Chapter 6:

ADSORPTION

MISS. RAHIMAH BINTI OTHMAN

(Email: rahimah@unimap.edu.my)

COURSE OUTCOMES
CO
APPLY principles of batch
adsorption and fixedbed adsorption.
CALCULATE and
EXAMINE adsorption
isotherms. DEVELOP
basic design of gas or
liquid adsorber.

OUTLINES

Introduction to adsorption.

Adsorption equipments.

Adsorption Isotherms Analysis.

Principles of Adsorption.
Basic Equation for Adsorption.
Adsorber Design Calculation.

INTRODUCTION TO ADSORPTION
ADSORPTION ABSORPTION !

Absorption a fluid phase is transferred from one medium

to another.

Adsorption certain components of a fluid (liquid or gas)

phase are transferred to and held at the surface of a solid
(e.g. small particles binding to a carbon bed to improve
water quality)

Adsorbent the adsorbing phase (carbon, silica gel,

zeolite)

Adsorbate the material adsorbed at the surface of

adsorbent .

INTRODUCTION TO ADSORPTION
APPLICATION OF ADSORPTION:

Used in many industrial processes:

Adsorbing the desired product from
fermentation broths.
Isolation of proteins.
Dehumidification.
odour/colour/taste removal.
gas pollutant removal (H2S).
water softening and deionisation.
hydrocarbon fractionation.
pharmaceutical purification.

INTRODUCTION TO ADSORPTION
* NATURE OF ADSORBENT

Porous material - Large surface area per unit mass

- internal surface area greater than the external surface area
- often 500 to 1000 m 2/g.

Granular (50m - 12 mm diameter), small pellets or beads.

Suitable for packed bed use.

Activated carbon, silica gel, alumina, zeolites, clay minerals, ion

exchange resins.

Separation occurs because differences in molecular weight,

shape or polarity of components.

Rate of mass transfer is dependent on the void fraction within the

pores.

Silica structure

Zeolite structure

INTRODUCTION TO ADSORPTION
TYPES OF ADSORPTION
1. Ion exchange

Electrostatic attachment of ionic species to site of the opposite charge

at the surface of an adsorbent

2. Physical Adsorption

result of intermolecular forces causing preferential binding of certain

substances to certain adsorbents
Van der Waal forces, London dispersion force
reversible by addition of heat (via steam, hot inert gas, oven)
Attachment to the outer layer of adsorbent material

3. Chemisorption

result of chemical interaction

Irreversible, mainly found in catalysis
change in the chemical form of adsorbate

ADSORPTIO
N
EQUIPMENT

Fixed-bed
adsorbers

Gas-drying
equipment

Pressure-swing
adsorption

Fixed-bed
adsorbers

Gas-drying
Equipment

ADSORPTION
EQUIPMENT
Adsorption
From
Liquids

Pressureswing
Adsorption

FIXED-BED ADSORBERS

Adsorbent particles: 0.3 1.2 m deep supported

on a perforated plate

Feed gas passes down through the bed.

Downflow is preffered because upflow at high rates

may fluidize the particles, causing attrition and loss
of fines.

The feed gas is switched to the other bed when the

conc. Of solute in exit gas reaches a certain value.

The bed is regenerate by steam / hot inert gas.

FIXED-BED ADSORBERS
Regeneration

To remove unwanted particles from the adsorbent

surface after the adsorption process.

using steam/hot inert gas.

Steam condenses in the bed, raising the temp. of

the solid, provide energy for desorption.

The solvent is condensed, separated from water.

Then the bed is cooled and dried with inert gas.

Fixed-bed
adsorbers

Gas-drying
Equipment

ADSORPTION
EQUIPMENT
Adsorption
From
Liquids

Pressureswing
Adsorption

GAS-DRYING EQUIPMENT

Fig. 25.1 Vapor-phase Adsorption

System

The equipment for drying is similar

to the shown in Fig. 25.1, but hot
gas is used for regeneration.

The moist gas from the bed being

generated may be vented, or much
of the water may be removed in a
condenser and the gas
recirculated through a heater to
the bed.

For small dryers, electric heaters

are sometimes installed inside the
bed to provide the energy for
regeneration.

Fixed-bed
adsorbers

Gas-drying
Equipment

ADSORPTION
EQUIPMENT
Adsorption
From
Liquids

Pressureswing
Adsorption

PRESSURE-SWING ADSORPTION

Most often, adsorption is used as a purification

process to remove small amounts of material, but,
there is a number of applications involve
separations of gas mixtures with moderate to high
concentration of adsorbates.

These are called bulk separations, and they often

use different operating procedures than for gas
purification.

Pressure-swing adsorption (PSA) is a bulk

separation process that is used for small-scale air
separation plants and for concentration of hydrogen
in process streams.

