DOI: 10.1002/slct.
201600094 Full Papers
z Energy Technology & Environmental Science
Finding and Evaluating of Adequate Adsorbents for the
Adsorption of CO2 from Humid Gas Streams
Lenny Castro-Gonzales,[a] Klaus Kimmerle,[a] Egbert Schippert,[b] and Daniel Fickinger*[a]
By studying the literature adsorbent materials were identified
that are suitable for the physical and/or chemical adsorption of
anthropogenic CO2 from gas streams that are nearly saturated
with water vapor. Promising adsorbents (silica Tri-PE-MCM-41,
Zeolite 5 A BF, MOF Mg(DOBDC), MOF Basolite C300, and 3-
Aminopropyl-functionalized silica) were investigated regarding
their behavior in breakthrough experiments with CO2 and wa-
ter vapor. Only the amine-functionalized silica Tri-PE-MCM-41, if
preloaded with water, has suitable properties for this applica-
Introduction
The increase in CO2 concentration in the atmosphere, especially
during the second half of the 20th century, can be attributed to
mankind.[1] There is a linear correlation between increase in
temperature and the CO2 concentration in the atmosphere.[2]
For the stabilization of today’s average temperature, CO2 emis-
sions must be cut in half by the end of the 21st century.[2]
The main sources of anthropogenic CO2 emissions are fossil
fuel processes.[3] Fossil plant flue gases contribute 33–40 % to
worldwide CO2 emissions.[4, 5] However, due to its reliability and
profitability, future energy production will still involve fossil
fuel. Therefore, the objective, a massive reduction of CO2 emis-
sions, can only be achieved by CCS technology (carbon capture
and storage) as an alternative for the reduction of CO2 emis-
sions.[3] CCS allows the further use of fossil fuels.[4, 5] Further ap-
plications are the purification of landfill gas, mine gas, and oth-
er lean gases for the feed into the natural gas grid.
There are three main technologies being used at the mo-
ment for the sequestration of CO2: membrane separation, ab-
sorption in amine solution and adsorption onto porous materi-
als. A further method is the cryogenic distillation, which is too
energy-consuming.[6] Benchmark technology is the absorption
in amine solution.[6] An advantage in using adsorption onto po-
rous materials is that the regeneration of adsorbents consumes
less energy than the regeneration of an amine solution. How-
[a] Dipl.-Ing. L. Castro-Gonzales, Prof. Dr.-Ing. K. Kimmerle, Dr.-Ing. D. Fickinger
Institute of Physical Process Technology
University of Applied Sciences Saarbrcken
Goebenstraße 40, 66117 Saarbrcken (Germany)
E-mail: daniel.fickinger@htwsaar.de
[b] Dr. E. Schippert
Schippert + Partner
St Johanner Markt 41–43, 66111 Saarbrcken (Germany)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/slct.201600094
ChemistrySelect 2016, 1, 2834 – 2841
tion. This is also the case for pelletized Tri-PE-MCM-41, consid-
ering an industrial application. The thermodynamic analysis of
pure CO2 adsorption using the ALIc model shows that the
strongest binding forces between the CO2 molecule and the
adsorbent wall are present during the adsorption of CO2 onto
Tri-PE-MCM-41. Differential and integral enthalpies of the sys-
tem CO2/Zeolite 5ABF also show the strong affinity of this ad-
sorbent/adsorptive system.
ever, for adsorption, one has to consider all components of a
gas mixture, not only CO2. Especially water vapor can affect the
performance of physical adsorbents negatively regarding the
CO2 adsorption.[6]
Landfill gas consists of 40 to 60 %-vol of CO2;[1] however it
also contains from 5 up to 7 %-vol. water vapor.[7] The same ap-
plies for flue gas, which contains water vapor near saturation.
Therefore the search for an adequate adsorbent for the consid-
ered application is no trivial matter. The material has to exhibit
a high CO2 loading also in humid gas streams. The regeneration
has to consume less energy than it does in the benchmark
process. Finally the adsorbent also has to be stable over the
long term, appropriately shaped (considering pressure drop),
and has to be available at reasonable costs. Literature review,
together with screening experiments under conditions of the
considered application as well as thermodynamic evaluation,
are useful tools to find such an adsorbent.
Results and Discussion
Literature review
Four adsorbent classes were investigated here regarding the
adsorption of CO2, activated carbon (AC), zeolites (ZEO), metal-
organic frameworks (MOF) and silica-based adsorbents (SIL).
Those adsorbents, except for AC, which was chosen as it is
well-established and economic, are the most promising for an
application as an adequate CO2 adsorbent.[11,6] shows an over-
view of physical adsorbents (AC, ZEO), chemical adsorbents
(metal-based, like CaO, MgO, K2O etc.) and amine-functional-
ized adsorbents, regarding CO2 adsorption. Further review ar-
ticles exist.[1, 8–10] A strong increase, even exponential in the case
of MOF,[12] in research activity concerning the physical adsorp-
tion of CO2 can be observed in the last decade.[11] This is in-
dicated by the increase in publications per year.
