Faculty of Chemical Engineering

Universiti Teknologi MARA

Gas Dehydration Using

Solid Desiccants

Gas Process Engineering - CGE667

 Introduction
• All solid surfaces have some ability to adsorb, i.e.,
capture and hold vapours and liquids on their
surfaces.
• Two types of gas-solid adsorption:

Gas Process Engineering - CGE667

• Chemisorption (chemical adsorption): involves specific
bonding of the gas molecules (adsorbate) in a monolayer
onto the solid-surface atoms.
• Physisorption (physical adsorption): caused by van der
Waals forces between the gas molecules and the surface
thus forming multi layers of adsorbate on the surface.

Note that: this chapter only deals with physical adsoprtion.

 Desiccant Selection
• Large surface area for high capacity adsorption: This
lowers the required adsorbent volume, allowing the
use of smaller vessels with reduced capital
expenditures and reduced heat input for

Gas Process Engineering - CGE667

regeneration.
• High selectivity: This minimises the undesirable
removal of valuable components and reduces overall
operating expenses.
• Easy regeneration: The relatively low regeneration
temperature minimises overall energy requirements
and operating expenses.
 Desiccant Selection
• Low pressure drop
• High mechanical strength to resist crushing and dust
formation: These factors lower overall maintenance
requirements by reducing the frequency of adsorbent

Gas Process Engineering - CGE667

change out and minimising downtime-related losses.
• Others (inexpensive, non-corrosive, non-toxic,
chemically inert, high bulk density and no significant
volume changes upon adsorption and desorption of
water).
 Industrial Adsorbents for
Dehydration
• Silica gel, which is made of pure SiO2.
• Activated alumina, which is made of Al2O3.

Gas Process Engineering - CGE667

• Molecular sieves, which are made of alkali
aluminosilicates and can be altered to affect
adsorption characteristics.
 3A – potassium zeolite
 4A – sodium zeolite
 5A – calcium zeolite
 Comparison of Industrial
Adsorbents
Silica Gel Activated Alumina Molecular Sieve 4A
Pellets (extruded
Shape Spherical Spherical
cylinders) & beads

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Bulk density (lb/ft3) 49 48 40 - 45

Surface area (m2/g) 650 – 750 325 – 360 600 – 800

Pore volume (cm3/g) 0.36 0.5 0.28

Regeneration
375 320 – 430 400 – 600
Temperature (°F)
Minimum moisture
content of effluent 5 – 10 10 – 20 0.1
gas (ppmv)
 Adsorption Process

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 Typical operating conditions for
Molecular Sieve Dehydration
Feed Rate 10 to 1500 MMscfd

Superficial Velocity Approximately 30 to 35 ft/min

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Approximately 5 psi (35 kPa), not to exceed 10
Pressure Drop
psi (69 kPa)
Cycle Time 4 to 24 hours
Adsorption Temperature Temperature: 50 to 115 °F (10 to 45 °C)
and Pressure Pressure: up to 1500 psig
Regeneration Temperature Temperature: 400 to 600 °F (200 to 315 °C)
and Pressure: Pressure: adsorption pressure or lower
 Some Fundamentals
• Two steps are involved in adsorbing a trace gas
component.
• The first step is to have the gas travel through the
pathways inside the adsorbent.

Gas Process Engineering - CGE667

• The second step is to have the component contact the
surface.
• Properties that dictate adsorbate concentration on
the adsorbent surface:
• Partial pressure/concentration of the adsorbate
• Polarity of the adsorbate
• Size of the adsorbate
 Some Fundamentals
• Polar molecules, like water, will be more strongly
adsorbed than weakly polar or nonpolar compounds.
• Example: Methane is displaced by the weakly polar acid
gases that are displaced by the strongly polar water.

Gas Process Engineering - CGE667

• How adsorbate size affects adsorption depends upon
the pore size of the adsorbent. An adsorbate may be
too large to fit into the pores and may thus only
adsorbs on the outer surface of adsorbent.
• In practice, adsorption is carried out in a vertical
adsorption unit, with the feed gas flowing down
through the bed.
Adsorbate Concentration
Profile Inside an Adsorbent Bed

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 Adsorbate Concentration
Profile Inside an Adsorbent Bed
• The equilibrium zone: the adsorbate on the
adsorbent is in equilibrium with the adsorbate in the
inlet gas phase and no additional adsorption occurs.