Fixed-bed
adsorbers

Gas-drying
Equipment

ADSORPTION
EQUIPMENT
Adsorption
From
Liquids

Pressureswing
Adsorption

ADSORPTION FROM
LIQUIDS

Use of activated carbon to

remove pollutants from
aqueous wastes.

Use carbon beds up to 10 m

tall, several ft in diameter,
several bed operating in
parallel.

Tall beds are needed to

ensure adequate treatment.

PACKED EXTRACTION TOWERS

Tower packings;
(a) Raschig rings,
(b) metal Pall ring,
(c) plastic Pall ring,
(d) Berl saddle, (e) ceramic
Intalox saddle, (f) plastic Super
Intalox saddle,
(g) metal Intalox saddle

ADSORPTION
ISOTHERMS ANALYSIS

Adsorption isotherm equilibrium relationship

between the concentration in the fluid phase and the
concentration in the adsorbent particles.

For gas concentration in mole % or partial pressure

For liquid concentration in mg/L (ppm) or g/L

(ppb)

Concentration of adsorbate on the solid = mass

adsorbed (g) per unit mass of original adsorbent
(g).

TYPES OF ISOTHERMS
Amount of adsorbed
is independent of
concentration down
to very low values.
Amount of adsorbed
is proportional to
the concentration in
the fluid.

Concave upward; low solid loadings

are obtained and because it leads to
quite long mass-transfer zones in the
bed. (this shape are rare)

TYPES OF ISOTHERMS
Nearly linear isotherm
up to 50 percent
humidity, and the
ultimate capacity is
about twice that for the
other solids.
Water is held most strongly by
molecular sieves, and the
adsorption is almost
irreversible, but the pore
volume not as great as for
silica gel

Fig. 25.3 Adsorption

isotherms for water in air at
20 to 50 oC

ADSORPTI
ON DATA
FOR
VAPORS
ON
ACTIVATED
CARBON
Sometimes fitted to
Freundlich isotherms,
but data for wide range
of pressures show
isotherm slopes
gradually decrease as
the pressure is
increased.

Amount of adsorbed
depends on (T/V) log
(fs/f), where:
T: adsorption temperature
(Kelvin).
V: molar volume of the
liquid at the boiling point
fs: fugasity of the saturated
liquid at adsorption
temperature
f: fugasity of the vapor

For adsorption at
atmospheric pressure;
* fugasity = partial pressure
= vapor pressure

Volume adsorbed is
converted to mass by
assuming the adsorbed
liquid has the same density
as liquid at the boiling
point.

QUESTION 1
EXAMPLE
EXAMPLE 25.1.
25.1.
Adsorption
Adsorption on
on BPL
BPL carbon
carbon is
is used
used to
to treat
treat an
an
airstream
airstream containing
containing 0.2
0.2 percent
percent n-hexane
n-hexane at
at 20
20 ooC.
C.
(a)
(a) Estimate
Estimate the
the equilibrium
equilibrium capacity
capacity for
for aa bed
bed
operating
operating to
to 20
20 ooC.
C.
(b)
(b) How
How much
much would
would the
the capacity
capacity decrease
decrease ifif the
the heat
heat
of
of adsorption
adsorption raised
raised the
the bed
bed temperature
temperature to
to 40
40 ooC.
C.

ANSWER
(a)
(a)

Estimate
Estimate the
the equilibrium
equilibrium capacity
capacity for
for aa bed
bed operating
operating to
to 20
20 ooC.
C.

The
The MW
MWn-hexane
(C66H
H14
)= 86.17,
86.17, At
At 20
20oo C
C (from
(from Perrys
Perrys Handbook,
Handbook, 77ththed.)
ed.)
n-hexane (C
14)=
P=120mm
P=120mm Hg
Hg ffss.. At
At the
the normal
normal boiling
boiling point
point (68.7
(68.7 ooC),
C), LL=0.615
=0.615 g/cm
g/cm33.. The
The
adsorption
adsorption pressure
pressure P
P is
is 760
760 mm
mm Hg.
Hg.
p 0.002 x 760 1.52 mmHg f

86.17
140.1 cm 3 /gmol
0.615

T
f
293
120
log s
log
3.97
V
f
140.1
1.52
from Fig 25.4, volume adsorbed is 31 cm 3 liquid per100 g carbon;
W 0.31 x 0.615 0.19 g/g carbon.

(b)
(b) At
At 40
40 ooC,
C, P=
P= 276
276 mm
mm Hg
Hg
T
f
313
276
log s
log
5.05
V
f
140.1
1.52
from Fig 25.4, volume adsorbed is 27 cm 3 liquid per100 g carbon;
W 0.27 x 0.615 0.17 g/g carbon.

