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Sorbent Technology

Shuguang Deng
Chemical Engineering Department, New Mexico State University,
Las Cruces, New Mexico, U.S.A.
INTRODUCTION
This article covers the fundamentals, status, and future
developments of sorbent materials and their appli-
cations in adsorptive separation and purication pro-
cesses. A sorbent is usually a solid substance that
adsorbs or absorbs another type of substance. It is
the sorbent that makes a sorption process a unique
and different separation and purication process from
others. With the rapid development in novel sorbent
materials and innovative cyclic adsorption processes,
sorption has become a key separation process in many
process industries including chemical, petrochemical,
environmental, pharmaceutical, and electronic gases.
A brief review of the fundamentals of adsorption
and the basic requirements for sorbent materials is
presented, followed with a summary of the status of
commercial sorbents and their applications. The focus
of this article is placed on recent advances in novel sor-
bent materials including oxide molecular sieves, solgel
derived xerogels and aerogels, metal organic frame-
work, hydrogen storage media, p-complexation and
composite sorbents, and high-temperature sorbents
for oxygen or carbon dioxide sorption. A concluding
section outlines the future research needs and opportu-
nities in sorbent technology development for new
energy and environmental applications.
ADSORPTION MECHANISMS AND
SORBENT MATERIALS
According to King, a mass separating agent is needed
to facilitate separation for many separation processes.
[1]
The mass separating agent for adsorption process is
the adsorbent, or the sorbent. Therefore, the character-
istic of the sorbent directly decides the performance of
any adsorptive separation or purication process. The
basic denitions of adsorption-related terminologies
are giveninthe following toclarify andstandardize these
widely used terms in this eld.
Adsorption: The adhesion of molecules (as of gases,
solutes, or liquids) to the surfaces of solid bodies
or liquids with which they are in contact.
Absorption: The absorbing of molecules (as of
gases, solutes, or liquids) into the solid bodies
or liquids with which they are in contact.
Sorption: Formation fromadsorption and absorption.
Adsorbent: A usually solid substance that adsorbs
another substance on its surface.
Sorbent: A usually solid substance that adsorbs and
absorbs another substance.
Adsorbate: Molecules (as of gases, solutes, or
liquids) that are adsorbed on adsorbent surfaces.
Microporous: Pore size smaller than 20 A

.
Mesoporous: Pore size between 20 and 500 A

.
Macroporous: Pore size larger than 500 A

.
Adsorptive separation can be achieved through one
of the following mechanisms. Understanding the
fundamentals of adsorptive separation mechanisms
will allow us to better design or modify sorbent
materials to achieve their best possible separation
performance.
[24]
Adsorption equilibrium effect is because of the dif-
ference in the thermodynamic equilibria for each adsor-
bateadsorbent interaction. The majority of adsorptive
separation and purication processes are based on equili-
brium effect. One example is to generate oxygen-enriched
air or relatively pure oxygen (95%) from air using a zeo-
lite molecular sieve 5A or 13X in either a pressure swing
adsorption (PSA) or a vacuum swing adsorption (VSA)
process. In this case, nitrogen is selectively adsorbed by
the zeolite adsorbent, and oxygen is collected from the
adsorption efuent stream.
Adsorption kinetics effect arises because of the
difference of rates at which different adsorbate mole-
cules travel into the internal structure of the adsorbent.
There are only a few commercial successes using
adsorption kinetic difference to achieve adsorptive
separation of gases. The typical example is separation
of nitrogen from air using a carbon molecular sieve
(CMS). The CMS adsorbent has a similar adsorption
equilibrium capacity for both nitrogen and oxygen,
but the diffusivity of oxygen in CMS is at least 30 times
larger than that of nitrogen in CMS.
[5]
High-purity
Encyclopedia of Chemical Processing DOI: 10.1081/E-ECHP-120007963
Copyright # 2006 by Taylor & Francis. All rights reserved. 2825
nitrogen can be recovered from the adsorption efuent
stream in a PSA process because oxygen moves much
faster than nitrogen into the micropores of CMS
adsorbent. However, the cycle time of this CMS-based
PSA process is much shorter than that of a typical PSA
process based on adsorption equilibrium effect. This is
because there will be no separation if both nitrogen
and oxygen are allowed to reach adsorption equilib-
rium with the CMS adsorbent.
Molecular sieving effect, also called steric effect, is
derived from the molecular sieving properties of some
adsorbents with a microporous structure. In this case,
the pore openings of the adsorbent structure are small
enough to exclude large adsorbate molecules from
penetrating the micropores of the adsorbent. This is
the extreme case of the kinetic effect. There are several
commercial applications based on this mechanism in
adsorptive separation processes. One typical example
is separating normal parafn from iso-parafn and
aromatics in an adsorption process using zeolite 5A
as an adsorbent. n-Parafn, with a long straight chain,
has a smaller effective diameter than the well-dened
aperture of zeolite 5A. Therefore it adsorbs in the
micropores of the adsorbent during the adsorption
step, and is recovered from the adsorbed phase in the
desorption step. A representative process for n-parafn
separation from naphtha and kerosene is UOPs
Molex process that employs a simulated moving bed
with binderless zeolite 5A as an adsorbent and light
parafn as a desorbent.
[6]
We can dene separation factor and selectivity as
the ability of an adsorbent to separate molecule A
from molecule B as:
[7]
Separation factor : a
AB
=
X
A
=Y
A
X
B
=Y
B
(1)
Here X
A
, Y
A
are strictly equilibrium mole fractions for
component A in the adsorbed phase and adsorbate
(uid) phase, respectively; as are X
B
, Y
B
for component
B. For equilibrium-based adsorptive separation process,
the adsorbent selectivity is the same as the separation fac-
tor as dened in Eq. (1). Apparently, this denition is not
applicable to other processes based on kinetic and steric
effects. In a kinetically controlled adsorption process, the
adsorbent selectivity depends on both equilibrium and
kinetic effects. A simplied denition for adsorbent
separation factor is given by Ruthven et al.:
[8]
S
AB
=
K
A
K
B

