. P. Production of concentrated CO2 from flue gas using dry regener-
able carbonate sorbents in a thermal-swing process. Presented at the
Fifth Annual Conference on Carbon Capture and Sequestration, Alexandria,
VA, USA, May 8
11, 2006. (Available via the Internet at http://www.
netl.doe.gov/publications/proceedings/06/carbon-seq/Tech%20Ses-
sion%20009.pdf.)
(153) Nelson, T. O. The Dry Carbonate Process: Carbon Dioxide
Recovery from Power Plant Flue Gas. Annual NETL Capture Technol-
ogy for Existing Power Plant R&D Meeting, Pittsburgh, PA, March
24
26, 2009. (Available via the Internet at http://www.netl.doe.gov/
publications/proceedings/09/CO2/pdfs/43089%20RTI%20sorbent%
20(Nelson)%20mar09.pdf.)
(154) Yi, C. K.; Jo, S. H.; Seo, Y.; Lee, J. B.; Ryu, C. K. Continuous
operation of the potassium-based dry sorbent CO2 capture process with
two fluidized-bed reactors. Int. J. Greenhouse Gas Control 2007, 1, 31–36.
(155) Yi, C. K. Development of CO2 capture technology using solid
sorbents. Presented at APP (Asia Pacific Partnership), Power Generation
and Transmission Task Force Meeting, July 7, 2009, Seoul, Korea.
(156) Park, Y. C.; Jo, S. H.; Ryu, C. K.; Yi, C. K. Long-term operation
of carbon dioxide capture system from a real coal-fired flue gas using dry
regenerable potassium-based sorbents. Energy Procedia 2009, 1,
1235–1239.
(157) Li, W.; Choi, S.; Drese, J. H.; Hornbostel, M.; Krishnan, G.;
Eisenberger, P. M.; Jones, C. W. Steam-stripping for regeneration of
supported amine-based CO2 adsorbents. ChemSusChem 2010, 3,
899–903.
(158) Jones, C. W. CO2 capture from dilute gases as a component of
modern global carbon management. Annu. Rev. Chem. Biomol. Eng. 2011,
2, 31–52.
(159) Caplow, M. Kinetics of carbamate formation and breakdown.
J. Am. Chem. Soc. 1968, 90, 6795–6803.
(160) Danckwerts, P. V. The reaction of CO2 with ethanolamines.
Chem. Eng. Sci. 1976, 34, 443–446.
(161) Sartori, G.; Savage, D. W. Sterically hindered amines for CO2
removal from gases. Ind. Eng. Chem. Fundam. 1983, 22, 239–249.
(162) Donaldson, T. L.; Nguyen, Y. N. Carbon dioxide reaction
kinetics and transport in aqueous amine membranes. Ind. Eng. Chem.
Fundam. 1980, 19, 260–266.
(163) Przepiorski, J.; Skrodzewicz, M.; Morawski, A. W. High
temperature ammonia treatment of activated carbon for enhancement
of CO2 adsorption. Appl. Surf. Sci. 2004, 225, 235–242.
(164) Pevida, C.; Plaza, M. G.; Arias, B.; Fermoso, J.; Rubiera, F.; Pis,
J. J. Surface modification of activated carbons for CO2 capture. Appl. Surf.
Sci. 2008, 254, 7165–7172.
(165) Plaza, M. G.; Pevida, C.; Arias, B.; Fermoso, J.; Rubiera, F.; Pis,
J. J. A comparison of two methods for producing CO2 capture
adsorbents. Energy Procedia 2009, 1, 1107–1113.
(166) Gray, M. L.; Soong, Y.; Champagne, K. J.; Pennline, H.;
Stevens, R. W., Jr.; Toochinda, P.; Chuang, S. S. C. Solid amine CO2
capture sorbents. Div. Fuel Chem., Am. Chem. Soc.
Prepr. Symp. 2002,
47, 63
64.
