Sorbent Technology: January 2006

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Sorbent Technology
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Sorbent Technology
Shuguang Deng
Chemical Engineering Department, New Mexico State University,
Las Cruces, New Mexico, U.S.A.
INTRODUCTION Absorption: The absorbing of molecules (as of

gases, solutes, or liquids) into the solid bodies
This article covers the fundamentals, status, and future or liquids with which they are in contact.
developments of sorbent materials and their appli-
Sorption: Formation from adsorption and absorption.
cations in adsorptive separation and purification pro-
cesses. A sorbent is usually a solid substance that Adsorbent: A usually solid substance that adsorbs
adsorbs or absorbs another type of substance. It is another substance on its surface.
the sorbent that makes a sorption process a unique
Sorbent: A usually solid substance that adsorbs and
and different separation and purification process from
absorbs another substance.
others. With the rapid development in novel sorbent
materials and innovative cyclic adsorption processes, Adsorbate: Molecules (as of gases, solutes, or
sorption has become a key separation process in many liquids) that are adsorbed on adsorbent surfaces.
process industries including chemical, petrochemical,
Microporous: Pore size smaller than 20 Å.
environmental, pharmaceutical, and electronic gases.
A brief review of the fundamentals of adsorption Mesoporous: Pore size between 20 and 500 Å.
and the basic requirements for sorbent materials is
Macroporous: Pore size larger than 500 Å.
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- Adsorptive separation can be achieved through one
bent materials including oxide molecular sieves, sol–gel of the following mechanisms. Understanding the
derived xerogels and aerogels, metal organic frame- fundamentals of adsorptive separation mechanisms
work, hydrogen storage media, p-complexation and will allow us to better design or modify sorbent
composite sorbents, and high-temperature sorbents materials to achieve their best possible separation
for oxygen or carbon dioxide sorption. A concluding performance.[2–4]
section outlines the future research needs and opportu- Adsorption equilibrium effect is because of the dif-
nities in sorbent technology development for new ference in the thermodynamic equilibria for each adsor-
energy and environmental applications. bate–adsorbent interaction. The majority of adsorptive
separation and purification 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-
ADSORPTION MECHANISMS AND lite molecular sieve 5A or 13X in either a pressure swing
SORBENT MATERIALS adsorption (PSA) or a vacuum swing adsorption (VSA)
process. In this case, nitrogen is selectively adsorbed by
According to King, a mass separating agent is needed the zeolite adsorbent, and oxygen is collected from the
to facilitate separation for many separation processes.[1] adsorption effluent stream.
The mass separating agent for adsorption process is Adsorption kinetics effect arises because of the
the adsorbent, or the sorbent. Therefore, the character- difference of rates at which different adsorbate mole-
istic of the sorbent directly decides the performance of cules travel into the internal structure of the adsorbent.
any adsorptive separation or purification process. The There are only a few commercial successes using
basic definitions of adsorption-related terminologies adsorption kinetic difference to achieve adsorptive
are given in the following to clarify and standardize these separation of gases. The typical example is separation
widely used terms in this field. of nitrogen from air using a carbon molecular sieve
(CMS). The CMS adsorbent has a similar adsorption
Adsorption: The adhesion of molecules (as of gases, equilibrium capacity for both nitrogen and oxygen,
solutes, or liquids) to the surfaces of solid bodies but the diffusivity of oxygen in CMS is at least 30 times
or liquids with which they are in contact. 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
2826 Sorbent Technology
nitrogen can be recovered from the adsorption effluent effective diffusivity. Although the above equation is
stream in a PSA process because oxygen moves much strictly valid under the assumptions that components A
faster than nitrogen into the micropores of CMS and B have independent linear adsorption isotherms
adsorbent. However, the cycle time of this CMS-based and independent diffusion process, it provides a good
PSA process is much shorter than that of a typical PSA estimate of adsorbent selectivity for kinetically controlled
process based on adsorption equilibrium effect. This is processes.
because there will be no separation if both nitrogen Theoretically speaking, selectivity for adsorbents
and oxygen are allowed to reach adsorption equilib- with a molecular sieving effect should be infinitely
rium with the CMS adsorbent. large because the larger molecules are excluded from
Molecular sieving effect, also called steric effect, is getting into the adsorbent micropores. In reality, the
derived from the molecular sieving properties of some adsorbent selectivity for steric effect is somewhat
adsorbents with a microporous structure. In this case, reduced by combining with the equilibrium effect from
the pore openings of the adsorbent structure are small adsorption on the surface of large pores. So adsorption
enough to exclude large adsorbate molecules from processes based on molecular sieving are usually con-
penetrating the micropores of the adsorbent. This is sidered as adsorption equilibrium effect.
the extreme case of the kinetic effect. There are several Another very important adsorbent property affect-
commercial applications based on this mechanism in ing the adsorption process is the adsorption capacity
adsorptive separation processes. One typical example because it determines the size of an adsorbent vessel,
is separating normal paraffin from iso-paraffin and the amount of adsorbents required, and the related
aromatics in an adsorption process using zeolite 5A capital and operating costs. The requirements for
as an adsorbent. n-Paraffin, with a long straight chain, commercial sorbents are discussed briefly as follows.
has a smaller effective diameter than the well-defined
aperture of zeolite 5A. Therefore it adsorbs in the
micropores of the adsorbent during the adsorption Characteristics of Sorbent Materials
step, and is recovered from the adsorbed phase in the
desorption step. A representative process for n-paraffin Commercial sorbents used in cyclic adsorption pro-
separation from naphtha and kerosene is UOP’s cesses should ideally meet the following requirements:
Molex process that employs a simulated moving bed
with binderless zeolite 5A as an adsorbent and light Large selectivity derived from equilibrium, kinetic,
paraffin as a desorbent.[6] or steric effect;
We can define separation factor and selectivity as Large adsorption capacity;
the ability of an adsorbent to separate molecule A Fast adsorption kinetics;
from molecule B as:[7] Easily regenerable;
Good mechanical strength;
XA =YA Low cost.
Separation factor : aAB ¼ ð1Þ
XB =YB
The above adsorbent performance requirements can
simply transfer to adsorbent characteristic require-
Here XA, YA are strictly equilibrium mole fractions for ments as follows:
component A in the adsorbed phase and adsorbate
(fluid) phase, respectively; as are XB, YB for component Large internal pore volume;
B. For equilibrium-based adsorptive separation process, Large internal surface area;
the adsorbent selectivity is the same as the separation fac- Controlled surface properties through selected
tor as defined in Eq. (1). Apparently, this definition is not functional groups;
applicable to other processes based on kinetic and steric Controlled pore size distribution, preferably in
effects. In a kinetically controlled adsorption process, the micropore range;
adsorbent selectivity depends on both equilibrium and Weak interactions between adsorbate and adsorbent
kinetic effects. A simplified definition for adsorbent (mostly on physical sorbents);
separation factor is given by Ruthven et al.:[8] Inorganic or ceramic materials to enhance chemical
and mechanical stability;
rffiffiffiffiffiffiffi Low-cost raw materials.
KA DA
SAB ¼ ð2Þ
KB DB
These basic requirements are usually proposed for
adsorbents used in cyclic adsorption processes that
where SAB is the adsorbent selectivity, K is the adsorption are based on physical adsorption. There is an increas-
equilibrium constant or isotherm slope, and D is the ing demand for strong chemical adsorbents used in
Sorbent Technology 2827
purification processes to remove trace contaminants Silica gel: $71 million