4 TYPES OF ADSORPTION ISOTHERMS

1. Linear Isotherms
- Adsorption amount is proportional to the
concentration in the fluid
2. Irreversible independent of concentration
3. Langmuir Isotherm favorable type
4. Freundlich Isotherm strongly favorable type

LANGMUIR ISOTHERM

Often been used to correlate equilibrium adsorption data

for protein.
Isotherms that convex upward are called favorable.

Kc
W Wmax

1 Kc

Where:
W = adsorbate loading (g absorbed/g solid)
c = the concentration in the fluid (mg/L)
K = the adsorption constant
K >> 1 : the isotherm is strongly favorable.

Wmax and K are constants determined experimentally by

plotting 1/W against 1/c

FREUNDLICH ISOTHERM
strongly favourable
Describe the adsorption of variety of antibiotics, steroids
and hormones.
high adsorption at low fluid concentration

W bc

where b and m are constant

Linearize the equation: Log W = log b + m log c
Constant determined from experimental data by plotting
log W versus log c
Slope = m, intercept = b

PRINCIPLES OF
ADSORPTION
In fixed bed adsorption, the concentrations in the fluid
phase and the solid phase change with:
a) time
b) as well as the position in the bed.

At first, most of the mass transfer takes place near the inlet
of the bed, where the fluid contacts the adsorbent.

After a few minutes, the solid near the inlet is nearly

saturated.

Most of the mass transfer takes place farther from the inlet.

The concentration gradient become S-shaped.

The region where most of the change in concentration

occurs is called the mass-transfer zone (MTZ), and the
limits are often taken as c/c0 values of 0.95 to 0.05.

MASS TRANSFER ZONE AND

BREAKTHROUGH

Concentration Profile In Fixed Beds

Concentration Profile In Fixed Beds

t11: no part of the bed is saturated.
From t11 to t22: the wave had moved down the bed.
t22: the bed is almost saturated for a distance LSS, but is still clean at LFF.
Little adsorption occurs beyond LFF at time t22, and the adsorbent is still
unused.
The MTZ where adsorption takes place is the region between LSS and LFF.
The concentration of the adsorbate on the adsorbent is related to the
adsorbate concentration in the feed by the thermodynamic equilibrium.
Because it is difficult to determine where MTZ begins and ends, LFF can be
taken where C/CFF = 0.05, with LSS at C/CFF = 0.95.
tBB: the wave has moved through the bed, with the leading point of the MTZ
just reaches the end of the bed. This is known as the breakthrough point.
Rather than using C/CFF = 0.05, the breakthrough concentration can be
taken as the minimum detectable or maximum allowable solute
concentration in the effluent fluid, e.g. as dictated by downstream

Concentration profile in fixed beds

Is the ratio of solute

concentration to
inlet solute
concentration in the
fluid.

Figure 25.6(a)

BREAKTHROUGH
CURVES

t1, t2, t3: the exit

concentration is
practically zero.

Time for fluid living

the bed.

BREAKTHROUGH
CURVES

BREAKTHROUGH
CURVES
t time when the concentration reaches break
b

point
The feed is switched to a fresh adsorbent bed
Break point relative concentration c/co of 0.05 or
0.10
Adsorption beyond the break point would rise
rapidly to about 0.50
Then, slowly approach 1.0 (concentration liq in =
liq out)

BREAKTHROUGH
CURVES
t* is the ideal adsorption time for a vertical
breakthrough curve
t* is also the time when c/co reaches 0.50
Amount of adsorbed is proportional to the
rectangular area to the left of the dashed line at t*

BREAKTHROUGH
CURVES

Solute feed rate (FA) = superficial velocity (uo) X concentration (co)

Where:
Wo = initial adsorbate loading
Wsat = adsorbate at equilibrium with the fluid (saturation)
L = length of the bed
b = bulk density of the bed

LENGTH OF UNUSED BED (LUB)

For systems with favorable isotherm, the concentration

profile in the mass-transfer zone acquires a characteristic
shape and width that do not change as the zone moves
down the bed.

Test with different bed lengths have breakthrough curve of

the same shape, but with longer beds, the MTZ is a
smaller fraction of the bed length, and greater fraction of the
bed is utilized.

The scale-up principles

The amount of unused solid or length of unused bed does
not change with the total bed length.

LENGTH OF UNUSED BED (LUB)

To calculate

LUB, determine the total solute adsorbed up

to the break point by integration;

0 co dt
t

The

break point time, tb is calculated from the ideal time

and the fraction of bed utilized:

QUESTION 2

EXAMPLE
EXAMPLE
EXAMPLE25.2
25.2.
25.2. The
The adsorption
adsorption of
of n-butanol
n-butanol from
from air
air was
was studied
studied in
in
aa small
small (10.16
(10.16 cm
cm diameter)
diameter) with
with 300
300 and
and 600
600 gg carbon,
carbon, corresponding
corresponding
to
to bed
bed lengths
lengths of
of 88 and
and 16
16 cm.
cm.