2834  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Here, more than 200 research and review articles, PhD the-
ses, and technical reports were chosen, investigated, and eval-
uated from many more publications. The investigation was car-
ried out under consideration of the CO2 loading and its cross-
sensitivity to water vapor, the regenerability, the shape and
availability of adsorbents.
(Table 1) generically shows references which provide meas-
ured equilibrium data of the CO2 adsorption in the form of ad-
Table 1. References containing equilibrium data regarding the CO2 adsorp-
tion from dry and humid gases onto chosen adsorbent classes
CO2 adsorption from CO2 adsorption from hu-
dry gases mid gases
activated carbon [13] [15] [16] [14]
zeolite [17] [18] [19] [25] [17] [18] [19] [25]
silica-based ad- [19] [20] [43] [21] [22]
sorbents
MOF [8] [9] [23] [24] [8] [9]
sorption isotherms, XCO2 = f(pCO2), or even isotherm fields,
(XCO2 = f(pCO2, T). For all adsorbents under investigation here,
enough equilibrium data exists to design an adsorption proc-
ess with precision, at least for the pure CO2 adsorption. Despite
the existence of some equilibrium data for co-adsorption of
CO2 and water vapor onto different adsorbents, there is much
less equilibrium data for this special case. For example, there is
data concerning the influence of water vapor on the adsorbent
loading with CO2[9] of several MOF. However, there are mostly
only a few equilibrium points measured instead of adsorption
isotherms at constant relative humidity. For ZEO by contrast,
there are complete adsorption isotherm fields, XCO2 = f(pCO2, T,
f), e. g.,[25] so for these adsorbents, also in the case of humid air,
the design of an adsorption process seems possible.
For MOFs, in contrast,[9] points to the fact that varying data
is provided by literature for the same adsorbent/adsorptive sys-
tem, namely MOF/water vapor. The interpretation of such data,
which is already rare, is even harder if such uncertainties exist.
Deviations in measured values from several authors can also be
caused, especially if such a new material as MOF is inves-
tigated, using different procedures or recipes. Furthermore, dif-
ficulties can occur in the measurement setup and the appro-
priate evaluation of raw data, which both contribute to the lack
of MOF co-adsorption data.[26] Also new materials are being in-
vestigated regarding pure CO2 adsorption first, due to the sim-
plicity and the simultaneous determination of structural data
such as BET surface and pore size distribution.
Zeolites
Studies have shown that Zeolite 5 A and Zeolite 13X selectively
adsorb CO2 at room temperature[18, 27] whereby ZEO has been
sufficiently investigated for use in the separation of CO2 from
N2.[28] CO2 is mainly adsorbed physically in ZEO; a small amount
(up to 0.15 mmol/g) still exists in form of carbonate or carboxyl
groups.[29, 30] The adsorption of CO2 in ZEO is very temperature-
ChemistrySelect 2016, 1, 2834 – 2841
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sensitive, which is why their application is only useful in the
low-temperature region.[6] Pure CO2 adsorption isotherms of
the commercially available Zeolites 13X, NaY, HiSiv-3000, HY-5
and HZSM-5-30 are, for example, presented in,[31] where 13X ex-
hibits the greatest CO2 capacity over a broad range of CO2 par-
tial pressure, pCO2 > ~ 0.01 bar, of all ZEO investigated. Pre-
adsorbed water vapor can affect the CO2 adsorption kinetically
positive in ZEO.[6] Except in low concentrations (pCO2 <
300 ppm), CO2 capacity is lowered by water loading.[6] Due to
its polarity, water is strongly bound onto ZEO surface.[25] shows
CO2 adsorption isotherms onto water-preloaded ZEO. At
pCO2 = 0.15 bar and T = 295 K Zeolite 13 X exhibits ~ 13 %-
mass CO2 loading. With water preloading it is shown that only
9 % ( = 1.2 %-mass CO2 loading) can be preserved if the ZEO is
preloaded at relative humidity f of only 1.5 % (at 21 8C). Similar
observations can be made for Zeolite 5 A and others, see.[17, 18, 25]
The regeneration of ZEO is possible under mild conditions
due to its strong temperature dependency; they retain their
complete adsorption capacity after regeneration.[6] The avail-
ability of ZEO is given even in largest quantities; they are low-
cost, common adsorbent materials.
The ZEO considered here are, due to their hydrophilic char-
acter, only possible adsorbents, if the humid gas is dried prior
to CO2 adsorption.[32] If it is not dried, the CO2 capacity of the
ZEO is not only lowered, but the adsorbed water also has to be
removed at least partially during regeneration.