from main stream fluids such as the removal of very Polymeric adsorbents: $50 million
toxic contaminants from electronic process gas streams,
and the removal of toxic, or radioactive species from
contaminated water. In these cases, the sorbents are Activated Carbon
used as getter materials; no regeneration is needed,
and instead, the spent sorbent materials are disposed Activated carbons are unique and versatile adsorbents
of in designated areas regulated by government envi- because of their large surface area, microporous and
ronmental policies. 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
COMMERCIAL SORBENTS AND applications that include decolorizing sugar solutions,
APPLICATIONS personnel protection, solvent recovery, volatile organic
compound removal from air and water, water treat-
An excellent review and detailed coverage on commer- ment, hydrogen and synthesis gas separation, and
cial adsorbents and new adsorbent materials has been natural gas storage.[4,9,10] Activated carbons are
presented by Yang in his newly published monograph produced in two main steps: carbonization of the
on adsorbents.[2] A very brief overview of existing com- carbonaceous raw materials at temperatures below
mercial adsorbents is given here. Commercial sorbents 800 C in the absence of oxygen, and activation of
that have been used in large-scale adsorptive separa- the carbonized products.[10] The properties of activated
tion and purification processes include activated carbon, carbon depend largely on the nature of the raw materi-
zeolites, activated alumina, silica gel, and polymeric als, the activating agents and activation conditions.
adsorbents. Although the worldwide sales of sorbent For gas-phase applications, activated carbons are
materials are relatively small as compared with other usually made in pellets with mostly micropores; while
chemical commodities, sorbents and adsorption pro- for liquid-phase applications, activated carbon is pro-
cesses play a very important role in many process indus- duced in powder form with relatively large mesopores
tries. The estimated worldwide sales of these sorbents to enhance mass transfer rate in the carbons.
are as follows:[2] Fig. 1 compares the pore size distributions of major
commercial adsorbents discussed in this section. Acti-
Activated carbon: $1 billion vated carbons have a broad pore size distribution like
Zeolite: $1.07 billion activated alumina and silica gel. Although activated
Activated alumina: $63 million carbon is thought to be ‘‘hydrophobic,’’ it does adsorb
60 Activated carbon
Cumulative pore volume, cm3/100 gm
50
Silica gel
40
30
Zeolite 5A
20
Activated alumina
10
MSC Fig. 1 Pore size distributions for activated

MSC
0 carbon, silica gel, activated alumina, two mole-
2 5 10 20 50
cular sieve carbons (MSCs), and zeolite 5A.
Pore diameter, Å (From Ref.[3].)
quite significant amount of water (>30 wt%) when exist as minerals in nature, but all commercially
relative humidity is higher than 50%. An example iso- important zeolites are synthetic. Zeolites are unique
therm of water on activated carbon, along with water adsorbents owing to their special surface chemistries
isotherms on other commercial adsorbents, is plotted and crystalline pore structures. It should be pointed
in Fig. 2. The change from ‘‘hydrophobic’’ to ‘‘hydro- out that probably only 10% of $1 billion worldwide
philic’’ on the activated carbon surface is attributed to sales of zeolite is used as adsorbents; the majority of
the initial adsorbed water film on the carbon surface. commercial zeolites are used as detergent additives
This occurs because when the carbon surface is fully (zeolite 4A), animal food additives (zeolite 4A), ion
covered with a layer of water molecules, the adsorbed exchange, and catalyst supports. Among all commer-
water molecules exhibit strong affinity to other polar cial sorbents zeolites are probably the most extensively
molecules including water. Carbon molecular sieve investigated and documented. Many excellent mono-
(CMS) is a specially made carbonaceous material with graphs and review articles are available.[2,11–13] Please
very narrow pore size distribution (4–9 Å). The major refer to Tables 1 and 2 for properties and major appli-
application of CMS is in the generation of high-purity cations of zeolites.
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, Activated Alumina
respectively.
Activated alumina is a porous high-surface area form
of aluminum oxide with the formula of Al2O3nH2O.
Zeolites Commercially, it is prepared either from thermal
dehydration of aluminum trihydrate, Al(OH)3, or
Zeolites are porous crystalline aluminosilicates that are directly from bauxite (Al2O33H2O), as a by-product
made of assemblies of SiO4 and AlO4 tetrahedra joined of the Bayer process for alumina extraction from baux-
together through shared oxygen atoms. The general ite. Its surface is more polar than that of silica gel and,
chemical formula for zeolites is: reflecting the amphoteric nature of aluminum, has
both acidic and basic characteristics. Surface areas
Mx=n ½ðAlO2 Þx ðSiO2 Þy zH2 O ð3Þ are in the range 250–350 m2=g depending on the activa-
tion temperature and the source of raw materials.
where x and y are integers with y=x (Si=Al ratio) equal Because activated alumina has a higher capacity for
or larger than 1; n is the valance of cation M, and z is water than silica gel at elevated temperatures it is used
the number of water molecules in each unit cell. The mainly as a desiccant for warm gases including air, but
tetrahedra can be arranged in many different ways to in many commercial applications it has now been
form different crystalline structures. Some zeolites replaced by zeolitic materials in a thermal swing
40
Adsorption, kg H2O/100 kg adsorbent
E
30
D
20
10 B
A
Fig. 2 Equilibrium sorption of water vapor from
atmospheric air at 25 C on: (A) alumina (granular),
0 (B) alumina (spherical), (C) silica gel, (D) 5A
0 20 40 60 80 100 zeolite, and (E) activated carbon. The vapor pressure
Relative humidity, % at 100% relative humidity is 23.6 torr. (From Ref.[3].)
Table 1 Representative physical properties of commercial adsorbents

