What we introduced in Lecture 1

• About this module

• Introduction on Adsorption
• Adsorbent – micro-structures
• Adsorption equilibrium
– Dynamic equilibrium
– 5 adsorption isotherms
– Adsorption equations (pure gas)

https://www.youtube.com/watch?v=sqGJsIVCvq8
Adsorption technology

Lecture 2

 Adsorption in a fixed bed

 Kinetic and Transport considerations
 Concentration profiles
 Considerations for designs
Adsorption technology
• Background information
 Adsorption technology can be used for various applications, including those related
to energy, environment and water
 Depending on the applications, different adsorbents, adsorber designs and
operations are required
 Slurry adsorption, temperature and pressure swing adsorption, ion exchange,
chromatography and simulated-moving-bed systems are commonly used

Lab-scale Industrial-scale
 Adsorption technology

• Kinetic and Transport considerations

Flowing fluid phase Stationary sorptive phase (porous Adsorption

or resin particles)
1. Solute transport by bulk flow
(convection) and dispersion through
Packed column or
vessel interstices of the packed adsorbent
2. External solute transport from the bulk
flow to the outer perimeter of the
adsorbent particle, through a thin film
or boundary layer
3. Internal solute transport by diffusion in
quiescent fluid-filled pores inside
adsorbent
4. Surface diffusion along the internal
porous surface of adsorbent

Regeneration
 Transport through interstices between packed particles
Reverse of the 4 steps above
 Solute diffuse between the moving fluid phase and a
stationary fluid phase within pores of the solid
adsorbent
Heat effect (adsorption – exothermic; desorption - endothermic) 
temperature and concentration profiles along the column
 Adsorption technology

• Mass-transfer Process in Adsorption

Solute concentration and temperature profiles for a given particle, at a
given time and location inside vessel
Adsorption Desorption
(exothermic) (endothermic)
 Concentration gradient is usually
steepest within the particle
 Temperature gradient is usually
steepest in the boundary layer
Convection Convection surrounding the particle

Major resistance to mass transfer

resides in the adsorbent particle

Inside particle Inside particle

Boundary layer Boundary layer

Concentration and temperature profiles here are different from the one in a
Adsorption technology

• Kinetic and Transport Considerations

𝑧 =0 𝑧 =𝐿 𝐵
𝑄 𝐹𝑐 𝐹 𝑄 ′ 𝐹𝑐 𝑓

𝐼𝑛 𝑂 𝑢𝑡
Length of the bed

 solute concentration in the feed

Why we need such a
 discharge concentration controlled, or low value here?

 solute concentration profile along the bed

 flow rate at the inlet
 flow rate at the outlet and can be very similar, and can be
very different, why

https://www.youtube.com/watch?v=YVZ_rizK1FI
Adsorption technology
Stoichiometric front
• Ideal fixed-bed adsorption
Feed Effluent
• Negligible external and internal resistance
• Ideal plug flow
• Adsorption isotherm beginning at the origin
• Local equilibrium established instantaneously
• Shock-like stoichiometric front moves at a constant velocity throughout the
bed
 Adsorption technology

• Concentration profiles
Ideal fixed-bed adsorption, at time
Instantaneous equilibrium Concentration Instantaneous equilibrium
front at time

𝑐𝐹
, solute concentration

Spent adsorbent Unused adsorbent

From feed In adsorbents
∗
WES 𝑄 𝐹 𝑐 𝐹 𝑡 𝑖𝑑𝑒𝑎𝑙 = 𝑐𝑏 𝐴 ( 1 − 𝜖𝑏 ) 𝐿 𝑖𝑑𝑒𝑎𝑙
WUB
LES LUB
0 : the loading in equilibrium with
0 𝐿 𝐿𝐵
: bed cross-sectional area
, distance through the bed
: bed porosity
𝑄 𝐹 𝑐 𝐹 𝑡 𝑖𝑑𝑒𝑎𝑙 𝑄 𝐹 𝑐 𝐹 𝑡 𝑖𝑑𝑒𝑎𝑙
𝐿 𝑖𝑑𝑒𝑎𝑙 = 𝐿𝐸𝑆= ∗
= ∗
𝐿 𝐵𝑆= 𝐴 ( 1 −𝜖 𝑏 ) 𝐿 𝐵 𝐿𝑈𝐵=𝐿𝐵 − 𝐿𝐸𝑆
𝑐 𝑏 𝐴 ( 1− 𝜖 𝑏 ) 𝑐𝑏 𝑆

 The physical frontier of the plug flow fluid can move faster than the concentration frontier
 The outlet concentration is 0, until “breakthrough” occurs when suddenly becomes
WES: weight of equilibrium section WUB: weight of unused bed
LES: length of equilibrium section LUB: length of unused bed
Adsorption technology
• Concentration profiles
Realistic adsorption in a fixed bed

In contrast to the ideal bed:

• External and internal resistance are NOT negligible
• Non-ideal flow
• Adsorption isotherm NOT beginning at the origin
• Local equilibrium NOT established instantaneously

As a result, concentration profiles change with time

https://www.youtube.com/watch?v=_2YxVkgZ_aA

https://www.youtube.com/watch?v=RmS35Ac-FE0
Adsorption technology
• Concentration profiles
Realistic adsorption in a fixed bed – no instantaneous equilibrium
anymore
At ,
𝒄 - A small part close to entrance is nearly saturated
𝒄𝑭 - Some adsorbents are partially-used
- Most adsorbents are un-used

At ,
𝒄 - More adsorbents close to entrance are saturated
𝒄𝑭 - Some adsorbents are partially-used
- Some adsorbents are un-used

At ,
𝒄 - Further more adsorbents are saturated
𝒄𝑭 - Some adsorbents are partially-used
- No adsorbents are un-used
“Break-through” about to occur
Adsorption technology

𝒄
𝒄𝑭
Concentration profile
of solute in the fluid
phase

Loading distribution in
the solid phase or
adsorbent
 Adsorption technology
• Concentration profiles
Realistic adsorption in a fixed bed – no instantaneous equilibrium
anymore

Normalized

𝒄 𝒇/𝒄
/𝒄 𝑭𝑭
𝒄 / 𝒄 𝑭 =𝟎 .𝟗𝟓

(breakthrough time)  minimum

𝒄 / 𝒄 𝑭 =𝟎 . 𝟎𝟓 detectable or maximum allowable
concentration
𝐿𝑠 𝐿𝑓 𝐿𝐵 (equilibrium time)  from to
Distance through bed,
At , no part of the bed is saturated At , the leading point of the MTZ just
reaches the end of the bed.
At , , the bed is saturated
, little mass transfer, adsorbent still unused
, Mass Transfer Zone,
Adsorption technology
• Concentration profiles
– Breaking through curves

Analyse the composition of against time

For an ideal packed bed

1
𝑐 𝑓 ,𝑜𝑢𝑡 /𝑐 𝐹
𝑡𝑏
0
𝑇 𝑖𝑚𝑒
Adsorption technology
• Concentration profiles
– Breaking through curves

Analyse the composition of against time

For a real packed bed

Some adsorbents are not fully

used after break-through happen

• The steepness of the breakthrough curve determines the extent to which the capacity of an
adsorbent bed can be utilised.
• Thus, the shape of the curve is very important in determining the length of the adsorption bed.
• In actual practice, the steepness of the concentration profiles can increase or decrease,
depending on the type of adsorption isotherm involved.

https://www.youtube.com/watch?v=YVZ_rizK1FI
Adsorption technology
Broadening of the wave front, reflected by both wide MTZ zone and wide breakthrough
curve, is due to transport resistance, basically un-favourable adsorption isotherm, as we
assuming an ideal fixed-bed adsorber
 Broadening of the wave front with an unfavourable Type III
isotherm

Type I

Type III

high concentration constant pattern

regions (faster) front
 Favourable isotherm is the Langmuir or Freundlich type

the high concentration regions move faster than

the low concentration regions, and the wave front
steepens with time until a constant pattern
front is developed (self-sharping)

low concentration regions (slower)

Adsorption technology
• Self-sharping is eventually limited by persistent transport resistance 
ideal concentration front not achievable
• As a result, an asymptotic or constant-pattern front (CPF) is developed
• MTZ becomes constant and curves of and become coincident

• Scale-up using Constant-Pattern Front (Collins, 1967)

Pilot tests
A given length of bed & Loading at and
Measure the time required at
at at
or
at at

a time between and ,

𝑐 𝑓 /𝑐 𝐹
to equalize the area of A and B
Adsorption technology

• Scale-up using Constant-Pattern Front (Collins, 1967)

Bed length 𝐿𝐵 =𝐿𝐸𝑆 + 𝐿𝑈𝐵

𝑳𝑩 LES and LUB are both affected by the

CPF (constant-pattern front)

adsorbent loading of solute

bulk density of adsorbent
𝑐 /𝑐 𝐹
𝑐𝐹 𝑄𝐹 𝑡 𝑏
𝒕𝒃 𝒕𝒔 𝒕𝒆 At breakthrough 𝐿𝐸𝑆=
𝑞𝐹 𝜌 𝑏 𝐴

𝐿𝐸𝑆=
𝑐𝐹 𝑄𝐹 𝑡 𝑏
¿
( 𝑚𝑜𝑙
𝑐𝑚
3 )( ) = 1
𝑐𝑚3
𝑠
( 𝑠)
=𝑐𝑚
(
𝑞 𝐹 𝜌 𝑏 𝐴 𝑚𝑜𝑙
𝑔 ) ( 𝑐𝑚 )
𝑔
3
𝑐𝑚
1
𝑐𝑚
2
 Adsorption technology

• Scale-up using Constant-Pattern Front (Collins, 1967)

is determined by the MTZ width and

profile within this zone
𝑳𝑩 𝐿𝑒
𝐿𝑈𝐵= ( 𝑡 −𝑡 𝑏 )
𝑡𝑠 𝑠
entry length
the ideal wave-front velocity
Area of A and B is same
𝑐 /𝑐 𝐹 constant
𝒕𝒃 𝒕𝒔 𝒕𝒆

The stoichiometric time divides the MTZ (e.g. CPF zone) into equal areas A and B,
and corresponds to the ideal wave-front velocity.

( )
𝑡𝑒
𝑐𝑓
𝑡 𝑠=∫ 1 − dt Mathematically the area under the mirror curve of
0
𝑐𝐹

𝐋𝐔𝐁= 𝐌𝐓𝐙 /𝟐 𝐢𝐟 𝐭𝐡𝐞 𝐛𝐫𝐞𝐚𝐤 − 𝐭𝐡𝐫𝐨𝐮𝐠𝐡 𝐜𝐮𝐫𝐯𝐞𝐢𝐬 𝐬𝐲𝐦𝐦𝐞𝐭𝐫𝐢𝐜

Adsorption technology

• Scale-up using Constant-Pattern Front (Collins, 1967)

𝐿𝐵 =𝐿𝐸𝑆 + 𝐿𝑈𝐵

𝑳𝑩 𝑐𝐹 𝑄𝐹 𝑡 𝑏 𝐿𝑒
𝐿𝐸𝑆= 𝐿𝑈𝐵= ( 𝑡 −𝑡 𝑏 )
𝑞𝐹 𝜌 𝑏 𝐴 𝑡𝑠 𝑠

( )
𝒕𝒆
𝒄𝒇
∫ 𝟏−
𝒄𝑭
𝐝𝐭
𝟎

𝑐 /𝑐 𝐹

𝒕𝒃 𝒕𝒔 𝒕𝒆
𝒕 𝒔 =𝟏 × 𝒕 𝒔

The stoichiometric time divides the MTZ (e.g. CPF zone) into equal areas A and B,
and corresponds to the ideal wave-front velocity.

( )
𝑡𝑒
𝑐𝑓
𝑡 𝑠=∫ 1 − dt Mathematically the area under the mirror curve of
0
𝑐𝐹
Adsorption technology

• Scale-up using Constant-Pattern Front (Collins, 1967)

Procedure
 Use a pilot test column filled with the adsorbent to be used in full-
scale application. The column should be as large as possible, in
order for minimized side wall effects.
 Test filtration rates and contacting time that will be the same as the
full-scale application, but normalized by the dimensions of the pilot
test column, to obtain similar mass transfer characteristics.
 Obtain the breakthrough curves.
 Work on the curves for scaling-up.

Attention:
A favourable adsorption isotherm, such as the Freundlich one, is preferred
 Example – breakthrough curve

Nanotechnology Materials and Devices Conference (NMDC), 2013 IEEE 8th

Exercise II - Scale-Up for Fixed-Bed Adsorption

So,
Collins reports the experimental data below for water-vapour adsorption from nitrogen in
heig
a fixed bed of 4A molecular sieves for bed depth = 0.88 ft, temperature = 83 F, pressure
expe
= 86 psia, G = entering gas molar velocity = 29.6 lbmol/h-ft 2, entering water content =
and
1,440 ppm (by volume), initial adsorbent loading = 1 lb per100 lb sieves, and bulk density expe
of bed = 44.5 lb/ft3. For the entering gas moisture content, , the equilibrium loading, , = and
0.186 lb H2O/ 1 lb solid. calc
heig
abso
Q
a br
Determine the bed height
20h
required for a commercial unit see
to be operated at the same expe
temperature, pressure, and 9pp
entering gas mass velocity and and
water content to obtain an leng
exiting gas with no more than 9 but
ppm (by volume) of water vapor new
with a breakthrough time of 20 9.4p
h. lb-mol is equal to 453.59237 mol
One
Exercise II - Scale-Up for Fixed-Bed Adsorption
Here
sum
• What type of information we can have for u
Breakthrough curve brea
T= 83 F; P= 86 psia ts is
0.88 ft conc
G= 29.6 lbmol/h-ft2 the f
=1440 ppm Experimental adsorber call t
is us
= 1 lb per100 lb sieves LUB
= 0.186 lb H2O/ 1 lb solid We h
conc
• What does the Q want Tem
T= 83 F; P= 86 psia the l
expe
? ft
G= 29.6 lbmol/h-ft2 abso
=1440 ppm New adsorber < 9 ppm for over 20 h have
brea
= 1 lb per100 lb sieves We a
= 0.186 lb H2O/ 1 lb solid load
load
equi
 Exercise II - Scale-Up for Fixed-Bed Adsorption
We
ex
ca
the
tem
the
va
the
ha
(c1
ca
𝒕𝒃 𝒕𝒔 𝒕𝒆
ma
𝐿𝐵 =𝐿𝐸𝑆 + 𝐿𝑈𝐵=0.88 𝑓𝑡 = 9.4 h = 12.8 h 𝐿𝐸𝑆× 𝐴×𝑞 𝐹 × 𝜌 𝑏 =𝑐 𝐹 𝑄 𝐹 𝑡 𝑏slid
da
c c2
𝐿𝑒 𝑐 1 +𝑐 2
𝐿𝑈𝐵= ( 𝑡 −𝑡 𝑏 ) c1 ∆ 𝑐= W
𝑡𝑠 𝑠 2
be
integration of the breakthrough curve ca
∆ 𝑡 =𝑡 2 − 𝑡 1 si
t us
a time between and , to equalize the area of A and B
t1 t2
ne
Exercise II - Scale-Up for Fixed-Bed Adsorption

Integration of breakthrough curve

Cexit, ppm time, h ο‫ܥ‬ ο‫ݐ‬ ο ‫ ܥ‬ൈο‫ݐ‬
9 9.4 21 0.2 4.2
33 9.6 56.5 0.2 11.3
80 9.8 111 0.2 22.2
142 10 190 0.2 38
238 10.2 301.5 0.2 60.3
365 10.4 431.5 0.2 86.3
498 10.6 574 0.2 114.8
650 10.8 729 0.2 145.8
808 11 894 0.25 223.5
980 11.25 1047.5 0.25 261.875
1115 11.5 1175 0.25 293.75
1235 11.75 1282.5 0.25 320.625 So, we can use this data
1330 12 1370 0.5 685 equations to make this ta
1410 12.5 1425 0.3 427.5 the sum of ∆C x ∆t we ge
1440 12.8
෍ ο ‫ ܥ‬ൈο‫ݐ‬
2695.15
2695.15
 Wit
we
Exercise II - Scale-Up for Fixed-Bed Adsorption cur
hav
integration of the breakthrough curve = 2695.15 we
to c
rea
𝑡 𝑠=10.93 h we
equ
𝐿𝑒 0.88 (
𝐿𝑈𝐵= ( 𝑡 𝑠 −𝑡 𝑏 ) = 10.93 − 9.4 ) =0.12 𝑓𝑡 unk
𝑡𝑠 10.93
cal
This LUB does not change, as long as the same LU
adsorbent, operation conditions and adsorber diameter new
are used con
sta
For the new adsorber No
do
𝐿𝐸𝑆× 𝐴×𝑞 𝐹 × 𝜌 𝑏 =𝑐 𝐹 𝑄 𝐹 𝑡 𝑏=𝑐 𝐹 ×𝑄 × 𝐴×𝑡 𝑏
𝐿𝐸𝑆× ( 0.186 − 0.01 ) × 44.5=1440 ×2 9.6 × 20 ×18 /1000000Now we need to calculate LES
we have this equation where LE
𝐿𝐸𝑆=1.96 𝑓𝑡 is loading and Pb is density. So
area which equals volume time
𝐿𝐵 =𝐿𝐸𝑆 + 𝐿𝑈𝐵=1.96 +0.12=2.08 𝑓𝑡 mass times loading which equa
side of the equation). 0.186-0.0
minus initial loading. The value
20hour time. 44.5 is bulk densi
velocity, 18/1000000 the divisio
 1

Partially-used
𝒄
𝒄𝑭 Fully-used

0 𝑳𝑩

𝒄 𝒇 /𝒄 𝑭 =𝟎 . 𝟗𝟓 𝒄 𝒇 /𝒄 𝑭 =𝟎 . 𝟎𝟓