255

Adsorbent Materials for Carbon Dioxide

Yong Zou* and Alírio E. Rodrigues Laboratory of Separation & Reaction Engineering, Faculty of Engineer-
ing, University of Porto, Rua dos Bragas, 4050-123 Porto, Portugal.

(Received 2 January 2001; accepted 23 February 2001)

ABSTRACT: The adsorption of carbon dioxide on adsorbent materials at high

temperatures was critically reviewed. The present status of adsorbent materials for
CO2 including carbon-based adsorbents, zeolites and metal oxide sorbents at high
temperatures were discussed in detail. Research areas that may make a significant
impact on the future development of adsorbent materials were advanced.

INTRODUCTION

The removal and recovery of CO2 from hot gas streams is becoming increasingly significant in the
field of energy production. The combustion of fossil fuels such as coal or natural gas releases large
volumes of CO2 into the environment and has thereby become one of the most serious global
problems (Rao 1999; Herzog et al. 1997; Ruether 1999; Dave et al. 1999). This topic is also very
important in other areas such as natural gas treatment (Burchell et al. 1997), the production of
hydrogen gas (Hufton et al. 1999), high-temperature energy storage (Kyaw et al. 1997) and the
aerospace industry (Lila and Finn 1998).
A number of techniques may be employed for the separation of CO2 from fuel gas streams. The
large-scale separation of CO2 by absorption is a commercial operation used throughout the world.
Other techniques exist which could be considered for energy-related applications, such as cryo-
genic separation, membrane separation and adsorption processes including pressure swing adsorption
(PSA), vacuum swing adsorption (VSA) and temperature swing adsorption (TSA). Pressure swing
adsorption is well suited for the removal and recovery of CO2 from any hot fuel gas that contains it.
The PSA process can be operated at high temperatures (typically the temperature of a fuel gas
source) to remove most of the CO2, thereby overcoming the need to cool the fuel gas to ambient
temperature prior to the removal of CO2 (Gaffney et al. 1999).
Over the past two decades, active research efforts have been directed towards the separation of
CO2 by the PSA process and this technique has now been industrialized. However, to use the PSA
process for the removal and recovery of CO2 from hot fuel gas streams at high temperatures, the
first and most important issue is to find an appropriate adsorbent. Such an adsorbent must have (i)
high selectivity and adsorption capacity for CO2 at high temperatures; (ii) adequate adsorption/
desorption kinetics for CO2 under operating conditions; (iii) a stable adsorption capacity towards
CO2 after repeated sorption/desorption cycles; and (iv) adequate mechanical strength of adsorbent
particles after cyclic exposure to high-pressure streams (Dave et al. 1999; Hufton et al. 1997). For
these various reasons, a key requirement is the development of adsorbent materials for CO2 at high
temperatures, the experimental results from such studies being of particular interest both from a
theoretical and practical viewpoint.

*Author to whom all correspondence should be addressed. E-mail: zou_yong@yahoo.com.

256 Yong Zou and A.E. Rodriguez/Adsorption Science & Technology Vol. 19 No. 3 2001

The objective of this review is the collation of currently available literature on the adsorption of
CO2 on adsorbent materials at high temperature, focusing on data for the adsorption capacities of a
series of adsorbents, viz. carbon-based adsorbents, zeolites and metal oxides. Future directions for
research are suggested.

ADSORPTION BEHAVIOUR OF CARBON DIOXIDE

Although extensive research has been undertaken on the equilibrium behaviour of CO2 on adsorb-
ent materials under ambient conditions of temperature and pressure, directed mainly at the separation
and purification of gases, the elucidation of the pore structure and surface area of the adsorbents
and a discussion of the effect of the heat of adsorption on the gas uptake, few investigations have
been undertaken which are relevant to the adsorption of CO2 at high temperature. These are
reviewed below but the reader is strongly encouraged to refer to the original articles for further
information regarding the conditions employed.

Carbon-based adsorbents

It is well known that carbon-based adsorbents exhibit a high adsorption capacity towards CO2 at
ambient temperature and pressure (Kapoor and Yang 1989; Nakashima et al. 1995; Reich et al.
1980; Sircar et al. 1996; Zondlo and Sircar 1978; Yang 1987; Ruthven 1997). Several workers
(Kyaw et al. 1997; Song and Lee 1998; Yong and Rodrigues 2001) have studied the adsorption of
CO2 on various carbon-based adsorbents at high temperatures. The main physical properties of
these adsorbents are presented in Table 1, with the adsorption isotherms for CO2 on these adsorbents
at high temperatures being illustrated in Figures 1–3, respectively. Song and Lee (1998) and Yong
and Rodrigues (2001) also studied the effect of chemical modification on the adsorption capacities
for CO2 by several carbon-based adsorbents at high temperature. The corresponding results are
shown in Figures 4–6, respectively. Burchell et al. (1997) measured the adsorption capacity for
CO2 on carbon fibre composite molecular sieves (CFCMS) at high temperatures, CFCMS being
monolithic adsorbent carbon materials composed of petroleum pitch-derived carbon fibre and
phenolic resin-derived carbon binder. The adsorption isotherms for CO2 on two CFCMS samples
under various temperature conditions are depicted in Figure 7.