Specific surface Pore Particle
Adsorbent Nature area (m2/g) diameter (Å) Porosity density (g/cm3)
Activated carbon Hydrophobic amorphous
Small pore 400–1200 10–25 0.4–0.6 0.5–0.9
Large pore 200–600 > 30 0.5 0.6–0.8
Zeolite Hydrophilic=hydrophobic 600–700 3–10 0.6 1.0
crystalline
Activated alumina Hydrophilic crystalline=x-ray 200–350 10–75 0.5 1.25
amorphous
Silica gel Hydrophilic=hydrophobic
amorphous
Small pore 750–850 22–26 0.47 1.09
Large pore 300–350 100–150 0.71 1.62
Polymeric adsorbent Hydrophilic=hydrophobic 450–1100 25–90 0.5 1.25
Carbon molecular sieve Hydrophilic 400 3–9 0.5 1.0
adsorption (TSA) process. However, activated alumina amines, etc. by hydrogen bonding mechanisms. Other
has a low adsorption heat for water and other polar commercial applications include the separation of aro-
molecules as compared with zeolite; it is possible to matics from paraffins, the chromatographic separation
regenerate activated alumina under PSA conditions. of organic molecules, and modified silica in chromato-
Activated alumina also demonstrates moderate graphy columns.[2,18–20]
adsorption affinity for carbon dioxide, which makes
it a suitable sorbent for removing water and carbon
Polymeric Adsorbents
dioxide from air in a PSA process. These adsorption
properties of activated alumina have been explored
A wide range of synthetic, nonionic polymers are avail-
extensively for air purification applications by indus-
able for use as sorbents, ion-exchange resins, and par-
trial gas companies.[14–17] This is a perfect example to
ticularly for analytical chromatography applications.
demonstrate the importance of sorbent regenerability
Commercially available resins in bead form (typically
over sorption capacity and selectivity in pressure swing
0.5 mm in diameter) are based usually on copolymers
adsorption processes. Activated alumina is also an
of styrene=divinyl benzene (DVB) and acrylic acid
excellent catalyst support. More applications and
esters=divinyl benzene, and have a wide range of sur-
representative properties of activated alumina are
face polarities, porosities, and macropore sizes. The
listed in Tables 1 and 2.
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-
Silica Gels ing agent for the polymer. This creates a polymer
matrix with surface areas ranging up to 1100 m2=g.[2,4]
Silica gel is the most widely used desiccant because of The major application of polymeric adsorbents is in
its large adsorption capacity for water (40 wt%), as water treatment. The macroporous polymeric resins can
shown in Fig. 2, and easy for regeneration ( 150 C, be modified by attaching different functional groups to
compared with 350 C for zeolites). Silica is a partially mimic activated carbon, and to replace activated carbons
dehydrated polymeric form of colloidal silicic acid with for certain specific applications in food and pharmaceu-
the formula of SiO2nH2O. Its water content, which is tical industries where color contamination by the black
typically about 5 wt%, is presented in the chemically carbons of the final products is a major concern.
bonded hydroxyl groups. Silica is an amorphous mate-
rial comprising spherical particles of 20–200 Å in size,
which aggregate to form the sorbent with pore sizes NEW DEVELOPMENTS IN SORBENT
in the range of 60–250 Å and surface areas of 100– MATERIALS AND APPLICATIONS
850 m2=g, depending on gel density. Its surface has
mainly Si–OH and Si–O–Si polar groups; this is why The past two decades have witnessed major advances
it can be used to adsorb water, alcohols, phenols, in new nanostructured sorbent materials including
Table 2 Selected applications of commercial sorbents

