SHELL GLOBAL SOLUTIONS

81st ANNUAL GPA CONVENTION

March 11-13, 2002, Dallas, Texas

MAXIMIZING MOLECULAR SIEVE PERFORMANCE

IN NATURAL GAS PROCESSING

What is your competitive advantage when the same gas conditioning technology is
available to all of your competitors? This papers shows how integration of process
technologies and expert process know how make a difference.

You can turn the EPA Tier-2 sulfur spec on gasoline into a tool that works for you by
extending the mol sieve functionality in your plant to dehydration and desulfurisation.
Integration of amine and mol sieves gas treating process technologies can turn your
business away from the commodity it became during the liberalisation of the gas market,
into strong player of the NGL value chain.

Jacques N.H. de Bruijn, Michael A. Huffmaster,

Shell Global Solutions US Inc.
3333 HWY 6 Sth, Houston TX 77082 United States of America
e-mail ; j.debruijn@shell.com

J.M. van de Graaf, P.F.A. van Grinsven, H. Grootjans

Shell Global Solutions International BV.
P.O. Box 38000 1030 BN Amsterdam The Netherlands
e-mail ; Jolinde.M.vandeGraaf@opc.shell.com

2002 GPA mol sieve paper

1
MAXIMIZING MOLECULAR SIEVE PERFORMANCE
IN NATURAL GAS PROCESSING
Jacques N.H. de Bruijn, Michael A. Huffmaster,
Shell Global Solutions US Inc.
3333 HWY 6 Sth, Houston TX 77082 United States of America
e-mail ; j.debruijn@shell.com

J.M. van de Graaf, P.F.A. van Grinsven, H. Grootjans

Shell Global Solutions International BV.
P.O. Box 38000 1030 BN Amsterdam The Netherlands
e-mail ; Jolinde.M.vandeGraaf@opc.shell.com

SUMMARY
Guaranteed production of natural gas at the required water specification (< 1 ppmv) is
essential for a gas processing plant where cryogenic distillation or liquefaction is
performed like NGL and LNG plants. In most cases a mol sieve unit is used to perform
this critical dehydration task. Analysis of the NGL value chain with respect to the new
EPA specifications for sulfur levels in NGL products, has shown that these new market
forces may affect the functionality of the mol sieve unit to include the removal of organic
sulfur. The new functionality of the mol sieve units increases the importance to
understand the principles and operation of mol sieve units. The state of the art of water
adsorption on molecular sieves is presented, starting with the basic understanding of
molecular sieves. Due to the nature of the molecular sieve adsorbent and the thermal
cycles inherent to the process, the water adsorption capacity of the bed will decrease in
the course of its life. In some cases the dehydration unit becomes a bottleneck for
production because deactivation of the molecular sieve is faster then expected. It is
shown that much can be learned from spent molecular sieves, if properly analyzed.
Ageing of mol sieves is discussed in terms of coke formation and caking. This ageing
know how can be translated by Shell Global Solutions into operational procedures that
will maximize the lifetime of the molecular sieve, thus reducing the OPEX on adsorbents.
The know how may also be used to increase the Natural Gas (NG) plant revenue by
optimizing the amount of regeneration gas (to a minimum) while preventing cake
formation. For some plants a reduction of the amount of regeneration gas also saves
OPEX on fuel gas. It is concluded that the presented know how of Shell Global solutions
can sustain or improve your plants competitiveness and profitability.

1 Introduction
Beds of 3A and 4A molecular sieves are used in both NG and LNG plants, to do what
they do best: remove water from the natural gas, just before a cryogenic section where
liquids are recovered. Water needs to be removed to prevent hydrate formation in the
cryogenic section of the plant. Besides blockage of equipment and corrosion, hydrates
also effect the efficiency at which ethane and propane are recovered. Thus the molecular
sieves are a critical part of the NGL plant. The following paragraphs discuss how changs

2002 GPA mol sieve paper

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in the market can affect the functionality of the mol sieve unit to include the removal of
low levels of sulfur species.

