ADSORPTION - MODELING AND SIMULATION

Based on the operation mode

Liquids
Gases
Volumetric Gravimetric
Dynamic
Fixed bed adsorption: occurs in an
open system where adsorbate
solution continuously passes through
a column packed with adsorbent
Pulse chromatographic column:
measures the response of a
chromatographic column to a pulse
in adsorbate concentration for
determination of isotherms
Types of Adsorption
Static/Batch
A closed system containing a
desired amount of adsorbent
contacted with a certain volume
of adsorbate solution

Inside the particle/ Intraparticle
Intraparticle diffusion
is more complex and diverse,
is the keystone of modeling dynamic
adsorption

Mechanisms involved in
intraparticle transfer simultaneously:
Pore diffusion (Macropore / or
Micropore)
Surface diffusion
Adsorption

Set of equations are used to
consider all the possible or required
mechanisms
Particle Modeling
R
p
r
dr
Accumulation = Inlet Outlet
|
|
.
|

\
|
c
c
+
c
c
=
c
c
r
c
r r
c
D
t
c
p p
p
p
2
2
2
c
p
= conc inside particle
D
p
= Diffusion coefficient

p
= Particle porosity
Without Adsorption
|
|
.
|

\
|
c
c
c
c
=
c
c
r
c
r
r
D
r t
c
p
p
p 2
2
1
With Adsorption
Accumulation + Adsorption = Inlet Outlet
( )
|
|
.
|

\
|
c
c
+
c
c
=
c
c
+
c
c
r
c
r r
c
D
t
q
t
c
p p
p p p p
p
p
2
1
2
2
c c c
Batch Adsorption
0
1
2
3
4
5
6
7
8
9
10
0 0.2 0.4 0.6 0.8 1
q

(
c
m
3
/
g
)

Pressure (atm)
Adsorption Isotherm Diffusion Coefficients
Equilibrium Kinetic
Linear Isotherm
Langmuir Isotherm
Freundlich Isotherm
Kc q =
Kc
Kc q
q
m
+
=
1
n
Kc q
1
=
Batch Adsorption Modeling
Mass balance of bulk fluid
p
r r
p
p p
p
r
c
D
r t
c
=
c
c
|
.
|

\
|

=
c
c
c
c
c 3 1
Boundary Condition (t>0)
0
0
=
c
c
= r
p
r
c
) (t c c
p
r r
p
=
=
Initial Condition (t<0)
0 =
r
p
c
Linear Isotherm
Langmuir Isotherm
Freundlich Isotherm
Kc q =
Kc
Kc q
q
m
+
=
1
n
Kc q
1
=
Equilibrium relation
0
c c =
Estimate diffusivity by fitting the exp
data

Predict diffusivity and use in the
model
t
c
m p
p
D
D =
Constant Diffusivity
Diffusivity = f(bulk conc)
4.44
4.46
4.48
4.5
0 20 40 60 80 100
c

(
m
o
l
/
m
3
)

Time (sec)
28.60
28.61
28.62
28.63
0 20 40 60 80 100
c

(
m
o
l
/
m
3
)

Time (sec)
Monodisperse Pore Diffusion model with local Equilibrium
Volumetric adsorption study
Linear adsorption isotherm
D=exp(-a+bc)
Parallel Diffusion model with local Equilibrium
Very often that when dealing with adsorption of many gases and vapours in high
surface area solids such as activated carbon and silica gel that surface diffusion
can contribute significantly to the overall uptake
( ) ( )
|
|
.
|

\
|
c
c
+
c
c
+
|
|
.
|

\
|
c
c
+
c
c
=
c
c
+
c
c
r
q
r r
q
D
r
c
r r
c
D
t
q
t
c
s p
p p
p p p p
p
p
2
1
2
1
2
2
2
2
c c c c
Boundary Condition (t>0)
Initial Condition (t<0)
0
0
=
c
c
= r
p
r
c
) (t c c
p
r r
p
=
=
0 =
r
p
c
0
c c =
Bi-dispersed solids ex. zeolites
In these solids, we have macropore diffusion in the void space between the grains and
micropore diffusion in the channels within the grain.
Micropore diffusivity can have a strong concentration and temperature dependence
( )
c
r
c
c
p p p
p p
p
p
r
q
D
r R
c
R R
c
D
t
c
c
c

|
|
.
|

\
|
c
c
+
c
c
=
c
c c
c c
1 3
2
2
2
Bi-dispersed solids with local Equilibrium
|
|
.
|