D
A
D
B
r
(2)
where S
AB
is the adsorbent selectivity, K is the adsorption
equilibrium constant or isotherm slope, and D is the
effective diffusivity. Although the above equation is
strictly valid under the assumptions that components A
and B have independent linear adsorption isotherms
and independent diffusion process, it provides a good
estimate of adsorbent selectivity for kinetically controlled
processes.
Theoretically speaking, selectivity for adsorbents
with a molecular sieving effect should be innitely
large because the larger molecules are excluded from
getting into the adsorbent micropores. In reality, the
adsorbent selectivity for steric effect is somewhat
reduced by combining with the equilibrium effect from
adsorption on the surface of large pores. So adsorption
processes based on molecular sieving are usually con-
sidered as adsorption equilibrium effect.
Another very important adsorbent property affect-
ing the adsorption process is the adsorption capacity
because it determines the size of an adsorbent vessel,
the amount of adsorbents required, and the related
capital and operating costs. The requirements for
commercial sorbents are discussed briey as follows.
Characteristics of Sorbent Materials
Commercial sorbents used in cyclic adsorption pro-
cesses should ideally meet the following requirements:
v Large selectivity derived from equilibrium, kinetic,
or steric effect;
v Large adsorption capacity;
v Fast adsorption kinetics;
v Easily regenerable;
v Good mechanical strength;
v Low cost.
The above adsorbent performance requirements can
simply transfer to adsorbent characteristic require-
ments as follows:
v Large internal pore volume;
v Large internal surface area;
v Controlled surface properties through selected
functional groups;
v Controlled pore size distribution, preferably in
micropore range;
v Weak interactions between adsorbate and adsorbent
(mostly on physical sorbents);
v Inorganic or ceramic materials to enhance chemical
and mechanical stability;
v Low-cost raw materials.
These basic requirements are usually proposed for
adsorbents used in cyclic adsorption processes that
are based on physical adsorption. There is an increas-
ing demand for strong chemical adsorbents used in
2826 Sorbent Technology
purication processes to remove trace contaminants
from main stream uids such as the removal of very
toxic contaminants from electronic process gas streams,
and the removal of toxic, or radioactive species from
contaminated water. In these cases, the sorbents are
used as getter materials; no regeneration is needed,
and instead, the spent sorbent materials are disposed
of in designated areas regulated by government envi-
ronmental policies.
COMMERCIAL SORBENTS AND
APPLICATIONS
An excellent review and detailed coverage on commer-
cial adsorbents and new adsorbent materials has been
presented by Yang in his newly published monograph
on adsorbents.
[2]
A very brief overview of existing com-
mercial adsorbents is given here. Commercial sorbents
that have been used in large-scale adsorptive separa-
tionandpuricationprocesses include activated carbon,
zeolites, activated alumina, silica gel, and polymeric
adsorbents. Although the worldwide sales of sorbent
materials are relatively small as compared with other
chemical commodities, sorbents and adsorption pro-
cesses play a very important role in many process indus-
tries. The estimated worldwide sales of these sorbents
are as follows:
[2]
v Activated carbon: $1 billion
v Zeolite: $1.07 billion
v Activated alumina: $63 million
v Silica gel: $71 million
v Polymeric adsorbents: $50 million
Activated Carbon
Activated carbons are unique and versatile adsorbents
because of their large surface area, microporous and
mesoporous structure, universal adsorption effect,
high adsorption capacity for many nonpolar molecules
including organic molecules, and high degree of sur-
face reactivity. They are used widely in industrial
applications that include decolorizing sugar solutions,
personnel protection, solvent recovery, volatile organic
compound removal from air and water, water treat-
ment, hydrogen and synthesis gas separation, and
natural gas storage.
[4,9,10]
Activated carbons are
produced in two main steps: carbonization of the
carbonaceous raw materials at temperatures below
800

C in the absence of oxygen, and activation of


the carbonized products.
[10]
The properties of activated
carbon depend largely on the nature of the raw materi-
als, the activating agents and activation conditions.
For gas-phase applications, activated carbons are
usually made in pellets with mostly micropores; while
for liquid-phase applications, activated carbon is pro-
duced in powder form with relatively large mesopores
to enhance mass transfer rate in the carbons.
Fig. 1 compares the pore size distributions of major
commercial adsorbents discussed in this section. Acti-
vated carbons have a broad pore size distribution like
activated alumina and silica gel. Although activated
carbon is thought to be hydrophobic, it does adsorb
Activated alumina
Zeolite 5A
MSC
MSC
60
50
40
30
20
10
0
2 5 10 20 50
Pore diameter,
C
u
m
u
l
a
t
i
v
e

p
o
r
e

v
o
l
u
m
e
,

c
m
3
/
1
0
0

g
m
Activated carbon
Silica gel
Fig. 1 Pore size distributions for activated
carbon, silica gel, activated alumina, two mole-
cular sieve carbons (MSCs), and zeolite 5A.
(From Ref.
[3]
.)
Sorbent Technology 2827
quite signicant amount of water (>30 wt%) when
relative humidity is higher than 50%. An example iso-
therm of water on activated carbon, along with water
isotherms on other commercial adsorbents, is plotted
in Fig. 2. The change from hydrophobic to hydro-
philic on the activated carbon surface is attributed to
the initial adsorbed water lm on the carbon surface.
This occurs because when the carbon surface is fully
covered with a layer of water molecules, the adsorbed
water molecules exhibit strong afnity to other polar
molecules including water. Carbon molecular sieve
(CMS) is a specially made carbonaceous material with
very narrow pore size distribution (49 A

). The major
application of CMS is in the generation of high-purity
nitrogen from air in a PSA process. The representative
physical properties of commercial adsorbents and their
major applications are summarized in Tables 1 and 2,
respectively.
Zeolites
Zeolites are porous crystalline aluminosilicates that are
made of assemblies of SiO
4
and AlO
4
tetrahedra joined
together through shared oxygen atoms. The general
chemical formula for zeolites is:
M
x=n
[(AlO
2
)
x
(SiO
2
)
y
[zH
2
O (3)
where x and y are integers with y=x (Si=Al ratio) equal
or larger than 1; n is the valance of cation M, and z is
the number of water molecules in each unit cell. The
tetrahedra can be arranged in many different ways to
form different crystalline structures. Some zeolites
exist as minerals in nature, but all commercially
important zeolites are synthetic. Zeolites are unique
adsorbents owing to their special surface chemistries
and crystalline pore structures. It should be pointed
out that probably only 10% of $1 billion worldwide
sales of zeolite is used as adsorbents; the majority of
commercial zeolites are used as detergent additives
(zeolite 4A), animal food additives (zeolite 4A), ion
exchange, and catalyst supports. Among all commer-
cial sorbents zeolites are probably the most extensively
investigated and documented. Many excellent mono-
graphs and review articles are available.
[2,1113]
Please
refer to Tables 1 and 2 for properties and major appli-
cations of zeolites.
Activated Alumina
Activated alumina is a porous high-surface area form
of aluminum oxide with the formula of Al
2
O
3
nH
2
O.
Commercially, it is prepared either from thermal
dehydration of aluminum trihydrate, Al(OH)
3
, or
directly from bauxite (Al
2
O
3
3H
2
O), as a by-product
of the Bayer process for alumina extraction from baux-
ite. Its surface is more polar than that of silica gel and,
reecting the amphoteric nature of aluminum, has
both acidic and basic characteristics. Surface areas
are in the range 250350 m
2
=g depending on the activa-
tion temperature and the source of raw materials.
Because activated alumina has a higher capacity for
water than silica gel at elevated temperatures it is used
mainly as a desiccant for warm gases including air, but
in many commercial applications it has now been
replaced by zeolitic materials in a thermal swing
40
30
20
10
0
0 20 40 60 80 100
Relative humidity, %
A
d
s
o
r
p
t
i
o
n
,

k
g

H
2
O
/
1
0
0

k
g

a
d
s
o
r
b
e
n
t
E
D
C
B
A
Fig. 2 Equilibrium sorption of water vapor from
atmospheric air at 25