Adsorbent Applications (the first 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 SOx, and NOx
Purification of helium
Clean-up of nuclear off-gases
Decolorizing of syrups, sugars, and molasses
Water purification, 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
Purification 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 paraffins
Separation of olefins and aromatics from paraffins
Recovery of carbon monoxide from methane and hydrogen
Purification of nuclear off-gases
Separation of cresols
Drying of refrigerants and organic liquids
Separation of solvent systems
Pollution control, including removal of Hg, NOx, and SOx from gases
Recovery of fructose from corn syrup
Activated alumina Drying of gases, organic solvents, transformer oils
Removal of HCl from hydrogen
Removal of fluorine and boron–fluorine 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 purification, including removal of phenol, chlorophenols, ketones, alcohols,
aromatics, aniline, indene, polynuclear aromatics, nitro- and chlor-aromatics,
polychlorinated biphenyls (PCBs), pesticides, antibiotics, detergents, emulsifiers,
wetting agents, kraftmill effluents, dyestuffs, and radionuclides
Recovery and purification 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
Refining of mineral oils
Removal of PCBs
(From Ref.[4].)
mesoporous molecular sieves, sol–gel-derived metal hydrocarbons (49 wt% for n-hexane at 40 torr and
oxide xerogels and aerogels, metal organic framework, 21 C, and 67 wt% for benzene at 50 torr and 25 C).[24]
p-complexation and composite adsorbents, new carbo- Other significant members of the M41S family include
naceous materials (carbon nanotubes, carbon fibers, MCM-48 (cubic phase), MCM-50 (stabilized lamellar
superactivated carbons), high-temperature ceramic sor- phase), SBA-1 (cubic phase), and SBA-2 (cubic
bents, and strong chemical sorbent materials. Although phase).[21]
these new sorbent materials have demonstrated promis- Although M41S type mesoporous oxide molecular
ing sorption properties for many existing and new sieves have exhibited unique properties of large surface
applications, systematic studies on synthesis methods area and exceptionally large pore volume (> 0.7 cm3=g),
and characterization of these new materials are necessary their large pore volume may not be attractive for gas
to fully explore and realize their potential as commercial sorption because the adsorbate–adsorbent interactions
sorbents. The review that follows aims at attracting more are not enhanced inside the internal pores of these mate-
research efforts to develop novel sorbent materials to rials.[2] Therefore, M14S type mesoporous oxide molecu-
meet the increasing needs of new energy, environmental, lar sieves without surface modification are rarely used as
and other emerging technologies. sorbents. Significant research efforts were devoted to
surface modification of M41S materials for different
applications.[2] An amine-grafted MCM-48 sorbent,
Oxide Molecular Sieves synthesized from tetraethoxysilane (TEOS), has been
shown to have a surface area of 1389 m2=g, a silanol
Microporous and mesoporous oxide molecular sieves number of 8, higher thermal stability than MCM-41,
that have the characteristics of large internal surface high adsorption selectivity, and high capacity for both
area and pore volume are ideal candidates for use as carbon dioxide and hydrogen sulfide.[25]
sorbent materials and catalyst supports of many hetero-
geneous catalysts. Oxide molecular sieves are generally
synthesized by hydrothermal methods that involve both Sol–Gel-Derived Xerogels and Aerogels
chemical and physical transformations within an
amorphous oxide gel, often in the presence of a tem- Sol–gel processing refers to the fabrication process of
plate species. The gel eventually converts to a crystal- ceramic materials by preparation of a sol, gelation
line material in which the template species and=or of the sol, and removal of the solvent.[26] Sols are
solvent molecules are guests within the channels and dispersions of colloidal particles in a liquid solvent,
cages of an oxide host framework. A porous material and a gel is a solid matrix encapsulating a solvent. In
is obtained upon removal of the guest molecules from a sol–gel process, the sol can be formed from a solution
the oxide framework. By manipulating the synthesis of colloidal powders or hydrolysis and condensation of
parameters, including starting precursors, synthesis alkoxides or salt precursors. In the latter approach,
temperature, pH, template species, drying, and calcina- which is much more popular, primary particles of uni-
tion conditions, it is possible to tailor the pore size and form size are formed and grow in a sol and connect to
shape of these porous materials for different applica- each other to form aggregates during gelation. These
tions. However, tailoring of porosity in oxide molecu- aggregates forming the network of the gel are broken
lar sieves in terms of a priori structural design is apart into the primary particles in the drying step.
extremely difficult because of the inherent complexity Upon calcination and sintering, these primary particles
of the synthetic procedures employed.[21] are bound together strongly to form a very rigid solid
Recent advances and applications of oxide molecu- network, and large interparticle space with uniform
lar sieves have been summarized in several review arti- nanoscale pores is formed. Xerogels are obtained by
cles.[2,21–23] Microporous zeolite materials synthesized drying the gels through evaporation at normal condi-
with molecular templates and their applications in tions under which capillary pressure causes shrinkage
host–guest chemistry have been covered elsewhere.[13] of the gel network, while areogels are produced by
A new class of silicate=aluminosilicate mesoporous drying the wet gels at supercritical conditions where
molecular sieves designated as M41S was discovered the liquid–vapor interface is eliminated, and relatively
in the former Mobil research laboratory by extending little shrinkage of the gel network occurs. Xerogels
the concept of zeolite templating with small organic and aerogels typically have relatively large surface
molecules to large long-chain surfactant molecules.[24] area, high porosity, and internal pore volume, and
A representative member of this family is MCM-41, are ideal candidates as sorbent and catalyst support
which has a honeycomb-shaped hexagonal arrange- materials for many applications. The sol–gel process
ment of uniform mesopores in the range of 15–100 Å, offers a very high flexibility to tailor xerogels and
specific surface area of 1040 m2=g, pore volume above areogels for specific applications by manipulating the
0.7 cm3=g, and significantly high sorption capacity for synthesis conditions.
Silica xerogel is probably the most studied and Table 3 Pore texture sol–gel-derived alumina, zirconia, and
documented porous material in the sol–gel sys- titania (calcined at 450 C for 3 hr)
tem.[27,28] Although silica has several crystalline forms, Average Pore BET surface
only amorphous silica gel is used as a desiccant (sor- Xerogel pore size (Å) volume (cm3/g) area (m2/g)
bent). A microporous silica that was synthesized with g-Al2O3 28 0.33 373
TEOS as precursor has an average pore size of 6.4 Å,
ZrO2 38 0.11 57
pore volume of 0.24 cm3=g, and Brunauer–Emmett–
Teller (BET) surface area of 588 m2=g.[29] However, TiO2 34 0.21 147
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 One of the outstanding characteristics of sol–
silica was significantly improved.[29] gel-derived g-alumina xerogel is its excellent mechanical
Crystalline sorbent materials including g-alumina, properties. Preparation of porous g-alumina granules
zirconia, and titania were also synthesized using the with good mechanical properties and desirable pore
sol–gel process in Lin’s group;[29] the representative structure is of great importance in the development
pore size distribution and pore texture data of xerogels of novel catalysts and sorbents for various applica-
of g-alumina, zirconia, and titania are summarized in tions. The superior mechanical properties can be
Fig. 3 and Table 3, respectively. As shown in Fig. 3, derived from the unique microstructure of the granule,
the pore size distributions of these materials are rather which is defined by compacting small g-alumina crys-
narrow, with an average pore diameter of about 3 nm. tallite particles bound together by the bridges of the
Such narrow size distribution and nanoscale average same material formed through coarsening or sintering.
pore size are determined by the primary crystallite Such nanostructured g-alumina can be prepared by
particles. The particles of the sol–gel-derived alumina, combining the Yoldas process and the ‘‘oil-drop’’
titania, and zirconia, owing to the Ostwald ripening method.[30–34] Table 4 compares the crush strength
mechanism,[26] are usually of nanoscale size; the uni- and attrition rate of sol–gel-derived g-alumina xerogel
form particle size distributions of g-alumina crystallites granules with those of several commercial sorbents. It
are plate-shaped with size ranging from about 5 to is clearly shown in Table 4 that the sol–gel-derived g-
20 nm. The sol–gel-derived g-alumina consists of alumina xerogel granules have excellent mechanical
such plate-shaped crystallite particles, which give properties as compared with commercial sorbents.
rise to a relatively large surface area. Crystallites of The excellent mechanical properties makes sol–
tetragonal zirconia and rutile are of more spherical gel-derived alumina granules very suitable for fluidized
shape, with a crystallite size of about 15 and 11 nm, bed and other applications including separation and
respectively.[29] purification process for food and healthcare products
that have very strict regulations on sorbent power
contamination.
Sol–gel-derived xeorgel sorbents have been inves-
γ-Alumina tigated for gas separation, purification, and envi-
Titania ronmental applications. g-Alumina sorbents and
1.6 Zirconia membranes doped with cuprous and silver ions have
been studied for selective adsorption or transfer of
CO and ethylene through p-complexation.[35–37]
1.2 Significant efforts have been devoted to explore the
dV/dlog(D)
possibility of using CuO-doped g-alumina sorbents