Metal-Organic Frameworks
Metal-organic frameworks (MOF) are formed by knots (metal or
metal oxide centers) and organic linkers for cross-linking. This
relatively new class of materials exhibit special structural prop-
erties, like their great volume porosity of up to 90 % and BET
surfaces of up to 6200 m2/g.[1, 33] Many thousands of possible
combinations of linkers and metal centers are conceivable and
have been synthesized. Properties like the pore size can be ac-
tively influenced by choosing basic materials. If the metal cen-
ter is unsaturated, MOF have higher affinity towards CO2 than
MOF with saturated metal centers.[34, 35]
Meanwhile many MOF are known which exhibit extra-
ordinarily high CO2 loadings compared to zeolites.[8] One MOF
is declared to be the MOF with the highest overall CO2 loading
gCO2 / gMOF by many researchers, Mg(DOBDC).[8, 9] It is also
known as MOF-74 or CPO-27.[9, 34] The CO2 loading at room tem-
perature and pCO2 = 1 bar is 37.3 %-mass ( = 8.48 mmol/g;
207 cmN3/g).[8] Existing equilibrium data for the adsorption of
CO2 from mixtures of CO2/H2/CH4/N2 show that MOF can be
very selective for CO2.[9] In actual processes, water vapor is of-
ten present. Despite this fact, publications on the cross-sensi-
tivity of CO2 towards water vapor adsorption in MOF are rare.[8]
In real applications at least traces of other gases such as re-
active ones like NOx und SOx can be present, which can also
affect the CO2 adsorption or lead to an aging process of the
adsorbent. Nothing is known about that so far.[8] There are also
some publications on the co-adsorption of water and CO2 onto
MOF. According to those, one MOF that could be interesting
regarding application considered here is Mg(DOBDC).[9] Un-
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fortunately also here there are only a few publications that
have carried out breakthrough experiments under real con-
ditions, meaning with a relative humidity near saturation. Gen-
eral statements about the cross-sensitivity of the CO2 adsorp-
tion onto MOF or especially Mg(DOBDC) towards water vapor
are difficult to make.
According to representatives from the chemical industry,
MOF are not yet appropriate for use in industrial processes due
to their powder form. Pressure drops are then too high to han-
dle or too energy-consuming.[36] Long-term stability, pellet-
ization and further issues are still not being studied enough at
the moment. Some MOF exhibit extraordinarily high heats of
adsorption for CO2. Partially they exceed the heat needed for
regeneration of the well-known amine solution Mono-
ethanolamin (MEA).[8] This makes them less favorable due to
the energy-consuming regeneration. Many MOF are, even if the
production is scaled up, expensive due to the rarity of raw ma-
terials used.[37] If they are commercially available, then at the
moment only in laboratory scale quantities.[38] Furthermore, ba-
sic substances are available in a modular system for synthesis
and modification of MOF.[39] Still one has to keep in mind that
MOF is in its infancy right now and major progress is to antici-
pate even if it cannot be quantified at this point. Also MOF not
mentioned here have a high potential for the capture of CO2,
e. g. the MOF SIFSIXCu-3, SIFSIXNi-3[59, 60] and UTSA-16.[61]
Silica–based adsorbents
The following section only considers silica-based adsorbents
which are functionalized with amine groups on its surface. This
is the logical choice, since the benchmark technology for CO2
separation is absorption in amine solution.[6] Several mecha-
nisms are responsible for the interaction of the CO2 molecule
with amines. Primary and secondary amines can form carbo-
nates with CO2.[6] In a first step, a CO2 molecule and an amine
group form a dipolar ion, followed by the formation of carba-
mate through free bases (amines, H2O or OH-). Under dry con-
ditions, if H2O and OH-, are absent, the maximum loading
amounts to 0.5 mol CO2 per mol N. Under humid conditions it
is 1 mol CO2 per mol N.[6, 40] The detailed mechanism is pre-
sented for example in[41] and can also be found in.[6, 40] The de-
scribed mechanism is valid for primary and secondary amines;
tertiary amines catalyze the formation of bicarbonates.[42]
One of many functionalized silica is Tri-PE-MCM-41. The car-
rier structure is MCM-41, a mesoporous silica like SBA-15 or
MCM-48.[43] The mean pore size is 3.3 nm.[43] By hydrothermal
pore expansion in Dimethyldecylamine (DMDA), the pores can
be expanded to 11.7 nm. The material is then called PE-MCM-
41.[44] Through pore expansion, the following amine loading
can be increased without completely blocking pores. After
functionalization with 3-[2-(2-aminoethylamino)ethyl-amino]
propyltrimethoxysilane (TRI), the pore size is 9.4 nm, the mate-
rial is then called Tri-PE-MCM-41. Through this procedure, the
BET surface is lowered from 1490 m2/g (MCM-41) to 367 m2/g
(Tri-PE-MCM-41).[43] The CO2 capacity of such adsorbents is ex-
traordinarily high.[40] Long-term stability and CO2 capacity even
increase if water vapor is present in the atmosphere or in the
ChemistrySelect 2016, 1, 2834 – 2841
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adsorbent’s pores.[40] This behavior can be reduced to the
mechanism of urea formation by the reaction of CO2 with pri-
mary amine groups.[40] The further reaction to bicarbonate is
then hindered and fewer adsorption sites are available for fol-
lowing adsorption cycles. This then is called aging of the ad-
sorbent.