(a)
(a) From
From the
the following
following data
data for
for effluent
effluent concentration,
concentration, estimate
estimate the
the
saturation
saturation capacity
capacity of
of the
the carbon
carbon and
and the
the fraction
fraction of
of the
the bed
bed used
used
at
at c/c
c/c00== 0.05.
0.05.
(b)
(b) Predict
Predict the
the break-point
break-point time
time for
for aa bed
bed length
length of
of 32
32 cm.
cm.
Data
Data for
for n-butanol
n-butanol on
on Columbia
Columbia JXC
JXC 4/6
4/6 carbon
carbon are
are as
as follows
follows::
300 g

600 g

t,h

c/c0

t,h

c/c0

0.005

0.0019

u0 58 cm/s

D p 0.37 cm

1.5

0.01

5.5

0.003

c0 365 ppm

S 1,194 m 2 /g

0.027

0.0079

T 25 o C

b 0.461 g/cm 3
0.457

2.4

0.050

6.5

0.018

2.8

0.10

0.039

3.3

0.20

7.5

0.077

0.29

0.15

P 737 mmHg

ANSWER

The concentration profiles are plotted in Fig 25.8, and extended to c/c0=1.0
assuming the curves are symmetric about c/c0=0.5.
Per square centimeter
of bed cross section, the solute feed rate is
F u c M
A

0 0

cm 365 x 10 6 273 737 mol

58
x
x
x 74.12 g/mol
s 22,400
298 760 cm 3
6.22 x10 -5 g/cm 2 .s or
0.224 g/cm 2 .h

The total solute adsorbed is the area above the graph multiplied by FA. For the
8 cm bed, the area is;

8.5

c
1 dt 4.79 h
c0

ANSWER

This area corresponds to the ideal time that would be required to adsorb the
same amount if the breakthrough curve were a vertical line.
The mass of carbon per unit cross-sectional area of bed is; 8 x 0.461 = 3.69 g/cm 2
Thus,
Trapezoidal rule:

h
f ( x0 ) f ( x1 )
x2
2
where h x1-x0
x1

At the break point, where c/c0 = 0.05, and t = 2.4 h

f ( x)dx

The amount adsorbed up to the break point is then

Thus 50 percent of the bed capacity is unused, which can be represented by a

length of 4 cm.

ANSWER (-cont)

For the 16-cm bed the breakthrough curve has the same initial slope as the
curve for the 8-cm bed, and although data were not taken beyond c/c0 = 0.25,
the curves are assume to be parallel.
For the entire bed,

At c/c0 = 0.05, t = 7.1 h, and

At the break point, 74 percent of the bed capacity is used, which corresponds to an
unused section of length 0.26 x 16 = 4.2 cm.
Within experimental error, the lengths of unused bed agree, and 4.1 cm is the
expected value for a still longer bed.

ANSWER (-cont)

(b) For L = 32 cm, the expected length of the fully used bed is;
32 - 4.1 = 27.9 cm.
The fraction of the bed used is:

The break-point time is

QUESTION 3
A
A waste
waste stream
stream of
of n-butanol
n-butanol vapor
vapor in
in air
air from
from aa process
process was
was adsorbed
adsorbed by
by activated
activated
carbon
carbon particles
particles in
in aa packed
packed bed
bed having
having aa diameter
diameter of
of 44 cm
cm and
and length
length of
of 14
14 cm
cm
containing
containing 79.2
79.2 gg of
of carbon.
carbon. The
The density
density of
of the
the activated
activated carbon
carbon is
is 0.461
0.461 g/cm
g/cm33.. The
The
inlet
inlet gas
gas stream
stream having
having aa concentration,
concentration, C
C00 of
of 600
600 ppm
ppm and
and aa density
density of
of 0.00115
0.00115
g/cm
g/cm33 entered
entered the
the bed
bed at
at the
the solute
solute feed
feed rate,
rate, F
FAA of
of 0.063
0.063 g/cm
g/cm22.s.
.s. Data
Data in
in Table
Table 3.1
3.1
give
give the
the concentrations
concentrations of
of the
the fluid
fluid in
in the
the bed,
bed, C.
C. The
The break
break point
point concentration
concentration is
is
set
set at
at C/C
C/Coo == 0.05.
0.05.
QUESTION;
QUESTION;
1.
1. Plot
Plot aa breakthrough
breakthrough curve.
curve.
2.
2. Determine
Determine the
the break-point
break-point time.
time.
3.
3. Calculate
Calculate the
the saturation
saturation capacity
capacity of
of
the
.
the carbon,
carbon, W
Wsat
sat.
4.
4. Calculate
Calculate the
the length
length of
of unused
unused bed
bed
(LUB).
(LUB).

