An Introduction to

Zeolite Molecular Sieves

Dry Purify Separate Dry Purify Separate Dry Purify Sep

What are zeolite molecular sieves?
Why they are used

H
undreds of systems for the
drying and purification of
liquids and gases rely on the
high adsorption efficiency of zeolite
molecular sieves. These unique
adsorbents are a result of synthetically
produced crystalline metal alumino-
silicates that have been activated for
adsorption by removing their water of
hydration. Since little or no change
in structure occurs during this
Unlike other adsorbents, zeolite
molecular sieves have precisely
uniform pore sizes and molecular
dimensions. This translates into a
sieve-like selectivity where molecules
of varying size and polarity may be
readily adsorbed, slowly adsorbed or
completely excluded. This selectivity,
combined with a high capacity over
a wide range of operating conditions,
gives each zeolite molecular sieve a
Use of zeolite molecular sieves to dry,
purify and separate liquids and gases
prevents unwanted side reactions,
helps meet product specifications,
and avoids costly complications from
equipment corrosion and freeze-up.
Other beneficial performance
characteristics include:
• Dehydration to water content less

dehydration, highly porous adsorbents high level of adsorption efficacy. than 0.1ppm

are formed that have a strong affinity • High capacity for water above
for water and specific molecules. 200°F (93°C)

Used successfully in hundreds of commercial systems

for drying and purifying liquids and gases, zeolite molecular
sieves are the most universally applicable adsorbents in the
process industries.

• Purification and dehydration
in one operation
• Dehydration without adsorbing
valuable product or altering the
composition
• High product recovery
• Numerous purification and
dehydration cycles are possible due
to the reversible adsorption process
• High cyclic capacity with sufficient
thermal or pressure swing purging
Table of Contents
Specific, uniform
pore size is the key to Page 2 What are zeolite
adsorbent efficiency molecular sieves?
and selectivity…
Based on size and charge distribution Page 4 Zeolite research and
in a molecule, zeolite molecular sieves synthetic production
can adsorb individual molecules
readily, slowly or not at all.
Page 6 Crystal structure
and molecular
sieve types
Page 8 Adsorption based
on molecular size,
polarity and degree
of unsaturation
Page 12 Zeolite molecular
sieves and adsorption
efficiency
Page 13 Zeolite molecular sieves
and co-adsorption
Page 15 Regeneration cycles
Page 17 Applications
Page 18 Put UOP’s experience
and technology to
work for you
TM
MOLSIVTM
Adsorbents

Sodium
Silicate
Sodium
Aluminate
Makeup
Tank
Crystallization
Tank
Naturally occurring crystalline
zeolites, a subset of molecular sieves,
were first noted two centuries ago.
Their ability to release water when
heated and readsorb upon cooling
was known at that time, but their
capacity to selectively adsorb
molecules other than water was not
recorded until the 1920s. In the early
1930s, X-ray diffraction studies
revealed the zeolites as crystalline
materials with precisely arrayed
cavities and pores within each crystal.
Since zeolites found in nature have a
high degree of chemical and physical
variability, these products were not
viable for commercial separation
processes. In the early 1950s,
a division of Union Carbide
Corporation, that is now part of UOP,
was searching for an adsorbent to
separate atmospheric gases and to be
used in other industrial applications.
As a result of this research, structures
of silicon and aluminum oxides with
uniform pore sizes and precise
Salt
Steam
Ion Exchange Tank
Ion-Substituted Zeolite
Wash Clay
Water Binder
Steam
Zeolite
Crystals
Crystal Slurry
Filter
Weigh
Hopper
molecular dimensions were had for commercial use, they began to
synthesized and patented. The delve into adsorption technology and
synthetic zeolites’ sieve-like selectivity design processes that could rely on
offered the consistent performance these new materials.
necessary for commercial use. By
1953, more than 30 pure zeolite
species had been prepared. Their
crystal structures and adsorption
properties had been characterized,
and researchers had learned how to
regenerate them for repeated use in
commercial applications.
Extensive QC testing insures superior
product quality and consistency
As a consequence of their research,
Zeolite research zeolite molecular sieves were
and synthetic substituted into existing dryer and
production simple adsorber systems with amazing
results. The use of zeolite molecular
sieves improved the drying and
Zeolite research spawns
purifying of various gas and liquid
commercial adsorption
process streams with minimal changes
technology
in technology. For more advanced
O
nce engineers recognized
uses, however, additional process
the incredible potential
engineering knowledge was required.
zeolite molecular sieves
To address this problem, Union
4
 Wash
Water

Manufacturing process
Filter
for the production of activated
zeolite molecular sieves.