The regeneration of such adsorbents in general is less en-
ergy-intensive, since it is possible at lower temperatures, than
the regeneration of amine solutions for the absorption of
CO2.[10] This is due to the lower heat capacity of adsorbent car-
rier structures compared to carrier fluid ( = water) in amine sol-
utions.[6] Our own inquiry indicated that the production of Tri-
PE-MCM-41 in a laboratory scale is very expensive due to the
required purity of compounds as stated by the literature.[40, 44]
Tri-PE-MCM-41 is not commercially available.
Activated carbon
Meso- and microporous AC are well-known, diverse adsorbents
which have an economic advantage over many other adsorb-
ents due to their industrial production and low-cost raw mate-
rials.[45] Their general adsorption capacity for CO2 is within the
low-pressure region (pCO2 < 1 bar), below the capacity of zeo-
lites and molecular sieves.[6] Only in the high-pressure region
do AC exhibit considerable loadings as compared to other ad-
sorbents investigated here. If in addition water vapor is present
during the CO2 adsorption, this is massively lowered. Due to
the general hydrophobicity of the AC surface, the negative ef-
fect of water vapor is not as distinct as it is for zeolites. It is
possible to enhance the hydrophobicity of AC by surface mod-
ification;[47] the CO2 capacity then increases.[48] However, if the
relative humidity is near saturation, the adsorption of other
components, namely CO2, is affected very negatively. This influ-
ence usually takes place at f > ~ 50 %[26] due to a steep in-
crease in pure water vapor loading of AC at this stage of f. For
example the CO2 loading of water-preloaded AC at 275 K is
lowered from ~ 3.5 mmol/g at dry conditions to ~ 0.5 mmol/g if
preloaded with water.[46] AC does not seem to be suitable for
the application considered here. Still, it is regarded for reasons
of comparison with its reliability and low cost.
CO2-adsorption from dry and humid gas streams
The following section presents results of breakthrough experi-
ments with the chosen adsorbents. Equilibrium loadings are
not presented. The comparison of breakthrough behavior can
be used to screen different adsorbents for a certain application.
Zeolites – Zeolite 5 A BF
(Figure 1) shows breakthrough curves of CO2, from dry (green)
and humid (black) air, onto Zeolite 5 A BF, each at a raw gas
concentration of ~ 4.8 %-vol. CO2 (black, dashed). In dry air, the
CO2 concentration at the column outlet approaches, after an in-
itial decrease to nearly zero, the raw gas concentration. The
CO2 concentration in humid air, f ~ 88 %, on the other hand
(black) shows the great cross-sensitivity of the CO2 adsorption
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 Full Papers
through curves of CO2 in a humid atmosphere present the
same results as for Zeolite 5 A BF. CO2 breaks through early; wa-
ter vapor is adsorbed strongly and leads to the desorption of
CO2 by displacement. The capacity for CO2 tends towards zero,
at 5 %-Vol CO2, f = 90 % and T = 25 8C.

Silica - 3-Aminopropyl–functionalized silica gel

First experiments with this commercially available silica-based
adsorbent showed a certain CO2-capacity, even in a humid at-
mosphere. Further investigations are needed to prove this.

Figure 1. Breakthrough curves of CO2 (black, continuous: clean gas, dashed: Silica - Tri-PE-MCM-41
raw gas) and H2O (blue, continuous: clean gas; dashed: raw gas) onto Zeoli-
Tri-PE-MCM-41 was available as a fine powder (see Figure S1 in
te 5 A BF, red checkered area represents the adsorption of CO2, the blue
checkered area represents the desorption of CO2 due to adsorbing water va- the Supporting Information)). To maintain a tolerable pressure
por, pure CO2 breakthrough curve (green, continuous: Reingas; dashed: raw drop, experiments had to be carried out with a very small
gas), temperature in each case 25 8C. amount of adsorbent. The complete retention of CO2 during
breakthrough experiments was not always possible. At a con-
centration of 17 % CO2 in the raw gas, the breakthrough occurs
towards water vapor. The CO2 breakthrough takes place earlier immediately after switching the flow to the adsorption column
and is steeper than in dry air. Furthermore, the CO2 concen- (see (Figure 2) and (Figure 3)).
tration exceeds the raw gas concentration after breakthrough.
By the further adsorption of water vapor, CO2 molecules are
displaced in Zeolite 5 A BF. Almost all initially adsorbed CO2 is
desorbed by water vapor. This is indicated by the roll-over phe-
nomenon, the exceeding of the raw gas concentration (red-
checkered area, (Figure 1)) at the column outlet (= desorption
of CO2, blue-checkered area, (Figure 1)). Water vapor break-
through finally takes place after 2500 s. The adsorption of wa-
ter not only lowers the CO2 capacity of the zeolite, it also
makes regeneration more energy-intensive than the re-
generation of dry, only CO2-loaded adsorbent.