Time
(hour)
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.2
6.5
6.8

Concentration of
fluid, C (ppm)
0.1
1.2
18.0
93.0
237.6
394.8
541.8
559.8
585.0
595.8

ANSWER
Given;
Packed bed, D = 4 cm
L = 14 cm
adsorbent = 79.2 g
carbon = 0.461 g/cm3
Inlet gas stream, C0 = 600 ppm
= 0.00115 g/cm3
FA = 0.063 g/cm2.s
C/C0 = 0.05
1. Plot a breakthrough curve.
t (h)

C/C0

3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.2
6.5
6.8

0.1
1.2
18.0
93.0
237.6
394.8
541.8
559.8
585.0
595.8

1.667E-04
0.002
0.030
0.155
0.396
0.658
0.903
0.933
0.975
0.993

1.0
0.9
0.8
0.7
0.6

C/C0
0.5
0.4
0.3
0.2
0.1
0.0
0

t, h

ANSWER- cont
2.

Determine the break-point time.

From the breakthrough curve, breakthrough time at C/C0 = 0.05 is tb = 4.1 h
1.0
0.9
0.8
0.7
0.6

C/C0

0.5
0.4
0.3
0.2
0.1
0.0
0

t, h

ANSWER- cont
3. Calculate the saturation capacity of the carbon, Wsat.
The total solute adsorbed is the area above the graph multiplied by FA

C
0 1 C0 dt
7

Simpsons Rule of
integration. (pp. 872)

h
f 0 4 f1 2 f 2 4 f 3 f 4
3
x x0 7 0
h 4

1.75
4
4

x4

f ( x)dx

x0

From the graph plotted, the following data

is obtained;

Wsat

C
C0

dt

t (h)

C/C0

f(x) = (1-C/C0)

0.00

1.75

3.50

0.002

0.998

5.25

0.5

0.5

7.00

1.75
1 41 2(0.998) 4(0.5) 0 5.248h
3

FA x total solute adsorbed

mass of carbon per unit cross sectional area

0.063 g/cm 2 .s (5.248 h) 3600 s

x
14 cm x 0.461 g/cm 3
1h
g solute
184.42
g carbon


W
LUB L 1 b
Wsat

At break point, where C / C0 0.05 and tb 4.1 h

4.

Calculate the length of

unused bed (LUB).

4 .1
C
Area 1
0
C0

Trapezoida l rule

x1

x2

f ( x)dx

h
f ( x0 ) f ( x1)
2

h x1 x0

h 4.1 0 4.1
C
4.1

1 0.95 3.9975 h
1

dt

t0 C0
2
t1

The amount adsorbed up to the break point is, Wb

0.063 g / cm 2 .s (3.9975h) 3600 s
Wb
x
14 cm x 0.461 g / cm3
1h
g solute
140.48
g carbon
Wb 140.48

0.7617
Wsat 184.42

W
LUB L 1 b 14(1 0.7617) 3.33 cm
Wsat

Thus, 23.8 percent of the bed capacity is unused.

t (h)

C/C0

f(x) = (1-C/C0)

0.00

4.1

0.05

0.95

OUTLINES

Introduction to adsorption.

Adsorption equipments.

Adsorption Isotherms Analysis.

Principles of Adsorption.

Basic Equation for Adsorption.

Adsorber Design Calculation.

BASIC EQUATION
FOR ADSORPTION
Rate of Mass Transfer
Internal and External
Mass-transfer
Coefficients
Solution to MassTransfer Equations
Irreversible Adsorption
Linear isotherm
YIELD
YIELD

RATE OF MASS TRANSFER

Equation for mass transfer in fixed-bed adsorption are obtained by making a solute
material balance for a section dL of the bed, as in Fig. 25.9.
The rate of accumulation in the fluid and in the difference between input and output
flows. The change in superficial velocity is neglected:
Fig.25.9 Mass balance for
a section of a fixed bed

(25.5)
(25.6)

is the external
void fraction of the
bed
solute dissolved in
the pore fluid is
included with the
particle fraction 1.

Adsorption from a gas or

a dilute solution Accumulation in the fluid
is negligible compare to
accumulation on the solid.

The transfer process is approximated using an overall volumetric coefficient and an

driving force:
The mass transfer area, a is taken as the
external surface of the particles, which is
6(1-)/DP for spheres. The concentration c* is
the value that would be in equilibrium with
the average concentration W in the solid.
(25.7)
Kca= volumetric overall mass-transfer coefficient.