Activated
Molecular
Sieve Product
Mixer Particle Dryer Kiln
Forming
Screen

Carbide formed a large, process engineering group to develop new and Forming final product
comprehensive adsorption technology and design guidelines. Starting with Once separated and washed, the filter
fundamental adsorbent data, the researchers studied adsorption equilibria, cake is conveyed to hoppers. To form
adsorption kinetics, deactivation phenomena, cyclic life and scale-up factors. commercial 1/16-in and 1/8-in (about
After much research, the group discovered how to economically manufacture 1.6-mm and 3.2-mm) pellets (extrudates) or
the zeolites in commercially useful forms without adversely affecting their beads (spheres), crystals from the filter are
adsorption properties. mixed with specially formulated clay
In November of 1954, Union Carbide announced the availability of the first binders. The crystals are then fed through
limited commercial quantities. The pure zeolites were then used within the forming equipment to produce pellets
chemical, manufacturing and petroleum refining industries to solve difficult gas or beads. The various product forms are
purification and dehydration problems. Today, by altering existing crystalline then dried, screened and fired in a rotary
structures for improved functionality, UOP continues to manufacture many kiln to drive out the water and activate the
types of zeolites for a myriad of industries. zeolite molecular sieves. The adsorbents are
then immediately packaged to prevent any
How zeolite products are manufactured moisture pick up.
Sodium silicate, alumina trihydrate and sodium hydroxide are batch-weighed
Many tests are used to determine product
into mix tanks and stirred until homogenous. The mixture forms a gel that is
quality from crystallization to final firing.
pumped into a crystallization tank where it is monitored under closely
Examples include x-ray diffraction, McBain-
controlled conditions.
Bakr adsorption, loss on ignition, crush
Filter, wash and exchange strength, density and particle size. Quality
After crystallization is complete, a rotary filter separates and washes the control techniques including Statistical
zeolite crystal slurry. For cationic exchange to take place (calcium, potassium Process Control and adherence to ISO 9000
or other cations substituted for sodium in the crystal), the filter cake is standards ensure that crystallization and
transferred to a heated tank where it will be mixed with a solution of the other manufacturing processes achieve
appropriate metal salt. The exchanged forms will then be washed and exact specifications.
filtered in the same manner as the original crystal slurry.

5
Structural model of a zeolite.

Crystal structure and

molecular sieve types

T
he basic formula for zeolite molecular sieves is M2/nO • Al2O3 • xSiO2 • yH2O
where M is a cation of n valence. The fundamental building block of the
molecular sieve crystal structure is a tetrahedra with four oxygen anions
surrounding a smaller silicon or aluminum cation. Sodium ions or other cations make up
the positive charge deficit in the alumina tetrahedra, and each of the four oxygen anions is
shared, in turn, with another silica or alumina tetrahedron to extend the crystal lattice in
three dimensions. In all molecular sieve types, the sodium ion can be exchanged to form
other functional products.

The crystal structure of zeolite molecular sieves is honeycombed with relatively large
cavities. Each cavity is connected through apertures or pores. The water of hydration is
contained within these cavities. Before product is used, the water of hydration is
removed by heating.

Skeletal Packed Solid

Tetrahedron Spheres Tetrahedron

Illustrations of the rigid, three-dimensional

framework of SiO4 and Al04 tetrahedra

1 2

The crystallization of molecular sieve Type A from a hydrous

gel as seen through the electron microscope. Photo 1 shows
development of crystallization after two hours at 100º C.
Photo 2 shows completely crystallized A.