MOF - Basolite C300 Figure 2. Breakthrough curves of CO2- and H2O onto water preloaded Tri-PE-
MCM-41, each with retry (continuous: CO2 concentration at the column out-
The commercially available Basolite C300 could not satisfy our let, left y-axis, plateaus after the CO2 breakthrough present the raw gas con-
needs in experiments. Similar to Zeolite 5 A BF, Basolite C300 centration: blue ~ 3 %-vol, green: ~ 10 %-vol, red: ~ 17 %-vol; dashed: relative
humidity f at the column outlet, right y-axis), temperature each 25 8C.
shows a certain (but lower) CO2 loading if exposed to dry gas
streams, however, in the presence of water vapor, in the experi-
ment f = ~ 90 %, the capacity is lowered dramatically too.
Like for Zeolite 5 A BF, breakthrough curves show a roll-over
phenomenon, CO2 is desorbed by adsorbing water vapor. The
roll-over was less distinct than for the zeolite and a certain frac-
tion of the dry CO2 loading could be preserved after complete
breakthrough.

MOF - Mg(DOBDC)
In experiments, the CO2 loading of Mg(DOBDC) after a com-
plete CO2-breakthrough, was lower than values reported in the
literature.[9] It can be concluded that the yield of Mg(DOBDC)
synthesis was too low for the presentation of profound results Figure 3. Breakthrough curves of CO2 (continuous) and H2O (dashed) onto
here. The adsorbent mass for experiments was ~ 5 g. However unloaded (red) and onto water preloaded (green) Tri-PE-MCM-41, raw gas
conditions: ~ 10 %-vol CO2, f = ~ 90 %, T = 25 8C.
the success of the synthesis is proven by XRD and comparison
with references. Also, adsorption behavior towards CO2, even if
very low, shows that Mg(DOBDC) was synthesized. Break-

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The adsorbent was preloaded with water vapor by expos-
ing it to a constant gas flow of the relative humidity that is also
used in the following CO2 breakthrough experiment. (Figure 2)
presents the CO2 breakthrough onto Tri-PE-MCM-41 at a con-
stant f of > 90 %. It shows in particular that even if the ad-
sorbent is preloaded with water vapor and the atmosphere is
nearly saturated, the adsorbent exhibits an extraordinary CO2
adsorption capacity. For all raw gas concentrations of CO2 con-
sidered in (Figure 3), the equilibrium loadings are about the
same, as the adsorption isotherm of CO2 onto Tri-PE-MCM-41 is
very steep with a sharp knee and flat plateau, type I IUPAC,[45]
which is already reached at a CO2 concentration of 0.3 %-
vol.[21, 44] Due to the variation of adsorbent mass for retry experi-
ments in (Figure 3), the course of breakthrough curves is not
always congruent. Still, CO2 is retained at all CO2 concentrations
considered. Furthermore, f remains constant during break-
through; no more water adsorption occurs. During re-
generation in a constant N2 flow, all CO2 adsorbed before could
be recaptured.
The importance of water preloading of Tri-PE-MCM-41 is
shown in (Figure 3). Water vapor adsorbs strongly onto the ad-
sorbent, f (dashed, red) decreases. In contrast, the CO2 break-
through (continuous, red) occurs immediately after switching
the flow to the adsorption column. A small drop in CO2 con-
centration indicates the further CO2 adsorption after Tri-PE-
MCM-41 already adsorbed a small amount of water vapor. The
CO2 capacity increases if Tri-PE-MCM-41 adsorbs water vapor.
This has to be investigated more precisely in further studies.
Still, the amount of CO2 adsorbed onto dry Tri-PE-MCM-41 is
small compared to the amount adsorbed onto samples pre-
loaded with water (green curves, (Figure 3)).
Presented experiments were carried out with Tri-PE-MCM-
41 powder. The following pelletization was performed without
any binding agent using a tablet press. The prepared pellets
were crushed, which finally led to irregular shaped fragments,
approx. (2*3*2) mm3. These pellets were used for breakthrough
experiments. It shows that the breakthrough is much steeper
for powder. Breakthrough curves of pellets are smeared and
broad due to wall effects and the insufficient amount of ad-
sorbent mass. No complete retention could be carried out. Still,
it can be seen that the favorable behavior of the powder can
be preserved for pellets. CO2 is retained better if the adsorbent
is preloaded with water vapor. Water vapor then breaks
through immediately. It also shows that the absolute CO2 load-
ing of Tri-PE-MCM-41 pellets is lower than the loading of the
same amount of powder.
For an industrial use and the simulation of adsorption proc-
esses, detailed studies have to investigate the CO2 capacity of
Tri-PE-MCM-41 pellets as a function of f, T and the CO2 concen-
tration ( = co-adsorption isotherm field) as well as the water
preloading. Furthermore, studies on the influence of pellet-
ization on capacity and kinetics, considering shape, possible
binding agents and pressing pressure, have to be carried out.