1.1 The NGL market and its changing environment

Recently, the US Environmental Protection Agency (EPA i) issued regulations
establishing lower sulfur requirements for all gasoline, and establishing stricter tailpipe
emissions standards for all passenger vehicles (the Tier 2 rule). The low sulfur program
will be phased-in beginning 2004, and, in general, refiners must meet an average sulfur
standard of 30 ppmwt beginning 2005.

Natural gasoline, being one of the products obtained from NGLs, will also need to
comply with the new low sulfur spec. The North American NGL market ii, representing
more than 50% of the global market, is challenged by the EPA new sulfur specification
for gasoline. In many instances capital investment will be required. Coupled with the
knowledge that new gas fields are relatively more sour then current fields, extensive
modifications to facilities will be required to meet these new standards. To come to a
solution, Shell Global Solutions has studied the NGL value chain, which is schematically
shown in Figure 1. For this study, the NGL value chain is assumed to consist of five
elements. Some background information is presented.

Gas
Gas Conditioning Fractio-
production & Liquid nation
recovery
Figure 1 NGL value chain

1.2 Dynamics of the NGL Value Chain

Over 30 percent of all natural gas produced in the lower-48 states today is considered
sub-quality. This is because it contains acid gases such as carbon dioxide, hydrogen
sulfide or other sulfur-bearing compounds and other trace components. In most cases the
large number of gas production plants have several options to transport their gas to a gas
conditioning and liquid recovery plants. As the gas processing industry is working hard to
condition the gas, the more difficult the challenge becomes for with each passing year the
volume of natural gas that is produced must be drawn from a resource pool that is, on the
average, more sour than it was in the past. In most cases, gas conditioning and liquid
recovery plants have 2 or 3 options for transporting their product to a fractionation plant.
A fractionation plant is usually connected to only one gas gathering system. There are
approximately 10 major fractionation plants in the Texas/Louisiana gulf coast area. Each
fractionation plant has its own NGL gathering system and usually owns the NGL
gathering system.

2002 GPA mol sieve paper

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The dynamics of the NGL value chain as described above, and the competitive strength
of each partner in the value chain will drive the decision where in the value chain to treat
for sulfur in order to meet the new EPA sulfur spec for gasoline. For each element of the
value chain one can analyze the five forces of competition as described by Porter and
shown in Figure 2.

NEW
ENTRANTS

OTHER
SUPPLIERS BUYERS
PLANTS

SUBSTITUTE
PRODUCTS

Figure 2 Porters five forces of competition

The competitive strength depends on

The cost effectiveness of the plant compared to other plants in the same part of
the value chain.
The bargaining power with its suppliers
The bargaining power with its buyers.
The ability to prevent losing market share to new plants in the value chain, whose
design is based on the latest design best practices.
The ability to prevent losing market share to alternative products.

The new sulfur spec on gasoline has increased the risk of loosing market share to new
gasoline formulations. A strategic significant technology to deal with that new threat,
either for grass root or existing plants, provides the ability to become a strong player in
the value chain by using the opportunities in the value chain i.e. reducing the power of all
five competitive forces. The requirements of a strategic important technology with
respect to the five competitive forces for a gas processing plant in the NGL market are
shown in Figure 3.

The preferred process technology should

Be able to comply with sulfur specifications for gas and liquid products.
Be able to process different feeds.
Be cost effective compared to alternatives used elsewhere in the value chain.
Require less capital investment compared to alternatives used in the value chain.

2002 GPA mol sieve paper

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 LOWER
INVESTMENT
LEVELS

ABILITY TO ABILITY TO
PROCESS COST COMPLY
DIFFERENT EFFECTIVE WITH SULFUR
NG FEEDS SPECIFICATION

SULFUR
FREE
NGLs

Figure 3 Five forces for a NGL plant

1.3 The process line-up

The line-up shown in Figure 4 is representative for most gas conditioning and liquid
recovery plants built since 1975, with minor differences in the way the mol sieve
regeneration gas is recycled. Gas from the gas gathering system is treated for H2S and
CO2 using an aqueous amine or Sulfinol solution, followed by a molsieve dehydration
unit. Most liquids are recovered from the treated gas by cryogenic separation. The
recovered liquids are sent to a fractionation unit.