6
Commercially useful
zeolite species
In general, the elasticity and kinetic
energy of incoming molecules allows
for easy passage of molecules of up
to 0.5 angstroms larger than the
free diameter of the aperture. In
addition, the size and position of the
exchangeable cations may affect the
free aperture size in any type of
molecular sieve. The zeolite molecular
sieves that are most commonly used
include Types A and X. Unit cell
formulas and structural details for
each type are outlined below.
Type A
Na12 [(AlO2)12 (SiO2)12] • 27H2O
Note: Na+ (sodium) can be replaced
• The Type A molecular sieve
has a framework composed of
truncated octahedra joined in
a cubic array. The result is
a central truncated
cube-octahedron with an
internal cavity 11 angstroms
in diameter (alpha cage).
• Each central cavity, or alpha
cage, is entered through six
circular apertures formed by
a nearly regular ring of eight
oxygen atoms with a free
diameter of 4.2 angstroms.
• The cavities are arranged in a
continuous three-dimensional
Type 3A
Type 3A crystals are produced when
some of the sodium ions are replaced
by potassium ions. Since potassium
ions are larger than sodium ions, the
pore size is effectively reduced to
about 3.2 angstroms.
Type 4A
Type 4A sodium-bearing crystals have
a free aperture size of 3.5 angstroms
in diameter. At typical operating
temperatures, molecules with an
effective diameter of up to four
angstroms may be passed through
this aperture.

by other cations. pattern forming a system of 4.2 A°

unduloid-like channels with a
Type A contains roughly spherical
maximum diameter of 11 2.6 A°
cavities that are approximately 11 11.4 A°
angstroms and a minimum
angstroms in diameter and about 925
of 4.2 angstroms. 6.6 A°
cubic angstroms in volume. They
• The truncated octahedra enclose
account for nearly half of the total
a second set of smaller cavities
crystalline volume that is available
6.6 angstroms in internal
for adsorption.
diameter (beta cages). The
4 A°
smaller cavities are connected to
2 the larger cavities via a distorted Above: Two adjacent unit cells of
Type 4A — light circles represent
ring of six oxygen atoms of
1 oxygen ions and dark circles
2.2 angstroms free diameter. represent sodium cations.

(1) Truncated octahedron. (2) Face of cubic

array of truncated octahedra.

7
Type 5A
When some of the sodium ions in
Type 4A are replaced with calcium
ions,Type 5A is produced. It features
the largest pore opening of the A
types, with a free aperture size of
4.2 angstroms.
High silica molecular sieves
Like Types A and X, high silica zeolites selectively adsorb molecules based
on their size. However, they differ from Types A and X in that they have
a significantly higher proportion of SiO2 to AlO2 in their molecular
structure. With the reduced amount of AlO2 and the corresponding
reduction in cation density, the high silica zeolites are hydrophobic and
organophilic adsorbents. The high silica zeolites are also stable at low

Type X pH ranges and high temperatures up to 1,292ºF (700ºC).

Na86 [(AlO2)86 (SiO2)106] • 264H2O

Note: Na+ (sodium) can be replaced
by other cations. Adsorption based on molecular size,
Although Type X is based on the
same building blocks as Type A, the
polarity and degree of unsaturation
beta cages are linked tetrahedrally

instead of in a cubic arrangement.
The Type X crystal has a larger,
elliptical-shaped internal cavity of 13
angstroms in diameter with a pore
diameter of approximately 8
angstroms for the sodium form.
N
umerous zeolite species that differ in chemical composition, crystal
structure and adsorption properties are known. By selecting the
appropriate adsorbent — one that allows entry of those molecules small
enough to pass into the pore system — and by choosing the proper operating
conditions, zeolite molecular sieves can be adapted to suit specific applications.
While the external surface area of the molecular sieve crystal is available for
adsorption of molecules of all sizes, the internal area is available only to those

Zeolite molecular sieve characteristics and applications

Type† Nominal Pore Common Bulk Density Heat of Adsorption Equilibrium Molecules
Diameter Form lb/cu-ft (max) btu/lb H2O H2O Capacity* Adsorbed**
Angstroms (gm/cc) (kcal/kg H2O) wt-%
3A 3 Powder 35 (0.56) 1800 26 Molecules with an effective
1/16-inch Pellets 40(0.64) (1,000) 21 diameter <3 angstroms
1/8-inch Pellets 40 (0.64) 21 including H2O and NH3
8 x 12 Beads 44 (0.71) 21
4 x 8 Beads 44 (0.71) 21