(167) Gray, M. L.; Soong, Y.; Champagne, K. J.; Baltrus, J.; Stevens,
R. W., Jr.; Toochinda, P.; Chuang, S. S. C. CO2 capture by amine-
enriched fly ash carbon sorbents. Sep. Purif. Technol. 2004, 35, 31–36.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
(168) Maroto-Valer, M. M.; Lu, Z.; Zhang, Y.; Tang, Z. Sorbents for
CO2 capture from high carbon fly ashes. Waste Manage. 2008, 28,
2320–2328.
(169) Arenillas, A.; Smith, K. M.; Drage, T. C.; Snape, C. E. CO2
capture using some fly ash-derived carbon materials. Fuel 2005, 84,
2204–2210.
(170) Plaza, M. G.; Pevida, C.; Arenilla, A.; Rubiera, F.; Pis, J. J. CO2
capture by adsorption with nitrogen enriched carbons. Fuel 2007,
86, 2204–2212.
(171) Alesi, W. R.; Gray, M.; Kitchin, J. R. CO2 adsorption on
supported molecular amidine systems on activated carbon. Chem-
SusChem 2010, 3, 948–956.
(172) Drage, T. C.; Arenillas, A.; Smith, K. M.; Pevida, C.; Piippo, S.;
Snape, C. E. Preparation of carbon dioxide adsorbents from the chemical
activation of urea-formaldehyde and melamine-formaldehyde resins.
Fuel 2007, 86, 22–31.
(173) Xu, X.; Song, C.; Andresen, J. M.; Miller, B. G.; Scaroni, A. W.
Novel polyethyleneimine-modified mesoporous molecular sieve of
MCM-41 type as high-capacity adsorbent for CO2 capture. Energy Fuels
2002, 16, 1463–1469.
(174) Xu, X.; Song, C.; Miller, B. G.; Scaroni, A. W. Influence of
moisture on CO2 separation from gas mixture by nanoporous adsorbent
based on polyethyleneimine-modified molecular sieve MCM-41. Ind.
Eng. Chem. Res. 2005, 44, 8113–8119.
(175) Yue, M. B.; Sun, L. B.; Cao, Y.; Wang, Y.; Wang, Z. J; Zhu, J. H.
Efficient CO2 capturer derived from as-synthesized MCM-41 modified
with amine. Chem.—Eur. J. 2008, 14, 3442–3451.
(176) Son, W. J.; Choi, J. S.; Ahn, W. S. Adsorptive removal of
carbon dioxide using polyethyleneimine-loaded mesoporous silica ma-
terials. Microporous Mesoporous Mater. 2008, 113, 31–40.
(177) Chen, C.; Yang, S. T.; Ahn, W. S.; Ryoo, R. Amine-impreg-
nated silica monolith with a hierarchical pore structure: enhancement of
CO2 capture capacity. Chem. Commun. 2009, 24, 3627–3629.
(178) Drage, T. C.; Arenillas, A.; Smith, K. M.; Snape, C. E. Thermal
stability of polyethyleneimine based carbon dioxide adsorbents and its
influence on selection of regeneration strategies. Microporous Mesopor-
ous Mater. 2008, 116, 504–512.
(179) Qi, G.; Wang, Y.; Estevez, L.; Duan, X.; Anako, N.; Park, A. H. A.;
Li, W.; Jones, C. W.; Giannelis, E. P. High efficiency nanocomposite
sorbents for CO2 capture based on amine-functonalized mesoporous
capsules. Energy Environ. Sci. 2011, 4, 444–452.
(180) Goeppert, A.; Meth, S.; Prakash, G. K. S.; Olah, G. A.
Nanostructured silica as a support for regenerable high-capacity orga-
noamine-based CO2 sorbents. Energy Environ. Sci. 2010, 3, 1949–1960.
(181) Lee, S.; Filburn, T.; Gray, M.; Park, J. W.; Song, H. J. Screening
test of solid amine sorbents for CO2 capture. Ind. Eng. Chem. Res. 2008,
47, 7419–7423.