SRU

NG
Acid
Mol
Gas Gas Liquid NGL
Sieve
production Amine Recovery Frac
Dehy
Treating Unit

Figure 4 Typical Gas conditioning and NGL recovery process line-up

Other process line-ups are more cost effective when the removal of organic sulfur however
becomes a requirement. Aqueous amine solutions have a lower absorption capacity for
organic sulfur components which makes it uneconomical to remove all acid gas component
with an aqueous amine solvent. Sulfinol on the other hand is known to have a significantly

2002 GPA mol sieve paper

5
higher removal capability for organic sulfur because of the higher physical solubility for these
components, due to the presence of the Sulfolane. However, the removal of all organic
sulfur in only one absorber requires high Sulfinol circulation rates compared to cases where
only H2S and CO2 are removed. Alternatively a design can allow for slipping organic sulfur
through the main Sulfinol absorber, while removing it further downstream from the treated
gas with molsieve technology as shown in Figure 5.

The molecular sieve regeneration gas can be treated in a dedicated absorber column as
shown in Figure 5. The treated molsieve regeneration gas can either be recycled to the inlet
of the molsieve unit, or the inlet of the main absorber.

Amine
SRU
Treating
NG
Acid
Mol
NG Gas Liquid
Sieve NGL
production Amine Recovery
Dehy Frac
Treating
Unit

Figure 5 Process integration to meet both NG and NGL specifications

Examples of applications configurations as shown in Figure 5, can be found at the Gas

Zuiverings Installlatie at Emmen in the Netherlandsiii, the Manistee gas plant in Michigan
and the Golden Spike gas plant Alberta Canada.

The line up shown in Figure 5 is considered a cost effective solution, requiring the lowest
capital investment, for an existing plant to be converted to one that meets new NGL sulfur
specifications, while offering some flexibility in the feed composition. In some cases an
existing mol sieve unit can be redesigned for both dehydration and mercaptan removal
which in most cases makes the mol sieve unit the bottleneck of the plant. At places where a
mol sieve unit is the bottleneck, on-site extensive know how of mol sieves has shown to
improve the performance of the mol sieve unit.

2 What you should know about molecular sieves

2.1 What molecular sieves are made of
3A, 4A and 5A molecular sieves, are made of a mixture of a clay and type A zeolite
crystals. The zeolite-A crystals are build from -cages. Water is adsorbed in the -cages
of the zeolite. The clay binds the zeolite crystals into a particle.

2002 GPA mol sieve paper

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The structure of a 4A unit-cell of the zeolite is shown in Figure 6. Water is adsorbed in
the inner space of the cubic unit-cell, so called the -cage, but does not fit in the 8
smaller cubical building units, called -cages (or sodalite ages), as shown in Figure 6.
The -cage has a free inner diameter of 1.14 nm and is accessible through the eight
membered ring, shown in blue in Figure 6 in the front of the unit cell. All entrances are
partially obstructed by the sodium cations inside the -cage and the effective opening of
the 8-membered entrance ring is thus reduced to 0.4 nm. The opening of the -cage truly
acts as a sieve as water, methane and ethane can move through the entrance whereas
propylene and heavier components can not because the entrance is just too small for a
molecule like propylene.

In the process of 4A zeolite synthesis, the formation of the 4A zeolite does not stop at the
unit cell as shown in Figure 6. The 4A zeolite grows to a zeolite crystal of typically 1 to
10 micro meter. It is this micro meter size crystal that is the actual active part of the 4A
molecular sieve particles as used in the LNG plant. A 4A zeolite crystal of 6 micrometer
consists of some 109 unit cells. Perfect crystals have a nice cubic structure that has a
three dimensional system of channels interconnecting all a cages.

In the production of molecular sieve particles, a mineral clay is used as binder material.
The clay may be considered the glue that holds millions of 4A zeolite crystals together in
a single particle. A molecular sieve particle has typically a diameter between 1 and 5 mm,
and can be formed either with a spherical shape (bead) or as an extrudate (cylinder
shape).