C on: (A) alumina (granular),


(B) alumina (spherical), (C) silica gel, (D) 5A
zeolite, and (E) activated carbon. The vapor pressure
at 100% relative humidity is 23.6 torr. (From Ref.
[3]
.)
2828 Sorbent Technology
adsorption (TSA) process. However, activated alumina
has a low adsorption heat for water and other polar
molecules as compared with zeolite; it is possible to
regenerate activated alumina under PSA conditions.
Activated alumina also demonstrates moderate
adsorption afnity for carbon dioxide, which makes
it a suitable sorbent for removing water and carbon
dioxide from air in a PSA process. These adsorption
properties of activated alumina have been explored
extensively for air purication applications by indus-
trial gas companies.
[1417]
This is a perfect example to
demonstrate the importance of sorbent regenerability
over sorption capacity and selectivity in pressure swing
adsorption processes. Activated alumina is also an
excellent catalyst support. More applications and
representative properties of activated alumina are
listed in Tables 1 and 2.
Silica Gels
Silica gel is the most widely used desiccant because of
its large adsorption capacity for water (40 wt%), as
shown in Fig. 2, and easy for regeneration (~150

C,
compared with 350

C for zeolites). Silica is a partially


dehydrated polymeric form of colloidal silicic acid with
the formula of SiO
2
nH
2
O. Its water content, which is
typically about 5 wt%, is presented in the chemically
bonded hydroxyl groups. Silica is an amorphous mate-
rial comprising spherical particles of 20200 A

in size,
which aggregate to form the sorbent with pore sizes
in the range of 60250 A

and surface areas of 100


850 m
2
=g, depending on gel density. Its surface has
mainly SiOH and SiOSi polar groups; this is why
it can be used to adsorb water, alcohols, phenols,
amines, etc. by hydrogen bonding mechanisms. Other
commercial applications include the separation of aro-
matics from parafns, the chromatographic separation
of organic molecules, and modied silica in chromato-
graphy columns.
[2,1820]
Polymeric Adsorbents
A wide range of synthetic, nonionic polymers are avail-
able for use as sorbents, ion-exchange resins, and par-
ticularly for analytical chromatography applications.
Commercially available resins in bead form (typically
0.5 mm in diameter) are based usually on copolymers
of styrene=divinyl benzene (DVB) and acrylic acid
esters=divinyl benzene, and have a wide range of sur-
face polarities, porosities, and macropore sizes. The
porosities can be built through emulsion polymeriza-
tion of relevant monomers in the presence of a solvent
that dissolves the monomers and serves as a poor swell-
ing agent for the polymer. This creates a polymer
matrix with surface areas ranging up to 1100m
2
=g.
[2,4]
The major application of polymeric adsorbents is in
water treatment. The macroporous polymeric resins can
be modied by attaching different functional groups to
mimic activated carbon, and to replace activated carbons
for certain specic applications in food and pharmaceu-
tical industries where color contamination by the black
carbons of the nal products is a major concern.
NEW DEVELOPMENTS IN SORBENT
MATERIALS AND APPLICATIONS
The past two decades have witnessed major advances
in new nanostructured sorbent materials including
Table 1 Representative physical properties of commercial adsorbents
Adsorbent Nature
Specic surface
area (m
2
/g)
Pore
diameter (A

) Porosity
Particle
density (g/cm
3
)
Activated carbon Hydrophobic amorphous
Small pore 4001200 1025 0.40.6 0.50.9
Large pore 200600 >30 ~0.5 0.60.8
Zeolite Hydrophilic=hydrophobic
crystalline
600700 310 0.6 1.0
Activated alumina Hydrophilic crystalline=x-ray
amorphous
200350 1075 0.5 1.25
Silica gel Hydrophilic=hydrophobic
amorphous
Small pore 750850 2226 0.47 1.09
Large pore 300350 100150 0.71 1.62
Polymeric adsorbent Hydrophilic=hydrophobic 4501100 2590 0.5 1.25
Carbon molecular sieve Hydrophilic ~400 39 0.5 1.0
Sorbent Technology 2829
Table 2 Selected applications of commercial sorbents
Adsorbent Applications (the rst molecule is the product)
Activated carbon Hydrogen separation from syngas and hydrogenation processes
Ethylene from methane and hydrogen
Vinyl chloride monomer (VCM) from air
Removal of odors from gases
Recovery of solvent vapors
Removal of SO
x
, and NO
x
Purication of helium
Clean-up of nuclear off-gases
Decolorizing of syrups, sugars, and molasses
Water purication, including removal of phenol, halogenated compounds,
pesticides, caprolactam, chlorine
Carbon molecular sieve Nitrogen separation from air
Zeolite Oxygen from air
Drying of gases
Removing water from azeotropes
Sweetening sour gases and liquids
Purication of hydrogen
Separation of ammonia and hydrogen
Recovery of carbon dioxide
Separation of oxygen and argon
Removal of acetylene, propane, and butane from air
Separation of xylenes and ethyl benzene
Separation of normal from branched parafns
Separation of olens and aromatics from parafns
Recovery of carbon monoxide from methane and hydrogen
Purication of nuclear off-gases
Separation of cresols
Drying of refrigerants and organic liquids
Separation of solvent systems
Pollution control, including removal of Hg, NO
x
, and SO
x
from gases
Recovery of fructose from corn syrup
Activated alumina Drying of gases, organic solvents, transformer oils
Removal of HCl from hydrogen
Removal of uorine and boronuorine compounds in alkylation processes
Removing of water and carbon dioxide from air in a PSA process
Silica gel Drying of gases, refrigerants, organic solvents, transformer oils
Desiccant in packings and double glazing
Dew point control of natural gas
Polymeric adsorbents Water purication, including removal of phenol, chlorophenols, ketones, alcohols,
aromatics, aniline, indene, polynuclear aromatics, nitro- and chlor-aromatics,
polychlorinated biphenyls (PCBs), pesticides, antibiotics, detergents, emulsiers,
wetting agents, kraftmill efuents, dyestuffs, and radionuclides
Recovery and purication of steroids, amino acids and polypeptides
Separation of fatty acids from water and toluene
Separation of aromatics from aliphatics
Separation of hydroquinone from monomers
Recovery of proteins and enzymes
Removal of colors from syrups
Removal of organics from hydrogen peroxide
Clays (acid treated and pillared) Removal of organic pigments
Rening of mineral oils
Removal of PCBs
(From Ref.
[4]
.)
2830 Sorbent Technology
mesoporous molecular sieves, solgel-derived metal
oxide xerogels and aerogels, metal organic framework,
p-complexation and composite adsorbents, new carbo-
naceous materials (carbon nanotubes, carbon bers,
superactivated carbons), high-temperature ceramic sor-
bents, and strong chemical sorbent materials. Although
these new sorbent materials have demonstrated promis-
ing sorption properties for many existing and new
applications, systematic studies on synthesis methods
and characterization of these new materials are necessary
to fully explore and realize their potential as commercial
sorbents. The review that follows aims at attracting more
research efforts to develop novel sorbent materials to
meet the increasing needs of new energy, environmental,
and other emerging technologies.
Oxide Molecular Sieves
Microporous and mesoporous oxide molecular sieves
that have the characteristics of large internal surface
area and pore volume are ideal candidates for use as
sorbent materials and catalyst supports of many hetero-
geneous catalysts. Oxide molecular sieves are generally
synthesized by hydrothermal methods that involve both
chemical and physical transformations within an
amorphous oxide gel, often in the presence of a tem-
plate species. The gel eventually converts to a crystal-
line material in which the template species and=or
solvent molecules are guests within the channels and
cages of an oxide host framework. A porous material
is obtained upon removal of the guest molecules from
the oxide framework. By manipulating the synthesis
parameters, including starting precursors, synthesis
temperature, pH, template species, drying, and calcina-
tion conditions, it is possible to tailor the pore size and
shape of these porous materials for different applica-
tions. However, tailoring of porosity in oxide molecu-
lar sieves in terms of a priori structural design is
extremely difcult because of the inherent complexity
of the synthetic procedures employed.
[21]
Recent advances and applications of oxide molecu-
lar sieves have been summarized in several review arti-
cles.
[2,2123]
Microporous zeolite materials synthesized
with molecular templates and their applications in
hostguest chemistry have been covered elsewhere.
[13]
A new class of silicate=aluminosilicate mesoporous
molecular sieves designated as M41S was discovered
in the former Mobil research laboratory by extending
the concept of zeolite templating with small organic
molecules to large long-chain surfactant molecules.
[24]
A representative member of this family is MCM-41,
which has a honeycomb-shaped hexagonal arrange-
ment of uniform mesopores in the range of 15100 A