4A 4 Powder 32 (0.51) 1800 27 Molecules with an effective

1/16-inch Pellets 44 (0.71) (1,000) 22 diameter <4 angstroms
1/8-inch Pellets 44 (0.71) 22 including ethanol, H2S, CO2, SO2,
8 x 12 Beads 44 (0.71) 22 C2H4, C2H6 and C3H6
4 x 8 Beads 44 (0.71) 22
14 x 30 Mesh 44 (0.71) 22

5A 5 Powder 32 (0.51) 1800 26 Molecules with an effective

1/16-inch Pellets 44 (0.71) (1,000) 21.5 diameter <5 angstroms including
1/8-inch Pellets 44 (0.71) 21.5 n-C4H9OH, n-C4H10,
C3H8 to C22H46, R-12

13X 8 Powder 27(0.43) 1800 30 Molecules with an effective

1/16-inch Pellets 40 (0.64) (1,000) 26 diameter <8 angstroms
1/8-inch Pellets 40 (0.64) 26 including C6H6, C7H8
8 x 12 Beads 40 (0.64) 26
4 x 8 Beads 40 (0.64) 26

†Chart depicts basic molecular sieve types only. In all applications, these basic forms are customized for specific use.
*Lbs H2O/100 lbs activated adsorbent at 17.5 torr H2O at 25ºC. **Each type adsorbs listed molecules plus those of preceding type.

molecules small enough to enter the
pores. The external area is about one
percent of the total surface area.
Materials that are too large to be
adsorbed internally will typically be
adsorbed externally to the extent of
0.2 to 1 weight percent.
Zeolites will preferentially adsorb
molecules based on polarity and
degree of unsaturation in organic
molecules, in addition to selectivity
based on size and configuration. In a
mixture of molecules small enough to
enter the pores, the molecules with
lower volatility, increased polarity, and
a greater degree of unsaturation will be
more tightly held within the crystal.
Molecules
Excluded
Molecules with an effective
diameter >3 angstroms (ethane)
Molecules with an effective
diameter >4 angstroms (propane)
Molecules with an effective
diameter >5 angstroms
(iso compounds and all 4-carbon rings)
Molecules with an effective diameter >8
angstroms (C4F9)3N
The role of cations
The strong adsorptive forces in
zeolite molecular sieves are primarily
due to the cations that are exposed
within the crystal lattice. They act as
sites of strong localized positive
charges that electrostatically
attract the negative end
Exposed cations within the
crystal structure act as sites of strong
localized positive charge. These sites
electrostatically attract the negative
end of polar molecules.
of polar molecules. The greater the
polarity of the molecule, the more
strongly it will be attracted
and adsorbed.
Polar molecules are generally those
that are asymmetrical and contain O,
Applications
• Preferred adsorbent for commercial dehydration of unsaturated
hydrocarbon streams (cracked gas, propylene, butylene
and acetylene)
• Dries polar liquids such as methanol and ethanol
• Static desiccant in household refrigeration systems
• Adsorbent for static dehydration in a closed gas or liquid system
• Used in the packaging of drugs, electronic components and
perishable chemicals
• Water scavenger in paint and plastic systems
• Used commercially in drying saturated hydrocarbon streams
• Separates normal paraffins from branched-chain and cyclic
hydrocarbons through a selective adsorption process
• Pressure swing purification of hydrogen
• Used commercially for general gas drying, air plant feed purification
(simultaneous removal of H2O and CO2), and liquid
hydrocarbon and natural gas sweetening
(H2S and mercaptans removal)
S, Cl or N atoms. Carbon monoxide,
for example, will be adsorbed in
preference to argon.
In fact, under the influence of
localized, strong positive charges on
the cations, polarity may be induced
in the molecules. The polarized
molecules are then adsorbed strongly
due to the electrostatic attraction of
the cations. In hydrocarbons, the more
unsaturated the molecule, the more
polarizable it is and the more strongly
it is adsorbed. As an example, zeolite
molecular sieves will effectively
remove acetylene from olefins and
ethylene or propylene from saturated
hydrocarbons.
Adsorption, desorption
and hysteresis
Since zeolite molecular sieves rely on
strong physical forces rather than
chemisorption to retain adsorbates,
their adsorption is characterized by a
Langmuir-type isotherm (the amount
of a given compound adsorbed
increases rapidly to a saturation
value as its pressure or concentration
increases in the external bulk phase).
Any further increase in pressure at
constant temperature causes no
further increase in the amount
adsorbed. With zeolite molecular
sieves, this equilibrium saturation
value typically corresponds to a
complete filling of the internal void
volume with the adsorbate. When
adsorbed molecules are desorbed
via heat or by displacement with
another material, the crystal’s
chemical state remains unchanged.
 Water Vapor Adsorption at 25° C 2. The relative size of molecules to purify the fluid while the other
(Equilibrium Data)
25 and molecular sieve pores bed is being heated, purged and
Molecular
Sieve 3. The strength of adsorptive cooled. When the process design
Type A
20
forces between molecular requires less than six hours for the
sieves and adsorbate adsorption step, additional beds can
15
Capacity