Figure 6 A unit cell (eg pseudo cell) of 4A zeolite

II

I
III

One essential part of the manufacturing process of molecular sieve particles from the clay
and the zeolite crystals, is to maintain the cages of the zeolite crystal accessible for the
adsorbing water molecule. In the water adsorption process, transport of water through the

2002 GPA mol sieve paper

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meso pores and macro pores of the particle plays an significant role. A typical pore size
distribution of a 4A molecular sieve is shown in Figure 7.

The blue line in Figure 7 shows the total volume of all the pores in the range from 10-5 m
till the given pore size (measured from right to left). The red line in Figure 7 shows the
fraction of the pores as a function of the pore size. Note how the red line enables one to
distinguish the micro (<10-9 m), meso (10-9 m .. 10-7 m) and macro (>10-7 m) pores (left to
right). A good molecular sieve has sufficient meso and macro pores such that the micro
porous zeolite particle are well accessible for adsorption.

Figure 7 A typical pore size distribution of a 4A molecular sieve.

pore volume
and
pore size distribution
0.5000

0.4000

0.3000
pore volume [ ml ]

pore fraction [ - ]
or

0.2000

0.1000

0.0000
1.0E-10 1.0E-09 1.0E-08 1.0E-07 1.0E-06 1.0E-05
pore size [ m ]

As adsorption of water of molecular sieves on 4A zeolite molecular sieve involves van

der Waals attraction forces only, the adsorption of water on type A zeolites is reversible,
e.g. water can be removed from the a-cages of the zeolite by increasing the temperature
or lowering the water vapor pressure. Thus the water adsorption capacity of molecular
sieves can be restored by heating of the molecular sieves with dry gas. It is therefore
essential that the molecular sieve particle is stable under such thermal regeneration
conditions. Stable in the way that it maintains its macroscopic structure and its micro
porous adsorption properties.

Besides the effect of temperature swings, there is also an effect due to static and dynamic
pressure on the particles. Static pressure is caused by the weight of the particles on top of
the particles in the bottom. The dynamic pressure is due to the pressure drop as a results

2002 GPA mol sieve paper

8
of the fluid phase flowing through a packed bed of particles. The particle must be strong
enough not to be crushed due to the pressures put on it. Crushing of the particles will
cause the pressure drop to increase, even up to a level where it will be necessary to
replace the molecular sieves from a processing point of view. Crushing of the particles
and the consequential pressure drop over the adsorber also results in both poor flow
distribution within a reactor and flow mal distribution between two parallel adsorbers
resulting in unexpected early breakthrough of the adsorber.

2.2 adsorption properties of molecular sieves

Shell Global Solutions has developed a method to characterize molecular sieves in a cost
effective way. This method delivers characteristic parameters that can be used in the new
Shell Global Solutions model for numerical simulation of adsorptive processes. The
results from the characterization measurements can be translated into an adsorption
isotherm and an expression for water adsorption kinetics.

2.2.1 The water adsorption isotherm

The adsorption isotherm of water on 4A molecular sieves is a typical example of a type I
isotherm. Usually these adsorption isotherms fit the Langmuir equation. However
measurements at SRTCA have shown that the Langmuir equation does not fit the
measured data accurately enough. An improved Langmuir Freundlich type equation fits
the measured data much better.

Figure 8 shows the fit of the improved Langmuir Freundlich model to a range of
conditions that is representative for LNG and NG plants. It shows the water adsorption
capacity (vertical axis in mole H2O/kg molecular sieve) as a function of the water partial
pressure (horizontal axis Pascal). The lines in Figure 8 represent the calculated isotherm
using the ILF model whereas the dots represent the measured data. Statistics so far have
shown that the relative error by the ILF model over the whole range of measured
conditions is less than 6% which is meets the requirements for accurate simulation of
molecular sieve dryers.