Gas Process Engineering - CGE667

• The mass transfer zone (MTZ): the volume where
mass transfer and adsorption take place.
• The active zone: the volume where no adsorption has
yet taken place.
• In the mass transfer zone (MTZ), the concentration
drops from the inlet value (yin), to the outlet value
(yout) in a smooth S-shaped curve.
 Adsorbate Concentration
Profile Inside an Adsorbent Bed
• The MTZ usually assumed to form quickly in the
adsorption bed and to have a constant length as it
moves through the bed, unless particle size or shape

Gas Process Engineering - CGE667

is changed.
• The length of the MTZ is usually 0.5 to 6 ft, and the
gas is in the zone for 0.5 to 2 seconds.
• To maximise bed capacity, the MTZ needs to be as
small as possible because the zone only holds 50% of
the adsorbate held by a comparable length of
adsorbents at equilibrium.
 MTZ Calculation
• Accurate calculation of the MTZ thickness is complex.
• The following equation is suggested for estimation.

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LMTZ (ft) = 2.5 + 0.025u (7.1)

where u = superficial velocity in ft/min

• Equation 7.1 is used for adsorbent size of 1/8 inch (3

mm)
• For 1/16 inch (1.5 mm) adsorbent, the length is 70%
of the value obtained from equation 7.1.
 Adsorbent Capacity and Bed
Pressure Drop
• The most common reasons for replacing a bed are loss
of adsorbent capacity and unacceptable pressure
drop, which usually occur simultaneously.

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• The following equation is used to compute pressure
drop:
∆P 2
(psi/ft) = Bµu + Cρu (7.2)
L
where μ = viscosity in centipoise;
ρ = density in lb/ft3;
u = superficial velocity in ft/min;
B and C = coefficient values for adsorbents
Adsorbent Capacity and Bed
Pressure Drop

Gas Process Engineering - CGE667

 Adsorbent Capacity and Bed
Pressure Drop
• The design water content of a bed when at
equilibrium with saturated water at 75 °F (24 °F) is 13
lb H2O/100 lb adsorbent.

Gas Process Engineering - CGE667

• Note that, new adsorbents can actually hold about
20 lb H2O/100 lb adsorbent.
• Two factors affect this number:
 Water content of entering gas
 Adsorption temperature
• Corrections for capacity as a function of percent
relative water saturation and temperature are
necessary
Capacity Correction for
Unsaturated Inlet Gas

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Capacity Correction for Inlet
Gas Temperature

Gas Process Engineering - CGE667

 Example 1
4A molecular sieve bed has been used for dehydrating natural gas
flowing at 80 MMscfd. The gas enters the bed at 120°F and 950 psig.
Water content is 60% of saturation at 120°F. The molar mass of the gas
is 18.5, with a viscosity of 0.014 cp and a compressibility factor of 0.84.
The adsorption bed contains 41,000 lbs of 1/8 inch diameter beads

Gas Process Engineering - CGE667

with a bulk density of 44 lb/ft3. The inside wall diameter of the bed is
7.5 ft. The adsorbent was installed 2 years ago.

If the gas flow is increased to 100 MMscfd,

a) Determine whether the bed pressure drop is still within a good
operating range?
b) Determine whether the bed capacity allows continued operation
on a 12-hour cycle with two beds, or the cycle time should be
changed?
Solution to Example 1a

mass
The volume of adsorbent V =
adsorbent density

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41,000
= = 932 ft 3
44

πD2
The cross sectional area of the bed A =
4
π (7.5 )
2
= = 44.2 ft 2
4
Solution to Example 1a

V 932
The bed height L = = = 21.1 ft
A 44.2

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MW P
The gas density ρ =
z RT

18.5 × (950 + 14.7 )

= = 3.41 lb/ft 3
0.84 × 10.73(460 + 120 )
 Solution to Example 1a
To obtain superficial velocity, we first need the
increased actual volumetric flow rate, Q.
 14.7  T1(°R )  z1 

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Q = scfm    
 P1( psia )  520  zR 