Further investigations regarding industrial use include the
long-term stability, regenerability and the cross-sensitivity to-
wards other gases besides water vapor. Finally, cost-effective-
ness cannot be disregarded. Considering this, Tri-PE-MCM-41 is
ChemistrySelect 2016, 1, 2834 – 2841
Full Papers
an adsorbent with high potential for the adsorption of CO2
from humid gases.
Model fitting and thermodynamic evaluation of
CO2-adsorption
In contrast to the Dubinin-Astakhov and Toth models, the ALIc
Model is explicit in the adsorptive pressure pi. Like DA, the
ALIc model states the adsorbent loading as a function of the
degree of pore filling and considers condensation. The basic
formulation is:[50, 51]
 pstd 
  DGm;ads:Conc ðT; XÞ
1X
pi ðT; XÞ ¼ pstd  X  ð1  XÞ X  exp
Rm  T
Eq:ð1Þ
The ALIc model is based on the assumption of the division
of the adsorption process into the binding of adsorptive mole-
cules onto the surface of the adsorbent followed by mixing of
occupied adsorptive sites with empty ones. Therefore the basic
equation is also divided into a term concerning the mixing (first
bracket Equation (1)) and a term concerning the adsorbate con-
centrate (exponential term Equation (1), see also[26, 50]). The mix-
ing process is assumed to be athermic, (see temperature in-
dependence of the first term in Equation (1)). Therefore one
obtains a finite value of the molar free enthalpy of adsorption
for the adsorbate concentrate DGpm;ads:Conc
std
ðT; XÞ at X ! 0. This
value describes the interaction between adsorptive molecules
and adsorbent wall at X ! 0. At standard pressure and boiling
temperature a direct comparison of different adsorptive/ad-
sorbent systems is possible. DG0AA , the value of
DGpm;ads:Conc
std
ðT; XÞ, DGpm;ads:Conc
std ;Tb
ðXÞ is obtained. For X ! 0,
pstd ;Tb
DGm;ads:Conc ðXÞ is 0 due to the vanishing enthalpy of con-
densation at boiling temperature. For more information
see.[26, 50] Five fitting parameters, DGexp.0, kG.exp.0, DGexp.1, kG.exp.1.
and KT (description of temperature dependency) are used to fit
the ALIc model to the measured data. Furthermore 5 physical
parameters, DG0AA , the specific adsorption volume vads, the
thermal coefficient of expansion bas, the average density of the
adsorbate 1 as ðT; XÞ, and the Henry coefficient kHenry are used.
With the ALIc model the isochoric adsorption enthalpy, Equa-
tion (2), and entropy can be calculated:
0  1
pALIC ðT;XÞ
d ln pstd
Dhisochor ðT; XÞ ¼ Rm  @ 1 A Eq:ð2Þ
ads
d T
X
Comparison of adsorbents regarding their CO2 loading
capacity
A fitting method (Monte Carlo, followed by Levenberg-Mar-
quart)[26, 56] was used to determine ALIc-parameters for the ad-
sorption of pure CO2 onto ACC,[52] GAC,[53] Zeolite 5 A,[18] Zeolite
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 Full Papers
13X,[54] MOF Mg(DOBDC),[55] PE-MCM-41[21] and Tri-PE-MCM-
41[21, 44] (see (Table 2)).

Table 2. Determined parameters of the ALIc model and average relative er-
rors to the measured data for the adsorption of CO2 onto 7 adsorbents[a]

adsorbent Vads [ml/ 1as.TB [g/ bas·103 DG0AA [J/ kHenry

100 g] cm3] [1/K] mol] [-]

ACC Chemviron 51 1.305 -0.0024 -5367 0.03

GAC F400 56.74 1.211 -0.0026 -4361 0.1385
zeolite 5 A 17.42 1.331 0.0002 -22980 0.0005
zeolite 13X 45.00 1.280 -0.0036 -34503 0
pi > 1 bar
zeolite 13X 35.57 1.280 -0.0018 -26352 0
pi < 1 bar
Mg(DOBDC) 44.74 1.08 0 -19379 0.0116
PE-MCM-41 45.42 0.93 0.0001 -12690 0
TRI-PE-MCM-41 53.69 1.01 -0.0034 -39119 0 Figure 4. ALIc fit of adsorption isotherms of CO2 onto different adsorbent
KT [-] DGexp.0 kG.exp.0 [-] DGexp.1 kG.exp.1 Ddr.X [%] Ddr.p materials within the low pressure range, from 0 to2 bar, T = 20 8C, log-log-
[J/mol] [J/mol] [-] [%] scale.