BASIC EQUATION
FOR ADSORPTION
Rate of Mass Transfer
Internal and External
Mass-transfer
Coefficients
Solution to MassTransfer Equations
Irreversible Adsorption
Linear isotherm
YIELD
YIELD

INTERNAL AND EXTERNAL MASS-TRANSFER COEFFICIENTS

The overall coefficient, Kc depends on the external coefficient kc, ext and on an
effective internal coefficient, kc, int.
Diffusion within the particle is actually an unsteady-state process, and the value
of kc, int decreases with time, as solute molecules must penetrate farther and farther
into the particle to reach adsorption sites.
Average effective coefficient can be used to give an approximate fit to uptake data
for spheres.

This leads to
(25.8)
De = effective diffusion
coefficient, depends on particle
porosity, the pore diameter, the
tortuosity, and the nature of the
diffusing species.
Dp = diameter of particle.

BASIC EQUATION
FOR ADSORPTION
Rate of Mass Transfer
Internal and External
Mass-transfer
Coefficients
Solution to MassTransfer Equations
Irreversible Adsorption
Linear isotherm
YIELD
YIELD

SOLUTION TO MASS-TRANSFER EQUATIONS

There are many solutions to Eq. (25.6) and (25.7) for different isotherm shapes
and controlling steps, and all solution involve a dimensionless time, and a
parameter N representing the overall number of transfer units:
(25.9)
(25.10)
The term L/u0 in Eq. (25.9) is the time to displace fluid from external voids in the
bed, which is normally negligible.
p(1- ) is the bed density, b
is the ratio of the time to the ideal time t* from Eq. (25.3).
(25.3)
If there were no mass-transfer resistance, the adsorber could be operated with
complete removal of solute up to = 1.0, and the the concentration would jump
from 0 to c/c0 = 1.0.

BASIC EQUATION
FOR ADSORPTION
Rate of Mass Transfer
Internal and External
Mass-transfer
Coefficients
Solution to MassTransfer Equations
Irreversible Adsorption
Linear isotherm
YIELD
YIELD

IRREVERSIBLE ADSORPTION
Irreversible adsorption with a constant mass transfer coefficient is the simplest
case to consider, since the rate of mass transfer is then just proportional to the
fluid concentration.
Strongly favorable adsorption gives almost the same results as irreversible film,
because the equilibrium concentration in the fluid is practically zero until the solid
concentration is over one-half the saturation value.
If the accumulation term for the fluid is neglected, Eq. (25.6) and (25.7) are
combine to give;
(25.6)

(25.12)

(25.7)

The initial shape of the concentration profile is obtained by integration Eq. (25.12)
(25.13)
Since the term KcaL/u0 is defined as N in Eq. (25.10), the concentration at the end
of the bed is given by
(25.14)

(25.10)

IRREVERSIBLE ADSORPTION
The rate of mass transfer to the first layer of particles is assumed to be constant
until the particles reach equilibrium with the fluid, and until this happens, the
concentration profile in the bed remains constant.
The time to saturate the first portion of the bed, t1 is the equilibrium capacity
divided by the initial transfer rate (W0= 0 to simply the analysis):
(25.15)
After this time, the concentration profile moves steadily down the bed, keeping the
same shape.
The transfer zone moves at a velocity vz, which is equal to the amount of solute
removed per unit time divided by the amount retained on the solid per unit
length of bed:
(25.16)
The concentration is constant at c0 for the saturated portion of the bed and then falls
exponentially in the mass-transfer zone, as shown Fig. 25.10.
Fig. 25.10

IRREVERSIBLE ADSORPTION
To predict the break point, Eq. (25.17) is applied for a bed of length L with c/c0
set at 0.05 or another selected value.
(25.17)
The length of the saturated bed is the product of transfer zone velocity and the
time since the zone started to move:
(25.18)
(25.19)
Substituting the equation for Lsat in Eq. (25.17) and using the dimensionless terms
and N [Eq. (25.9) and (25.10) give:
(25.20)
(25.21)

IRREVERSIBLE ADSORPTION
The predicted breakthrough curve is shown as a solid line in Fig. 25.11.
The slope increases with time, and c/c0 becomes 1.0 at N(-1)=1.0.
In practice, the breakthrough curves are usually S-shaped, because the internal diffusion
resistance is not negligible, and it increases somewhat when the solid becomes nearly
saturated.

Fig 25.11

When both internal and external resistances are significant, the breakthrough curve is Sshaped, as shown by the dashed line in Fig 25.11.
For this plot, the value of N is based on the overall mass-transfer coefficient given by Eq.
(25.8), or it can be expressed in Halls terminology as;

(25.22)

EXAMPLE 25.3
(a)
(a) Use
Use the
the breakthrough
breakthrough data
data in
in Example
Example 25.2
25.2 to
to determine
determine N
N and
and K
Kccaa for
for the
the 8-cm
8-cm
bed,
bed, assuming
assuming irreversible
irreversible adsorption.
adsorption. (b)
(b) Compare
Compare K
Kccaa with
with the
the predicted
predicted kkccaa for
for the
the
external
external film.
film.
SOLUTION:
SOLUTION:
(a)
= 0.495, -1= -0.505. Assume equal
(a) From
From Example
Example 25.2,
25.2, at
at c/c
c/c00 == 0.05,
0.05, W/W
W/Wsat
sat = 0.495, -1= -0.505. Assume equal
internal
internal and
and external
external resistances
resistances to
to determine
determine N
N from
from Fig.
Fig. 25.11:
25.11:

