Adsorption

The use of solids for removing substances from either gaseous or liquid solutions
has been widely used since biblical times. This process, known as adsorption, involves
nothing more than the preferential partitioning of substances from the gaseous or liquid
phase onto the surface of a solid substrate. From the early days of using bone char for
decolorization of sugar solutions and other foods, to the later implementation of activated
carbon for removing nerve gases from the battlefield, to today's thousands of
applications, the adsorption phenomenon has become a useful tool for purification and
separation.
Adsorption phenomena are operative in most natural physical, biological, and
chemical systems, and adsorption operations employing solids such as activated carbon
and synthetic resins are used widely in industrial applications and for purification of
waters and wastewaters.
The process of adsorption involves separation of a substance from one phase
accompanied by its accumulation or concentration at the surface of another. The
adsorbing phase is the adsorbent, and the material concentrated or adsorbed at the
surface of that phase is the adsorbate. Adsorption is thus different from absorption; a
process in which material transferred from one phase to another (e.g. liquid)
interpenetrates the second phase to form a "solution". The term sorption is a general
expression encompassing both processes.
Mainly van der Waals forces and electrostatic forces between adsorbate molecules
and the atoms, which compose the adsorbent surface, cause physical adsorption. Thus
adsorbents are characterized first by surface properties such as surface area and polarity.
A large specific surface area is preferable for providing large adsorption capacity,
but the creation of a large internal surface area in a limited volume inevitably gives rise to
large numbers of small sized pores between adsorption surfaces. The size of the micro
pores determines the accessibility of adsorbate molecules to the internal adsorption
surface, so the pore size distribution of micro pores is another important property for
characterizing adsorptivity of adsorbents. Especially materials such as zeolite and carbon
molecular sieves can be specifically engineered with precise pore size distributions and
hence tuned for a particular separation.
Surface polarity corresponds to affinity with polar substances such as water or
alcohols. Polar adsorbents are thus called "hydrophilic" and aluminosilicates such as
zeolites, porous alumina, silica gel or silica-alumina are examples of adsorbents of this
type. On the other hand, no polar adsorbents are generally "hydrophobic". Carbonaceous
adsorbents, polymer adsorbents and silicalite are typical nonpolar adsorbents. These
adsorbents have more affinity with oil or hydrocarbons than water.

Adsorbents

The adsorbent is the separating agent used to express the difference between
molecules in a mixture: adsorption equilibrium or kinetics.Micro porous, high specific
surface material (200 - 2000 m2/g)
Most commonly used:
Alumina (drying)
Silica gel (drying)
 Zeolite molecular sieves (gas & liquid separations, drying)
Highly specific, single pore size may be fine-tuned: cations +
structure
A type or LTA
X and Y or FAUjasites
Mordenite, other natural zeolites
Silicalites or ZSMx (hydrophobic, carbon like)
Active carbon (gas & liquid separations, guard beds)
Carbon molecular sieves (narrow pore distribution)
Impregnated carbons (Cu-chlorides - CO separation)
Clays (natural and pillared clays)
Resins, polymers (biological, ions, large molecules)

Applications
Representative Commercial Gas Phase Adsorption Separation
Gas Bulk Separations
Separation Adsorbent
Normal paraffins, isoparafins, aromatics Zeolite
N2/O2 Zeolite
Carbon molecular
O2/N2 sieve
Zeolite, activated
CO, CH4, CO2, N2, A, NH3/H2 carbon
Acetone/vent streams Activated carbon
C2H4/vent streams Activated carbon
H2O/ethanol Zeolite
Gas Purifications
Separation Adsorbent
H2O/olefin-containing cracked gas, natural gas, air, synthesis gas,
etc. Silica, alumina, zeolite
CO2/C2H4, natural gas, etc. Zeolite
Activated carbon,
Organics/vent streams others
Sulfur compounds/natural gas, hydrogen, liquified petroleum gas
(LPG), etc. Zeolite
Solvents/air Activated carbon
Odors/air Activated carbon
NOx/N2 Zeolite
SO2/vent streams Zeolite
Hg/chlor-alkali cell gas effluent Zeolite

