+ BKC3492

SEPARATION PROCESS

Zulkifly Jemaat, PhD

2016/2017-I
019-7261616
email:
zulkifly@ump.edu.my
room: Technical Office,
FKKSA Lab

Chapter:
Adsorption
1
+ Adsorption Process
2

 One or more components of gas or liquid stream are adsorbed on the

surface of solid adsorbent.
 Physical adsorption or van der Waals adsorption occurs between the
adsorbed molecule and pore surface and is readily reversible
 Overall adsorption process consist several steps – solute diffuses from the
bulk liquid to the exterior surface of adsorbent, then diffuse inside the pore
to the surface of the pore
 Saturated adsorbent can be regenerated by several method
 Temperature swing (unfavourable)
 Pressure swing
 Inert/Purge stripping
 Displacement purge cycle
+ Adsorbent
3

 Adsorbent
 pellets, beads, orgranules from 0.1 mm-12 mm
 Porous structure, with many fine pores and pore
volumes up to 50% of total particle volume
 Physical adsorption or van der Waals adsorption
occurs between the adsorbed molecule and pore
surface and is readily reversible
+ Adsorbent
4

• Microcrystalline material made

by thermal decomposition of
wood, vegetable shells, coal and
Activated etc.
carbon • Surface area 300 – 1200 m2/g
• Average pore diameter 10 – 60A
• Adsorb organic compound
+ Adsorbent
5

• Made by acid treatment of

sodium silicate solution and
then drying
• Surface area 600 – 800 m2/g
Silica gel • Average pore diameter 20 –
50A
• To dehydrate gases and
liquids, and to fractionate
hydrocarbon
+ Adsorbent
6

• Hydrated aluminum oxide is

activated by heating to drive
off the water
Activated • Surface area 200 – 500 m2/g
alumina • Average pore diameter 20 –
140A
• Mainly used to dry gases and
liquids
+ Adsorbent
7

• Porous crystalline
aluminosilicates that form an
open crystal lattice containing
Molecular precisely uniform pores
sieve zeolite • Pore diameter 3 – 10A
• Used for drying, separation of
hydrocarbon mixture, etc
+ Adsorbent
8

• By polymerizing two major

types of monomers
• Made from styrene and
Synthetic divinylbenzene used to
polymer or adsorb nonpolar organics
resin from aqueous solution
• Made from acrylic esters used
to adsorb more polar solutes
in aqueous solution

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Adsorbents (Ion Exchange)

Anion Resin Cation Resin

 Adsorbent - Applications
Typical Applications of Commercial Adsorbents

Type Typical Applications

Silica Gel Drying of gases, refrigerants, organic solvents
Dessicants in packings and double glazing
Dew point control of natural gas
Activated alumina Drying of gases, organic solvents, transformer oils
Removal of HCl from hydrogen
Removal of fluorine and boron-fluorine
compounds in alkylation process
Activated carbon Nitrogen from air
Hydrogen from syn-gas and hydrogenation
processes
Ethene from methane and hydrogen
Removal of odours from gases
Removal of solvent vapors
Removal of SOx and NOx
Decolorising of syrups, sugars and molasses
Water purification

10
 Adsorbent - Applications
Typical Applications of Commercial Adsorbents (cont’d)
Type Typical Applications
Zeolites Oxygen from air
Drying of air
Removing water from azeotropes
Purification of hydrogen
Separation of ammonia and hydrogen
Recovery of carbon dioxide
Separation of and oxygen argon
Removal of acetylene, propane and butane from air
Separation of xylenes and ethyl benzene
Separation of olefins and aromatics from paraffins
Pollution control (removal of Hg, SOx, NOx )
Polymers and resins Water purification
Recovery and purification of steroids, amino acids
and polypeptides
Separation of fatty acids from water and toluene
Recovery of proteins and enzymes
Removal of colours from syrups

11
+ 12

Regeneration of Adsorbent
Temperature Swing
• Also known as thermal swing cycle
• Heating with embedded stream coils or with
a hot purge gas stream
• The elevation of temperature shift the
adsorption equilibrium curve
• Bed must be cooled for used in the next
cycle
• Time taken few hours or more
Pressure Swing Cycle
• Pressure is reduced at constant temperature
and then purging the bed at this low pressure
• Reduction of pressure shift the adsorption
equlibrium
• Time taken is very short compared to
temperature swing cycle