-0.0392 -1345.6 -5.6694 0 0 0.94 1.18
-0.0205 -3836.8 -0.6607 920.25 -0.238 0.97 2.16
0.2682 -1400.6 -23.877 5618 -3.0551 7.74 12.0
1.6107 -9889.1 -1.0468 627.7 -7.0137 5.2 10.4 only at high pressures at which the pore system is filled that
0.9424 -912.98 -2.3533 134.9 -10.319 2.4 5.8 GAC and ACC exhibit high loadings. Despite the fact that the
0.3097 -15214.3 -0.7682 8833.1 -16.132 2.66 5.07
0.1313 -3726 -82.825 6604 -0.0001 3.57 5.19
highest overall loading can be observed on Mg(DOBDC), for
0.1889 -29940 -5.9801 21266 -0.5683 3.18 15.1 some applications of pure CO2 adsorption, such as the adsorp-
tion from atmosphere, Tri-PE-MCM-41 exhibits the highest CO2-
[a] column 2 to 6, top, of the table present ALIc-parameters with physical
meaning, column 7 to 11, bottom, present fitting parameters, column 12 loading of all adsorbents investigated here.
and 13 present the ARE of measured data to the model equation
concerning the partial pressure pi and the adsorbent loading Xi
Comparison of adsorbents regarding the thermodynamics of
their CO2-adsorption
For reasons of accuracy, the parameter determination of the (Figure 5), left, shows the isochoric-molar-enthalpy of adsorp-
system CO2/Zeolite 13X has been divided into two sections, tion calculated by the ALIc model, according to Equation (2), as
pCO2 < 1 bar and pCO2 > 1 bar. The ARE (dr.X = S(j a function of the adsorbent loading. It shows that, as adsorp-
Xmeasured.i – XALIc(pi) j)/Xmeasured.i, i stands for the number of meas- tion isotherms implied, adsorbents that perform a higher load-
ured values) regarding partial pressure or adsorbent loading, ing at low pressures also show higher enthalpy of adsorption in
are mostly below 5 %. kHenry can only be determined if meas- this region. As expected, ACC, GAC and PE-MCM-41 show only
ured data is available at pi ! 0. The physical parameter of the low adsorption enthalpies over the entire pressure range. In
adsorbate density, 1as.TB, lies in the region of the density of the contrast, the amine-functionalized PE-MCM-41, namely Tri-PE-
free fluid at boiling temperature (= 1.277 g/cm3[57]). DG0AA or MCM-41, exhibits an extraordinarily high adsorption enthalpy.
the function of DGpm;ads:Conc
std ;Tb
ðXÞ represents the affinity or binding This is similar to Zeolite 5 A, which proves the chemical
strength of the adsorptive molecules to the adsorbent wall. As sorption character of these systems. (Figure 5), right, shows
expected, DG0AA is low for AC and high for amine-functional- DGpm;ads:Conc
std ;Tb
ðXÞ for systems investigated. Tri-PE-MCM-41 and Mg
ized SIL, and polar adsorbents like ZEO. The coefficient of ex- (DOBDC) exhibit a strong affinity, i. e. binding strength, towards
pansion, bas, of the adsorbate concentrate is very small and the CO2 molecules. These three adsorbents show a similar be-
negative for almost every system considered. The adsorbate ex- havior, whereas the decrease is steeper for Tri-PE-MCM-41 due
pands as the temperature rises. KT, which represents the tem- to its steeper isotherm and sharp knee followed by a flat pla-
perature dependency of equilibrium adsorption, is, as ex- teau. A higher value of DGpm;ads:Conc
std ;Tb
ðXÞ for Zeolite 5 A BF, at X !
pected, very strong for ZEO.[6] 0, in comparison to 13X, is due to its smaller pores. AC and PE-
Adsorption isotherms, calculated by the ALIc model, are MCM-41 bind CO2 much more weakly than other adsorbents in-
presented in (Figure 4). Mg(DOBDC) possesses an exceptionally vestigated.
high CO2 capacity in the high pressure region, > 0.01 bar. It is For the evaluation of the occurring heat during adsorption
only in the lower pressure region that zeolites and Tri-PE-MCM- processes, the integral adsorption enthalpy is used. The in-
41 can exceed this. The steepest increase in loading, at p < 1 R max isochor
X¼X
tegral adsorption enthalpy, Xmax  Dhads ðXÞT dX, at 20 8C is
0.01 bar, is exhibited by Tri-PE-MCM-41. This was anticipated X¼0
due to the chemical sorption character of the CO2 adsorption presented in (Figure 6) for adsorbent/adsorptive systems inves-
onto Tri-PE-MCM-41. In contrast, PE-MCM-41 shows no chem- tigated and certain conditions. For the adsorption of CO2 onto
ical sorption behavior. The same applies to ACC and GAC. It is Tri-PE-MCM-41 (at 0.15 bar CO2 partial pressure, 20 8C, re-

ChemistrySelect 2016, 1, 2834 – 2841 2839  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 5. Isochoric heat of adsorption for 7 CO2-adsorbent systems at
T = 20 8C as a function of the adsorbent loading X, on top, molar free en-
thalpy of adsorption at standard pressure and boiling temperature of the ad-
sorptive gas as a function of the degree of pore filling, all characteristic
curves at T = Tb run through one point (0 J·mol1), when pores are entirely
filled (X = 1), at the bottom.