Representative Commercial Liquid Phase Adsorption Separations

Liquid Bulk Separations
Separation Adsorbent
Normal paraffins / isoparaffins, aromatics Zeolite
p-Xylene/o-xylene, m-xylene Zeolite
Detergent-range olefins/paraffins Zeolite
p-Diethyl benzene/isomer mixture Zeolite
Fructose /glucose Zeolite
Liquid Purifications
Separation Adsorbent
H2O/organics, oxygenated organics, chlorinated organics, etc. Silica, alumina, zeolite
Organics, oxygenated organics, chlorinated organics, etc./H2O Activated carbon
Odor, taste bodies/drinking H2O Activated carbon
Sulfur compounds/organics Zeolite, others
Various fermentation products/fermentor effluent Activated carbon
Decolorizing petroleum fractions, sugar syrups, vegetable oils, etc. Activated carbon
What is adsorption?

Adsorption is a process that uses special solids (called adsorbents) to remove

substances from either gaseous or liquid mixtures. The term "adsorption" was first coined
in the late 19th century, but the process itself was not widely used until the 1940s and 50s
when activated carbon was first used for municipal water treatment. These days, it is not
always adsorption that matters, but desorption. This is because the simple uptake of a
component generally only changes its phase (i.e., from either gas- or liquid-phase to
adsorbed- or solid-phase). In order to be economical and to protect the environment, it is
usually important to desorb the component in a fluid that is richer than that from which it
was originally adsorbed. This accomplishes enrichment or purification in a cyclic manner.
There are a variety of standard methods to force an adsorbent to take-up then release
certain components. One, that applies only to gas-phase separations, is cycling the
pressure - resulting in what is called pressure swing adsorption (PSA). Another method,
which works for either gases or liquids, is temperature swing adsorption (TSA). In addition
to those, some chemicals are used as regenerants. Some function as a diluent or carrier,
and they elute adsorbed components from an adsorbent, because they are less strongly
adsorbed. Others work by displacing adsorbed components. Since they are more strongly
adsorbed than the ones being displaced, there must be a subsequent step to drive those
off the adsorbent.

Uses of Adsorption

Adsorption is effective for purifications, e.g. taking a contaminant ranging from 1

ppb to 1000 ppm out of a stream of gas or liquid. In addition, adsorption is good for bulk
separations, e.g. taking 1 to 50% out of a stream of gas, or maybe 1 to 10% out of a
liquid. Adsorption is also used for recovery of certain constituents (solvents from air),
preventing pollution, purifying materials that will react, and so on. The above by no means
represents a comprehensive list of the ways that adsorption can be used. As with any
science, adsorption is constantly evolving and research is ongoing.

Benefits of Adsorption in Industrial Settings

Over the years, advancements in the field have resulted in substantial cost benefits
from and expanded usage of adsorption in a number of industrial settings. One prominent
example is in refineries and petrochemical plants where pressure swing adsorption (PSA)
has replaced cryogenic distillation as the most economical method for separating
hydrogen from various compounds used in these settings. By replacing cryogenic
distillation with PSA, refineries and petrochemical plants have been able to reduce costs
by anywhere from 60% - 90%. Another example of the cost benefits of adsorption is ARI's
recent development of the Sulfur Dioxide Recovery System (SDRS). In this instance, the
SDRS uses PSA techniques pioneered by ARI to enable foundry operators to recover and
reuse more than 98% of the sulfur dioxide used in forming cold box molds for metal
casting. According to ARI's estimates, a mid-size foundry running three shifts a day can
expect to save up to 40% of their annual cost of SO2 by using the SDRS.

Adsorption and Adsorbates

When Gas Molecules Get Stuck on Surfaces
When a gas molecule hits a surface, several things may happen:
It may be reflected,
it may bind to the surface, remaining intact as a molecule (molecular adsorption),
or
it may dissociate, and its fragments (e.g., the atoms it consists of) bind to the
surface (dissociative adsorption).
In a few special cases, gas molecules can dissociate as they hit a surface, and
only part of the fragments remain on the surface, and part of the molecule is
abstracted, i.e., leaves the surface (abstractive adsorption).

If the molecule or its fragments are bound to the surface, they are known as adsorbates.
When they leave the surface, we speak of desorption. Understanding adsorption and
adsorbates is essential for gaining insight into catalysis, e.g. exhaust gas purification by
catalysts, where different toxic gases adsorb on the catalyst, react there and the reaction
products (non-toxic gases) desorb from the surface.

