EKB3143: SEPARATION

PROCESSES
ADSORPTION
Muhammad Syafiq Alias
e-mail: muhammad.syafiq@miu.edu.my

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 Items Covered in Part 2
Students should be able to :
1. Perform calculations for Stirred Batch Adsorber
2. Design a fixed bed adsorption column
3. Explain the methods for the regeneration of
adsorbents

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Contacting Modes for Adsorption

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 Agitated vessel
• A batch of liquid to which is added a powdered adsorbent
such as activated carbon particle diameter typically less than
1mm, to form a slurry.
• With good agitation and small particles, the external
resistance to mass transfer from the bulk liquid to the
external surface of the adsorbent particles is small.
• For small adsorbent particles, the internal resistance to mass
transfer within the pores of the particles is also small. Hence,
the adsorption rate is rapid.
• Main application: removal of very small amounts dissolved,
and relatively large molecules, such as coloring agents, from
water.
• Slurry adsorption system (also called contact filtration) is
also operated4 continuously.
 Batch Adsorption
• When quantities to be treated are of small amount in a
batch, isotherms and material balance are needed.
• Material balance on the adsorbate:

qF M + cF S = q M + cS (12.2-1)

where:
qF = initial concentration of solute on the solid
q = final concentration at equilibrium
cF = initial concentration of solute in the feed
c = final concentration of solute in the solution
M = amount of adsorbent, kg
S = volume of feed solution, m3
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 Example: Batch Adsorption

• Example 12.2-1:
• A wastewater solution having a volume of 1.0 m3
contains 0.21 kg phenol/m3 of solution .
• A total of 1.40 kg of fresh granular activated
carbon is added to the solution , which is then
mixed thoroughly to reach equilibrium.
• Using the isotherm from Example 12.1-1, what
are the final equilibrium values, and what
percent of phenol extracted?

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 Example: Batch Adsorption
Example 12.2-1:
qF M + cF S = q M + cS

0(1.40) + 0.21(1.0) = q (1.40) + c (1.0)

q = 0.15- 0.714 c (a)

From the isotherm

q = 0.199 c 0.229 (b)

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 Example: Batch Adsorption
Example 12.2-1:
• At the intersection
q = 0.106 kg
phenol/kg carbon
c = 0.062 kg
phenol/m3
• % adsorbed
• = (cF - c)(100)/cF =
(0.21- 0.062) (100)/0.21
= 70.5 %

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 Fixed Bed Adsorber Design-
Introduction
• Usually employs fixed bed of granular particles
• The fluid to be treated usually passes down
through the packed bed at a constant flow rate.
• Mass transfer resistances are important in the
fixed-bed process, and the process is at
unsteady state.
• The overall dynamics of the system determines
the efficiency of the process, rather than just the
equilibrium considerations.

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 Cyclic fixed-bed batch operation-
widely used with both liquid and gas feeds

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 Fixed Bed Adsorption Design
concentration profiles
• The concentration of the solute in the fluid phase and
in the solid adsorbent change with time & position in
the fixed bed as the adsorption proceeds
• Inlet: Solid is assumed to contain no solute at the
start of the process.
• As the fluid first comes into contact with the inlet,
most of the MASS TRANSFER and ADSORPTION
takes place here.
• As fluid passes thru the bed, the concentration in this
fluid DROPS VERY RAPIDLY with distance in bed
and REACHES ZERO well before the end of the bed
reached.
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Fixed Bed Adsorption Design-Breakthrough
• After a some time, solid near entrance is almost
SATURATED and most of the mass transfer and adsorption
now takes place at a point slightly farther from the inlet.
• Then, the outlet conc starts to rise, and at tb the outlet conc
has risen to cb, which is called the breakthrough point

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Fixed Bed Adsorption Design
Capacity of Column and Scale-Up Design
Method
- Mass Transfer Zone (MTZ) width and shape depends on:
- the adsorption isotherm, flowrate, mass transfer rate
to the particles and diffusion in the pores.
- For systems with a favorable isotherm, similar to
Freundlich and Langmuir;
- MTZ acquires the typical S shape. MTZ is constant in
height as it moves through the column
- For unfavorable isotherm i.e. Isotherm is linear; MTZ
width increases with bed length.

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Fixed Bed Adsorption Design
Time equivalent to the
total or stoichiometric (12.3-1)
capacity
Total or stoichiometric capacity of the packed tower

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Fixed Bed Adsorption Design
Usable capacity of bed up to the break-point time, tb

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Fixed Bed Adsorption Design
• tu : time equivalent to the usable capacity or
time at which the effluent concentration
reaches its maximum permissible level.

(12.3-2)

• tu very close to tb
• tu/tt is the fraction of the total bed capacity or
length utilized up to the break point
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 Fixed Bed Adsorption Design
HUNB: Length of Unused Bed (mass transfer zone)
Depends on fluid velocity.
HB : Length of the bed used until breakthrough point

(12.3-4)

HT = HUNB + HB (12.3-5)

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Fixed Bed Adsorption Design Steps
Design Steps
1. Determine the length of bed needed to
achieve the required usable capacity, HB at the
breakpoint.. HB is proportional to tb
2. Determine HUNB at laboratory scale at the same
velocity as in full scale.
3. Then, Calculate HT

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 Alternative method:
•Assume that the breakthrough curve is symmetrical
at c/co at ts. Then, ts = tt (Eqn. 12.3-1)
•Therefore, area below the curve between tb and ts is
equal to the area above the curve between t s and td

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Fixed Bed Adsorption Design
Scale-up principle

1. If a system is tested with different bed

length, it gives breakthrough curve of the
same shape.