Adsorbent
Regeneration

Inert Purge Gas Stripping Cycle Displacement Purge Cycle

• By passing a nonadsorbing or inert gas
through the bed
• The partial pressure or concentration around
the particle is low and desorption occurs
• Regeneration time only a few minute
• The pressure and tempearture are kept
constant as in purge gas stripping, but a gas
or liquid is used that is adsorbed more
strongly than the adsorbate and displace the
adsorbate
• Regeneration time only a few minute

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+ Adsorption Isotherm
13

Linear Freundlich Langmuir

• Is not common, normally • By plotting log q vs loq c, • Only a fixed number of

valid in dilute region slope is n actives available for
adsorption
• Monolayer adsorption
• Adsorption is reversible
and reaches an
equilibrium condition
• By plotting 1/q vs 1/c,
slope is K/q0 and intercept
is 1/q0

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Example 12.1-1
Batch tests were performed in the laboratory using solutions
of phenol in water and particles of granular activated carbon.
The equilibrium data at room temperature are shown in Table
1 below. Determine the isotherm that fits the data.

Table 1. Equilibrium data for phenol in wastewater adsorbed

using activated carbon
c, q,
(kg phenol/m3 solution) (kg phenol/ kg carbon)
0.322 0.150
0.117 0.122
0.039 0.094
0.0061 0.059
0.0011 0.045

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Batch Adsorption
 To adsorb solutes from liquid solutions when the quantities
treated are small in amount, as in pharmaceutical.
 Material balance

qF = initial concentration of solute in adsorbent (kg/kg adsorbent)

cF = initial concentration of solute in solution (kg/m3)
q = concentration of solute in adsorbent (kg/kg adsorbent)
c = concentration of solute in solution (kg/m3)
M = amount of adsorbent, kg
S = volume of feed solution, m3

 The intersection of material balance equation and

equilibrium line intersection gives the final equilibrium
value of q and c.

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Batch Adsorption
 The intersection of material balance equation and
equilibrium line intersection gives the final equilibrium
value of q and c.

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Example 12.2-1
A waste water (volume 1 m3) contains 0.21 kg phenol/m3. A
total of 1.40 kg of fresh granular AC is added to the solution,
mixed thoroughly to reach equilibrium. Using isotherm in
Example 12.1-1, calculate the final equilibrium values and
percentage of phenol adsorbed by the AC.

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+ Design of Fixed Bed Adsorption
18

Column
 The fluid to be treated is usually passed down through the packed bed
of adsorbent at constant flow rate
 Mass transfer resistances are important in the fixed bed process and the
process is unsteady state
 The overall dynamics of the system determine the efficiency of the
process rather than just the equilibrium consideration
 The concentrations of the solute in the fluid phase and of the solid
adsorbent phase change with time and with position in the fixed bed as
adsorption proceeds.
 No solute contain at the bed inlet at the start of the process
 As the fluid first comes in contact with the inlet of the bed, most of the
mass transfer and adsorption takes place here
 As the fluid passes through the bed, the conc in this fluid drops very
rapidly with distance in the bed and reaches zero well before the end of
the bed is reached
 After a short time, the solid near the entrance is almost saturated and
most of the mass transfer and adsorption now takes place at slightly
farther from the inlet
 At a later time, the mass tranfer zone where most of the conc change
takes place has moved farther down the bed

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+ Design of Fixed Bed Adsorption
19

Column
 Concentration profile at various positions and times in the
fixed bed adsorption.

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+ Breakthrough Concentration Curve 20

 The break point occurs when the concentration of the fluid leaving the
bed rise to cb, which call break point.
 The concentration rises very rapidly up to point cd, which is the end of
the breakthrough curve, where the bed become ineffective.
 The break point conc represent the maximum that can be discarded and
is often taken as 0.01 to 0.05 for cb/co
 The value cd/co is taken as the point where cd is approximately equal to
co
 For narrow mass transfer zone, the breakthrough curve is very step and
most of the bed capacity is used at the break point. This makes efficient
use of the adsorbent and lowers energy cost for regeneration

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+ Breakthrough Concentration Curve 21

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+ Capacity of Column and Scale-Up 22

Design Method
 Mass transfer zone width and shape depend on the adsorption isotherm, flow
rate, mass transfer rate to the particles and diffusion in the pores
 The total or stoichiometric capacity of the packed bed tower is proportional
to the area between the curve and a line at c/co = 1.0 (shaded area)
 Time equivalent to the total capacity, tt