,
specic surface area of 1040 m
2
=g, pore volume above
0.7 cm
3
=g, and signicantly high sorption capacity for
hydrocarbons (49wt% for n-hexane at 40torr and
21

C, and 67 wt% for benzene at 50torr and 25

C).
[24]
Other signicant members of the M41S family include
MCM-48 (cubic phase), MCM-50 (stabilized lamellar
phase), SBA-1 (cubic phase), and SBA-2 (cubic
phase).
[21]
Although M41S type mesoporous oxide molecular
sieves have exhibited unique properties of large surface
area and exceptionally large pore volume (>0.7 cm
3
=g),
their large pore volume may not be attractive for gas
sorption because the adsorbateadsorbent interactions
are not enhanced inside the internal pores of these mate-
rials.
[2]
Therefore, M14S type mesoporous oxide molecu-
lar sieves without surface modication are rarely used as
sorbents. Signicant research efforts were devoted to
surface modication of M41S materials for different
applications.
[2]
An amine-grafted MCM-48 sorbent,
synthesized from tetraethoxysilane (TEOS), has been
shown to have a surface area of 1389 m
2
=g, a silanol
number of 8, higher thermal stability than MCM-41,
high adsorption selectivity, and high capacity for both
carbon dioxide and hydrogen sulde.
[25]
SolGel-Derived Xerogels and Aerogels
Solgel processing refers to the fabrication process of
ceramic materials by preparation of a sol, gelation
of the sol, and removal of the solvent.
[26]
Sols are
dispersions of colloidal particles in a liquid solvent,
and a gel is a solid matrix encapsulating a solvent. In
a solgel process, the sol can be formed from a solution
of colloidal powders or hydrolysis and condensation of
alkoxides or salt precursors. In the latter approach,
which is much more popular, primary particles of uni-
form size are formed and grow in a sol and connect to
each other to form aggregates during gelation. These
aggregates forming the network of the gel are broken
apart into the primary particles in the drying step.
Upon calcination and sintering, these primary particles
are bound together strongly to form a very rigid solid
network, and large interparticle space with uniform
nanoscale pores is formed. Xerogels are obtained by
drying the gels through evaporation at normal condi-
tions under which capillary pressure causes shrinkage
of the gel network, while areogels are produced by
drying the wet gels at supercritical conditions where
the liquidvapor interface is eliminated, and relatively
little shrinkage of the gel network occurs. Xerogels
and aerogels typically have relatively large surface
area, high porosity, and internal pore volume, and
are ideal candidates as sorbent and catalyst support
materials for many applications. The solgel process
offers a very high exibility to tailor xerogels and
areogels for specic applications by manipulating the
synthesis conditions.
Sorbent Technology 2831
Silica xerogel is probably the most studied and
documented porous material in the solgel sys-
tem.
[27,28]
Although silica has several crystalline forms,
only amorphous silica gel is used as a desiccant (sor-
bent). A microporous silica that was synthesized with
TEOS as precursor has an average pore size of 6.4 A

,
pore volume of 0.24 cm
3
=g, and BrunauerEmmett
Teller (BET) surface area of 588 m
2
=g.
[29]
However,
this material lost about 90% of its microporosity when
it was heated at 600

C for 30 hr. By doping with 1.5%


of alumina, the thermal stability of this microporous
silica was signicantly improved.
[29]
Crystalline sorbent materials including g-alumina,
zirconia, and titania were also synthesized using the
solgel process in Lins group;
[29]
the representative
pore size distribution and pore texture data of xerogels
of g-alumina, zirconia, and titania are summarized in
Fig. 3 and Table 3, respectively. As shown in Fig. 3,
the pore size distributions of these materials are rather
narrow, with an average pore diameter of about 3 nm.
Such narrow size distribution and nanoscale average
pore size are determined by the primary crystallite
particles. The particles of the solgel-derived alumina,
titania, and zirconia, owing to the Ostwald ripening
mechanism,
[26]
are usually of nanoscale size; the uni-
form particle size distributions of g-alumina crystallites
are plate-shaped with size ranging from about 5 to
20 nm. The solgel-derived g-alumina consists of
such plate-shaped crystallite particles, which give
rise to a relatively large surface area. Crystallites of
tetragonal zirconia and rutile are of more spherical
shape, with a crystallite size of about 15 and 11 nm,
respectively.
[29]
One of the outstanding characteristics of sol
gel-derived g-alumina xerogel is its excellent mechanical
properties. Preparation of porous g-alumina granules
with good mechanical properties and desirable pore
structure is of great importance in the development
of novel catalysts and sorbents for various applica-
tions. The superior mechanical properties can be
derived from the unique microstructure of the granule,
which is dened by compacting small g-alumina crys-
tallite particles bound together by the bridges of the
same material formed through coarsening or sintering.
Such nanostructured g-alumina can be prepared by
combining the Yoldas process and the oil-drop
method.
[3034]
Table 4 compares the crush strength
and attrition rate of solgel-derived g-alumina xerogel
granules with those of several commercial sorbents. It
is clearly shown in Table 4 that the solgel-derived g-
alumina xerogel granules have excellent mechanical
properties as compared with commercial sorbents.
The excellent mechanical properties makes sol
gel-derived alumina granules very suitable for uidized
bed and other applications including separation and
purication process for food and healthcare products
that have very strict regulations on sorbent power
contamination.
Solgel-derived xeorgel sorbents have been inves-
tigated for gas separation, purication, and envi-
ronmental applications. g-Alumina sorbents and
membranes doped with cuprous and silver ions have
been studied for selective adsorption or transfer of
CO and ethylene through p-complexation.
[3537]
Signicant efforts have been devoted to explore the
possibility of using CuO-doped g-alumina sorbents
for removing SO
x
and NO
x
from ue gas.
[3844]
The solgel-derived CuO=g-alumina sorbents have
demonstrated high sorption capacity, high reactivity
for SO
2
, and high thermal and chemical stability.
The excellent mechanical and desulfurization pro-
perties of solgel-derived sorbents make them ideal
sorbent candidates for uidized bed desulfurization
process. However, the relatively high cost of sol
gel-derived alumina xerogels may prevent them from
being used in many large-scale adsorption processes.
Research efforts are needed to look for less expen-
sive precursors to replace alkaoxides used in the
Yoldas process.
Titania
Zirconia
-Alumina
1 10
2 3 4 5 6 7 8 9 2 3
Pore Diameter (nm)
d
V
/
d
l
o
g
(
D
)
1.6
1.2
0.8
0.4
0.0
Fig. 3 Pore size distribution of solgel-derived alumina,
zirconia, and titania. (From Ref.
[29]
.)
Table 3 Pore texture solgel-derived alumina, zirconia, and
titania (calcined at 450