for removing SOx and NOx from flue gas.[38–44]
0.8 The sol–gel-derived CuO=g-alumina sorbents have
demonstrated high sorption capacity, high reactivity
for SO2, and high thermal and chemical stability.
0.4 The excellent mechanical and desulfurization pro-
perties of sol–gel-derived sorbents make them ideal
sorbent candidates for fluidized bed desulfurization
0.0 process. However, the relatively high cost of sol–
2 3 4 5 6 7 8 9 2 3 gel-derived alumina xerogels may prevent them from
1 10 being used in many large-scale adsorption processes.
Pore Diameter (nm)
Research efforts are needed to look for less expen-
Fig. 3 Pore size distribution of sol–gel-derived alumina, sive precursors to replace alkaoxides used in the
zirconia, and titania. (From Ref.[29].) Yoldas process.
Table 4 Comparison of crush strength and attrition rate of sol–gel-derived g-alumina xerogel granules with commercial sorbents
Granular size Average crush strength Attrition rate
Sorbents Granular shape (mm) (N/granule) (wt%/hr)
Sol–gel alumina Spherical 2.0–2.5 160 0.033
Sol–gel alumina Spherical 2.6–2.8 190
Alcoa alumina (LD-350) Spherical 4.0–4.6 42 0.177
UOP silicalite Cylindrical 1.4–1.6 16 0.575
Degussa DAY zeolite Cylindrical 3.5–3.5 40 0.073
Sol–gel-derived metal oxide xerogels were also major role in environmental protection. However, more
investigated for water adsorption because most of studies on their synthesis and adsorption properties are
these metal oxides are good sorbent candidates for needed.
desiccant applications.[45–47] Significant research works
have been carried out to study the adsorption=
complexation properties of heavy metal ions including Metal Organic Framework (MOF)
mercury, Cu(II), CdCl2, etc. in waste water on different
sol–gel-derived xerogels.[48–54] The sol–gel-derived Recently, Yaghi’s group reported a novel crystalline
xerogels seem to be promising sorbent candidates for nanoporous material that consists of metal atoms
waste water treatment. Modified xerogel sorbents also occupying the vertices of a lattice, with the lattice size,
showed promising adsorption properties for removing porosity, and chemical environment defined by the
acid gas CO2 and H2S from natural gas, or as CO2 organic linker molecules that bind the metal atoms into
storage sorbents.[25,55] There are several advantages a robust periodic structure.[74–76] These so-called metal
of using xerogels for enzyme immobilization, including organic framework (MOF) materials have been
the opportunity to produce them in defined shapes or demonstrated to have an exceptionally high specific
thin films and the ability to manipulate their physical surface area of 4526 m2=g, and find use as adsorbents
characteristics including porosity, hydrophobicity, for methane and as hydrogen storage materials.[74,77–80]
and optical properties.[56,57] Metal oxide composite A reticular synthesis method was developed to realize
xerogels can also adsorb methyl orange.[58] There are the bottom-up synthesis through top-down design
also reports on microporous and mesoporous carbon logic by using inorganic, metal organic, and organic
xerogels for gas separation and purification.[59,60] molecules to build frameworks and large molecules.[81]
As compared with xerogels, aerogels have larger Well-defined molecular building blocks that will
surface area, larger pore volume, and higher poros- maintain their structural integrity throughout the
ity.[61–64] Alumina aerogels with a specific surface area construction process were used to build the MOF
as high as 1000 m2=g, and a pore volume as high as molecules. It allows remarkable control over composi-
17.3 cm3=g have been synthesized by supercritical carbon tion and structure of the material formed and employs
dioxide drying, but a very limited information on their the full range of the molecular synthetic methods and
adsorption properties was found.[61,62] A super water compounds in the preparation of this new type of
adsorbent consisting of 17–30% of CaCl2 doped on porous sorbent materials. The ability to molecularly
SiO2 aerogel showed an effective reversible adsorption engineer the lattice size, chemical environment, and
capacity of 100 wt%; the adsorption capacity of hydro- possibly structure by careful choice of the metal cen-
philic silica aerogels can be fully recovered after regen- ters and organic linkers offers the opportunity for the
eration.[64–66] CaO- and MgO-modified SiO2 aerogel development of new types of sorbents that could
sorbents can be used to capture pollution gases includ- potentially meet the Department of Energy (DOE)
ing CO2, SO2, CO, and NOx emitted from power plants target for hydrogen storage and that can be used
based on fossil fuels.[67] Several studies reported the use for other applications in separation and purification.
of aerogels as destructive sorbents for toxic gases and It is reported that metal organic framework-5
radionuclide removal from contaminated environ- (MOF-5) of composition Zn4O(BDC)3 (BDC: 1,4-
ments.[64,68–70] Carbon aerogels can also be made from benzenedicarboxylate) with a cubic three-dimensional
carbon materials under supercritical carbon dioxide extended porous structure and octahedral Zn–O–C
drying conditions; these carbon aerogels were studied clusters with benzene links can adsorb hydrogen up
for removing uranium and other inorganic ions from to 4.5 wt% at 78 K, and 1.0 wt% at room temperature
contaminated water.[71–73] Aerogels are special sorbent and pressure of 20 bar.[74,79] It is identified by inelastic
candidates with excellent pore texture, which may play a neutron scattering spectroscopy of the rotational
transitions of the adsorbed hydrogen molecules that Table 5 USDOE FreedomCAR hydrogen storage system
zinc and the BDC linker in MOF-5 are the two hydro- targets
gen binding sites responsible for hydrogen adsorption Year
on this material. Higher hydrogen adsorption capacity
at ambient temperature and 10 bar were observed on Target factor 2005 2010 2015
similar isoreticular metal organic framework-6 and -8 Specific energy (MJ=kg) 5.4 7.2 10.8
(IRMOF-6 and -8) having cyclobutylbenzene and Hydrogen (wt%) 4.5 6.0 9.0
naphthalene linkers.[79] A different microporous MOF Energy density (MJ=L) 4.3 5.4 9.72
sorbent [microporous metal coordination materials
System cost ($=kg=system) 9 6 3
(MMOM)] was reported to have hydrogen sorption
capacities ( 1.0 wt% at room temperature and 48 bar) Operating temperature ( C) 20=50 20=50 20=50
similar to those of the best single-wall carbon nano- Cycle life-time (adsorption= 500 1000 1500
tubes.[80] The adsorbed hydrogen can be released when desorption cycles)
the gas pressure is reduced. Flow rate (g=sec) 3 4 5
MOF sorbents have also been investigated for Delivery pressure (bar) 2.5 2.5 2.5
methane adsorption.[77] The reported methane storage Transient response (sec) 0.5 0.5 0.5
capacity of MOF-6 is 155 cm3 (STP)=cm3 at 298 K and
Refueling rate (kg H2=min) 0.5 1.5 2.0
36 atm, which is significantly higher than that of zeolite
(From Ref.[84].)
5A (87 cm3 (STP)=cm3) and other coordination
framework (213 cm3 (STP)=cm3).[77] Adsorption and
desorption of carbon dioxide, nitrogen, and argon on
a microporous manganese-based MOF sorbent has Hydrogen can be stored both physically and chemi-
been reported.[78] Another interesting porous MOF cally in a confined vessel with or without the assistance
sorbent, Cu-BTC (polymeric copper(II) benzene-1,3,5- of a storage media. The most commonly used methods
tricarboxylate) with molecular sieve character, was stu- for hydrogen storage are: gaseous and liquid hydrogen
died for its sorption properties of various adsorbates storage, solid state storage in complex metal hydrides,
including nitrogen, oxygen, carbon monoxide, carbon chemical storage materials, and in nanostructured
dioxide, nitrous oxide, methane, ethylene, ethane, and materials.[2,85] The representative hydrogen storage
n-dodecane.[82,83] A detailed investigation of sorption capacities, hydrogen storage, and release conditions
thermodynamics was performed for carbon dioxide in various materials are summarized in Table 6.
by a sorption-isosteric method. It was demonstrated Carbon nanotubes are probably the most investi-
that Cu-BTC sorbent can be used for the separation gated and documented hydrogen storage sorbent mate-
of carbon dioxide–carbon monoxide, carbon dioxide– rials. Several excellent reviews on carbon nanotubes
methane, and ethylene–ethane mixtures. In addition, for hydrogen storage are available.[2,86] As shown in
this sorbent can also be used to remove carbon Table 6, the hydrogen storage capacities on representa-
dioxide, nitrous oxide, high molecular weight hydro- tive carbon nanotubes are below 6 wt%, the most
carbons, and moisture from ambient air before referred DOE target for 2010.[84,87,88] The following
cryogenic separation to produce oxygen and nitrogen.[82] concerns about carbon nanotubes as hydrogen storage
materials have driven research in this area to other
directions:[85]
Hydrogen Storage Media
The development of hydrogen-fueled transportation 1. Difficult to meet the DOE’s long-term target
system and portable electronics will demand new mate- (9 wt%);
rials that can store large amounts of hydrogen at ambi- 2. Mechanisms for hydrogen sorption in carbon
ent temperature and relatively low pressures with small nanotubes are not well understood;
volume, light weight, fast charging and discharging 3. Part of the adsorbed hydrogen can only be
time, cyclic stability, and low cost. Table 5 summarizes recovered at high temperatures;
the targets for hydrogen storage system for automotive 4. Preparation and purification of carbon nano-
applications set by USDOE. The hydrogen storage tubes involve complicated and expensive pro-
capacities are calculated as both weight and volume cesses, which leads to high cost of carbon
percentage of the storage system.[84] To achieve these nanotubes;
goals, the hydrogen storage media (sorbent) should 5. Hydrogen storage capacity is quite sensitive to
have a high reversible hydrogen sorption capacity, sorbent preparation conditions;
low weight and high packing density as well as fast 6. Mixed results on hydrogen adsorption capacity
sorption=desorption kinetics, and low cost. have been reported.
Table 6 Summary of hydrogen storage capacity of various nanostructured materials