2002 GPA mol sieve paper

9
 Figure 8 qi* measured data v.s. qi* predicted from ILF model

WATER ADSORPTION ISOTHERM

15.00

12.00

298 K
water adsorption capacity [ mol/kg ]

348 K
9.00

6.00

423 K
3.00

523 K
0.00
1E-01 1E+00 1E+01 1E+02 1E+03 1E+04 1E+05 1E+06
water partial pressure [ Pa ]

2.2.2 Kinetics of water adsorption

Up until 1998, based on academic data from literature, it was assumed that water
adsorption in 4A molecular sieves could be described by a linear driving force (LDF)
model, the driving force for adsorption being the difference between the equilibrium and
the actual loading of the sieve. This model was proven in literature to fit the adsorption of
water in 4A zeolite crystals.

When Shell Global Solutions studied the water adsorption on 4A molecular sieve
particles in more detail, it was found that the water adsorption is not the simple linear
driving force process as proposed in literature. Measured kinetic data is shown in Figure
9, where the adsorption rate (vertical axis in mole H2O/kg molecular sieve/second) is
given as a function of the driving force of adsorption (x-axis mol H2O/kg molecular
sieve). The recorded data starts on the right hand side on the x-axis, moving towards 0
driving force e.g. equilibrium. According to the LDF theory, Figure 9 should have shown
a straight line which is clearly not the case.

Figure 9 shows that part of the adsorption rate increases linearly with the driving force
for adsorption but as shown in Figure 9, it seems that the adsorption rate has an off-set at
1.10-3 mol.kg-1.s-1. A second term is introduced, that fits the curve at low driving forces
for adsorption. Shell Global Solutions has found a mathematical way to simulate this kind
of adsorption kinetics.

2002 GPA mol sieve paper

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 Figure 9 Water adsorption rate of water in 4A molecular sieves
Adsorption rate

6.000E-03

5.000E-03

4.000E-03
q/ t (mol/kg/min)

3.000E-03

2.000E-03

1.000E-03

0.000E+00
0.00 2.00 4.00 6.00 8.00 10.00

eq
q - q t (mol/kg)

2.2.3 Kinetics of water desorption

Many text books consider desorption just the reverse of adsorption. On a macroscopic
scale that is true for the adsorbate that was first physisorbed in a mono layer on the
surface of an adsorbent. Study of 4A molecular sieves by Shell Global Solutions has
shown that both on a particle and a plant scale, water desorption and water adsorption are
not at all just the reverse process. A new model for desorption of water is incorporated
in the new Shell Global Solutions model for numerical simulations of adsorptive
processes. The new desorption kinetics has a large impact on the simulation of the
regeneration of molecular sieve dryers for the kinetics are an integral part of the heat and
mass balance that are solved by the model. With the new model for water desorption
Shell Global Solutions can predict the formation of free water more accurately and thus
prevent caking (as explained below).

3 What you should know about deactivation or ageing

The molecular sieves used in the adsorbers suffer from ageing; the water adsorption
capacity decreases during adsorbent life time. A decrease in water adsorption capacity is
determined by two factors; the maximum water content and the amount of residual water
after regeneration . The maximum adsorption capacity is determined by the total amount
of water that can possibly fit in the pores of the adsorbent. However, due to mass transfer
limitations during the regeneration, not all water may be removed from the adsorbent
resulting in some residual water after regeneration. The consequence being that since not
all water is removed, less water can be adsorbed on the adsorbent in the adsorption
period. The same mass transfer limitations may also lead to a significant increase of the
mass transfer zone during adsorption which also decreases the effective capacity of the
bed. Samples of spent molecular sieves from two plants were analyzed to study severity

2002 GPA mol sieve paper

11
and type of deactivation and to identify the factors that contribute to the deactivation of
molecular sieves.

3.1 Ageing mechanisms

The effect of ageing usually decreases from the inlet to the outlet of an adsorber. Coke
deposition is one of the mechanisms in the ageing process observd. Coke deposition has
two effects. Where coke is deposited, no water can adsorb and thus the maximum water
content is decreased. Coke also forms a mass transfer limitation for water diffusion in and
out of the adsorbent particle, probably through pore mouth blocking. Coke formation can
be prevented by preventing all carry over of treating solvents to the adsorbers.