(182) Gray, M. L.; Hoffman, J. S.; Hreha, D. C.; Fauth, D. J.; Hedges,
S. W.; Champagne, K. J.; Pennline, H. W. Parametric study of solid
amine sorbents for the capture of carbon dioxide. Energy Fuels 2009, 23,
4840–4844.
(183) Yue, M. B.; Chun, Y.; Cao, Y.; Dong, X.; Zhu, J. H. CO2
capture by as-prepared SBA-15 with an occluded organic template. Adv.
Funct. Mater. 2006, 16, 1717–1722.
(184) Yue, M. B.; Sun, L. B.; Cao, Y.; Wang, Z. J.; Wang, Y.; Yu, Q.;
Zhu, J. H. Promoting the CO2 adsorption in the amine-containing SBA-
15 by hydroxyl group. Microporous Mesoporous Mater. 2008, 114, 74–81.
(185) Ma, X.; Wang, X.; Song, C. Molecular basket sorbents for
separation of CO2 and H2S from various gas streams. J. Am. Chem. Soc.
2009, 131, 5777–5783.
(186) Dasgupta, S.; Nanoti, A.; Gupta, P.; Jena, D.; Goswami, A. N.;
Garg, M. O. Carbon dioxide removal with mesoporous adsorbents in a
single column pressure swing adsorber. Sep. Sci. Technol. 2009, 44,
3973–3983.
(187) Jadhav, P. D.; Chatti, R. V.; Biniwale, R. B.; Labhsetwar, N. K.;
Devotta, S.; Rayalu, S. S. Monoethanol amine modified zeolite 13X for
CO2 adsorption at different temperatures. Energy Fuels 2007, 21,
3555–3559.
1462
REVIEW
(188) Su, F.; Lu, C.; Kuo, S. C.; Zeng, W. Adsorption of CO2 on
amine-functionalized Y-type zeolites. Energy Fuels 2010, 24, 1441–1448.
(189) Fisher, J. C.; Tanthana, J.; Chuang, S. S. C. Oxide-supported
tetraethylenepentamine for CO2 capture. Environ. Prog. Sustain. Energy
2009, 28, 589–598.
(190) Birbara, P. J.; Nalette, T. A. A process for forming a regener-
able supported amine-polyol sorbent. U.S. Patent 5,620,940, 1997.
(191) Satyapal, S.; Filburn, T.; Trela, J.; Strange, J. Performances and
properties of a solid amine sorbent for carbon dioxide removal in space
life support application. Energy Fuels 2001, 15, 250–255.
(192) Gray, M. L.; Fauth, D. J.; Soong, Y.; Champagne, K. J.;
Pennline, H.; Baltrus, J.; Filburn, T. Temperature effect on the capture
of carbon by immobilized amine sorbents. Presented at the Fourth
Annual Conference on Carbon Capture & Sequestration, Alexandria, VA,
USA, May 2
5, 2005, Paper 239, 21 pp. (Available via the Internet at
www.netl.doe.gov/publications/proceedings/05/carbon-seq/Tech%
20Session%20Paper%20239.pdf.)
(193) Li, P.; Zhang, S.; Chen, S.; Zhang, Q.; Pan, J.; Ge, B. Preparation
and adsorption properties of polyethylenimine containing fibrous adsor-
bent for carbon dioxide capture. J. Appl. Polym. Sci. 2008, 6, 3851–3858.
(194) Li, P.; Ge, B.; Zhang, S.; Chen, S.; Zhang, Q.; Zhao, Y. CO2
capture by polyethylenimine-modified fibrous adsorbent. Langmuir
2008, 24, 6567–6574.
(195) Yang, Y.; Li, H.; Chen, S.; Zhao, Y.; Li, Q. Preparation and
characterization of a solid amine adsorbent for capturing CO2 by grafting
allylamine onto PAN fiber. Langmuir 2010, 26, 13897–13902.
(196) Xu, X.; Song, C.; Andresen, J. M.; Miller, B. G.; Scaroni, A. W.