\
|
c
c
+
c
c
=
c
c
r
q
r r
q
D
t
q
c
2
2
2
p
Kc q =
At r = rp (microcrystal radius)
At R = Rp (particle radius)
) (t c c
p
R R
p
=
=
Modeling of Batch Adsorption
Film diffusion
The flux film diffusion can be expressed in linear form by
multiplying its driving force and the film mass transfer
coefficient
J
f
is the mass transfer flux
a is the volumetric surface area
c
s
is the adsorbate concentration at the exterior surface of adsorbent
k
f
is the film diffusion coefficient
The symmetry condition at the center of the particles and continuity condition on the external
surface of the adsorbent bed are expressed as:

At t > 0
) (
s f f
c c a k J
dt
dq
= =
0
0
=
c
c
= r
p
r
c
p
r r
p
p p s f
r
c
D c c k
=
c
c
= c ) (

The fixed bed adsorption
processes utilize a solid mass
separating agent/ adsorbent
packed inside a column to effect
separation of one or more
components from a mixture in a
gas or liquid stream as it flows
through the packed bed.
Applications include
air purification
gas dehydration
solvent or hydrocarbon vapor
recovery
water purification, and many
others
Fixed Bed Adsorption
Breakthrough curve provides the basic but
predominant information for the design of
a column adsorption system
Scale of a column adsorption for practical
application

Breakthrough curve determination
direct experimentation
mathematical modeling

Experimental methods provide a direct and
concise breakthrough curve of a given system
time-consuming
economically undesirable process, particularly
for the trace contaminants and long residence
time
greatly depends upon the experimental
conditions, such as ambient temperature and
residence time

Mathematical modeling
Simple
no experimental apparatus
Why there is a need to model Fixed Bed Adsorption Column?
Fixed Bed Adsorption Modeling
(1) Mass transfer including convective
mass transfer and molecular diffusion
(2) Interface diffusion between bulk and the
exterior surface of the adsorbent (i.e., film
diffusion)
(3) Intraparticle mass transfer involving pore
diffusion
(4) Adsorption
Fixed Bed Adsorption Modeling
Mass balance over the bed
( )
|
|
.
|

\
|
=

=
p
p
p p
p
L
r r
dr
dc
D
r dz
dc
u
dz
c d
D
dt
dc
c
c
c 1 3
2
2
t
q
z
c
u
z
c
D
t
c
L
c
c

c
c

c
c
=
c
c
c
c ) 1 (
2
2
Neglecting Dispersion
t
q
z
c
u
t
c
c
c

c
c
=
c
c
c
c) 1 (
( )
|
|
.
|

\
|
=

=
p
p
p p
p
r r
dr
dc
D
r dz
dc
u
dt
dc
c
c
c 1 3
Assumptions:
(1) Isothermal process
(2) The packing material is made of porous particles that are spherical and uniform in
size
(3) The bed is homogenous and the concentration gradient in the radial direction of the bed
is negligible
(4) The flow rate is constant and invariant with the column position
(5) The activity coefficient of each species is unity
Fixed Bed Adsorption Modeling
Boundary Condition (t>0)
( )
( ) ( )
0
, 0
, 0
c t c u
dz
t dc
D
L
=
( ) 0 , = t L
dz
dc
Initial Condition (t<0)
( ) 0 0 , = z c
( )
0
, 0 c t c =
Step input
Fixed Bed Adsorption Modeling
Parameters used:
Length of the column = 6 m
Diameter of column = 0.5 m
Amount of adsorbent = 795 kg
Flowrate = 2.058 m
3
/hr

Superficial Velocity = 10.44 m/hr
Diffusivity of oleic acid = 2.95 10
-6
m
2
/hr
Dispersion coefficient = 2.16 10
-6
m
2
/hr
Initial concentration of feed = 0.0165 kg/m
3

Equations used:
Bed
( )
|
|
.
|

\
|
=
c
c

c
c

c
c
=
c
c
p
p
p p
p
L
r r
r
c
D
r z
c
u
z
c
D
t
c
c
c
c 1 3
2
2
Particle
(

c
c
c
c
=
c
c
+
c
c
r
c
r
r
D
r t
q
t
c
p
p
p
p
p
p
2
2
) 1 (
c
c c
Equilibrium relation
p d
p d m
c K
c K q
q
+
=
1
Fixed Bed Adsorption Modeling
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
0 5 10 15 20 25 30
c
o
n
c

(
k
g
/
m
3
)

Time (hr)
1 day = 24 hr
1 m
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
0 200 400 600 800
c
o
n
c

(
k
g
/
m
3
)

Time (hr)
1 month = 720 hr
1 m
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
0 1000 2000 3000 4000 5000
c
o
n
c

(
k
g
/
m
3
)

Time (hr)
6 months = 4320 hr
1 m
2 m
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
0 2000 4000 6000 8000 10000
c
o
n
c