Caking is the second mechanism in the ageing process and is mostly observed in the
middle of the adsorber, even though an optimized regeneration procedure is applied
(TRAM profile). Caking is the result of the hydrothermal instability of the clay binder.
Transmission electron microscopy analysis showed changes in the structure of the clay
binder of the molecular sieves. Caking leads to an irreversible loss of adsorption capacity.
Caking has an effect on the mass transfer behavior of the molecular sieve. Water
desorption experiments showed that for deactivation by caking, loss of water adsorption
capacity is due to an increased residual water content upon regeneration rather than loss
of maximum water capacity.
It will be difficult to prevent all form of deactivation since the molecular sieves are just
hydrothermal unstable during regeneration conditions. When purchasing a new batch of
adsorbent, the hydrothermal stability of the adsorbent should be considered of equal
importance as the maximum water load.

3.1.1 Coke formation

From heats of adsorption (calculated from the adsorption isotherms) it is easily seen that
water is in more strongly adsorbed on molecular sieves than hydrocarbons; compared to
hydrocarbons, more water is adsorbed at the same partial pressure. Logically water
should dissipate any hydrocarbon that is adsorbed onto the molecular sieve. It is therefore
most remarkable that, in line-ups where mol sieves are downstream of an amine unit,
more coke is formed in the top (inlet) of the adsorber. It becomes even more peculiar
when one realizes that only methane and ethane can fit into the 4A pores of the zeolite,
molecules that one assumes to be inert under regeneration conditions. Adsorption of these
light hydrocarbons on the clay binder can also be ignored for water will also drive these
hydrocarbons from the surface of the clay.

For molecules with basic properties such as amines and sulfur containing organic
compounds as present in the treating solvents, other forces are in involved as well. The
base components will adsorb strongly on to the acid sites as present on the surface of the
molecular sieve crystals, as can be shown by infrared analysis. These strong bonds will
not be broken for the adsorption of water for these acid-base attraction forces are much
too strong.

Large base molecules like di-isopropanol amine can effectively block the pores that form
the entrance to the inner part of a zeolite crystal. In an adsorber this will preferably occur

2002 GPA mol sieve paper

12
at the position where the gas enters the adsorber thus at the top of the bed. Therefore the
amines are considered coke precursors in the top of the bed whereas the coke in the other
part of the bed may also result from heavy paraffinic or aromatic hydrocarbons.

3.1.2 Caking
Caking is the second parameter in molecular sieve ageing that is seen all over the bed. It
concerns an irreversible form of deactivation. It is the major cause of deactivation of
sieves in the top and middle of the bed. In its most extreme form, caking of the molecular
sieve is shown by the formation of lumps or doughnuts in the top of the bed.

Water desorption experiments on molecular sieve particles that suffer from caking have
shown that the maximum water adsorption capacity of the caked material is
approximately the same as measured for the fresh material. This indicates that the total
micro pore volume (i.e. total volume of the a-cages) of the zeolite crystals is not affected
by mild forms of caking. This indication is supported by results from other analysis on
the molecular sieves showing that a good zeolite crystal structure is still present in the
particles.

Transmission electron microscopy analysis showed that the structure of the clay binder
phase had changed. The elemental composition of the binder had not changed but the size
of the clay particles was increased as was its orientation around the zeolite crystals. The
changes in clay structure is considered to cause the increased mass transfer resistance
involved in caked molecular sieve particles.

From transmission electron microscopy it is known that the clay in fresh adsorbent is
highly disordered (amorphous). The disordered clay is quite voluminous. The clay in de
spent sieve from the middle of the bed is much more ordered and the density of the clay
phase is increased significantly.