Preparation and characterization of novel CO2 “molecular basket”
adsorbents based on polymer-modified mesoporous molecular sieve
MCM-41. Microporous Mesoporous Mater. 2003, 62, 29–45.
(197) Xu, X. C.; Song, C. S.; Andresen, J. M.; Miller, B. G.; Scaroni,
A. W. Adsorption Separation of CO2 from simulated flue gas mixtures by
novel CO2 “Molecular Basket” adsorbents. Int. J. Environ. Technol.
Manage. 2004, 4, 32–52.
(198) Xu, X.; Song, C. S.; 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.
(199) Gargiulo, N.; Caputo, D.; Colella, C. Preparation and char-
acterization of polyethylenimine-modified mesoporous silicas as CO2
sorbents. In From Zeolites to Porous MOF Materials— 40th Anniversary of
International Zeolite Conference; Proceedings of the 15th International
Zeolite Conference, Beijing, China, 2007; pp 1938
1943.
(200) Pirngruber, G. D.; Cassiano-Gaspar, S.; Louret, S.; Chaumon-
not, A.; Delfort, B. Amines immobilized on a solid support for
postcombustion CO2 capture
A preliminary analysis of the perfor-
mance in a VSA or TSA process based on the adsorption isotherms and
kinetic data. Energy Procedia 2009, 1, 1335–1342.
(201) Chew, T. L.; Ahmad, A. L.; Bhatia, S. Ordered mesoporous
silica (OMS) as an adsorbent and membrane for separation of carbon
dioxide (CO2). Adv. Colloid Interface Sci. 2010, 153, 43–57.
(202) Leal, O.; Bolivar, C.; Ovalles, C.; Garcia, J. J.; Espidel, Y.
Reversible adsorption of carbon dioxide on amine surface-bonded silica
gel. Inorg. Chim. Acta 1995, 240, 183–189.
(203) Delaney, S. W.; Knowles, G. P.; Chaffee, A. L. Hybrid
mesoporous materials for carbon dioxide separation. Div. Fuel Chem.,
Am. Chem. Soc.
Prepr. Symp. 2002, 47, 65.
(204) Knowles, G. P.; Delaney, S. W.; Chaffee, A. L. Amine-
functionalized mesoporous silicas as CO2 adsorbents. Stud. Surf. Sci.
Catal. 2005, 156, 887–896.
(205) Knowles, G. P.; Graham, J. V.; Delaney, S. W.; Chaffee, A. L.
Aminopropyl-functionalized mesoprous silicas as CO2 adsorbents. Fuel
Process. Technol. 2005, 86, 1435–1448.
(206) Chaffee, A. L. Molecular modeling of HMS hybrid materials
for CO2 adsorption. Fuel Process. Technol. 2005, 86, 1473–1486.
(207) Knowles, G. P.; Delaney, S. W.; Chaffee, A. L. Diethylen-
etriamine[propyl(silyl)]- (DT) mesoporous silicas as CO2 adsorbents.
Ind. Eng. Chem. Res. 2006, 45, 2626–2633.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463
Industrial & Engineering Chemistry Research
(208) Liang, Z.; Fadhel, B.; Schneider, C. J.; Chaffee, A. L. Stepwise
growth of melamine-based dendrimers into mesopores and their CO2
adsorption properties. Microporous Mesoporous Mater. 2008, 111,
536–543.
(209) Acosta, E. J.; Carr, C. S.; Simanek, E. E.; Shantz, D. F.
Engineering nanospaces: iterative synthesis of melamine-based dendri-
mers on amine-functionalized SBA-15 leading to complex hybrids with
controllable chemistry and porosity. Adv. Mater. 2004, 16, 985–989.
(210) Hiyoshi, N.; Yogo, K.; Yashima, T. Adsorption of carbon
dioxide on amine modified SBA-15 in the presence of water vapor. Chem.
Lett. 2004, 33, 510–511.
(211) Hiyoshi, N.; Yogo, K.; Yashima, T. Adsorption characteristics
of carbon dioxide on organically functionalized SBA-15. Microporous
Mesoporous Mater. 2005, 84, 357–365.