Silica
4. Adsorption temperature be added to permit continuous
wt-%

Gel

10 processing of the feed.

Activated
Fundamental adsorption systems
Alumina
5
Depending on the type of operation, Single-bed adsorption
zeolite molecular sieves may be used Single-bed adsorption can be used
0
10 20 30 40 50
in one of three basic types of when interrupted product flow can
Relative Humidity Percent adsorption systems: be tolerated. When the adsorption
Adsorption on zeolite molecular sieves • Multiple-bed adsorption capacity of the bed is reached, it can
produces a Langmuir-type isotherm.
• Single-bed adsorption be regenerated for further use either
• Static adsorption in place or at another location.
With zeolite molecular sieve
Alternatively, it can be discarded
powders, no hysteresis occurs Multiple-bed adsorption
if economically feasible.
during desorption. Adsorption and Multiple bed adsorption is ideal for

desorption are completely reversible most commercial, large-scale fluid Static adsorption
with their respective isothermal purification operations. Conventional When manufactured into various
curves coinciding completely. fixed-bed, heat-regenerated adsorption physical forms, zeolite molecular
However, with zeolite molecular sieve systems are commonly used. A typical sieves can be used as static desiccants
pellets or beads, further adsorption dual-bed installation places one bed in closed gas or liquid systems.
may occur at pressures near the on-stream

saturation vapor pressure. This can

occur as a result of condensation in
the pellet or bead voids external to
Out
the zeolite crystals. In addition,
hysteresis may take place during Cooling
Heater Gas
desorption of the adsorbate in the Out
Adsorption

Desorption

In
macro-pore region of the binder. Liquid
Stream
In
A brief review of adsorption
In
principles and systems Purge
Gas
The rate at which molecules are
adsorbed into formed zeolite Out

molecular sieves depends on the

following four variables: Cooler Condenser

1. The rate at which molecules

being adsorbed can diffuse to General flow chart for liquid drying.

activated crystals within the

pellet or bead Multiple bed adsorption for
H20 and C02 removal from natural gas
before methane liquification.
10
11
Zeolite molecular sieves and adsorption efficiency

Z
eolite molecular sieves are
employed in numerous
installations and operations
due to their exceptional adsorption
efficiency. The following details
typical conditions where they
are effectively used.
When very dry streams
are required
In industry, drying by adsorption is
favored due to its ability to produce
a much drier liquid or gas than
other commercial methods. When
extremely dry streams are required,
zeolite molecular sieves are selected
because they can reduce water
concentrations to less than 0.1 ppm.
In addition, they are effective over a
wide range of operating conditions.
When operating at
high temperatures
Water Adsorbed
The isobars plotted below illustrate zeolite molecular sieve performance
over a spectrum of operating temperatures. The solid lines assume the
use of completely regenerated adsorbents. The capacity is lowered by any
residual water left on the adsorbent, a factor of particular importance in
high temperature drying operations. As an example, the dotted line isobars
show the effect of two percent residual water at the start of adsorption
on silica gel, zeolite molecular sieves and activated alumina. In some
applications, this residual water can completely consume the adsorption
capacity of silica and alumina type adsorbents. For this reason, it is best
to use silica and alumina type adsorbents for the bulk separation of water.
They are very effective for this purpose and offer the additional benefit
of extending the life of zeolite molecular sieves. After bulk separation
processes have taken place, zeolite molecular sieves can then be used
to achieve very low dew point levels.
Water Vapor Adsorption Isobars
at 10mm Hg Partial Pressure
(Equilibrium Data)
25
Silica Gel
20
Zeolite