 The usable capacity of the bed up to the break point time tb (i.e time at
which the effluent conc reaches its maximum permissible level)is given as

• The can be determine graphically

or numerically, or
• Assume breakthrough curve
symmetrical at c/co = 0.5 and ts,
then tt = ts
• This assume that the area below
the curve between tb and ts is
equal to the area above the curve
between ts and td

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+ Capacity of Column and Scale-Up 23

Design Method
 Length of bed used up to the break point, HB

 Length of unused bed, HUNB

 The HUNB represent the mass transfer section or zone. It depends on the fluid
velocity and is essentially independent of the total length of the column, HT
 The full scale adsorber bed can be designed simple by first calculating the
length of bed need to achieve the required usable capacity, HB. Then the total
length , HT is simply added HB with HUNB

 The mass velocity in the bed remain constant for scale-up, the diameter of
the bed should be adjusted to keep it constant.
 Typical packed bed operation: height 0.3-1.5m, 15 – 50cm/s gas velocity, 0.3-
5mm adsorbent particle size, adsorption time 0.5-8h, 0.3-0.7cm/s liquid
velocity, practical bed depth is 5-10 times the length of bed of the mass
transfer zone

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+ Example 12.3-1
24

A waste stream of alcohol vapor in air from a process was adsorbed by

activated carbon particles in a packed bed having a diameter of 4 cm and
length of bed of 14 cm containing 79.2 g of carbon. The inlet stream having a
concentration, co of 600 ppm and a density of 0.00115 g/cm3 entered the bed at
a flow rate of 754 cm3/s. Data in the table give the concentrations of the
breakthrough curve. The break point concentration is set at c/co = 0.01. Do as
follows.
a) Determine the breakpoint time, the fraction of total capacity used up to the
break point, and the length of the unused bed. Also determine the
saturation loading capacity of the carbon.
b) If the break point time required for a new column is 6.0 h, what is the new
total length of the column required?

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 Adsorption - Equipments
Equipment for adsorption:
•The precise way in which adsorption and regeneration are achieved
depend on the phases involved and the fluid-solid contacting systems
•The three types of contacting systems are:
i) Adsorbent and contacting vessels are fixed whilst
the inlet and the outlet for process and regenerating systems are
moved when the adsorbent becomes saturated - e.g fixed bed
adsorber
ii) The containing vessel is fixed but the adsorbent
moves with respect to it. - e.g fluidised beds and moving beds
with solids in plug flow
iii)The adsorbent is fixed relative to the containing
vessel which moves relative to fixed inlet and outlet positions for
process and regenerating fluids-e.g rotary bed adsorber

25
 Adsorption - Equipments
Equipment for adsorption:
A) Fixed (or packed) beds
•The fluid to be treated is usually
passed down through the packed
bed at a constant flow rate
•The adsorption stage continues
Figure 17.16, pg
until the adsorbate wave is about
771 (ChemE Vol 2)
to emerge from the bed and the
effluent concentration begins to
rise
•The equilibrium condition has
then to be changed for
regeneration to occur
•Regeneration is done by changing
the temperature/pressure so that
the driving force is now reversed
(from solid to fluid)

26
 Adsorption - Equipments
Equipment for adsorption:
B) Plug flow of solids (hypersorber)
•The mixture to be separated is fed into
the centre of the column down which
activated carbon moves slowly
•The adsorbent with its adsorbate Figure 17. 68, pg
continues down the column into an 788 (ChemE Vol 2)
enriching section where it meets an
upwards stream of recycled top-product
•The heavy components continue
downwards on the carbon until adsorbed
by stream (recovered as bottom
product)
•The carbon, now stripped off all the
adsorbents, is lifted to the top of the
column and cooled before the cycle is
started again

27
 Adsorption - Equipments
Equipment for adsorption:
C) Rotary bed adsorber
•The solid and vessel move together,
relative to a fixed inlet for the feed and
a fixed outlet for the product
•Example of application: Solvent
recovery from air on to activated Figure 17. 78, pg
carbon 793 (ChemE Vol 2)
•Activated carbon is contained in a
thick, annular layer, divided into cells
by radial positions
•Air can enter through most of the
drum circumference,and passes
through the carbon layer to emerge
free of solvent
•Clean air leaves the equipment
through a duct connected along axis of
rotation