C for 3 hr)
Xerogel
Average
pore size (A

)
Pore
volume (cm
3
/g)
BET surface
area (m
2
/g)
g-Al
2
O
3
28 0.33 373
ZrO
2
38 0.11 57
TiO
2
34 0.21 147
2832 Sorbent Technology
Solgel-derived metal oxide xerogels were also
investigated for water adsorption because most of
these metal oxides are good sorbent candidates for
desiccant applications.
[4547]
Signicant research works
have been carried out to study the adsorption=
complexation properties of heavy metal ions including
mercury, Cu(II), CdCl
2
, etc. in waste water on different
solgel-derived xerogels.
[4854]
The solgel-derived
xerogels seem to be promising sorbent candidates for
waste water treatment. Modied xerogel sorbents also
showed promising adsorption properties for removing
acid gas CO
2
and H
2
S from natural gas, or as CO
2
storage sorbents.
[25,55]
There are several advantages
of using xerogels for enzyme immobilization, including
the opportunity to produce them in dened shapes or
thin lms and the ability to manipulate their physical
characteristics including porosity, hydrophobicity,
and optical properties.
[56,57]
Metal oxide composite
xerogels can also adsorb methyl orange.
[58]
There are
also reports on microporous and mesoporous carbon
xerogels for gas separation and purication.
[59,60]
As compared with xerogels, aerogels have larger
surface area, larger pore volume, and higher poros-
ity.
[6164]
Alumina aerogels with a specic surface area
as high as 1000 m
2
=g, and a pore volume as high as
17.3cm
3
=g have been synthesized by supercritical carbon
dioxide drying, but a very limited information on their
adsorption properties was found.
[61,62]
A super water
adsorbent consisting of 1730% of CaCl
2
doped on
SiO
2
aerogel showed an effective reversible adsorption
capacity of 100 wt%; the adsorption capacity of hydro-
philic silica aerogels can be fully recovered after regen-
eration.
[6466]
CaO- and MgO-modied SiO
2
aerogel
sorbents can be used to capture pollution gases includ-
ing CO
2
, SO
2
, CO, and NO
x
emitted from power plants
based on fossil fuels.
[67]
Several studies reported the use
of aerogels as destructive sorbents for toxic gases and
radionuclide removal from contaminated environ-
ments.
[64,6870]
Carbon aerogels can also be made from
carbon materials under supercritical carbon dioxide
drying conditions; these carbon aerogels were studied
for removing uranium and other inorganic ions from
contaminated water.
[7173]
Aerogels are special sorbent
candidates with excellent pore texture, which may play a
major role in environmental protection. However, more
studies on their synthesis and adsorption properties are
needed.
Metal Organic Framework (MOF)
Recently, Yaghis group reported a novel crystalline
nanoporous material that consists of metal atoms
occupying the vertices of a lattice, with the lattice size,
porosity, and chemical environment dened by the
organic linker molecules that bind the metal atoms into
a robust periodic structure.
[7476]
These so-called metal
organic framework (MOF) materials have been
demonstrated to have an exceptionally high specic
surface area of 4526 m
2
=g, and nd use as adsorbents
for methane and as hydrogen storage materials.
[74,7780]
A reticular synthesis method was developed to realize
the bottom-up synthesis through top-down design
logic by using inorganic, metal organic, and organic
molecules to build frameworks and large molecules.
[81]
Well-dened molecular building blocks that will
maintain their structural integrity throughout the
construction process were used to build the MOF
molecules. It allows remarkable control over composi-
tion and structure of the material formed and employs
the full range of the molecular synthetic methods and
compounds in the preparation of this new type of
porous sorbent materials. The ability to molecularly
engineer the lattice size, chemical environment, and
possibly structure by careful choice of the metal cen-
ters and organic linkers offers the opportunity for the
development of new types of sorbents that could
potentially meet the Department of Energy (DOE)
target for hydrogen storage and that can be used
for other applications in separation and purication.
It is reported that metal organic framework-5
(MOF-5) of composition Zn
4
O(BDC)
3
(BDC: 1,4-
benzenedicarboxylate) with a cubic three-dimensional
extended porous structure and octahedral ZnOC
clusters with benzene links can adsorb hydrogen up
to 4.5 wt% at 78 K, and 1.0 wt% at room temperature
and pressure of 20 bar.
[74,79]
It is identied by inelastic
neutron scattering spectroscopy of the rotational
Table 4 Comparison of crush strength and attrition rate of solgel-derived g-alumina xerogel granules with commercial sorbents
Sorbents Granular shape
Granular size
(mm)
Average crush strength
(N/granule)
Attrition rate
(wt%/hr)
Solgel alumina Spherical 2.02.5 160 0.033
Solgel alumina Spherical 2.62.8 190
Alcoa alumina (LD-350) Spherical 4.04.6 42 0.177
UOP silicalite Cylindrical 1.41.6 16 0.575
Degussa DAY zeolite Cylindrical 3.53.5 40 0.073
Sorbent Technology 2833
transitions of the adsorbed hydrogen molecules that
zinc and the BDC linker in MOF-5 are the two hydro-
gen binding sites responsible for hydrogen adsorption
on this material. Higher hydrogen adsorption capacity
at ambient temperature and 10 bar were observed on
similar isoreticular metal organic framework-6 and -8
(IRMOF-6 and -8) having cyclobutylbenzene and
naphthalene linkers.
[79]
A different microporous MOF
sorbent [microporous metal coordination materials
(MMOM)] was reported to have hydrogen sorption
capacities (~1.0wt% at room temperature and 48bar)
similar to those of the best single-wall carbon nano-
tubes.
[80]
The adsorbed hydrogen can be released when
the gas pressure is reduced.
MOF sorbents have also been investigated for
methane adsorption.
[77]
The reported methane storage
capacity of MOF-6 is 155 cm
3
(STP)=cm
3
at 298 K and
36 atm, which is signicantly higher than that of zeolite
5A (87 cm
3
(STP)=cm
3
) and other coordination
framework (213 cm
3
(STP)=cm
3
).
[77]
Adsorption and
desorption of carbon dioxide, nitrogen, and argon on
a microporous manganese-based MOF sorbent has
been reported.
[78]
Another interesting porous MOF
sorbent, Cu-BTC (polymeric copper(II) benzene-1,3,5-
tricarboxylate) with molecular sieve character, was stu-
died for its sorption properties of various adsorbates
including nitrogen, oxygen, carbon monoxide, carbon
dioxide, nitrous oxide, methane, ethylene, ethane, and
n-dodecane.
[82,83]
A detailed investigation of sorption
thermodynamics was performed for carbon dioxide
by a sorption-isosteric method. It was demonstrated
that Cu-BTC sorbent can be used for the separation
of carbon dioxidecarbon monoxide, carbon dioxide
methane, and ethyleneethane mixtures. In addition,
this sorbent can also be used to remove carbon
dioxide, nitrous oxide, high molecular weight hydro-
carbons, and moisture from ambient air before
cryogenic separation to produce oxygen and nitrogen.
[82]
Hydrogen Storage Media
The development of hydrogen-fueled transportation
system and portable electronics will demand new mate-
rials that can store large amounts of hydrogen at ambi-
ent temperature and relatively low pressures with small
volume, light weight, fast charging and discharging
time, cyclic stability, and low cost. Table 5 summarizes
the targets for hydrogen storage system for automotive
applications set by USDOE. The hydrogen storage
capacities are calculated as both weight and volume
percentage of the storage system.
[84]
To achieve these
goals, the hydrogen storage media (sorbent) should
have a high reversible hydrogen sorption capacity,
low weight and high packing density as well as fast
sorption=desorption kinetics, and low cost.
Hydrogen can be stored both physically and chemi-
cally in a conned vessel with or without the assistance
of a storage media. The most commonly used methods
for hydrogen storage are: gaseous and liquid hydrogen
storage, solid state storage in complex metal hydrides,
chemical storage materials, and in nanostructured
materials.
[2,85]
The representative hydrogen storage
capacities, hydrogen storage, and release conditions
in various materials are summarized in Table 6.
Carbon nanotubes are probably the most investi-
gated and documented hydrogen storage sorbent mate-
rials. Several excellent reviews on carbon nanotubes
for hydrogen storage are available.
[2,86]
As shown in
Table 6, the hydrogen storage capacities on representa-
tive carbon nanotubes are below 6 wt%, the most
referred DOE target for 2010.
[84,87,88]
The following
concerns about carbon nanotubes as hydrogen storage
materials have driven research in this area to other
directions:
[85]
1. Difcult to meet the DOEs long-term target
(9 wt%);
2. Mechanisms for hydrogen sorption in carbon
nanotubes are not well understood;
3. Part of the adsorbed hydrogen can only be
recovered at high temperatures;
4. Preparation and purication of carbon nano-
tubes involve complicated and expensive pro-
cesses, which leads to high cost of carbon
nanotubes;
5. Hydrogen storage capacity is quite sensitive to
sorbent preparation conditions;
6. Mixed results on hydrogen adsorption capacity
have been reported.
Table 5 USDOE FreedomCAR hydrogen storage system
targets
Year
Target factor 2005 2010 2015
Specic energy (MJ=kg) 5.4 7.2 10.8
Hydrogen (wt%) 4.5 6.0 9.0
Energy density (MJ=L) 4.3 5.4 9.72
System cost ($=kg=system) 9 6 3
Operating temperature (