Zeolite molecular sieves are also a Molecular

15
Sieves
good choice when drying streams at
wt-%

high temperatures. In fact, they are

10 Activated
the only adsorbents that remain
Alumina
effective under very hot conditions.
For example, at 200ºF (93ºC) and 5
above, zeolite molecular sieves have
more than 13 weight-percent capacity
while other adsorbents have none. 0
0 100 200 300 400 500
(-18) (38) (93) (149) (204) (260)
Temperature °F (°C)

Drying power of silica gel, zeolite molecular sieves and activated alumina
under various operating temperatures.

12
 When purifying acidic streams
T
he chemical stability of
zeolite molecular sieves
allows them to dry, purify
and separate numerous types of
materials including inorganic
gases, hydrocarbons, halogenated
Zeolite molecular sieves
and co-adsorption
I
n some drying applications, components other than water may be adsorbed.
In many chemical process streams, this altering of stream composition, or
co-adsorption, can cause serious problems. When product composition is
critical, zeolite molecular sieves can be used to solve these co-adsorption difficulties.
Co-adsorption and pore size
Co-adsorption can be avoided through
proper selection of zeolite molecular
sieve type. The zeolite molecular sieve
should have a critical pore diameter small
enough to prevent all stream components
except water from being admitted to the
active inner surfaces of the adsorption
cavities. In this way,co-adsorption of
molecules other than water (including
polar and unsaturated components),is
eliminated. By eliminating co-adsorptions
the molecular sieve will provide
maximum capacity for water and
reduce outlet water concentrations
to less than 10 ppm.
Co-adsorption and
affinity for water
Zeolite molecular sieves feature an
extremely high adsorptive attraction
for water. This affinity is so strong
that water will normally displace any
other material that is already
hydrocarbons, alcohols, esters, ethers, of 5 to 12, and a few are stable in
amines, amides, ketones and others. solutions having a pH as low as 3.
They are stable in most organic
Zeolite molecular sieves are alkaline
streams, however in vapor phase
in nature with a pH range in water
processes, gases that will hydrolize to
slurry of 9 to 11. Most types are
form strong acids will readily react
stable in solutions within a pH range
with the adsorbents.
adsorbed. To further enhance this
selectivity for water, the temperature
of the adsorbent bed can be raised.
Although the rate of adsorption will
be somewhat reduced if the water
has to displace another material
before it can be adsorbed, zeolite
molecular sieves still offer better
performance when compared
to other adsorbents.
Due to the ability of zeolite molecular
Zeolite molecular
sieves to produce a drier liquid or gas,
industry operations typically favor
sieves’strong attraction
drying by adsorption over other
commercial methods. for water prevents
co-adsorption
problems in chemical
process streams.
13
 Carbon Dioxide Capacity at 25° C
Molecular Sieve Type A
(Equilibrium Data)
20 One-step drying and purifying
In addition to water, impurities in a process stream can be
15 removed via proper operating conditions and appropriate zeolite
molecular sieve selection. Since zeolite molecular sieves adsorb
Capacity

15
wt-%

water more strongly than other material, the adsorbed water

10 10
concentrates at the inlet end of the bed. Here, it displaces other
5
impurities that have been previously adsorbed. These desorbed
5 0
0 2 4 6 8 10 impurities are then re-adsorbed farther down the column. The
desorbed impurities will begin to appear in the effluent stream
0 as displacement continues. This displacement can be allowed to
0 100 200 300 400 500 600 700
continue until little adsorbate, other than water, is left on the bed.
Carbon Dioxide Pressure, mm Hg
However, it is possible to design and operate a zeolite molecular
Hydrogen Sulfide Capacity at 25° C sieve adsorption system so that impurities are retained on
Molecular Sieve Type A the adsorbent rather than re-entering the purified stream.
(Equilibrium Data)
To accomplish this, sufficient bed must be provided to contain
20
the impurities in addition to the water. See the figure below
for an example of a co-adsorption system.
15
Capacity