Dissociative adsorption - hot adatoms?

When an oxygen molecule (O2) hits an aluminum surface, dissociates and the oxygen
atoms are bound to the aluminum atoms, a lot of energy is released (coming from the
high binding energy between oxygen and aluminum). If all this energy (more 5 eV per O
atom) were transferred to the O atoms, they would be really hot, about ten times the
temperature of the atoms at the surface of the sun! So even a part of this energy would
be sufficient to call the O atoms "hot adatoms", and people have been wondering what
the oxygen atoms do with all this energy ...
With these thoughts in mind, and based on STM images interpreted as showing single
oxygen atoms widely apart, it was claimed in a famous article [H. Brune et al., Phys. Rev.
Lett. 68 (1992) 624] that the hot oxygen atoms "fly apart at least 80 before their excess
energy is dissipated." One ngstrm (1 ) is 1/10000000 of a millimeter, or about 1/2 to
1/3 of the size of an atom, so 80 is not particularly far by usual standards, but it is quite
a lot for an atom: almost 30 times the distance between two Al atoms.

This motion has been called transient mobility, because it occurs only for a very short
moment after adsorption.
Theoretical studies triggered by this work could not confirm this result, the Al surface is
too bumpy and the oxygen atoms - even if receiving the maximum energy possible -
would be slowed down very efficiently. Although there may be some ways out of this
dilemma (abstractive adsorption, "cannon-ball" trajectories over the surface) we decided
to have a look with our STM - in the meanwhile the state of the art had advanced a bit
and we could get somewhat better resolution.

Now, we see the lattice of the aluminum atoms (faint gray texture in the left frame), and
the oxygen atoms betray their existence by dark spots. That's because the oxygen atoms
themselves don't carry tunneling current, while they suck electrons from the Al atoms.
With fewer electrons less tunneling current can flow through the Al, and that's why it looks
darker (deeper) at the sites of the oxygen atoms (see the introduction to STM).
If we look carefully, we note that the dark spots are not round, but elongated - so they
can't be single oxygen atoms! We have enlarged two parts of the image (red and purple
frames) and drawn black lines over the Al atoms - here it becomes obvious that the
elongated black spots are due to two oxygen atoms (positions marked as yellow dots),
each of them between three Al atoms.
In other words, we see pairs of oxygen atoms, whereas with lower resolution, one could
mistake them for single O atoms.
If there were only pairs, everything could be simple: the pairs would simply correspond to
the O2 molecules. In the STM images, we also see groups of three (or more) oxygen
atoms, however, one of them marked with a "3" in the image above. But we certainly did
not have any ozone (O3) in the gas!
The solution to the puzzle finally came from STM measurements with the aluminum
surface at low temperature. Whereas this should not affect the transient mobility, at low
temperature (-190 C) we can be sure that the atoms don't move (diffuse) after they have
lost the adsorption energy. And that's what the surface looks like after oxygen has been
adsorbed at room temperature:

The aluminum lattice is not resolved, but we see the individual oxygen atoms as dark
spots as in the previous image, and we note that they are either elongated (as the pairs of
O atoms in the previous image) or come in pairs of two clearly separated O atoms. We
have labeled each pair with the distance between the two O atoms, given in multiples of
the distance between two aluminum atoms ("1" stands for 2.86 , "2" for 5.72 , etc.). In
our experiments we hardly ever observe a distance above 7.6 (" " in the image), far
below the 80 distance claimed in the study mentioned above.
Summing up all these and some more of our results, we can now understand what
happens when O2 adsorbs on aluminum: After dissociation, the two oxygen atoms can
either land next to each other (resulting in the pairs marked "1" in the low-temperature
image) or part of the adsorption energy can allow them to jump over a few aluminum
atoms before they lose all their energy. At -190C the atoms remain there. At room
temperature, single oxygen adatoms are mobile and diffuse over the surface until they
either form a stable pair with the second atom of the molecule they originate from or they
can attach to a pre-existing pair (or larger group) and form a group of three (or more)
oxygen atoms on the surface. Pairs and larger groups of oxygen adatoms do not move
any more at room temperature.
So it is quite a long story what can happen when one oxygen molecule hits a pure metal
surface and starts to oxidize it - imagine how much more can happen on more complex
surfaces...