(212) Huang, H. Y.; Yang, R. T.; Chinn, D.; Munson, C. L. Amine-
grafted MCM-48 and silica xerogel as superior sorbents for acidic gas
removal from natural gas. Ind. Eng. Chem. Res. 2003, 42, 2427–2433.
(213) Chang, A. C. C.; Chuang, S. S. C.; Gray, M.; Soong, Y. In-situ
infrared study of CO2 adsorption on SBA-15 grafted with
γ-(aminopropyl)triethoxysilane. Energy Fuels 2003, 17, 468–473.
(214) Gray, M. L; Soong, Y.; Champagne, K. J.; Pennline, H.;
Baltrus, J. P.; Stevens, R. W., Jr.; Khatri, R.; Chuang, S. S. C. Capture
of carbon dioxide by solid amine sorbents. Int. J. Environ. Manage. 2004,
4, 82–88.
(215) Khatri, R.; Chuang, S. S. C.; Soong, Y.; Gray, M. Carbon
dioxide capture by diamine-grafted SBA-15: A combined Fourier trans-
form infrared and mass spectrometry study. Ind. Eng. Chem. Res. 2005,
44, 3702–3708.
(216) 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.
(217) Zheng, F.; Tran, D. N.; Busche, B.; Fryxell, G. E.; Addleman,
R. S.; Zemanian, T. S.; Aardahl, C. L. Ethylenediamine-modified SBA-15
as regenerable CO2 sorbents. Div. Fuel Chem., Am. Chem. Soc.
Prepr.
Symp. 2004, 49, 261
262.
(218) Zheng, F.; Tran, D. N.; Busche, B.; Fryxell, G. E.; Addleman,
R. S.; Zemanian, T. S.; Aardahl, C. L. Ethylenediamine-modified SBA-15
as regenerable CO2 sorbents. Ind. Eng. Chem. Res. 2005, 44, 3099–3105.
(219) Harlick, P. J. E.; Sayari, A. Applications of pore-expanded
mesoporous silicas. 3. Triamine silane grafting for enhanced CO2
adsorption. Ind. Eng. Chem. Res. 2006, 45, 3248–3255.
(220) 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.
(221) Sayari, A.; Hamoudi, S.; Yang, Y. Applications of pore
expanded mesoporous silica: 1. Removal of heavy metal cations and
organic pollutants from wastewater. Chem. Mater. 2005, 17, 212–216.
(222) Serna-Guerrero, R.; Da’na, E.; Sayari, A. New insights into the
interactions of CO2 with amine-functionalized silica. Ind. Eng. Chem. Res.
2008, 47, 9406–9412.
(223) Serna-Guerrero, R.; Belmabkhout, Y.; Sayari, A. Influence of
regeneration conditions on the cyclic performance of amine-grafted
mesoporous silica for CO2 capture: An experimental and statistical
study. Chem. Eng. Sci. 2010, 65, 4166–4172.
(224) Serna-Guerrero, R.; Belmabkhout, Y.; Sayari, A. Further
investigations of CO2 capture using triamine-grafted pore-expanded
mesoporous silica. Chem. Eng. J. 2010, 158, 513–519.
(225) Serna-Guerrero, R.; Belmabkhout, Y.; Sayari, A. Triamine-
grafted pore-expanded mesoporous silica for CO2 capture: Effect of
moisture and adsorbent regeneration strategies. Adsorption 2010,
16, 567–575.
(226) Serna-Guerrero, R.; Belmabkhout, Y.; Sayari, A. Adsorption of
CO2-containing gas mixtures over amine-bearing pore-expanded MCM-
41 silica: Application for gas purification. Ind. Eng. Chem. Res. 2010, 49,
359–365.
(227) Belmabkhout, Y.; Sayari, A. Isothermal versus non-isothermal
adsorption-desorption cycling of triamine-grafted pore-expanded MCM-41
1463
REVIEW
mesoporous silica for CO2 capture from flue gas. Energy Fuels 2010, 24,
5273–5280.