TABLE 1. Principal Physical Properties of Carbon-based

Adsorbents Studieda

Carbon-based Surface Total pore

adsorbent area (m2/g) volume (cm3/g)

Super activated carbon 3700 2.2

AC1 3000 1.6
AC1(Ca) 1500 0.97
AC2 1371 1.26
AC2(Ca) 630 0.62
CB 225 0.31
CB(Ca) 141 0.19
MSC-30 3370 1.8
G08H 2250 1.1
a
Data taken from Kyaw et al. (1997), Song and Lee (1998) and Yong
and Rodrigues (2001).
Adsorbent Materials for Carbon Dioxide 257

Figure 1. Adsorption/desorption isotherms for CO2 on super activated carbon: , adsorption at 30ºC; , desorption at
30ºC; , adsorption at 100ºC; , desorption at 100ºC; , adsorption at 200ºC; , desorption at 200ºC; , adsorption at
300ºC; , desorption at 300ºC [taken from Kyaw et al. (1997)].

Figure 2. Adsorption isotherms for CO2 on AC1, AC2 and CB: , AC1 at 25ºC; , AC1 at 100ºC; , AC1 at 250ºC; ,
AC2 at 25ºC; +, AC2 at 100ºC; , AC2 at 250ºC; , CB at 25ºC; ×, CB at 100ºC; , CB at 250ºC [taken from Song and Lee
(1998)].
258 Yong Zou and A.E. Rodriguez/Adsorption Science & Technology Vol. 19 No. 3 2001

Figure 3. Adsorption isotherms for CO2 on MSC-30 and G08H: , MSC-30 at 28ºC; ×, MSC-30 at 300ºC; , G08H at
28ºC; , G08H at 300ºC [taken from Yong and Rodrigues (2001)].

Figure 4. Adsorption isotherms for CO2 on AC1(Ca), AC2(Ca) and CB(Ca): , AC1(Ca) at 25ºC; , AC1(Ca) at 100ºC;
, AC1(Ca) at 250ºC; , AC2(Ca) at 25ºC; ×, AC2(Ca) at 100ºC; , AC2(Ca) at 250ºC; , CB(Ca) at 25ºC; +, CB(Ca) at
100ºC; e , CB(Ca) at 250ºC [taken from Song and Lee (1998)].
Adsorbent Materials for Carbon Dioxide 259

Figure 5. Adsorption isotherms for CO2 on MSC-30 before and after chemical modification at 28ºC: , unmodified MSC-
30; , MSC-30 No. 5, ×, MSC-30 No. 6; , MSC-30 No. 7; , MSC-30 No. 8; , MSC-30 No. 9 [taken from Yong and
Rodrigues (2001), where details regarding chemical modifications are given].

The results obtained indicate that the adsorption of CO2 on carbon-based adsorbents may be
summarized as follows:

1. Carbon-based adsorbents exhibit an adequate adsorption capacity towards CO2 at low pres-
sures and ambient temperature. However, the adsorption capacity is reduced with increasing
adsorption temperature.
2. The adsorption behaviour of CO2 on carbon-based adsorbents is completely reversible at all
temperatures.
3. CFCMS is the best carbon-based adsorbent material for CO2 adsorption, exhibiting a high
affinity for CO2 relative to conventional carbon-based adsorbents (Burchell et al. 1997).
4. The adsorption capacity towards CO2 on carbon-based adsorbents at high temperatures may
be enhanced considerably through chemical modification. Such modification introduces base
sites on the surface of porous carbon adsorbents, the affinity of the sites for CO2 being stronger
than that of pure porous carbon adsorbents but too weak to induce pure chemisorption towards
CO2.
5. The effect of the surface area of carbon-based adsorbents on their adsorption capacity towards
CO2 becomes less important as the adsorption temperature is increased. This indicates that the
adsorption mechanism of CO2 at high temperatures may not be purely via physical adsorption.
260 Yong Zou and A.E. Rodriguez/Adsorption Science & Technology Vol. 19 No. 3 2001

Figure 6. Adsorption isotherms for CO2 on MSC-30 before and after chemical modification at 300ºC: , unmodified
MSC-30; ×, MSC-30 No. 5; , MSC-30 No. 6; , MSC-30 No. 7; , MSC-30 No. 8; , MSC-30 No. 9 [taken from Yong
and Rodrigues (2001), where details regarding chemical modifications are given].