The face to face reorientation of the plate like clay particles is known in literature. This
type of association is known to lead to thicker and possibly larger clay flakes which are
less voluminous. The ordered clay structure is considered to form a mass transfer
resistance in such a way that the effective diffusion path for water to diffuse into a zeolite
crystal is much longer in caked particles due to the ordered clays compared to particles
with disordered clays as shown in Figure 10, will definitely take place when a molecular
sieve particle is soaked in water. The clay will dissolve in the water phase and when the
molecular sieve particle is slowly dried, a the clay will tend to form a more ordered
structure. When a structured clay is thoroughly dried, water is removed from between the
clay particles and a stable clay structure is formed. In the stable clay structure, ionic
bonds are formed between clay particles resulting in a very short distance between the
clay particle like the 0.9nm measured by Shell Global Solutions. The ionic bonds
between the clay particles will never be broken and water will have to find its way
through the small space between the clay particles. Thus the enormous mass transfer
resistance can be explained.

2002 GPA mol sieve paper

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Figure 10 The process of clay structuring in mildly caked molecular sieves
fresh material
zeolite phase
water

amorphous
clay phase

gas phase

caked material
water zeolite phase

ordered
clay phase

gas phase

increased diffusion path

The regeneration efficiency will decrease due to the severe mass transfer resistance
formed by the ordered clay. Upon prolonged and thus more complete regeneration of a
caked molecular sieve, the full adsorption capacity becomes available. However, due to
the mass transfer limitation, it takes over 10 hours to regenerate the full adsorption
capacity of caked sieves.

The same mass transfer limitation, that limits the (re)generated capacity, will also leads to
a decreased rate of adsorption, thus forming a kinetic limitation. H2O break through of a
fully regenerated caked bed (considered unrealistic though) will occur before the full
(re)generated adsorption capacity can be used due to the very long mass transfer zone. It
is therefore not worthwhile to extend to period of regeneration of a caked bed.

4 How to use this ageing know how to reduce opex

Preventing the deactivation of molecular sieves is direct way to save on OPEX and to
increase the on stream time of a NG plant. Some deactivation of a molecular sieve is
inevitable however, Shell Global Solutions has found ways to minimize the effect of the
deactivation mechanisms.

4.1 Prevent coke formation

Amines and sulfolane are used in the amine treating units designed for NGL and LNG
plants. The first thing that can be done to prevent deactivation of molecular sieves due to
coke formation is to minimize the amount of amine and sulfolane that enters the adsorber.
Washes, separators and SMSM internals upstream the molecular sieve dryers clearly
minimize the amount of amine and sulfolane than enter the adsorber. Still these devices
can not remove all amine and sulfolane from the gas. Some amine and sulfolane will pass

2002 GPA mol sieve paper

14
as a mist droplets, typically smaller than one micro meter. So for there has been no
technology that can remove these mist droplets and therefore it is considered inevitable
that some amine and sulfolane will end up in the molecular sieve dryers.

From the above it will be clear that some coke formation from amine and sulfolane is
inevitable. However, this does not mean that the amine or the sulfolane should end up on
the molecular sieve. To extend the lifetime of a bed of molecular sieves, the amount of
entrained amines and free water that end up in the molecular sieves is to be minimized. A
recent study by Shell Global Solutions investigated the possibility to apply a layer of
adsorbent, placed on top of the molecular sieve bed, that acts as an amine guard. From
the test results it was concluded that certain grades of silica gel will prevent amine
fouling of molecular sieve dryers.

4.2 Prevent caking

Deactivation by cake can be minimized when proper regeneration conditions are chosen.
Shell Global Solutions can perform numerical simulations of the regeneration process.
The results of the simulation show whether and if so, where water is condensed during
regeneration of a bed of molecular sieves. Figure 11 shows the adsorber on the right hand
side. The heat transfer and mass transfer are shown in the left hand side of Figure 11 as
indicated by the red and blue arrows respectively. In Figure 11, warm regeneration gas
enters the adsorber in the bottom. Heat is transferred from the warm regeneration gas to
the cold adsorbent. Meanwhile as the adsorbent is heated, water is desorbed and
transferred to the gas phase as indicated by the blue arrow. As the gas travels through the
bed, more water is transferred to the gas phase and more heat is transferred to the
adsorbent. The gas phase will become saturated whereas the heat transfer from the gas
phase to the adsorbent will remain to take place.