28
+ Adsorption - Equipments
29

Application:
- sulfur removal
using zinc oxide
+ Adsorption - Equipments
30

Application:
-Molecular sieves
are used as adsorbents
to remove contaminant
gas such as H2O, CO2
and H2S.
+ Adsorption - Equipments
31

Gas phase adsorption system

(simplified)

H 2O
Feed gas

solvent
molecul H 2O
ar
sieves
clean gas
+ Adsorption - Equipments
PROCESS FLOW DIAGRAM – Crude Palm Oil Processing Plant

CPO LOADING CPO STORAGE PRETREATMENT

TANK PLANT
OLEIN PRODUCT
80.00 RBDPO
95.50
%
%
4.00
20.00
%
%STEARIN
PRODUCT TANK FRACTIONATION PLANT BYPRODUCT DEODORIZING
PFAD PLANT
+ Adsorption - Equipments
33

BLEACHING
EARTH

SPENT EARTH
+
BLEACHING
• DOSE ACTIVATED CLAY INSIDE OIL
• TEMPERATURE 90-110°C
• CLAY CONSUMPTION DEPENDS ON OIL QUALITY
• VACUUM 600-680 mmHG
• TIME 30 – 40 MINUTES

PURPOSE
• AGGLOMERATE PHOSPHOLIPIDS AND TRACE METAL
• ADSORB COLOUR,SOAP,PHOSPHOLIPIDS,METAL
• REMOVE MOISTURE
+ 35

Regeneration of Adsorbent
Temperature Swing
• Also known as thermal swing cycle
• Heating with embedded stream coils or with
a hot purge gas stream
• The elevation of temperature shift the
adsorption equilibrium curve
• Bed must be cooled for used in the next
cycle
• Time taken few hours or more
Pressure Swing Cycle
• Pressure is reduced at constant temperature
and then purging the bed at this low pressure
• Reduction of pressure shift the adsorption
equlibrium
• Time taken is very short compared to
temperature swing cycle

Adsorbent
Regeneration

Inert Purge Gas Stripping Cycle Displacement Purge Cycle

• By passing a nonadsorbing or inert gas
through the bed
• The partial pressure or concentration around
the particle is low and desorption occurs
• Regeneration time only a few minute
• The pressure and temperature are kept
constant as in purge gas stripping, but a gas
or liquid is used that is adsorbed more
strongly than the adsorbate and displace the
adsorbate
• Regeneration time only a few minute

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Temperature Swing Adsorption

 Temperature Swing Adsorption (TSA)
 Regeneration of adsorbent in a TSA process is ahieved by an
increase in temperature. The Figure below showed
schematically the effect of temperature on the adsorption
equilibrium (Type I isotherm) of a single adsorbate.


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Temperature Swing Adsorption

 For any given partial pressure of the adsorbate in the gas phase (or
concentration in the liquid phase), an increase in temperature leads to a
decrease in the quantity adsorbed. If the partial pressure remains
constant at p1, increasing the temperature from T1 to T2 will decrease
the equilibrium loading from q1 to q2.
 A relatively modest increase in temperature can effect a relatively large
decrease in loading. It is therefore generally possible to desorb any
components provided that the temperature is high enough. However, it
is important to ensure that the regeneration temperature does not cause
degradation of the adsorbents.
 A change in temperature alone is not used in commercial processes
because there is no mechanism for removing the adsorbate from the
adsorption unit once desorption from the adsorbents has occurred.
Passage of a hot purge gas or steam, through the bed to sweep out the
desorbed components is almost always used in conjunction with the
increase in temperature.
 A very important characteristic of TSA processes is that they are used
virtually exclusively for treating feeds with low concentrations of
adsorbates.

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Temperature Swing Adsorption

 2-Bed TSA System
 The Figure below shows one of the simplest practical temperature swing adsorption (TSA) cycles based on 2 beds. The feed stream containing
adsorbate at partial pressure p1 is passed through the first bed (Bed 1) at temperature T1. Adsorption occurs and the partial pressure of adsorbate in the
effluent p2 may be zero or very low. The loading on the adsorption bed is improved by operating the bed at the lowest temperature which avoids
condensation. In practice, ambient temperature is often used. In this process, the heat of adsorption is mostly carried out of the bed with the effluent, and
in such a situation the bed approaches isothermal operation.
 When breakthrough is about to occur this bed is taken off-line and the feed is switched to the second bed (Bed 2).
 Simultaneously Bed 1 is regenerated by raising its temperature to T2 and purging with a hot inert gas normally in a flow direction opposite to that used
for the adsorption step. The regenerated bed is then cooled to temperature T1 by using either cold feed or inert fluid. Bed 1 is now ready for adsorption
again. Although the desorption step can be accomplished in the absence of a purge by simply vapourizing the adsorbate at elevated temperature, re-
adsorption of some solute vapour would occur upon cooling the bed.
 [ Back on Top ]