100 × 10 6  14.7  460 + 120  0.84 

=    
1440  950 + 14.7  520  1 

992 ft 3 / min

R refers to the conditions used to define the reference state, in

this case, 14.7 psia and 60 °F (So ZR = 1).
Solution to Example 1a
Q 992
The superficial velocity, u = = = 22.4 ft/min
A 44.2

Using equation 7.2

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∆P
(psi/ft) = Bµu + Cρu 2
L
For 1/8 inch bead, B = 0.0560 and C = 0.0000889
∆P
= (0.0560 )(0.014 )(22.4 ) + (0.0000889 )(3.41)(22.4 )
2

L
0.170 psi/ft
Solution to Example 1a

Total bed pressure drop = 0.170 psi/ft × 21.1 ft

Gas Process Engineering - CGE667

= 3.58 psi

This pressure drop is in a good operating range

 Solution to Example 1b
• To determine the capacity, first calculate the capacity
per pound of adsorbent.
• The bed has aged, so at 75°F the adsorbent should

Gas Process Engineering - CGE667

hold 13 lb water/ 100 lb of sieve if the entering gas is
saturated with water vapour.
• However, the gas enters at 60% of saturation.
• Using capacity correction figure, the adsorbents holds
only 97% of capacity.

0.97 × 13 = 12.6 lb water/100 lb of sieve

 Solution to Example 1b
• From another capacity correction figure, the
temperature effect reduce the capacity to 88%
0.88 × 12.6 = 11.1 lb water/100 lb of sieve

Gas Process Engineering - CGE667

• So the bed should hold 11.1 lb water/100 lb sieve in
the equilibrium zone.
• The MTZ must be taken into consideration.
• The length of MTZ is calculated using equation 7.1.
LMTZ (ft) = 2.5 + 0.025u
= 2.5 + 0.025(22.4 ) = 3.1 ft
 Solution to Example 1b
3.1
× 100 = 15%
21.1
• This means, 15% of the total bed length is MTZ

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• Assume that MTZ holds only 50% of the equilibrium
loading,. Therefore, the bed should hold
 11.1   11.1 
 × 41000 × 0.85  +  × 41000 × 0.15 × 0.5  = 4210 lb of water
 100   100 

• From the water content determination chart (previous

lecture), the water content for a gas at 120 °F and 950
psig is 100 lb/MMscf.
 Solution to Example 1b
• The gas enters at 60% of saturation, which means the
water content is 60 lb/MMscf.
• Essentially, all water into the bed must be removed.

Gas Process Engineering - CGE667

• For as 12-hour cycle, the water that must be adsorbed
is:
60 lb 100 MMscf 0.5 day
× × = 3000 lb water
MMscf day

• Since the bed capacity is 4210 lb of water, the bed

can remain on a 12-hour cycle.
Gas dehydration: Liquid versus
Solid Desiccant

Gas Process Engineering - CGE667

 Gas dehydration with liquid desiccant Gas dehydration with solid
desiccant
Advantages - Lower installed cost compared to solid - Dew points as low as -150°F
desiccant plant (1 ppmv of H2O) are
- Lower pressure drop compared to solid obtainable
desiccant - Less affected by small
- Glycol dehydration is continuous rather changes in gas pressure,
than batch temperature, or flow rate
- Can operate in the presence of - Less susceptible to corrosion
materials that would foul solid or foaming.
desiccant

Gas Process Engineering - CGE667

- Glycol makeup is easily accomplished.
Recharging solid desiccant towers is
time-consuming and sometimes
requires interruption of gas sales.
- Glycol units require less regeneration
heat per pound of water removed thus
lowering utility costs.
- TEG unit are simple to operate and
maintain.
- TEG units are easily automated for
unattended operation in remote
locations.
 Gas dehydration with liquid Gas dehydration with solid desiccant
desiccant

Disadvantages - Water dewpoints below -25°F - Higher capital cost

require stripping gas and a Stahl - Higher pressure drop
column. - Desiccant poisoning by heavy
- Glycol is susceptible to hydrocarbons, H2S, CO2 etc.

Gas Process Engineering - CGE667

contamination. - Mechanical breaking of desiccant
- Glycol is corrosive when - High regeneration heat
contaminated or decomposed requirements and high utility cost