= 23.0 s-1

(b)
(b) Prediction
Prediction of
of kkccaa from
from Re,
Re, Sc
Sc (k
(kcc is
is the
the external
external coefficient):
coefficient):
D
Dpp == 0.37
0.37 cm
cm
At
At 25
25ooC,
C, 11 atm,
atm, /
/ == 0.152
0.152 cm
cm22/s
/s and
and D
Dvv == 0.0861
0.0861 cm
cm22/s.
/s. Then
Then

EXAMPLE 25.3
(a)
(a) Use
Use the
the breakthrough
breakthrough data
data in
in Example
Example 25.2
25.2 to
to determine
determine N
N and
and K
Kccaa for
for the
the 8-cm
8-cm
bed,
bed, assuming
assuming irreversible
irreversible adsorption.
adsorption. (b)
(b) Compare
Compare K
Kccaa with
with the
the predicted
predicted kkccaa for
for the
the
external
external film.
film.
SOLUTION:
SOLUTION:
(a)
= 0.495, -1= -0.505. Assume equal
(a) From
From Example
Example 25.2,
25.2, at
at c/c
c/c00 == 0.05,
0.05, W/W
W/Wsat
sat = 0.495, -1= -0.505. Assume equal
internal
internal and
and external
external resistances
resistances to
to determine
determine N
N from
from Fig.
Fig. 25.11:
25.11:

= 23.0 s-1

(b)
(b) Prediction
Prediction of
of kkccaa from
from Re,
Re, Sc
Sc (k
(kcc is
is the
the external
external coefficient):
coefficient):
D
Dpp == 0.37
0.37 cm
cm
At
At 25
25ooC,
C, 11 atm,
atm, /
/ == 0.152
0.152 cm
cm22/s
/s and
and D
Dvv == 0.0861
0.0861 cm
cm22/s.
/s. Then
Then

SOLUTION:
From Eq. (17.74)

Since Kca is slightly less than one-half the predicted value of kca, the external
resistance is close to one-half the total resistance, and the calculated value of N
need to be revised. The internal coefficient can be obtained from;

If diffusion into the particle occurred only in the gas phase, the maximum possible
value of De would be about Dv/4, which leads to;

Since the measured value of kc, int is an order of magnitude greater than this value,
surface diffusion must be the dominant transfer mechanism.

BASIC EQUATION
FOR ADSORPTION
Rate of Mass Transfer
Internal and External
Mass-transfer
Coefficients
Solution to MassTransfer Equations
Irreversible Adsorption
Linear isotherm
YIELD
YIELD

ADSORBER DESIGN CALCULATION

The
The design
design of
of adsorber
adsorber for
for gas
gas or
or liquid
liquid purification
purification involves;
involves;
-- choosing
choosing the
the adsorbent
adsorbent and
and the
the particle
particle size,
size, selecting
selecting an
an appropriate
appropriate velocity
velocity to
to get
get
the
the bed
bed area,
area, and
and either
either determining
determining the
the bed
bed length
length for
for aa given
given cycle
cycle time
time or
or
calculating
calculating the
the break-through
break-through time
time for
for aa chosen
chosen length.
length.

For
For gas
gas purification/
purification/ adsorption:
adsorption:
-- 44 xx 66- or
or 44 xx 10-mesh
10-mesh carbon
carbon is
is needed
needed and
and pressure
pressure drop
drop is
is not
not aa problem.
problem.
-- The
The gas
gas velocity
velocity is
is usually
usually between
between 15
15 and
and 60
60 cm/s
cm/s (0.5
(0.5 and
and 22 ft/s)
ft/s)
-- Because
and k c, int
increase as D
Because the
the external
external area
area varies
varies with
with 1/D
1/Dpp and
and both
both kkc,ext
c,ext and kc,
int increase as Dpp
decreases,
decreases, kkccaa is
is expected
expected to
to vary
vary with
with the
the -1.5
-1.5 to
to -2.0
-2.0 power
power of
of D
Dp.p.