H2 storage H2 storage H2 release
Materials capacity (wt%) conditions 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]
TiS2 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
Mg2NiH4 3.6 1 bar, 500 K 1 bar, > 528 K [91]
NaAlH4 8.0 90 bar, 403 K [92]
Mg(AlH4)2 6.6 1 bar, > 436 K [93]
LiBH4 13.3 1 bar, > 473 K [94]
Nitrides
Li3N 9.3 1 bar, 443–473 K 1 bar, > 700 K [95]
Clathrate=molecular compounds
H2(H2O)2 5.3 1 bar, 77 K 1 bar, > 77 K [97]
H2(H2O) 10.0 6000 bar, 190 K < 6000 bar, > 190 K [97]
(H2)4(CH4) 33.3 2000 bar, 77 K < 2000 bar, > 77 K [97]
Noncarbonaceous nanotubes including boron storage system because they have the following
nitride (BN) and titanium sulfide (TiS2) have been pre- characteristics:[2,84,91–94]
pared and studied for hydrogen sorption.[89,90] Hydro-
gen storage capacity (2.5–4.5 wt%) similar to those for 1. Relatively high hydrogen storage capacity at
carbon nanotubes have been obtained on these noncar- modest pressures as indicated in Table 6;
bonaceous materials. MOF-based sorbents for hydrogen 2. Fast hydrogen charging and discharging rates;
sorption was discussed in the previous section. As and
suggested in Table 6, the hydrogen sorption capacities 3. Moderate temperature for hydrogen desorption.
on MOF-5 and MMOM are lower than those on car-
bon nanotubes. However, MOF sorbents look more
However, metal hydrides also suffer from the fol-
promising than carbon nanotubes as hydrogen sto-
lowing disadvantages as hydrogen storage materials:
rage media for the following reasons:
1. High sensitivity to impurities in hydrogen (CO,