(228) Belmabkhout, Y.; Sayari, A. Stabilization of amine-containing
CO2 adsorbents: Dramatic effect of water vapor. J. Am. Chem. Soc. 2010,
132, 6312–6314.
(229) Hicks, J. C.; Drese, J. H.; Fauth, D. J.; Gray, M. L.; Qi, G.;
Jones, C. W. Designing adsorbents for CO2 capture from flue
gas
Hyperbranched aminosilicas capable of capturing CO2 reversibly.
J. Am. Chem. Soc. 2008, 130, 2902–2903.
(230) Drese, J. H.; Choi, S.; Lively, R. P.; Koros, W. J.; Fauth, D. J.;
Gray, M. L.; Jones, C. W. Synthesis-structure-property relationships for
hyperbranched aminosilica CO2 adsorbents. Adv. Funct. Mater. 2009,
19, 3821–3832.
(231) Knofel, C.; Descarpentries, J.; Benzaouia, A.; Zelenak, V.;
Mornet, S.; Llewellyn, P. L.; Hornebecq, V. Functionalised micro-/
mesoporous silica for the adsorption of carbon dioxide. Microporous
Mesoporous Mater. 2007, 99, 79–85.
(232) Zelenak, V.; Badanicova, M.; Halamova, D.; Cejka, J.; Zukal,
A.; Murafa, N.; Goerigk, G. Amine-modified ordered mesoporous silica:
Effect of pore size on carbon dioxide capture. Chem. Eng. J. 2008,
144, 336–342.
(233) Kim, S. N.; Son, W. J.; Choi, J. S.; Ahn, W. S. CO2 adsorption
using amine-functionalized mesoporous silica prepared via anionic
surfactant-mediated synthesis. Microporous Mesoporous Mater. 2008,
115, 497–503.
(234) Lu, C.; Su, F.; Hsu, S. C.; Chen, W.; Bai, H.; Hwang, J. F.; Lee,
H. H. Thermodynamics and regeneration of CO2 adsorption on
mesoporous spherical-silica particles. Fuel Process. Technol. 2009,
90, 1543–1549.
(235) Contarini, S.; Barbini, M.; Del Piero, G.; Gambarotta, E.;
Mazzumurro, G.; Riocci, M.; Zappelli, P. Solid sorbents for the reversible
capture of carbon dioxide. In Proceedings of the Sixth International
Conference on Greenhouse Gas Control Technologies: GHGT-6, Kyoto,
Japan, 2003; Gale, J., Kaya, Y., Eds.; Elsevier Science, Ltd.: Oxford, U.K.,
2003; Vol. II, pp 169
174.
(236) Plaza, M. G.; Pevida, C.; Arias, B.; Fermoso, J.; Arenillas, A.;
Rubiera, F.; Pis, J. J. Application of thermogravimetric analysis to the
evaluation of aminated solid sorbents for CO2 capture. J. Therm. Anal.
Calorim. 2008, 92, 601–606.
(237) Sjostrom, S.; Krutka, H. Evaluation of solid sorbents as a
retrofit technology for CO2 capture. Fuel 2010, 89, 1298–1306.
(238) Ho, M. T.; Allinson, G. W.; Wiley, D. E. Reducing the cost of
CO2 capture from flue gases using pressure swing adsorption. Ind. Eng.
Chem. Res. 2008, 47, 4883–4890.
(239) Ho, M. T.; Allinson, G.; Wiley, D. E. Reducing the cost of CO2
capture from flue gases using membrane technology. Ind. Eng. Chem. Res.
2008, 47, 1562–1568.
(240) Yang, W. C.; Hoffman, J. Exploratory design study on reactor
configurations for carbon dioxide capture from conventional power
plants employing regenerable solid sorbents. Ind. Eng. Chem. Res. 2009,
48, 341–351.
dx.doi.org/10.1021/ie200686q |Ind. Eng. Chem. Res. 2012, 51, 1438–1463