Figure 7. Adsorption isotherms for CO 2 on two CFCMS samples (specimen 21-2B, BET surface area 1152 m2/g; specimen
21-11, BET surface area 512 m2/g): , 21-2B at 30ºC; , 21-2B at 60ºC; , 21-2B at 100ºC; , 21-11 at 30ºC; , 21-11
at 60ºC; , 21-11 at 100ºC (taken from Burchall et al. (1997)].
Adsorbent Materials for Carbon Dioxide 261

Zeolites

Zeolites are very important adsorbents for CO2 gas separation and purification (Kyaw et al. 1997;
Yang 1987; Ruthven 1997; Ustinov and Klyuev 1999; Rouf and Eic 1998; Huesca et al, 1999;
Suzuki et al. 1997; Ghosal et al. 1999; Khelifa et al. 1999) because CO2 has a high linear quadrupole
moment which interacts with intra-zeolite cations (Khelifa et al. 1999). Unfortunately, few papers
have been published to date concerning the adsorption behaviour of CO2 on zeolites at high tem-
peratures. Kyaw et al. (1997) and Lila and Finn (1998) studied CO2 adsorption on Zeolite 13X and
ASRT 5A zeolite (manufactured by AlliedSignal Inc.), the results obtained being shown in Figures
8 and 9, respectively. From these figures it can be seen that (i) the adsorption capacity of zeolites
towards CO2 decreases greatly with increasing temperature, the shape of the adsorption isotherms
changing to a linear form from the typical Langmuirian form with increasing temperature and (ii)
ASRT 5A zeolites provide a better adsorbent for CO2 at high temperatures.

Metal oxide sorbents

Auroux and Gervasini (1990) have reported that, as an acidic gas, CO2 would be expected to adsorb
strongly at basic sites. A metal oxide with a low charge/radius ratio is more ionic in character and
should therefore present more basic sites. Carbon dioxide molecules can be adsorbed on the posi-
tive and negative surface sites of metal oxides, although when CO2 is adsorbed on particular types

Figure 8. Adsorption isotherms for CO 2 on Zeolite 13X: , at 30ºC; , at 100ºC; , at 200ºC; , at 300ºC [taken from
Kyaw et al. (1997)].
262 Yong Zou and A.E. Rodriguez/Adsorption Science & Technology Vol. 19 No. 3 2001

Figure 9. Adsorption isotherms for CO 2 on ASRT 5A zeolite: , at 25ºC; , at 175ºC; , at 250ºC [taken from Lila and
Finn (1998)].

Figure 10. Adsorption isotherms for CO2 on MgO (BET surface area 180 m2/g): , at 300ºC; , at 400ºC; , at 500ºC
[taken from Sircar et al. (1995)].
Adsorbent Materials for Carbon Dioxide 263

Figure 11. Adsorption isotherms for CO2 on basic alumina 98AA1149: , at 20ºC; , at 200ºC; , at 300ºC [taken from
Yong and Rodrigues (2000)].

of metal oxides [such as CaO (unidentate species) and MgO (bidentate species)], this adsorption
capacity for CO2 may be removed reversibly. Li (1997) has reported a new adsorbent made from
metal oxides which exhibits a high capacity towards CO2 and requiring a higher regeneration tem-
perature than other types of adsorbent (such as zeolites). All-alumina PSA systems have been
proposed (Jain 1993) whose advantages include lower adsorbent cost, a vessel design which does
not need screens to separate two different adsorbents and a system which has a high adsorption
capacity, resistance to steam, good mechanical properties and high thermal stability (Gaffney et al.
1999; Jain 1993; Golden et al. 1997, 1998; Slaugh and Willis 1984).
Sircar et al. (1995) reported on the adsorption of CO2 by MgO, the corresponding isotherms
measured at 300ºC, 400ºC and 500ºC being shown in Figure 10. Yong and Rodrigues (2000)
measured the adsorption capacity for CO2 on two types of basic alumina at 20ºC, 200ºC and 300ºC
and at pressures up to 1 bar. Their results are shown in Figures 11 and 12, respectively. Gaffney et
al. (1999) studied the adsorption capacity of CO2 on alumina before and after chemical modifica-
tion at 400ºC and 500 Torr. These results are listed in Table 2.
Studies of metal oxide sorbents for CO2 at high temperatures, such as alkali metal oxides (Na2O,
K2O), alkaline earth oxides (CaO, MgO) and alumina, have all been described in the literature. One
important consideration is that CO2 is an acidic gas, alkali metal oxides and alkaline earth oxides
are basic materials, whilst alumina is a weakly basic material. Hence, all these should exhibit a
good adsorption capacity for CO2 at high temperatures. This is particularly true for alumina modi-
fied by the introduction of alkali metal oxides such as Li2O, K2O or Na2O or alkaline earth metal
carbonates such as Li2CO3, K2CO3 or Na2CO3, when its reversible adsorption capacity towards CO2
264 Yong Zou and A.E. Rodriguez/Adsorption Science & Technology Vol. 19 No. 3 2001