C) 20=50 20=50 20=50


Cycle life-time (adsorption=
desorption cycles)
500 1000 1500
Flow rate (g=sec) 3 4 5
Delivery pressure (bar) 2.5 2.5 2.5
Transient response (sec) 0.5 0.5 0.5
Refueling rate (kg H
2
=min) 0.5 1.5 2.0
(From Ref.
[84]
.)
2834 Sorbent Technology
Noncarbonaceous nanotubes including boron
nitride (BN) and titanium sulde (TiS
2
) have been pre-
pared and studied for hydrogen sorption.
[89,90]
Hydro-
gen storage capacity (2.54.5 wt%) similar to those for
carbon nanotubes have been obtained on these noncar-
bonaceous materials. MOF-based sorbents for hydrogen
sorption was discussed in the previous section. As
suggested in Table 6, the hydrogen sorption capacities
on MOF-5 and MMOM are lower than those on car-
bon nanotubes. However, MOF sorbents look more
promising than carbon nanotubes as hydrogen sto-
rage media for the following reasons:
1. MOF is easy to make and is less expensive;
2. Sorption sites for hydrogen on MOF are better
dened;
3. MOF sorbents may have extremely high specic
surface area (>4000 m
2
=g);
4. It is possible to tailor the interaction between
hydrogen and MOF by manipulating syn-
thesis parameters including different building
blocks.
Metal hydrides were widely investigated for hydro-
gen storage, and are believed to be ideal hydrogen
storage system because they have the following
characteristics:
[2,84,9194]
1. Relatively high hydrogen storage capacity at
modest pressures as indicated in Table 6;
2. Fast hydrogen charging and discharging rates;
and
3. Moderate temperature for hydrogen desorption.
However, metal hydrides also suffer from the fol-
lowing disadvantages as hydrogen storage materials:
1. High sensitivity to impurities in hydrogen (CO,
H
2
O, O
2
, CO
2
, and H
2
S);
2. Storage capacity and rates decay with hydrogen
chargedischarge cycles; and
3. Relatively high cost as compared with gaseous
and liquid hydrogen storage methods.
Another interesting hydrogen storage material is
lithium nitride (Li
3
N), which shows 9.3 wt% useful
hydrogen storage capacity between thermal swing cycles
(473700 K).
[95]
The requirement for high-temperature
desorption will greatly limit its applications.
Most recently, hydrogen clathrate hydrate and other
Table 6 Summary of hydrogen storage capacity of various nanostructured materials
Materials
H
2
storage
capacity (wt%)
H
2
storage
conditions
H
2
release
conditions Reference
Carbon nanotubes
Single-walled 4.2 10 MPa, 300 K 1 bar, 300 K [87]
Multi-walled 3.6 7 MPa, 298 K 1 bar, 298 K [88]
Non-carbonaceous nanotubes
BN 4.2 108 bar, 298 K 1 bar, 298 K [89]
TiS
2
2.5 40 bar, 298 K 1 bar, 298 K [90]
Microporous MOF
MOF-5 4.5 0.75 bar, 77 K 1 bar, >77 K [74]
MMOM ~1.0 48 bar, 298 K 1 bar, 298 K [80]
Metal hydrides
Mg
2
NiH
4
3.6 1 bar, ~500 K 1 bar, >528 K [91]
NaAlH
4
8.0 90 bar, 403 K [92]
Mg(AlH
4
)
2
6.6 1 bar, >436 K [93]
LiBH
4
13.3 1 bar, >473 K [94]
Nitrides
Li
3
N 9.3 1 bar, 443473 K 1 bar, >700 K [95]
Clathrate=molecular compounds
H
2
(H
2
O)
2
5.3 ~1 bar, 77 K 1 bar, >77 K [97]
H
2
(H
2
O) 10.0 ~6000 bar, 190 K <6000 bar, >190 K [97]
(H
2
)
4
(CH
4
) 33.3 ~2000 bar, 77 K <2000 bar, >77 K [97]
Sorbent Technology 2835
molecular compounds were foundto have hydrogen sto-
rage capacities as high as 33.3 wt%.
[9698]
This is a very
innovative way to store hydrogen with exceptionally
high capacity to meet the DOE long-term target. How-
ever, these clathrate and hydrogen storage compounds
were synthesized at extremely high pressures and at
liquid nitrogen temperature. It is unlikely these clathrate
hydrates will be used for hydrogen storage until we
nd new clathrate hydrate compounds that can be
synthesized and are stable at much lower pressures.
p-Complexation Sorbents and
Composite Sorbents
A very good review article based on a panel study of
status, future research needs, and opportunities for
porous sorbent materials was published several years
ago.
[99]
It was pointed out that very signicant
advances have been made in tailoring the porosity of
porous sorbent materials in terms of size and shape
selectivity. Relatively little progress has been achieved
in terms of chemoselectivity of sorbents based on spe-
cic interactions between adsorbate molecules and
functional groups in the sorbents. Incorporation of
active sites into sorbents is of high priority in the devel-
opment of sorbents.
The p-complexation bond is a weak chemical bond
that is slightly stronger than van der Waals interaction,
which governs physical sorption processes. Sorbents
with p-complexation capability tend to have higher
selectivity than other physical sorbents for certain
adsorbate molecules. Several different types of p-com-
plexation sorbents with Cu