For
For liquid
liquid adsorption:
adsorption:
-- smaller
smaller particle
particle sizes
sizes are
are chosen,
chosen, and
and the
the fluid
fluid velocity
velocity is
is much
much lower
lower than
than with
with
gases.
gases.
-- Typical
Typical conditions
conditions for
for water
water treatment
treatment are
are 20
20 xx 50-mesh
50-mesh carbon
carbon (D
(Dpp == 0.3
0.3 to
to 0.8
0.8 mm)
mm)
and
and aa superficial
superficial velocity
velocity of
of 0.3
0.3 cm/s
cm/s (0.01
(0.01 ft/s
ft/s or
or about
about 44 gal/min.
gal/min. ft
ft22))
-- Even
Even with
with these
these conditions
conditions K
Kcca/u
a/u00 is
is smaller
smaller than
than for
for typical
typical gas
gas adsorption,
adsorption, and
and LUB
LUB
may
may be
be 10
10 to
to 20
20 cm
cm or
or even
even as
as much
much as
as 11 m
m if
if internal
internal diffusion
diffusion controls.
controls.

QUESTION 25.4
Adsorption on activated carbon is being considered to
treat a process airstream that has 0.12 volume percent
methyl ethyl ketone (MEK), C44H88O. The gas is at 25ooC
and 1 atm, and the flow is 16,000 ft33/min. The pressure
drop across the bed should not exceed 12 in. H22O.
a. If BPL 4 x 10-mesh carbon is used, predict the
saturation capacity and the working capacity if the
average bed temperature is 35 ooC and the
regeneration is stopped when W = 1/3 Wsat
.
sat
b. What gas velocity and bed size could be used to give
reasonable cycle time if the length of unused bed is
0.5 ft? How much carbon is needed?

ANSWER
(a) From the handbooks, P = fs = 151 mmHg at 35 oC and L = 0.805 g/cm3 at 20 oC.
The normal boiling point is 79.6 oC, and the estimated density at this temperature
is L = 0.75 g/cm3. The molecular weight is 72.1.
At 35 oC.

From Fig. 25.4, the volume adsorbed is 24 cm3 per 100 g carbon:

Working capacity = Wsat W0 = 12g/ 100 g carbon = 0.12 lb/lb carbon.

(b) What gas velocity and bed size could be used to give reasonable cycle time if the
length of unused bed is 0.5 ft? How much carbon is needed?
Try u0 = 1 ft/s:

Amount of adsorbed
depends on (T/V) log
(fs/f), where:
T: adsorption temperature
(Kelvin).
V: molar volume of the
liquid at the boiling point
fs: fugasity of the saturated
liquid at adsorption
temperature
f: fugasity of the vapor

For adsorption at
atmospheric pressure;
* fugasity = partial pressure
= vapor pressure

Volume adsorbed is
converted to mass by
assuming the adsorbed
liquid has the same density
as liquid at the boiling
point.

ANSWER
For a circular cross section, D = 18.4 ft. a rectangular bed 10 ft x 27 ft might be more
suitable if the bed depth is only 3 to 4 ft.
Try L = 4 ft. From Eq. (25.3)

(25.3)

At 25 oC,

=18.1 h
If the length of unused bed is 0.5 ft, 3.5 ft is used, and

If the bed length is 3 ft with 2.5 ft used,

ANSWER
Allowing for uncertainties in the calculations, a bed length of 3 ft would be
satisfactory with regeneration once per 8-h shift.
Check P using the Ergun equation, Eq. (7.22). Note that gc is needed when fps units
are used. For granular carbon, assume s = 0.7 (see Table 7.1). Assume external void
fraction = 0.35 (see Table 7.2). From handbooks, the properties of air at 25 oC are

From Perry, 7th ed., p. 19-20, for 4 x 10-mesh carbon,

ANSWER
For L = 3 ft, P = 9.9 in H2O, which is satisfactory.
A velocity of 1.5 ft/s would give P/L = 6.06 in. H 2O/ft and require L 2 ft to keep
P < 12 in. H2O. However, the breakthrough time would be reduced to
11.3/1.5 x (1.5/2.5) = 4.5 h, and the bed would have to be regenerated twice each
shift. This design might be satisfactory but does not give as great a margin for error.
The recommended design is for two beds 10 x 27 x 3 ft placed in horizontal cylinders.
The total inventory of carbon is;
mc = 2 (270 x 3)ft3 x 30 lb/ft3 = 48, 600 lb

QUESTION 25.5
Water contaminated with 1.2 ppm TCE is to be
purified in a fixed bed of 20 x 50-mesh
Ambersorb 563.
(a) For a bed length of 2 ft and a flow rate of 4.5
gal/min.ft22, estimate the breakthrough time if
the length of the unused bed is 0.6 ft.
(b) What is the effective capacity in volume
treated per unit bed volume? The adsorbent
will be regenerated by steam to remove 85
percent of the TCE. The bulk density of the
adsorbent is 0.53 g/cm33.

ANSWER
(a) From Fig. 25.5

From Eq. (25.3),

Breakthrough time is;

(b) Bed volumes treated,

THANK YOU
Prepared by,
MISS RAHIMAH OTHMAN