TABLE 2. Chemical Modification Conditions for F-200 ALCOA Alumina and Reversible
Adsorption Capacity for CO2 Before and After Chemical Modification at 400ºC and 500 Torra

Run Adsorbents Solution pH Reversible adsorption

(wt%) capacity (mmol/g)

0 0 N.A. N.A. 0.06

1 4.73 CaO 0.5 M Ca(NO3)2 5.61 0.19
2 7.11 CaO 2.0 M Ca(NO3)2 5.40 0.22
3 11.08 CaO 5.0 M Ca(NO3)2 4.77 0.32
4 1.23 Na2O 0.5 M NaNO3 5.25 0.11
5 3.44 Na2O 2.0 M NaNO3 – 0.25
6 6.51 Na2O 5.0 M NaNO3 5.51 0.29
7 2.32 Na2CO3 0.5 M NaCH3CO2 7.58 0.11
8 7.49 Na2CO3 2.0 M NaCH3CO2 7.82 0.23
9 19.57 Na2CO3 5.0 M NaCH3CO2 – 0.28
10 1.77 K2O 0.5 M KNO3 6.23 0.13
11 5.79 K2O 2.0 M KNO3 6.70 0.23
12 12.17 K2O 5.0 M KNO3 7.20 0.19
13 3.84 SrO 0.5 M Sr(NO3)2 – 0.14
14 10.43 SrO 2.0 M Sr(NO3)2 – 0.21
15 14.43 SrO 4.0 M Sr(NO3)2 – 0.22
16 4.95 Li2O 5.0 M LiNO3 5.95 0.20
17 8.94 Li2O 10.0 M LiNO3 5.95 0.52
18 14.24 Li2CO 3 10.0 M LiCH3CO 2 – 0.29
19 5.39 K 2CO3 0.5 M K2CO3 – 0.21
20 23.25 K 2CO3 2.0 M K2CO3 – 0.31
21 37.55 K 2CO3 5.0 M K2CO3 – 0.34

a
Data taken from Gaffney et al. (1999).

at high temperatures is greatly enhanced (see data in Table 2). Figure 11 shows an uncommon
phenomenon relating to the adsorption of CO2 on basic alumina, i.e. Q20ºC > Q300ºC > Q200ºC, which is
very interesting and deserving of further comment.

FUTURE DIRECTIONS FOR RESEARCH

It is very important that the adsorption of CO2 on adsorbent materials at high temperatures should
be expanded to solve problems associated with energy and environmental systems and which pro-
vide good prospects for economic development and social effects. Unfortunately, insufficient
information on these research areas exists in the literature to date. This review has highlighted
chemically modified carbon-based adsorbents, zeolites and basic alumina, all of which can be used
directly as adsorbents for the removal and recovery of CO2 from power plant fuel gases. Further-
more, ASTR 5 zeolite and basic alumina all offer good prospects for future adsorption applications
at high temperatures.
Adsorbent Materials for Carbon Dioxide 265

Figure 12. Adsorption isotherms for CO2 on basic alumina 98AX316: , at 20ºC; , at 300ºC [taken from Yong and
Rodrigues (2000)].

Much more work is required for the further development of adsorbent materials for CO2 at high
temperatures. Firstly, the adsorption mechanism for CO2 on different types of adsorbent materials
needs to be explored at high temperature. Secondly, the preparation of traditional adsorbent mate-
rials using new technologies, such as nano-technology to produce nanocrystalline metal oxides
(Khaleel et al. 1999) and functionalized adsorbent materials by the supercritical process (Shin et
al. 2000), needs to be explored further. Finally, more emphasis needs to be placed on the develop-
ment of new adsorbent materials.

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