or Ag

ions supported on
different supports (SiO
2
, g-Al
2
O
3
, TiO
2
, varietyof zeolites,
polymer resin, and activated carbon) were synthesized
using different methods including thermal dispersion,
wet-impregnation, solgel, microwave heating, ion-
exchange zeolite, and ion-exchange resin.
[3436,99105]
It
was found that the CO adsorption capacity increases
with Cu

loading in an activated alumina supported


sorbent.
[100,101]
To achieve the highest sorption capacity,
the active species should be dispersed as a monolayer
form.
[99]
The potential applications of these p-complexa-
tion sorbents include:
[2]
1. Desulfurization of gasoline and diesel fuels;
2. Separation of olens and parafns;
3. CO separation from synthesis gases;
4. CO removal from hydrogen;
5. Removal of aromatics; and
6. Removal of volatile organic compounds
(VOCs).
A p-complexation sorbent can also be viewed as a
composite sorbent especially when the sorbent support
contributes signicantly to the adsorption. Composite
sorbents are typically made by physically mixing the
powders of constituent sorbents with different sorption
properties; they tend to have multiple sorption sites for
different adsorbate molecules. One example of a com-
posite sorbent is a mixture of activated alumina and
zeolites for removing moisture, carbon dioxide, and
other trace components from air in an air-purication
process prior to cryogenic air separation.
[106108]
Con-
ventionally, moisture is removed by activated alumina,
carbon dioxide by zeolite 13X, and hydrocarbons by
zeolite 5A.
[107,108]
Traditional air-purication processes
employ multiple layers consisting of activated alumina,
zeolite 13X, and optional zeolite 5A sorbents in a sin-
gle vessel to achieve signicant removal of moisture,
carbon dioxide, and hydrocarbons from air. The major
disadvantages of layered bed are nonuniform sorbent
packing for a short sorbent layer, very signicant tem-
perature variation (>30

C, sometimes called cold


spots) between the zeolite and the activated alumina
sorbent layers. The large temperature difference could
upset the sorption process operation if it is designed to
be operated isothermally. It is benecial to have a sin-
gle sorbent with multiple sorption features for different
impurities and eliminate sorbent layering and tempera-
ture variations.
High-Temperature Ceramic O
2
Sorbents
Lin et al. disclosed in a U.S. patent a new group of sor-
bents for air separation and oxygen removal using
oxygen-decient perovskite-type ceramics as sorbents.
[109]
Perovskite-type ceramics are a group of metal oxides
having the general formula of ABO
3
. The ideal perov-
skite structure for ABO
3
is shown in Fig. 4. It consists
of cubic array of corner-sharing BO
6
octahedra, where
B is a transition metal ion. The A-site ion, interstitial
between the BO
6
octahedra, may be occupied by an
alkali, an alkaline earth, or a rare earth ion. Alternatively,
the perovskite structure may be regarded as a cubic
close packing of layers of AO
3
with B cations placed
in the interlayer octahedral interstices.
[110]
This group
of the sorbents can be viewed as chemisorbents that
can selectively adsorb a considerable amount of oxy-
gen at high temperatures (>300

C), and theoretically


has an innitely high selectivity for oxygen over nitrogen
or other nonoxygen species. The presence of other gases
has negligible effect on the separation properties of these
new sorbents. High-temperature membrane separation
of oxygen has also received increasing interest from
other industrial gas companies.
[111113]
Development of
high-temperature oxygen separation technology opens
up several high-temperature applications of oxygen
including syngas production, hydrogen production,
and partial oxidation fuel reforming processes.
2836 Sorbent Technology
The oxygen equilibrium and kinetic properties of
perovskite-type ceramics have been extensively studied
primarily for applications as fuel cell electrodes and
oxygen permeable membranes,
[110]
and only a few for
oxygen sorption.
[114117]
Oxygen nonstoichiometry (d)
occurs in some perovskite-type ceramics with B-site
cations of variable oxidation states and A-site cations
partially substituted by another cation with a lower
oxidation state. Oxygen nonstoichiometry, or oxygen
content, for a perovskite-type ceramic of a given com-
position is a function of temperature and oxygen par-
tial pressure. Therefore, by changing temperature or
oxygen partial pressure, the value of oxygen nonstoi-
chiometry or the degree of oxygen vacancy in the mate-
rial changes. Within a certain range of temperature and
oxygen partial pressure the change of the oxygen non-
stoichiometry does not affect the perovskite structure,
and the change of the oxygen content in the material is
a reversible process. The oxygen nonstoichiometry of
the perovskite sorbents can be measured gravimetrically
at different temperatures and oxygen partial pressures.
Oxygen sorption capacity on the sorbent can then be
calculated from the oxygen nonstoichiometry data once
the initial state (zero sorption capacity) of the sorbent
material is dened.
[114]
Figs. 5 and 6 are examples of
oxygen nonstoichiometry of La
1x
Sr
x
Co
1y
Fe
y
O
3d
perovskite oxide sorbents as a function of oxygen
partial pressure or temperature, respectively.
[114]
The corresponding oxygen sorption isotherm of
La
1x
Sr
x
Co
1y
Fe
y
O
3d
perovskite oxide sorbents that
were calculated from the oxygen nonstoichiometry
data are shown in Fig. 7.
[114]
From these oxygen
isotherms we can conceive a high-temperature
vacuum swing sorption or temperature swing sorption
process for oxygen separation or oxygen removing
applications by using the La
1x
Sr
x
Co
1y
Fe
y
O
3d
perovskite oxide sorbents. Future studies on
perovskite oxide sorbents are needed to address the
issues of slow desorption rate, potential sorbent
structure stability in cyclic processes, and effective
regeneration methods.
High-Temperature CO
2
Sorbents
Increased awareness of the global warming trend has
led to worldwide concerns regarding greenhouse
gas emissions. Greenhouse gases include CO
2
, CH
4
,
and N
2
O and are mostly associated with the production
and utilization of fossil fuels, with CO
2
being the sin-
gle greatest contributor to global warming. Signicant
research efforts are being devoted worldwide on look-
ing for economical ways of mitigating CO
2
emission
problem.
[118122]
Carbon capture and sequestration
costs can be considered in terms of four components:
capture, compression, transport, and injection. Typi-
cally about 75% of this cost is attributable to capture
A B
Fig. 4 Ideal perovskite structure for ABO
3
type oxides.
B
1 2 3
A
LSCF-2
LSCF-1
0.5
0.45
0.4
0.35
0.3
0.25
0.0001 0.001 0.01 0.1 1
0.5
0.45
0.4
0.35
0.3
0.0001 0.001 0.01 0.1 1
P
O2
(atm)
P
O2
(atm)