 Desorption with hot feed is practicable only if high purity is not required on the subsequent adsorption step.
 When the adsorbate is valuable and easily condensed, the purge fluid might be a non-condensable gas. When the adsorbate is valuable but not easily
condensed, and is essentially insoluble in water, steam may be used. Condensation of the steam allows the desorbed adsorbate to be separated. When
the adsorbate is not valuable, fuel and/or air can be used as the purge fluid, followed by disposal, e.g. by incineration.
 The heating and desorption steps must provide sufficient energy to perform the following functions:
 To raise the adsorbent, its associated adsorbate and the containment vessel to the desorption temperature.
To provide the heat of desorption
To raise the adsorbent and vessel temperature to final regeneration temperature (if greater than that for desorption)
 Because beds of adsorbent cannot normally be heated and cooled quickly, the cycle time of a typical TSA process may range from several hours for a
bulk separation to several days for a purification. Long cycle times inevitably mean large bed lengths resulting in high adsorbent inventories.
 During the period when Bed 1 is adsorbing, Bed 2 is being desorbed which includes the times required for heating and cooling. The 2-bed TSA process
requires that the time taken for desorbing gases from one bed matches the time allowed for adsorption in the other bed. Otherwise product flow would
be discontinuous. If a longer period is required for desorption, then due to the time constraint, only a fraction of the adsorbate can be removed during
the desorption step of the cycle. Bed capacity is consequently not fully utilised.
 Because of the long cycle times required for TSA processes this mode of operation is used almost exclusively for the removal of low concentrations of
adsorbable gases from feed streams.
 A practical problem in TSA processes is the reduction in the capacity or life of the adsorbent when it is subjected to repeated thermal cycling. Another
problem is the formation of coke in applications in which the reactive hydrocarbons are exposed to elevated temperatures during the desorption or
regeneration step.
 Common examples of TSA processes include solvent recovery with activated carbons, and drying of gases or liquids with Type A zeolites, removal of
water from VOCs with zeolites, gas sweetening, etc

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Temperature Swing Adsorption

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Pressure Swing Adsorption

Pressure swing adsorption (PSA) is a technology used to
separate some gas species from a mixture of gases under
pressure according to the species' molecular characteristics
and affinity for an adsorbent material. It operates at near-
ambient temperatures and differs significantly from
cryogenic distillation techniques of gas separation. Specific
adsorptive materials (e.g., zeolites, activated carbon,
molecular sieves, etc.) are used as a trap, preferentially
adsorbing the target gas species at high pressure. The
process then swings to low pressure to desorb the adsorbed
material.

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Pressure Swing Adsorption

 Process[edit]
 Pressure swing adsorption processes rely on the fact that under high
pressure, gases tend to be attracted to solid surfaces, or "adsorbed". The
higher the pressure, the more gas is adsorbed; when the pressure is
reduced, the gas is released, or desorbed. PSA processes can be used to
separate gases in a mixture because different gases tend to be attracted to
different solid surfaces more or less strongly. If a gas mixture such as air, for
example, is passed under pressure through a vessel containing an adsorbent
bed of zeolite that attracts nitrogen more strongly than it does oxygen, part
or all of the nitrogen will stay in the bed, and the gas coming out of the
vessel will be enriched in oxygen. When the bed reaches the end of its
capacity to adsorb nitrogen, it can be regenerated by reducing the pressure,
thereby releasing the adsorbed nitrogen. It is then ready for another cycle of
producing oxygen enriched air.
 This is the process used in portable oxygen concentrators used by
emphysema patients and others who require oxygen-enriched air to
breathe.
 Using two adsorbent vessels allows near-continuous production of the target
gas. It also permits so-called pressure equalisation, where the gas leaving
the vessel being depressurised is used to partially pressurise the second
vessel. This results in significant energy savings, and is common industrial
practice.

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Pressure Swing Adsorption

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Inert Purge Stripping Cycle

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Inert Purge Stripping Cycle

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Thank You

Dr SMS 2012/2013