ADSORPTION

Molecular Sieve Bed to Remove H2O

Lando Deardo Siringoringo

2002322012
 Molecular Sieve

Types of Molecular Sieve

Basic Principles

Outlines Mechanism of the Process & Technology

Applications

Factors Affecting Adsorption

Advantages & Disadvantages

 Overview
Prevention of
Dehydration methods :
hydrate formation
a. Absorbtion (Glycol drying)
b. Adsorption (Silica gels, Activated
Alumina, and Molecular Sieve)
c. Condensation (Cooling with
injection of hydrates inhibitors
(glycols or methanol)).
d. Membran processes.
e. Chemical method hygroscopic
salts.

There are two main reasons why the Avoid the

process needs to be done dehydration:
corrosion
Definitions
Adsorption
The afinity for a molecule to adhere to
the surfaceof a solid.

Gas dehydration : Adsorption Adsorption

• Silica Gel -65C (-85 F)
• Activated Alumina -80C (-112 F)
• Molecular sieve < 0.1 ppmv

Adsorbent Adsorbate

Adsorbent Adsorbate
The solid that holds the molecule on its The molecule is being held onto the
surface. surface.
 Molecular Sieve

Molecular Sieves are synthehtic zeolite materials engineered with pores

of precise and uniform structure and size.
This allows them to preventially adsorbt gas and liquids based on
molecular size and polarity.

Small pellets of inorganic materials with extremely small pores

(usually 3-5 Angstroms). Most organic solvents are too small to
fit into these pores, but water can.
Adsorption units are capable of reaching extremely low specifications, which
makes them viable pieces of equipment for incorporation into a process lineup.
A major advantage of molecular sieves is that they can be regenerated, which
reduces the required amount of molecular sieve to economically feasible
quantities..
 Types of Molecular Sieve
3A
The 3A molecular sieve is an alkali metal
aluminosilicate with a pore opening of
approximately 3 angstroms. The 3A
molecular sieve will exclude most molecules
except water, making it very selective. This
type of bead also has advantages in crush
strength, durability and high rate of
adsorption.
4A
The 4A molecular sieve is an alkali
metal aluminosilicate with an effective
pore opening of approximately 4
angstroms. Type 4A beads can be used
to adsorb water, ammonia, methanol,
ethanol and carbon dioxide. This type of
molecular sieve is often used to remove
moisture from gas and liquid streams,
where co-adsorption of sulfur
compounds and carbon dioxide is not a
concern.
Source : Leading Molecular Sieve Manufacturer & www.molecularsievedesiccant.com
5A
The 5A molecular sieve is an alkali metal
aluminosilicate with an effective pore
opening of 5 angstroms and is the calcium-
exchanged form of the type A zeolite. This
product is also effective for the bulk
separation of normal and iso-paraffin
hydrocarbons. This type of molecular sieve
has a high rate of adsorption and desorption,
a higher rate of contamination resistance
and a high crush strength.
13X
The 13X molecular sieve is the sodium form
of zeolite X and has a much larger pore
opening than the type A crystals, with an
effective pore diameter of 10 angstroms.
Type 13X offers enhanced adsorption
performance over the type A zeolite, and it
can remove impurities too large to fit into the
type A zeolite crystal cages. It is also often
used to separate nitrogen from the air to
produce a high-purity oxygen stream.
 Commercially Available Types
Natural gas dehydration when COS minimization and/or MeOH is present.
Type 3A
H2S + CO2  COS + H2O. Less water capacity and not as rugged as Type 4A.

Workshore of the industry. Used in most natural gas drying applications. Will
Type 4A
adsorb H2S on active sites.

Removal H2S and normal RSH from natural gas. Less water capacity and less COS
Type 5A
formation compared to type 4A. Coadsorbs propane and higher normal
hydrocarbons.
 

Type 13X Removal of H2S, nRSH, and iRSH from natural gas and LPG. Higher water capacity
than type 4A.
 Basic Principles

IV Regenerator Column
When heated the impurities are vaporized
and released by the adsorbents.
source : ChemSurvival entreprises, LLC - 2018

Adsorber Column
III
Impurities enter the pore space and are
held on the surface inside of the voids.

II Solid Adsorbents
Very porous solids with huge surface
areas.

It
The effectiveness for water removal is based on
two important characteristics:

• The channel diameter acting as a filter, which

limits the number of species that can co-adsorb.

• The polar environment created in the channels,

which creates an environment in which
preferentially polar molecules are adsorbed.
How It Works?
Mechanism of the
Process
An adsorption unit used for water
removal is called a dehydration unit
(DHU). A DHU often consists of two
or more vessels, filled with molecular
sieves, that adsorb water during an
adsorption period and are
subsequently regenerated using a
heated stream of treated gas.

• A & B (adsorber)  to adsorb the water.

• C (regenerator)  to regenerate the adsorbent.

• audience and add a unique zing and appeal to your

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Process in Adsorption
Vessel In the adsorbing bed, the capacity-limited portion is situated at the
top. It is saturated with water under the feed conditions of
temperature, pressure and water concentration, and is referred to
as the saturation zone (SZ).
The part of the bed below the SZ that is engaged in dehydrating the
gas from feed water concentration (wet) to effluent water
concentration (dry) is called the mass-transfer zone (MTZ) .
During adsorption, the MTZ migrates from the top of the bed to the
bottom of the bed, there by lengthening the SZ. Once the MTZ
leaves the bed, breakthrough occurs and the bed must be taken
offline for regeneration.