2. The amount of length of unused bed (HUNB)

does not change with the total bed length.

3. Hence, tb is proportional to HB.

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 Example: Fixed Bed Adsorption
Example 12.3-1 Design
A waste stream of alcohol vapour in air from a process was
adsorbed by activated carbon particles in a packed bed
having a diameter of 4 cm and length of 14 cm containing
79.2 g of carbon.
The inlet gas 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 Table 12.3-1 give the
concentrations of the breakthrough curve. The breakpoint
concentration is set at c/co = 0.01.

a) Determine the breakpoint time tb, the fraction of total

capacity used up to the breakpoint tu/tt, and the length of
the unused bed HUNB.
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Example: Fixed Bed Adsorption
Design
Example 12.3-1
Table 12.3-1
Time,h c/co Time, h c/co
0 0 5.5 0.658
3 0 6.0 0.903
3.5 0.002 6.2 0.933
4 0.030 6.5 0.975
4.5 0.155 6.8 0.993
5 0.396

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 Example: Fixed Bed Adsorption
Example 12.3-1 Design
The plotted data from Table 12.3-1

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 Example: Fixed Bed Adsorption
Example 12.3-1
Design
Based on Figure 12.3-3
At break point conc. 0.01: tb = 3.65 h; td = 6.95 h

= A1 + A2 = 3.65 + 1.51 = 5.16 h

= A1 = 3.65 h

tu / tt = 3.65/5.16 = 0.707

= 0.707(14) = 9.9 cm

= (1 - 0.707)14 = 4.1 cm
 Example: Fixed Bed Adsorption
Example 12.3-1 Design
b) If the breakpoint time required for a new column is 6.0 h,
what is the new total length?
tu is proportional to HB
tu = 3.65 HB = 9.9 cm; tb’ = 6 h

= A 1’ = 6 h

= (6 /3.65 )(9.9) = 16.3 cm

HT’= HB + HUNB = 16.3 + 4.1 = 20.4 cm

(Fraction of the new bed

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used up to the break point)
 Example: Fixed Bed Adsorption Design
Example 12.3-1
c) Determine the saturation loading capacity of the carbon.
Air flow rate= (754 cm3/s)(3600s)(0.0115g/cm3) =3122g air/h
600 ppm = 600 g alcohol in 1 million g of air

Total alcohol adsorbed =

= 9.67 g alcohol

Saturation capacity =

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 Processing Variables and
Adsorption Cycles
• Large scale adsorption:
1) cyclic batch system -alternately saturated &
then regenerated
2) continuous flow system- continuous flow of
adsorbent countercurrent to a flow of feed

• Bed regeneration method

• Temperature-swing cycle
• Pressure-swing cycle
• Inert-purge gas stripping cycle
• Displacement-purge cycle.
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Temperature Swing

Adsorption
(Purasiv process)

-Fluidized bed
for adsorption
-Moving bed for
desorption

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 Purasiv process
• Adsorbent particles are attrition-resistant
• In the adsorption section, sieve trays are used with the raw
gas passing up through the perforations and fluidizing the
adsorbent particles.
• The fluidized solids flow like a liquid across the tray, into the
downcomer, and onto the tray below.
• From the adsorption section, the solids pass to the
desorption section, where, as moving beds, they first flow
down through preheating tubes and then through desorption
tubes.
• Steam is used for indirect heating in both sets of tubes and
for stripping in the desorption tubes.
• At the bottom of the unit, the regenerated solids are picked
up by a carrier gas, which flows up through a gas-lift line to
the top, where the solids settle out onto the top tray to repeat
the adsorption part of the cycle.
Temperature Swing
Adsorption
• Effect of temperature
on the adsorption
equilibrium of a single
adsorbate
• If the partial pressure
remains constant at
p1, increasing the
temperature from T1
to T2 will decrease the
equilibrium loading
from q1 to q2.

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Bed TSA System

Cycle Steps
1-
adsorption at T1 to
breakthrough
2- heating of the bed to T2
(T2 > T1)
3- desorption at T2

4- cooling of the bed to T1

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Pressure Swing Adsorption
(Mechanical work)
• Regeneration process – reducing the partial
pressure of the adsorbate
• 2 ways: Introduction of an inert gas while
maintaining the total system pressure
• Cycle time very quick (minutes or second)
• Operate PSA close to ambient temperature – at
a given partial pressure, the loading is increased
as temperature decreased
• Popular for performing bulk separation of gases
– controlled by adsorption isotherm or
adsorption kinetics
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Pressure Swing Adsorption

• Effect of partial
pressure on
equilibrium loading at
temperature T1
• Reducing the partial
pressure from p1 to p2
causes the equilibrium
loading to be reduced
from q1 to q2

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 Bed PSA System
• Each bed operates alternately :
• Pressurisation followed by
adsorption
• Desorption by
depressurisation (blowdown)
followed by a purge
• Adsorption – pressure greater
than atmospheric
• Desorption – pressure at 1atm
Pressurisation – feed gas
• Purging – effluent (non-adsorbed)
product gas 35
 Displacement Purge
Adsorption
• Removal of adsorbates by replacing them with a more
preferentially adsorbed species
• Mechanism for desorption:
• Partial pressure (or concentration) of original adsorbate
in the gas phase surrounding the adsorbent is reduced
• There is competitive adsorption for the displacement
fluid
• One advantage – net heat generated or consumed will be
close to zero because heat of adsorption of the
displacement fluid is close to the original adsorbate –
adsorbent temperature constant throughout the cycle
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Displacement Purge
Adsorption

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Adsorption completed

THANK YOU.

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