8
wt-%

10 6
Pad Gas
4 Sweet LPG
Product Regeneration
5 2 Gas In
Heater
0
0 0.5 1.0 1.5 2.0 2.5 3.0 Adsorption Regeneration
(Desulfurization Step)

0
(Heating Step)
Cooling Line

0 50 100 150 200 250 300 350

Regeneration
Adsorption

Adsorption Regeneration
Hydrogen Sulfide Pressure, mm Hg (Desulfurization (Heating Fuel
Step) Step)

Ammonia Capacity at 25° C

Sulfur Dioxide Capacity at 25° C
Molecular Sieve Type A
Separator
(Equilibrium Data)
40 Cooler
Sour LPG Feed Liquids
30
Sulfur Dioxide Typical co-adsorption system. Since zeolite molecular sieves have the
ability to adsorb hydrogen sulfide, mercaptans and water, the propane
Capacity

feed is simultaneously purified (sweetened) and dried.

wt-%

20
Ammonia
10 These three graphs depict the equilibrium capacity of zeolite molecular sieves
for various gas impurities. Through co-adsorption, zeolite molecular sieves
will remove these materials in addition to water.
0
0 100 200 300 400 500 600 700
14
Pressure, mm Hg
 Regeneration cycles

C
yclic regeneration, surface. Once the reactivation Purge gas stripping
or desorption, temperature is reached, the bed is This method uses non-adsorbing
can be classified into flushed with a dry purge gas or purge gas. The purge gas desorbs the
four types. Used separately or in reduced in pressure. It is then bed by reducing the partial pressure
combination, the major adsorption- returned to adsorption conditions. of the adsorbed component. The
desorption cycles are: As a result, high loadings of water higher the operating temperature and
and impurities on the adsorbent the lower the operating pressure, the
• Thermal swing
can be obtained, following more efficient the stripping. The use
• Pressure swing
a cooling step. of a condensable purge gas offers
• Purge gas stripping
• Displacement the following advantages:
Pressure swing
Pressure swing cycles, operating at • Reduced power requirements
Thermal swing
nearly isothermal conditions, use gained by using a liquid pump
Thermal swing cycles reactivate the
either a lower pressure or a vacuum instead of a blower
sieve by elevating the temperature.
to desorb the bed. Advantages of this
Typically, the operating temperature • An effluent stream that may
technique include fast cycling with
is increased to 400 - 600ºF (204 – be condensed to separate the
reduced adsorber dimensions and
316ºC). The bed is heated either by desorbed material by simple
adsorbent inventory, direct production
direct heat transfer via hot fluid in distillation
of a high purity product and the
contact with the bed or by use of
ability to use gas compression as Displacement cycles
indirect heat transfer through a
the main source of energy. Displacement cycles use an
adsorbable purge to displace the
Residual Loading After Regeneration previously adsorbed material. The
Minimum Obtainable Dew Point stronger the adsorption of the purge
(Dynamic Data) media, the more completely the bed
120 (+49) 4.0 WT–% is desorbed. In this case, lesser
3.2 WT–%
+80 (+27) 2.3 WT–%
1.7 WT–%
amounts of purge can be used, but
Dew Point, °F (°C)

+40 (+4) 1.0 WT–%

0 WT–%
it is consequently more difficult to
0 (-18) remove the adsorbed purge.
-40 (-40)
-80 (-62)
-120 (-84)
-160 (-107)
This graph is used to find the minimum obtainable dew point as a function of
-200 (-129) residual loading and effluent gas temperature during adsorption. Also shown
0 100 200 300 400 500 600 700
is residual loading after regeneration as a function of regeneration
(-18) (38) (93) (149) (204) (260) (316) (371)
temperature and purge gas dew point.
Bed Temperature, °F (°C)

15
Air dryers with a desiccant-type in-line filtration system supplies
clean, dry air to truck air brake systems aiding in the prevention
of air line freezeups.

Zeolite molecular sieves keep Zeolite molecular sieves are

dual pane windows free of used to purify industrial gases
moisture and vapors. and for the bulk separation of
oxygen from air.