Feed gas enters the vessel Diffusion of water through

through the inlet stream. gas into the pores (MTZ).
Adsorbtion the water onto
the pore wall (Equilibrium
zone).

The cylical nature nature of The product exits through the

the process result in an active outlet stream.
zone.
During adsorption, a molecular sieve bed is modeled by a
three-zone system. Close to the inlet is the equilibrium
zone (EZ), where the adsorbent is in equilibrium with the
process fluid saturated with impurity at the partial
pressure and temperature conditions.
The EZ is followed by the mass transfer zone (MTZ),
where the dynamics of adsorption take place. The MTZ
shows a gradient of the impurity concentration, which
decreases to a required outlet specification and can be
defined as the length required for the adsorbent to bring
the impurities from their initial concentration to the final
specification.
The third area is made of fresh adsorbent that, for a
given adsorption time, has not been in contact with the
impurities.
 Typical Deactivation and
Molecular Sieve Changeout Profile

Another important parameter to take into

account is that the capacity of the
adsorbent decreases over time as a
function of the number of regeneration
cycles; therefore, end-of-run (EOR) capacity
must be used when considering the
required amount of adsorbent. When the
capacity of the adsorbent falls below the
level where all water in the feed can be
adsorbed during the minimum adsorption
time, then the adsorbent must be replaced.
Structure of Adsorber Bed
Regeneration
Regeneration Molecular Sieve should be in typical cyclic
systems constitutes removal of the adsorbate from the
molecular sieve bed by heating and purging with a carrier gas.

Sufficient heat must be applied to raise the temperature of the

adsorbate, the adsorbent and the vessel to vaporize the liquid
and offset the heat of wetting the molecular-sieve surface. The
bed temperature is critical in regeneration.

The high temperature during regeneration causes water to

desorb from the molecular sieve, a process called temperature
swing adsorption (TSA).

After regeneration, a cooling period is necessary to reduce the

molecular sieve temperature to within 15℃ of the temperature
of the stream to be processed.

For optimum regeneration, gas flow should be countercurrent

to adsorption during the heat up cycle and concurrent (relative
to the process stream) during cooling.
Regeneration
In classical applications, the TSA heater is realized as
an ordinary burner or as a shell and tube heat
exchanger warmed by steam or by hot oil. The
regeneration gas warms in the heater and flows into
the column. In the column passes through the
adsorbent and the water desorbs into the
regeneration gas.

The water saturated regeneration gas then flows into

the cooler. The cooler usually uses cold air to
decrease the temperature of the regeneration gas.
When the water saturated regeneration gas is cooled,
partial condensation of the water occurs. The
regeneration gas is led further into the separator,
where the condensed water is removed.
Typical Regeneration Temperatures
 Factors Affecting Adsorption

Characteristics
Temperature Contact Time
Polarity of the of adsorbent
Substance When the Contact time is very
temperature is low, The pore size, important because
The polar environment surface area of the
the ability the process reaches
created in the adsorbent., and the
adsorption the time of
channels, which Absorbate increases so that purify of adsorbent Agitation adsorption,
creates an pH are characteristic
environment in which Molecule Size the adsorbate The adsorption rate equilibrium and is
increases. Organic acids are important economical.
preferentially polar is controlled by
. The adsorbate molecules more easily adsorbent
molecules are both film and pore
that can adsorbed are adsorbed at low pH,
adsorbed. diffusion.
molecules whose whereas organic
depending on the
diameter is smaller or base adsorption is
level of agitation in
equal to the pore diameter effective at high pH.
the system.
of the adsorbent.
 Upstream of a LNG Plant

Upstream of Cryogenic Dehydration for LPG and

Gas Plants NGL streams.

Upstream of NGL etc.

Extraction Plants
Applications
in Industry
 Advantages
Very low dew point and
water content can be
obtained. Insensitive to moderate
change in gas temperature,
flow rate, and pressure.
Best suited for large volumes
of gas under very high
pressure.
Some types can be used for
simultaneous dehydration
and sweetening.
Dehydration of very small
quantities of natural gas at
low cost.
They are relatively free
from problems of corrosion,
foaming, etc.
 Disadvantages
The most expensive
adsorbent.
High space and weight
required.

The regeneration
temperature is very high
(operating cost).
Mechanical breaking and
contamination of liquid, oil,
and glycol are possible.
Pressure drop is too high.
“Love what you do;
Do what you love”
Wayne W. Dyer
Reference
Kidnay, Arthur J., William R. Parrish, and Daniel G. McCartney.
Fundamentals of natural gas processing. CRC press, 2019.

Malino, H.M., http://www.jmcampbell.com/tip-of-the-month/2015/05/

benefits-of-standby-time-in-adsorption-dehydration-process/,
PetroSkills – John M. Campbell, 2015

Hawes, P., “Molecular sieves in natural gas processing,” GPA Europe

Young Professional Training Day, Manchester, UK, February 11, 2016.

Gas Processing & LNG ; Gulf Publishing Holdings LLC

http://www.chemxin.com/news/html/?486.html

https://www.molecularsievedesiccants.com

http://m.pm-chem.com/desiccant/molecular-sieve-adsorbents/
molecular-sieve-type-5a.html

https://www.youtube.com/watch?v=4iWdidLLklc
Thank You!
Any Questions?