Adsorption on alloys - where the adsorbates want to sit

Today, catalysts are not only used for exhaust gas purification but also for many
processes in chemistry. Alloys often perform better in catalysis than pure metals, and
that's why many catalysts are based on alloys.
At a first view, if we have an alloy, we can expect that the atoms in an alloy simply behave
as usual, so a silver atom in a silver-palladium alloy behaves like the noble metal silver,
while the palladium atoms in the alloy are more reactive, as we know it for the metal
palladium. This means that adsorption on the alloy is simply governed by chemical
affinity.
If we adsorb oxygen on a silver-palladium (AgPd) alloy surface, we find this kind of
behavior, indeed:

What you see here is the alloy surface, consisting of 95% silver atoms (individual atoms
not resolved under these tunneling conditions) and about 5% palladium atoms visible as
white dots (this is a case of chemical contrast). The black dots are oxygen atoms (from
dissociative adsorption of the oxygen molecules). As these black dots appear as large as
the Pd atoms, we cannot directly determine whether the oxygen atoms bind to Pd atoms
on the surface or not.
Sometimes, the oxygen atoms can hop (diffuse) from one place to another. The right
image was taken 20 seconds after the left one, and you may notice that some black
oxygen atoms have changed their position (red arrows). The site an oxygen atom leaves
always appears bright thereafter, so there is a palladium atom. Similarly, the new position
an oxygen atom takes is always one that has been bright before, i.e., at a Pd atom. This
means that the oxygen atoms are strongly bound to palladium atoms, and remain there
for a while, but they have much lower chemical affinity to silver atoms and thus don't
remain on the pure silver surface for long.
Adsorption on alloys is not as simple as the AgPd example may suggest - the atoms in an
alloy do not always behave the same way they would behave in the respective pure
metal. Its environment influences the chemical properties of an atom. For example, a
platinum atom in a platinum-cobalt (PtCo) alloy does not behave like a platinum atom in
pure platinum. This effect is known as ligand effect - the word "ligand" stands for the
"neighbor", i.e., a neighboring atom in the alloy.
To see what this means, let us analyze these two STM images:

The upper image shows a PtCo alloy with about 80% Pt atoms (looking like white balls)
and 20% Co atoms (appearing gray or black and more blurred than the Pt atoms). At this
surface carbon monoxide (CO) molecules have adsorbed. The lower STM image shows
the same area of the surface, but here the tunneling conditions have been set to show the
CO molecules (white).
We can now superimpose these two images on the computer and make a map to see
where the CO molecules are bound - we have done this for the framed area in the STM
images. We first note that the CO molecules (blue circles) are always on top of one metal
atom (square dot in the map), not in a "bridge site" between two or a "hollow site"
between three metal atoms. Second, CO molecules are only on top of Platinum atoms
(white balls in the STM image, gray dots in the map), never on top of cobalt atoms (red
dots in the map). Up to now, what we have observed are the properties of the pure metals
platinum and cobalt: CO molecules sits on top of these atoms and bind more strongly to
Pt than to cobalt.
We come to the third observation when we look at the surroundings of the Pt atoms that
CO molecules bind to: CO never binds to a Pt atom having only Pt neighbors! If one
counts how many CO molecules are adsorbed on Pt atoms with one, two, ... cobalt
neighbors in the surface, we find that Pt atoms with more cobalt neighbors are more likely
to be the binding site of a CO molecule than Pt atoms with fewer cobalt neighbors. This is
a clear demonstration of the ligand effect showing that its neighbors modify the properties
of an atom.

There is much more that we can learn from our STM images, e.g., Some CO molecules
(dotted in the map above) appear mottled or fuzzy in the STM images, showing us that
they don't stay where they are but rather jump between different sites quite rapidly (in less
than 1/1000 of a second).
- CO bonding on the alloy in general is much weaker than on pure metal, platinum or
cobalt. Binding of CO molecules is stronger on Pt atoms, which are sitting just a tiny bit
higher than the others. And more, but we don't want to risk that you become tired before
you have seen all of our STM Gallery!