1. MOF is easy to make and is less expensive; H2O, O2, CO2, and H2S);
2. Sorption sites for hydrogen on MOF are better 2. Storage capacity and rates decay with hydrogen
defined; charge–discharge cycles; and
3. MOF sorbents may have extremely high specific 3. Relatively high cost as compared with gaseous
surface area (> 4000 m2=g); and liquid hydrogen storage methods.
4. It is possible to tailor the interaction between
hydrogen and MOF by manipulating syn-
thesis parameters including different building Another interesting hydrogen storage material is
blocks. lithium nitride (Li3N), which shows 9.3 wt% useful
hydrogen storage capacity between thermal swing cycles
(473–700 K).[95] The requirement for high-temperature
Metal hydrides were widely investigated for hydro- desorption will greatly limit its applications.
gen storage, and are believed to be ideal hydrogen Most recently, hydrogen clathrate hydrate and other
molecular compounds were found to have hydrogen sto- contributes significantly to the adsorption. Composite
rage capacities as high as 33.3 wt%.[96–98] This is a very sorbents are typically made by physically mixing the
innovative way to store hydrogen with exceptionally powders of constituent sorbents with different sorption
high capacity to meet the DOE long-term target. How- properties; they tend to have multiple sorption sites for
ever, these clathrate and hydrogen storage compounds different adsorbate molecules. One example of a com-
were synthesized at extremely high pressures and at posite sorbent is a mixture of activated alumina and
liquid nitrogen temperature. It is unlikely these clathrate zeolites for removing moisture, carbon dioxide, and
hydrates will be used for hydrogen storage until we other trace components from air in an air-purification
find new clathrate hydrate compounds that can be process prior to cryogenic air separation.[106–108] Con-
synthesized and are stable at much lower pressures. ventionally, moisture is removed by activated alumina,
carbon dioxide by zeolite 13X, and hydrocarbons by
zeolite 5A.[107,108] Traditional air-purification processes
p-Complexation Sorbents and employ multiple layers consisting of activated alumina,
Composite Sorbents zeolite 13X, and optional zeolite 5A sorbents in a sin-
gle vessel to achieve significant removal of moisture,
A very good review article based on a panel study of carbon dioxide, and hydrocarbons from air. The major
status, future research needs, and opportunities for disadvantages of layered bed are nonuniform sorbent
porous sorbent materials was published several years packing for a short sorbent layer, very significant tem-
ago.[99] It was pointed out that very significant perature variation (> 30 C, sometimes called cold
advances have been made in tailoring the porosity of spots) between the zeolite and the activated alumina
porous sorbent materials in terms of size and shape sorbent layers. The large temperature difference could
selectivity. Relatively little progress has been achieved upset the sorption process operation if it is designed to
in terms of chemoselectivity of sorbents based on spe- be operated isothermally. It is beneficial to have a sin-
cific interactions between adsorbate molecules and gle sorbent with multiple sorption features for different
functional groups in the sorbents. Incorporation of impurities and eliminate sorbent layering and tempera-
active sites into sorbents is of high priority in the devel- ture variations.
opment of sorbents.
The p-complexation bond is a weak chemical bond
that is slightly stronger than van der Waals interaction, High-Temperature Ceramic O2 Sorbents
which governs physical sorption processes. Sorbents
with p-complexation capability tend to have higher Lin et al. disclosed in a U.S. patent a new group of sor-
selectivity than other physical sorbents for certain bents for air separation and oxygen removal using
adsorbate molecules. Several different types of p-com- oxygen-deficient perovskite-type ceramics as sorbents.[109]
plexation sorbents with Cuþ or Agþ ions supported on Perovskite-type ceramics are a group of metal oxides
different supports (SiO2, g-Al2O3, TiO2, variety of zeolites, having the general formula of ABO3. The ideal perov-
polymer resin, and activated carbon) were synthesized skite structure for ABO3 is shown in Fig. 4. It consists
using different methods including thermal dispersion, of cubic array of corner-sharing BO6 octahedra, where
wet-impregnation, sol–gel, microwave heating, ion- B is a transition metal ion. The A-site ion, interstitial
exchange zeolite, and ion-exchange resin.[34–36,99–105] It between the BO6 octahedra, may be occupied by an
was found that the CO adsorption capacity increases alkali, an alkaline earth, or a rare earth ion. Alternatively,
with Cuþ loading in an activated alumina supported the perovskite structure may be regarded as a cubic
sorbent.[100,101] To achieve the highest sorption capacity, close packing of layers of AO3 with B cations placed
the active species should be dispersed as a monolayer in the interlayer octahedral interstices.[110] This group
form.[99] The potential applications of these p-complexa- of the sorbents can be viewed as chemisorbents that
tion sorbents include:[2] can selectively adsorb a considerable amount of oxy-
gen at high temperatures (> 300 C), and theoretically
1. Desulfurization of gasoline and diesel fuels; has an infinitely high selectivity for oxygen over nitrogen
2. Separation of olefins and paraffins; or other nonoxygen species. The presence of other gases
3. CO separation from synthesis gases; has negligible effect on the separation properties of these
4. CO removal from hydrogen; new sorbents. High-temperature membrane separation
5. Removal of aromatics; and of oxygen has also received increasing interest from
6. Removal of volatile organic compounds other industrial gas companies.[111–113] Development of
(VOCs). high-temperature oxygen separation technology opens
up several high-temperature applications of oxygen
A p-complexation sorbent can also be viewed as a including syngas production, hydrogen production,
composite sorbent especially when the sorbent support and partial oxidation fuel reforming processes.
A
A B 0.5
0.45
0.4
δ
0.35
LSCF-1
0.3
0.25
0.0001 0.001 0.01 0.1 1
PO2 (atm)
B
Fig. 4 Ideal perovskite structure for ABO3 type oxides.
0.5
The oxygen equilibrium and kinetic properties of 1 2 3

perovskite-type ceramics have been extensively studied 0.45
primarily for applications as fuel cell electrodes and
oxygen permeable membranes,[110] and only a few for
oxygen sorption.[114–117] Oxygen nonstoichiometry (d) δ 0.4
occurs in some perovskite-type ceramics with B-site
cations of variable oxidation states and A-site cations LSCF-2
0.35
partially substituted by another cation with a lower
oxidation state. Oxygen nonstoichiometry, or oxygen
content, for a perovskite-type ceramic of a given com- 0.3
position is a function of temperature and oxygen par- 0.0001 0.001 0.01 0.1 1
tial pressure. Therefore, by changing temperature or PO2 (atm)
oxygen partial pressure, the value of oxygen nonstoi-
chiometry or the degree of oxygen vacancy in the mate- Fig. 5 Change of oxygen nonstoichiometry d with oxygen
rial changes. Within a certain range of temperature and partial pressure (LSCF-1. La0.1Sr0.9Co0.5Fe0.5O3–d; LSCF-2,
oxygen partial pressure the change of the oxygen non- La0.1Sr0.9Co0.9Fe0.1O3–d). (From Ref.[114].)
stoichiometry does not affect the perovskite structure,
and the change of the oxygen content in the material is perovskite oxide sorbents are needed to address the
a reversible process. The oxygen nonstoichiometry of issues of slow desorption rate, potential sorbent
the perovskite sorbents can be measured gravimetrically structure stability in cyclic processes, and effective
at different temperatures and oxygen partial pressures. regeneration methods.
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 High-Temperature CO2 Sorbents
material is defined.[114] Figs. 5 and 6 are examples of
oxygen nonstoichiometry of La1–xSrxCo1–yFeyO3–d Increased awareness of the global warming trend has
perovskite oxide sorbents as a function of oxygen led to worldwide concerns regarding ‘‘greenhouse
partial pressure or temperature, respectively.[114] gas’’ emissions. Greenhouse gases include CO2, CH4,
The corresponding oxygen sorption isotherm of and N2O and are mostly associated with the production
La1–xSrxCo1–yFeyO3–d perovskite oxide sorbents that and utilization of fossil fuels, with CO2 being the sin-
were calculated from the oxygen nonstoichiometry gle greatest contributor to global warming. Significant
data are shown in Fig. 7.[114] From these oxygen research efforts are being devoted worldwide on look-
isotherms we can conceive a high-temperature ing for economical ways of mitigating CO2 emission
vacuum swing sorption or temperature swing sorption problem.[118–122] Carbon capture and sequestration
process for oxygen separation or oxygen removing costs can be considered in terms of four components:
applications by using the La1–xSrxCo1–yFeyO3–d capture, compression, transport, and injection. Typi-
perovskite oxide sorbents. Future studies on cally about 75% of this cost is attributable to capture
0.45 and compression processes. Sorption of carbon dioxide

on solid sorbents is receiving increased attention in view
PO2 = 0.209 atm of the importance of both the removal and the recovery
0.4
of carbon dioxide from flue gases.[123,124]
Physical sorbents for carbon dioxide separation and
0.35
removal were extensively studied by industrial gas
δ
companies.[125–127] Zeolite 13X, activated alumina,