16
The chart below provides a brief review of how and where zeolite molecular sieves are used in industry today.
Application Role of zeolite molecular sieves
Air dryers • Dehydration of plastic pellets before they are molded
• Dehydration for instrument air
• Dehydration of room air with molecular sieve impregnated dessicant wheels
Oxygen concentrators for respiratory patients • Adsorption of nitrogen from compressed air using a pressure or vacuum swing system to
obtain oxygen purity up to 95%
Air brakes • Dehydration of compressed air on brake systems of heavy- and medium-duty
trucks, buses and trains
• Pressure swing dryers are used to reduce the dew point of air in the brake reservoir
below ambient temperature to prevent freeze-up and corrosion
Insulated glass (dual-pane windows) • Removal of initial trapped moisture inside the dual-pane window and the moisture that will
permeate during the life of the unit to prevent fogging
• Removal of vapors from organic sealing materials, paint and cleaning solvents introduced
during window manufacture
Polymer formulations • Dehydration of moisture-sensitive formulations — added to poly coatings, epoxies
and urethanes to control the curing process and coatings, adhesives, sealants, elastomers,
metal-rich paints and vinyl foams to eliminate unwanted water reactions
Radioactive cleanup • Removal of radioactive nucleotides by ion exchange — cesium and strontium are exchanged
preferentially into the zeolite molecular sieves to greatly reduce the volume of liquid waste
Refrigeration and air-conditioning (A/C) systems • Dehydration of automotive A/C, transport refrigeration, home refrigerators, freezers, residential
A/C, heat pumps and commercial refrigerants to prevent freeze-up and corrosion
• Dehydration to protect system materials from adverse chemical reactions
Deodorization • Removal of odor or taste from personal-care products and plastics with high silica
(hydrophobic) zeolite molecular sieves. Odors are adsorbed, not masked
Package dehydration • Dehydration with zeolite molecular sieves when very low humidity conditions are required.
Small desiccant packets or tablets protect products such as pharmaceuticals, medical
diagnostic reagent kits, vitamins, food, candy, batteries, dry fuel propellants, machine parts,
film and instruments
Air separation • Removal of water and carbon dioxide from air before liquefaction and cryogenic separation
of nitrogen, oxygen and other atmospheric gases
• Separation of oxygen and nitrogen with pressure swing or vacuum swing adsorption systems
Natural gas • Dehydration before cryogenic recovery of hydrocarbon products and helium
• Dehydration of high acid gas content (CO2 and H2S) natural gas and natural gas
condensate streams
• Removal of sulfur compounds from ethane, propane and butane
• Removal of water and CO2 before methane liquefaction
• Removal of water and sulfur compounds to protect gas transmission pipelines
• Dehydration of natural gas liquids
• Desulfurization of feed streams for ammonia and other chemical plants
• Removal of mercury, preventing damage to aluminum heat exchangers
Petroleum refining • Dehydration of alkylation feed, refinery gas streams prior to cryogenic separation, naphtha
and diesel oil
• Purification of feedstocks to protect isomerization catalysts
• Removal of water, HCl and H2S from reformer streams
• Removal of oxygenates from etherification raffinate streams and alkylation feed
• Removal of nitriles from etherification feed
• Dehydration of ethanol
• Dehydration and desulfurization of LPG streams
• Separation of normal paraffins from branched chain and cyclic compounds
• Purification by pressure swing adsorption for upgrading hydrocarbon streams
Petrochemicals • Dehydration and purification of NGL/ethane/propane feed
• Dehydration of cracked gas, C2 and C3 splitter feed and hydrogen
• Dehydration and purification of salt-dome-stored ethylene, propylene and various
other feedstocks
• Removal of water, carbon dioxide, methyl alchohol and other oxygenates, hydrogen sulfide and
sulfur compounds, ammonia and mercury from ethylene, propylene, butylenes, amylenes and
various solvents and co-monomers
Volatile organic compound removal • Removal of trace volatile organic compounds from air streams
• Removal of volatile organic compounds from moisture-laden process streams

17
Put UOP's experience and technology to work for you
U
OP's expertise and innovation extends from
research and development to manufacturing
and from application product selection to
technical services. To meet customer needs, UOP offers
the broadest portfolio of molecular sieve and activated
alumina products in the world. With sales,
18
technical support staff, and manufacturing facilities
located around the globe, UOP continues to lead the
industry through our commitment to our customers.
Whether you are looking to dry, purify or separate,
you'll find the adsorbent solution with UOP.
urify
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