Logically, as the gas travels further through the bed, heat transfer to the adsorbent will
still remain to take place and as a result of that the temperature of the gas will drop below
the water dew point of the gas phase and water will condense. Thus free water is formed
when the heat transfer zone is too short. Free water will only be formed at the beginning
of the regeneration when the bed is cold and lots of water is present on the sieve.

Shell Global Solutions has found a way called TRAM regeneration (after the numerical
model) to prevent water condensation during regeneration of a bed of molecular sieves.
The idea behind the TRAM regeneration is taken from careful study of the water
adsorption isotherm. The water adsorption isotherm tells you that roughly only 30% of the
adsorbed water will desorb when the temperature of the adsorbent is raised from 25 to 120
C. When the temperature of the adsorbent is raised from 120 to 200 C some 60% of the
adsorbed water will desorb. Thus the idea is to pre-heat the adsorbent and than ramp it to
the final regeneration temperature as shown in Figure 12.

2002 GPA mol sieve paper

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 Figure 11 Drawing to explain formation of free water

INLET

4A adsorbent

OUTLET

Heating profiles in time as shown in Figure 12 can be simulated using the Shell Global
Solutions model TRAM. The blue line in Figure 12 shows the inlet heating profile in time
whereas the red line is the calculated gas temperature at the outlet of the bed. Figure 13
shows the same gas temperature at the outlet of the bed (the thin red line) and the
calculated dew point temperature of the gas phase represented by the thick solid line.
Note that the calculated dew point temperature of the gas phase comes close to the gas
phase temperature at the outlet of the bed. Simulations of the case as shown in Figure 13
where the inlet temperature was immediately raised to the final regeneration temperature,
showed that a lot of water was condensed near the top of the bed.

2002 GPA mol sieve paper

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 Figure 12 Example of TRAM regeneration
Regeneration profiles

700.00

600.00

500.00
Temperature, K

400.00

300.00

200.00

100.00

0.00
0 60 120 180 240 300 360 420 480 540 600 660 720 780 840 900

Time, minutes

TRAM furnace outlet temperature TRAM bed outlet temperature

Figure 13 Result of TRAM simulation

Regeneration profiles

700

600

500
Temperature, K

400

300

200

100

0
0 60 120 180 240 300 360 420 480 540 600 660 720 780 840 900

Time, minutes

Dew point outlet gas TRAM bed outlet temperature

Plant data give good indications when a lot of water is condensed near the top of the bed.
When lots of water is condensed, besides the vessel and the molecular sieve, this
condensed water must be heated as well to raise the outlet temperature. Generally the gas
outlet temperature will increase until the condensed water starts to boil. Water will
evaporate and as mass transfer (evaporation) is much faster than heat transfer, the gas
temperature will show a plateau at the boiling temperature of the condensed water. The
gas outlet temperature will only increase further when all condensed water is evaporated.
Thus a plateau in the outlet temperature is considered an indicator for free water
formation and thus possible caking.

2002 GPA mol sieve paper

17
4.3 Minimise the number of regenerations per year
Only recently leads have been found for a third molecular sieve deactivation mechanism;
thermal deactivation. Thermal deactivation is believed to involve shrinking of the micro
pores that form the entrance to the zeolite. Minimizing the number of regenerations per
year, to minimize the times that the molecular sieve is exposed to heat, has shown to
improve the lifetime of the molsieves.

EXCELLENT MOL SIEVE KNOW HOW

CAN IMPROVE YOUR PLANTS COMPETIVENESS AND PROFITABILITY

i Control of air pollution from new motor vehicles; Tier 2 motor vehicles emissions standards and gasoline
sulfur control requirements Final Rule, 65 FR 6698 (February 10, 2000). (See also 40 CFR part 80 dub H)
ii Worldwide gas processing rides, W.R. True, Oil & Gas Journal / June 26, 2000
iii N.A. Taylor, J.A. Hugill, M.M. van Kessel, R.P.J. Verburg, Oil & Gas Journal, Aug 19, 1991, Gas
desulfurization plant handles wide range of sour gas compositions,

2002 GPA mol sieve paper

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