Figure 6. Integral isochoric heat of adsorption for the adsorption of CO2 at
0.15 bar respectively 56.7 bar (saturation pressure) at T = 20 8C, the loading
at the corresponding condition is indicated on the top of each bar in
[weight %].
ChemistrySelect 2016, 1, 2834 – 2841
Full Papers
generation at 150 8C or 4·10-4 bar) the integral adsorption en-
thalpy is 7150 J/Mol or 161.5 kJ/kgCO2. An amount of energy
of 3.18 Wh/kgTri-PE-MCM-41 has to be spent for the desorption of
CO2.
Conclusions
By studying the literature we identified adsorbent materials
that are suitable for the physical adsorption of anthropogenic
CO2 from humid gas streams, i. e. those nearly saturated with
water vapor. The focus of this study lies on the adsorbent
classes of zeolites, AC, metal organic frameworks ( = MOF),
and silica-based adsorbents. From studying the literature our
conclusion was that the most suitable adsorbent for the appli-
cation investigated here is from the class of amine-functional-
ized silica-based adsorbents.
This is also shown by breakthrough experiments with silica
Tri-PE-MCM-41, Zeolite 5 A BF, MOF Mg(DOBDC), MOF Basoli-
te C300, and 3-Aminopropyl-functionalized silica gel. Tri-PE-
MCM-41 performs best, regarding the adsorption of CO2 from
humid, nearly saturated gas streams. Tri-PE-MCM-41 exhibits
exceptionally high CO2 loadings if preloaded with water under
the same conditions as in the following CO2 adsorption taking
place. In this case, CO2 is retained, while water vapor breaks
through the adsorbent bed immediately. This behavior is very
favorable regarding an industrial application. It eliminates, at
least partially, the need for energy-intensive desorption of wa-
ter during regeneration of the adsorbent. For an actual in-
dustrial application of such adsorbents, not only is adsorption
capacity important but also adsorbent shape. Therefore Tri-PE-
MCM-41, initially only available as powder, was pelletized. Pel-
lets also show the favorable behavior concerning the CO2 ad-
sorption from humid air. The absolute CO2 capacity, however, is
lowered. Tri-PE-MCM-41 is the most promising adsorbent for
the application under investigation here. Except for Tri-PE-MC-
41, other adsorbents investigated could not retain anywhere
near their dry air capacity for CO2. If water vapor is present in
the gas stream (especially at f > 90 %, like in the considered
application) or preloaded onto the adsorbent, CO2 equilibrium
loading is very low compared to the pure CO2 capacity. The us-
age of these adsorbents does not seem favorable.
The fitting of pure CO2 adsorption equilibrium data of 7 ad-
sorbents (PE-MCM-41, Tri-PE-MCM-41, GAC, ACC, Zeolite 13X,
Zeolite 5 A and Mg(DOBDC)) with the ALIc model shows very
good results. Obtained physical values show the strongest
binding forces between the CO2 molecule and the adsorbent
wall during the adsorption of CO2 onto Tri-EP-MCM-41. These
characteristic values of the ALIc model are very low for AC
(magnitude - 5000 J/mol) and high for Tri-PE-MCM-41 (-
39119 J/mol) and zeolites (- 22980 J/mol up to – 24503 J/mol).
The same is presented by the course of the molar-free-enthalpy
of the adsorbate concentrate over the degree of pore filling.
The strongest affinity to the CO2 molecule is present in Mg
(DOBDC) and Tri-PE-MCM-41. Mg(DOBDC) exhibits the highest
loading over the widest pressure range. Tri-PE-MCM-41 shows
the steepest increase in CO2 loading and therefore the highest
capacity even in low pressure ranges, pCO2 < ~ 10-3 bar. Zeolites
2840  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

also exhibit high capacity in low pressure ranges. Integral heat
of adsorption presents the amount of heat necessary for ad-
sorbent regeneration.
Information about experimental procedures, sample con-
ditions as well as the experimental setup and equipment can
be found in the Supplementary Information. Furthermore ma-
terial properties and methods of data handling are illustrated.
Acknowledgements
The authors thank Dr. rer. nat. Egbert Schippert for multiple illu-
minating discussions and his perpetual assistance, Chemiewerk
Bad Köstritz GmbH, Germany, for providing the Zeolite samples,
Prof. Abdelhamid Sayari, Ottawa, Canada, for providing the Tri-
PE-MCM-41 samples and the University of Applied Sciences in
Saarbrücken, Germany, for funding.
Keywords: Carbon dioxide (CO2) adsorption · carbon dioxide
capture and storage (CCS) · adsorbent characterization · co-
adsorption · selective gas adsorption
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Submitted: February 5, 2016
Accepted: June 28, 2016
2841  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim