ADSORPTION

Dr. Nonni Soraya Sambudi

2 Learning Outcome

By the end of this lecture, students should be able to:

 describe the principles of adsorption and factors
influencing its separation efficiency
 determine the type of adsorption equilibrium isotherm
for a given process
 design a batch adsorption process
 3
Adsorption

Concept:
 Separation due to adhesion of one or more components of a gas
or liquid on a surface of a solid adsorbent.

Adsorbate/

Porous solid
4 Applications
▪ 1) Water treatment
▪ 2) Gas separation, air separation
▪ 3) Chromatography
▪ 4) Ion Exchange
5
ADSORPTION PROCESS

The interaction between the adsorbent (solid surface) and the adsorbate
(atom/molecules/ions of gas or liquid) can be
❑ chemically bond with solid surface (chemisorption)
❑ held by weak inter-molecular forces (physisorption)
 DESORPTION PROCESS
6

Desorption is the act of purifying solid adsorbent for another cycle of adsorption

▪ Adsorption  Saturated  Desorption

▪ Regeneration process for desorption:
❑ to recover Adsorbate and Adsorbent to be reused
❑ desorbent
❑ change in TEMPERATURE
❑ change in PRESSURE
7
Physical Properties of Adsorbents
 Adsorbent particles are very porous in structure with
many fine pores.
 Pore volume can be up to 50% of total particle volume
 porous structure (Å : Angstrom)
 Macropore ( > 500 Å or 50 nm )
 Mesopore ( 20 - 500 Å )
 Micropore ( < 20 Å )
 Large pore surface area: 100 to 2000 m2/g
 Shape
 cylindrical pellets, beads, granules, spheres, flakes or
powders
 size: 50 m to 1.2 cm
 EQUILIBRIUM RELATIONS FOR ADSORBENTS -
8 ISOTHERM

 Consider a fluid system of a

solute B in a carrier C (mixture
of C+B)
 When you contact this system
with a solid A that can
interact with the solute, the
solute B will be aDsorbed on
A typical system of a solute
the surface solid A. partitioning among a fluid and
solid.
 The partitioning can be
represented by isotherms.
9 EQUILIBRIUM RELATIONS FOR ISOTHERMS

Concentration of a
solute in a fluid
phase

Data is plotted as
Equilibrium T, P Adsorption Isotherms

Concentration of a
solute in a solid
phase
10 Common models for isotherm

 There are several

models proposed
to predict
equilibrium
distribution
 However, only the
following four
models are
commonly
observed
11 Linear adsorption isotherm

 Also known as Henry’s

adsorption isotherm
 Only valid at low pressure
(validity of ideal gas law
 Example: adsorption isotherm of
argon, oxygen, nitrogen on
activated carbon at room
temperature with gas pressure
not exceeding atmospheric
Linear: q = K c pressure
q vs c
straight line with slope K
12
Langmuir adsorption isotherm

 Most common type of isotherm,

developed based on theoretical
basis
 Assumptions:
 Monolayer coverage
 Fixed number of active sites
are available for adsorption
Langmuir: q = qoc/(K+c)  Constant binding energy
1/q = (K/qo) (1/c) + 1/qo between surface and
adsorbate
Plot of 1/q vs 1/c  Adsorption is reversible once
slope: K/qo y-axis equilibrium is reached
intercept: 1/qo
13 Freundlich adsorption isotherm

 Empirical in nature and

widely used
 Most often used for liquids
 1/n measures the intensity
of adsorption (higher
Freundlich: q = Kcn values means favourable
adsorption)
log q = log K + n log c
 Most suitable at low
Plot of log q vs log c
pressure application
slope: n y-axis
intercept: log K
 14

EXAMPLE 1: ADSORPTION ISOTHERMS

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 the table below.
Determine the isotherm that fits the data.

c q
(kg phenol/m3 (kg phenol/kg
solution) carbon)
0.322 0.150
0.117 0.122
0.039 0.094
0.0061 0.059
0.0011 0.045
15

 The slope n is 0.229

 The constant K is 0.199
 Hence, q = 0.199c0.229
 BATCH ADSORPTION
❑ Material balance on adsorbate:
16
initial final equilibrium
qF M + cF S = qM+cS

qF = initial concentration of solute on solid

q = final concentration of solute on solid at equilibrium
cF = initial feed concentration (in solution)
c = final equilibrium concentration (in solution)
M = amount of adsorbent, kg
S= volume of feed solution, m3

• From equation above, q vs c result in a straight line.

• By plotting equilibrium isotherm on the same graph, the
intersection
of both lines gives the final equilibrium values of q and c.
 Example: Batch Adsorption
17
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 q= 0.199c0.229,
what are the final equilibrium values, and what percent of phenol
are extracted?

Given: S = 1.0 m3 ; cF= 0.21 kg phenol/m3 ; M= 1.4 kg

qF M + cF S = qM+cS
Initially concentration of solute on solid is zero; qF=0
18
qF M + cF S = q M + c S

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

q = 0.15 – 0.71 c (1)

From the isotherm

q = 0.199 c 0.229 (2)

 19
For isotherm
For material balance
c (kg phenol/m3 q (kg phenol/kg
3
solution) adsorbent) c (kg phenol/m q (kg phenol/kg
0 0 solution) adsorbent)
0.01 0.069319126 0.01 0.142857143
0.03 0.08914846 0.03 0.128571429
0.05 0.100211418 0.05 0.114285714
0.07 0.108238192 0.07 0.1
0.09 0.114650146 0.09 0.085714286
0.11 0.120041662 0.11 0.071428571
0.13 0.124722872 0.13 0.057142857
0.15 0.128877759 0.15 0.042857143
20

q, kg phenol/kg adsorbent
c, kg phenol/m3 solution

At intersection (1) and (2) q = 0.106 kg phenol/kg carbon

c = 0.062 kg phenol/m3
% extracted = (cF - c)(100)/cF = (0.21-0.062)(100)/0.21
= 70.5 %
21
Problem 1
Equilibrium isotherm data for adsorption of glucose from an
aqueous solution to activated alumina are as follows.
Determine the isotherm that fits the data and determine the
constant. (Hint: Langmuir)

c q
(g/cm3 ) (g solute/g alumina)
0.004 0.026
0.0087 0.053
0.019 0.075
0.027 0.082
0.094 0.123
0.195 0.129
 For Langmuir,
22

c q 1/c 1/q
0.004 0.026 250 38.46154
0.0087 0.053 114.9425 18.86792
0.019 0.075 52.63158 13.33333
0.027 0.082 37.03704 12.19512
0.094 0.123 10.6383 8.130081
0.195 0.129 5.128205 7.751938
𝐾
 Slope of line = = 0.1235
𝑞0
1
 Intercept = = 6.7784
𝑞0

 Hence, 𝑞0 = 0.1475 and 𝐾 = 0.01822

𝑞𝑜 𝑐 0.1475𝑐
𝑞 = =
𝐾+𝑐 0.01822+𝑐
23 For Freundlich,

c q
0.004 0.026
0.0087 0.053
0.019 0.075
0.027 0.082
0.094 0.123
0.195 0.129
 Problem 2
24
 A aqueous solution, with total volume of 1.0 m3, containing 10
ppm nitrobenzene is to be treated with activated carbon in
batch process to reduce the concentration of nitrobenzene to
0.0 1 ppm. If the adsorption isotherm of nitrobenzene on
activated carbon follows the Freundlich isotherm as given below,
calculate the minimum activated carbon required for the
process. (Note: qe in mg/g, Ce in mg/litre)

𝑞𝑒 = 68 𝐶𝑒 0.43

 Answer

𝑞𝑒 = 68(0.01)0.43 = 9.3866 mg nitrobenzene/g activated carbon

10 mg nitrobenzene
Minimum activated carbon =
9.3866 mg nitrobenzene/g activated carbon
= 1.065 g
25
Problem 3
 A waste water solution with a volume of 2.5m3 contains phenol with
concentration of 0.25kg/m3. The solution is treated in a batch
process with 3 kg of activated carbon. If the isotherm is given as
per figure below (q = 0.199c0.229), calculate the final equilibrium
values and the percentage of phenol extracted when equilibrium is
reached. 0,14

0,12
q, kg phenol/kg adsorbent

0,1

0,08

0,06

0,04

0,02

0
0 0,02 0,04 0,06 0,08 0,1 0,12 0,14
c, kg phenol/m3 of solution
26
 S = 2.5 m3 solution
 M = 3 kg carbon
 CF = 0.25 kg phenol/m3
 At initial condition, qF = 0

 Material balance:
qF M + CF S = q M + C S
(0) (3) + (0.25) (2.5) = q (3) + C (2.5)
0.625 = 3q + 2.5C (1)
27
 Plot isotherm, q = 0.199 C0.229

C (kg phenol/m3 solution) q (kg phenol/kg adsorbent)

0 0
0.01 0.069
0.03 0.089
0.05 0.1
0.07 0.108
0.09 0.115
0.11 0.12
0.13 0.125
0.15 0.129
28
29
30 FIXED BED ADSORPTION COLUMN
 Adsorption column is filled with
granular particles creating a fixed
bed
 Fluid (liquid or gases) to be treated is
passed down through the packed
bed at a constant flow rate
 efficiency depends on the overall
system dynamics
 equilibrium considerations + mass
transfer resistances → process is
unsteady state
 concentration of solute in the
fluid phase and of the solid
adsorbent phase change with
time and position in the fixed bed
as adsorption proceeds
FIXED BED ADSORPTION
Fluid passed down
through packed column
at constant flow rate Efficiency depends
on:

i. Equilibrium
Filled with consideration +
granular mass transfer
particles resistance
(unsteady state)
ii. Concentration of
solute in both fluid
and solid
adsorbent phase,
which changes
with time and
MTZ as
position
adsorption
31
 Mass Transfer Zone
32

mass-transfer zone = most concn. change

1.0

c/c
0.5 t1 t2 t3 t4
0

0
0 H1 H2 H3
Height of adsorption bed, H
Concentration profiles for adsorption in a fixed bed;
profiles at various position and time
 Breakthrough Concentration Curve
33
mass-transfer zone = most concn. change
1.0

c/c0
0.5 t1 t2 t3 t4

0
0 H1 H2 H3
Height of adsorption bed, H HT

Concentration profiles for adsorption in a fixed bed

❑ co = feed concn, c = outlet fluid concn. at a point in the bed
❑ At time t1, no part of the bed is saturated. From t1 to t2, the fluid had moved down the bed
❑ At time t2, the bed is almost saturated for a distance H1, but is still clean at H2
❑ The MTZ where adsorption takes place is the region between H1 and H2. As it is difficult to
determine where MTZ begins and ends, H1 can be taken where C/C0 = 0.95, with H2 at
C/C0 = 0.05.
❑ The MTZ moves forward until the whole column is saturated with adsorbate.
 Breakthrough Concentration Curve
Concentration profiles for adsorption in a fixed bed
34 1.0

c/c0
0.5 t1 t2 t3 t4

0
0 H1 H2 H3 HT
Height of adsorption bed, H
When the whole bed in the column is saturated/exhausted Breakthrough occurs
Breakthrough concentration profile in fluid at outlet cd
1.0
mass-transfer
c/c0 zone
0.5
break point,
cb
outlet concn zero until zone reaches outlet at t4
0
0 t1 t2 t3 t4 t5 t6
Time, t Bed ineffective
 Example: Fixed Bed Adsorption Design
35
Example 12.3-1 (ref [1])
Table 12.3-1
A waste stream of alcohol vapour in air from a Time (h) c/co
process was adsorbed by activated carbon
0 0
particles in a packed bed having a diameter of 4
cm and length of 14 cm containing 79.2 g of 3 0
carbon. 3.5 0.002
The inlet gas stream having a concentration co 4 0.030
of 600 ppm and a density of 0.00115 g/cm3 4.5 0.155
entered the bed at a flow rate of 754 cm3/s.
5 0.396
Data in Table 12.3-1 give the concentrations of
the breakthrough curve. The breakpoint 5.5 0.658
concentration is set at c/co = 0.01. 6.0 0.903
Plot the breakthrough curve and determine the 6.2 0.933
breakpoint time tb 6.5 0.975
6.8 0.993
 Example: Fixed Bed Adsorption Design
36 Example 12.3-1
 Scale-Up Design Method
37 Total or stoichiometric capacity of packed-bed tower - when the entire bed
comes equilibrium with the feed : proportional to area between curve and line at
(c/co = 1.0)

 tt, time equivalent to stoichiometric capacity is represented by the area above the
curve:
 Scale-Up Design Method
38
 Usable capacity up to break point time tb
proportionate to area bwn. line at c/co, line at tb &
curve
 c
tu = 
tb
1 − dt 12.3-2, ref[1]
0
 c0 
tu is defined as
time equivalent to the usable capacity
time at which effluent concentration reaches its
maximum permissible level
tu  tb
 Scale-Up Design Method
39 Time equivalent c
tu = 
tb
to usable
capacity
(1 − )dt (12.3-2, ref [1])
0 c0
Time equivalent to usable capacity of bed up to the break-point time, tb
 Bed length
40  tu/tt is the fraction of the total bed capacity or length utilized up to
the break point
 Used bed length (up to the break point), HB, is

tu
H B = HT HT = total bed
length
tt
 Unused bed length, HUNB, ( MTZ = mass-transfer zone)

 tu 
H UNB = 1 −  H T
 Total bed length
 tt 
HT = HUNB + HB 12.3-5, ref[1]
41
Bed length
 HUNB represents the MTZ

 HUNB depends on fluid velocity

 HUNB is independent of the total length of the column as can be

measured from the design velocity in the column

Design Steps
1. Determine length of bed needed to achieve required usable capacity, HB
2. Determine unused bed, HUNB
3. Calculate total bed height, HT
 Example: Fixed Bed Adsorption Design
42 Example 12.3-1 (ref [1])
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 and the length of the unused bed.
b) If the breakpoint time required for a new column is 6.0 h, what is the
new total length
c) Determine the saturation loading capacity of the carbon.

Use your the breakthrough curve

 Example: Fixed Bed Adsorption Design
43 Example 12.3-1
The plotted data from Table 12.3-1. Breakthrough curve is symmetrical at c/co at ts. ts = tt
(Eqn. 12.3-1). Therefore area below curve between tb & ts = area above curve between ts & td

c/co = 0.5

Given:
breakpoint
concn at
c/co = 0.01 ts = 5.16
 Example 12.3-1
Based on Figure 12.3-3
44
HT = total bed length; HB = length of bed used up to break point; HUNB =
length of unused bed
At break point conc. 0.01: tb = 3.65 h.
 c
tt =  (1 − )dt = A1 + A2 = 3.65 + 1.51 = 5.16 h
0 c0
tb =3.65 c
tu =  (1 − )dt = A1 = 3.65 h
0 c0
tu / tt = 3.65/5.16 = 0.707
tu
H B = H T = 0.707(14) = 9.9 cm
tt
t
HUNB = (1 − u ) H T = (1 - 0.707)14 = 4.1 cm
tt
 Example 12.3-1
45
b) If the breakpoint time required for a new column is 6.0 h, what is the
new total length
Tu (time equivalent to usable capacity) is proportional to HB
tu = 3.65 → HB = 9.9 cm
tb’ = 6 h
tb = 6 c
tu ' =  (1 − ) dt = A1’ = 6 h
0 c0 (New HB’ = ratio of break point times x old HB )

tu '
H B '= H B = (6 /3.65 )(9.9) = 16.3 cm
tu
HT’= HUNB + HB’ = 4.1+ 16.3 = 20.4 cm
tu ' H B ' 16.3 (Fraction of the new bed used up to the
= = = 0.799
tt ' H T ' 20.4 break point)
46
c) Determine the saturation loading capacity of the carbon.
Air flow rate= (754 cm3/s)(3600s)(0.0115g/cm3) = 3122 g
air/h
600 ppm = 600 g alcohol in 1 million g of air

 600g alcohol adsorbed  g air

Total alcohol adsorbed =  6

(3122 )(5.16 h)
 10 g air  h

= 9.67 g alcohol

9.67 g alcohol g alcohol

Saturation capacity = = 0.1220
79.2 g carbon g carbon
 Problem 1

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 85 g of carbon. The inlet gas stream having a
concentration c0 of 700 ppm and a density of 0.0015 g/cm3 entered the bed
at a flow rate of 655 cm3/s. The break through curve obtained from this
adsorption is given in the FIGURE 1. The break point concentration is set at
c/c0=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?
Find the saturation loading capacity of the carbon?
b) If the break point required for a new column is 8.5 h, what is the new
length of the column required?
c) Use the same condition as in part (b), but the flow rate is to be
increased to 2000 cm3/s. Estimate the new diameter of column.
FIGURE 1