Fig. 5 Change of oxygen nonstoichiometry d with oxygen


partial pressure (LSCF-1. La
0.1
Sr
0.9
Co
0.5
Fe
0.5
O
3d
; LSCF-2,
La
0.1
Sr
0.9
Co
0.9
Fe
0.1
O
3d
). (From Ref.
[114]
.)
Sorbent Technology 2837
and compression processes. Sorption of carbon dioxide
on solid sorbents is receiving increased attention in view
of the importance of both the removal and the recovery
of carbon dioxide from ue gases.
[123,124]
Physical sorbents for carbon dioxide separation and
removal were extensively studied by industrial gas
companies.
[125127]
Zeolite 13X, activated alumina,
and their improved versions are typically used for
removing carbon dioxide and moisture from air in
either a TSA or a PSA process.
[125128]
The sorption
temperatures for these applications are usually close
to ambient temperature. There are a few studies on
adsorption of carbon dioxide at high temperatures.
The carbon dioxide adsorption isotherms on two
commercial sorbents hydrotalcite-like compounds,
EXM911 and activated alumina made by LaRoche
Industries, are displayed in Fig. 8.
[123,124]
As shown in
Fig. 8, LaRoche activated alumina has a higher carbon
dioxide capacity than the EXM911 at 300

C. However,
the adsorption capacities on both sorbents are too
low for any practical applications in carbon dioxide
sorption at high temperature. Conventional physical
sorbents are basically not effective for carbon dioxide
capture at ue gas temperature (>400

C). There is a
need to develop effective sorbents that can adsorb
carbon dioxide at ue gas temperature to signicantly
reduce the gas volume to be treated for carbon
sequestration.
Only a handful of studies on high-temperature car-
bon dioxide sorbents have been published in the past
few years.
[123,124,129133]
It is believed that lithium zirco-
nate (Li
2
ZrO
3
) is one of the most promising sorbent
materials for carbon dioxide separation from ue gas
at high temperature because it can absorb a large amount
of carbon dioxide at around 400700

C.
[130,131]
The
carbon dioxide adsorption and desorption uptake
curves on lithium zirconate are shown in Fig. 9.
[131]
As shown in this gure, about 20% carbon dioxide
was captured by the lithium zirconate sorbent during
sorption step at 500

C based on the following reaction:


Li
2
ZrO
3
CO
2
Li
2
CO
3
ZrO
2
(4)
About 80% of adsorbed carbon dioxide can be des-
orbed with hot air 780

C. Addition of potassium car-


bonate (K
2
CO
3
) and Li
2
CO
3
into Li
2
ZrO
3
remarkably
improves the CO
2
sorption rate of the Li
2
ZrO
3
-based
sorbent materials. X-ray diffraction (XRD) analysis for
phase and structural changes during the sorption=
desorption process shows that the reaction between
Li
2
ZrO
3
and CO
2
is reversible.
[131]
Based on this work, a
TSAprocess canbe developedfor carbondioxide removal
from ue gas using Li
2
ZrO
3
-type sorbent materials.
High-temperature carbon dioxide sorbents can also
nd applications in fuel reforming process to enhance
fuel to hydrogen conversion efciency. It was reported
0.45
0.4
0.35
0.3
0.25
0.2
300 400 500 600 700 800
T(C)
LSCF-2
LSCF-1
P
O2
= 0.209 atm

Fig. 6 Change of oxygen nonstoichiometry d with tempera-


ture (LSCF-1, La
0.1
Sr
0.9
Co
0.5
Fe
0.5
O
3d
; LSCF-2, La
0.1
Sr
0.9
Co
0.9
Fe
0.1
O
3d
). (From Ref.
[114]
.)
A
500C
600C
0.5
0.4
0.3
0.2
A
m
o
u
n
t

A
d
s
o
r
b
e
d

(
m
m
o
l
/
g
)
0.1
0
0.0001 0.001 0.01 0.1 1
P
O2
(atm)
B
500C
600C
0.6
0.5
0.4
0.3
0.2
A
m
o
u
n
t

A
d
s
o
r
b
e
d

(
m
m
o
l
/
g
)
0.1
0
0.001 0.01 0.1 1
P
O2
(atm)
Fig. 7 Sorption isotherms of: (A) La
0.1
Sr
0.9
Co
0.5
Fe
0.5
O
3d
and (B) La
0.1
Sr
0.9
Co
0.9
Fe
0.1
O
3d
at 500 and 600

C. (From
Ref.
[114]
.)
2838 Sorbent Technology
that sorption of carbon dioxide can enhance the pro-
duction of hydrogen for a steammethane reforming
process using a mixture of Ni-based reforming catalyst
and a Ca-based sorbent. The rates of the reforming,
water-gas shift, and carbon dioxide removal reactions
are sufciently fast that combined reaction equilibrium
was closely approached, allowing for >95 mol%hydro-
gen to be produced in a single step.
[134]
CONCLUSIONS AND FUTURE DIRECTIONS
Existing commercial sorbents including activated car-
bon, zeolites, activated alumina, and silica gels will
continue to play important roles in adsorptive separa-
tion and purication for current process industries in
the near future. However, they cannot meet the needs
of future technological developments in the new energy
economy and the stringent environmental regulations.
The newly developed nanostructured sorbent materials
have shown some very promising features, but they are
basically unexplored and systematic investigations are
needed on both synthesis methods and adsorption
characteristic studies. The following are the authors
views on future research needs in both sorbent synthe-
sis and applications:
1. Explore entirely new sorbent synthesis routes to
better control of both sorbent pore texture and
surface property.
2. Design new sorbent materials from basic build-
ing blocks and introduce active sorption sites
according to sorbentadsorbate interaction
requirements. MOF material syntheses using
0.00
0.0 0.1 0.2 0.3 0.4 0.5
Pressure (bar)
Q

(
m
m
o
l
/
g
)
0.6 0.7
200C
20C
EXM911
300C
0.8 0.9 1.0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.0
0.0 0.1 0.2 0.3 0.4 0.5
Pressure (bar)
0.6 0.7
200C
20C Activated Alumina
B
A
300C
0.8 0.9 1.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
Fig. 8 Adsorption isotherms of carbon
dioxide on commercial sorbents. (A)
Hydrotalcite-like compound, EXM911;
(B) LaRoche Industries activated alumina
at 20, 200, and 300

C. (From Refs.
[123,124]
.)
Sorbent Technology 2839
the isoreticular method and solgel technique
are two examples of this approach.
8. A better understanding of the relationship
between sorbentadsorbate interaction, sorp-
tion equilibrium, and kinetics through molecu-
lar simulation, and provide guidance for
sorbent synthesis.
In terms of applications, new sorbents should be
developed to meet the following pressing needs:
1. Deep desulfurization of fossil fuels for fuel cell
application.
2. Hydrogen purication (H
2
S, CO, and CO
2
removal).
3. Hydrogen and methane storage sorbents and
processes.
4. Water treatment (arsenic, radionuclides and
heavy metal ions and anions removal).
5. Air pollution control (SO
x
, NO
x
, and other
toxic gases removal).
6. Chemisorbents as effective getter materials for
toxic process gas and liquid streams.
7. Effective high-temperature carbon dioxide sor-
bents for carbon dioxide sequestration.
ACKNOWLEDGMENT
Professor Y.S. Lin is acknowledged for providing his
publications and comments on high-temperature sor-
bents discussed in this entry.
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0 200 400
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
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e
i
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h
t

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h
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sorption and regeneration on the modied
Li
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ZrO
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balanced by dry air at
500

C. Desorption process: 50% CO


2
balanced by dry air
at 780

C dry air at 780

C. Gas ow rate: 150 ml=min.


(From Ref.
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