0.3 and their improved versions are typically used for
LSCF-2 removing carbon dioxide and moisture from air in
0.25 LSCF-1 either a TSA or a PSA process.[125–128] The sorption
temperatures for these applications are usually close
0.2 to ambient temperature. There are a few studies on
300 400 500 600 700 800 adsorption of carbon dioxide at high temperatures.
T(˚C) The carbon dioxide adsorption isotherms on two
commercial sorbents hydrotalcite-like compounds,
Fig. 6 Change of oxygen nonstoichiometry d with tempera-
ture (LSCF-1, La0.1Sr0.9Co0.5Fe0.5O3–d; LSCF-2, La0.1Sr0.9
EXM911 and activated alumina made by LaRoche
Co0.9Fe0.1O3–d). (From Ref.[114].) 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
A sorbents are basically not effective for carbon dioxide
0.5 capture at flue gas temperature (> 400 C). There is a
need to develop effective sorbents that can adsorb
Amount Adsorbed (mmol/g)
0.4 500˚C carbon dioxide at flue gas temperature to significantly

600˚C reduce the gas volume to be treated for carbon
0.3 sequestration.
Only a handful of studies on high-temperature car-
bon dioxide sorbents have been published in the past
0.2
few years.[123,124,129–133] It is believed that lithium zirco-
nate (Li2ZrO3) is one of the most promising sorbent
0.1 materials for carbon dioxide separation from flue gas
at high temperature because it can absorb a large amount
0 of carbon dioxide at around 400–700 C.[130,131] The
0.0001 0.001 0.01 0.1 1 carbon dioxide adsorption and desorption uptake
PO2 (atm) curves on lithium zirconate are shown in Fig. 9.[131]
As shown in this figure, about 20% carbon dioxide
B
was captured by the lithium zirconate sorbent during
0.6
sorption step at 500 C based on the following reaction:
Amount Adsorbed (mmol/g)
0.5 500˚C
600˚C Li2 ZrO3 þ CO2 ! Li2 CO3 þ ZrO2 ð4Þ
0.4
About 80% of adsorbed carbon dioxide can be des-
0.3 orbed with hot air 780 C. Addition of potassium car-
bonate (K2CO3) and Li2CO3 into Li2ZrO3 remarkably
0.2 improves the CO2 sorption rate of the Li2ZrO3-based
sorbent materials. X-ray diffraction (XRD) analysis for
0.1
phase and structural changes during the sorption=
desorption process shows that the reaction between
0
0.001 0.01 0.1 1 Li2ZrO3 and CO2 is reversible.[131] Based on this work, a
PO2 (atm) TSA process can be developed for carbon dioxide removal
from flue gas using Li2ZrO3-type sorbent materials.
Fig. 7 Sorption isotherms of: (A) La0.1Sr0.9Co0.5Fe0.5O3–d High-temperature carbon dioxide sorbents can also
and (B) La0.1Sr0.9Co0.9Fe0.1O3–d at 500 and 600 C. (From find applications in fuel reforming process to enhance
Ref.[114].) fuel to hydrogen conversion efficiency. It was reported
A
0.55
0.50
EXM911 20˚C
0.45
0.40
0.35
Q (mmol/g)
0.30
0.25
0.20
0.15 200˚C
0.10
0.05
300˚C
0.00
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Pressure (bar)
B
1.1
1.0
Activated Alumina 20˚C
0.9
0.8
0.7
0.6 200˚C
0.5
0.4
0.3
0.2 300˚C
Fig. 8 Adsorption isotherms of carbon
0.1 dioxide on commercial sorbents. (A)
0.0 Hydrotalcite-like compound, EXM911;
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 (B) LaRoche Industries activated alumina
Pressure (bar) at 20, 200, and 300 C. (From Refs.[123,124].)
that sorption of carbon dioxide can enhance the pro- of future technological developments in the new energy
duction of hydrogen for a steam–methane reforming economy and the stringent environmental regulations.
process using a mixture of Ni-based reforming catalyst The newly developed nanostructured sorbent materials
and a Ca-based sorbent. The rates of the reforming, have shown some very promising features, but they are
water-gas shift, and carbon dioxide removal reactions basically unexplored and systematic investigations are
are sufficiently fast that combined reaction equilibrium needed on both synthesis methods and adsorption
was closely approached, allowing for >95 mol% hydro- characteristic studies. The following are the author’s
gen to be produced in a single step.[134] views on future research needs in both sorbent synthe-
sis and applications:
CONCLUSIONS AND FUTURE DIRECTIONS 1. Explore entirely new sorbent synthesis routes to
better control of both sorbent pore texture and
Existing commercial sorbents including activated car- surface property.
bon, zeolites, activated alumina, and silica gels will 2. Design new sorbent materials from basic build-
continue to play important roles in adsorptive separa- ing blocks and introduce active sorption sites
tion and purification for current process industries in according to sorbent–adsorbate interaction
the near future. However, they cannot meet the needs requirements. MOF material syntheses using
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INTRODUCTION Absorption: The absorbing of molecules (as of

puriﬁcation processes to remove trace contaminants  Silica gel: $71 million

MSC Fig. 1 Pore size distributions for activated

Table 1 Representative physical properties of commercial adsorbents

Table 2 Selected applications of commercial sorbents

possibility of using CuO-doped g-alumina sorbents

Table 6 Summary of hydrogen storage capacity of various nanostructured materials

1. High sensitivity to impurities in hydrogen (CO,

The oxygen equilibrium and kinetic properties of 1 2 3

0.45 and compression processes. Sorption of carbon dioxide

companies.[125–127] Zeolite 13X, activated alumina,

0.4 500˚C carbon dioxide at ﬂue gas temperature to signiﬁcantly

1. King, C.J. Separation Processes, 2nd Ed.;

2. Yang, R.T. Adsorbents: Fundamentals and

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puriﬁcation processes to remove trace contaminants Silica gel: $71 million