(
k
g
/
m
3
)

Time (hr)
1 year = 8760 hr
1 m
2 m
3 m
4 m
Fixed Bed Adsorption Modeling
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
0 5000 10000 15000
c
o
n
c

(
k
g
/
m
3
)

Time (hr)
1 year 6 months = 13080 hr
4 m
5 m
6 m
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
0 5000 10000 15000 20000
c
o
n
c

(
k
g
/
m
3
)

Time (hr)
1 year 9 months = 15240 hr
5 m
6 m
Equilibrium capacity shows saturation period after about 3 years (1.17 kg/kg capacity-
795 kg bed-0.034 kg/hr feed)

FFA Adsorption bed simulation shows the bed will get completely saturated after about
14000 hr 583 days 1 year 7 months

Regeneration will be required after 1 year 7 months
Pulse Chromatography
Initial Condition
Fixed bed adsorption
Step input
( )
0
, 0 c t c =
Initial Condition
Chromatographic column
Pulse input
( )
i
t
t
e c t c

=
0
, 0
C
o
n
c

Time (sec)
Input Pulse
Input Step
Why Pulse Chromatography?
Batch adsorption systems masked with other rate limiting processes such as
external film mass transfer resistance and /or heat dissipation

These effects are less severe in flow systems

With sufficiently high velocity, external resistances to heat and mass transfer
can be reduced

Mainly used for diffusivity measurements

Measure exit concentration versus time

To analyze and interpret the data from
chromatographic experiment a
mathematical model is required

The equilibrium and kinetics is derived by
matching experimental response curves
to model predictions
Pulse Chromatographic Modeling
Mean residence time - measure of the affinity of adsorbate towards adsorbent

Variance/Spread - measure of its dynamic characteristics

Spread of the curve is a complex function of all dispersion forces
1. Axial dispersion
2. Film resistance
3. Pore diffusion resistance (macropore/mesopore/micropore)
C
o
n
c

Time (sec)
Pulse Chromatographic Modeling
( )
|
|
.
|

\
|
=

=
p
p
p p
p
L
r r
dr
dc
D
r dz
dc
u
dz
c d
D
dt
dc
c
c
c 1 3
2
2
Bed
Particle
( )
c
r
c
c
p p p
p p
p
p
r
q
D
r R
c
R R
c
D
t
c
c
c

|
|
.
|

\
|
c
c
+
c
c
=
c
c c
c c
1 3
2
2
2
|
|
.
|

\
|
c
c
+
c
c
=
c
c
r
q
r r
q
D
t
q
c
2
2
2
Linear Isotherm
Langmuir Isotherm
Freundlich Isotherm
Kc q =
Kc
Kc q
q
m
+
=
1
n
Kc q
1
=
Equilibrium relation
Pulse Chromatographic Modeling
Desired and undesired Response Curves
Pulse Chromatography for analytical techniques (GC, HPLC)
Desired : Symmetrical

Pulse Chromatography for diffusivity (micropore) measurements
Desired : Tailing (skewed)

Reasons of skewed response curve

Micropore diffusion control regime - Tailing
Non-linear isotherm Tailing, Fronting

Pulse Chromatographic Modeling
The elution peak travels in the form of waves through the chromatographic column at
a certain velocity
The concentration wave velocity is the velocity that a particular value of
concentration will propagate through the system
The velocity of the wavefront is a function of the type of isotherm
Shape of the wave/ response curve is a function of the velocity

t
c
c
q
t
q
c
c
c
c
=
c
c
Fluid mass balance
t
q
z
c
u
t
c
c
c

c
c
=
c
c
c
c) 1 (
c
q
u
u
z
c
c
+
=
c
c) 1 (
1
Velocity of wavefront
For Linear isotherm
Kc q = constant
c
q
=
c
c
Shape of wave does not
change during displacement
C
o
n
c

Time (sec)
Concentration velocity is retarded relative
to the interstitial velocity
Pulse Chromatographic Modeling
For Non-linear isotherm
constant
c
q
=
c
c
Langmuir Isotherm (Favorable isotherm)

Slope of isotherm reduces with
increasing concentration
c
q
u
u
z
c
c
+
=
c
c) 1 (
1
Velocity of wavefront
Wavefront velocity increases with
increasing concentrations

Sharp front and tailing rear
ation) f(concentr =
c
c
c
q
Pulse Chromatographic Modeling
w.r.t. Bed
length
Fronting
w.r.t. time
Tailing
Sharp front with diffuse rear
Pulse Chromatographic Modeling
For Non-linear isotherm
constant
c
q
=
c
c
Freundlich Isotherm (Favorable isotherm)

Slope of isotherm reduces with increasing
concentration and attains a constant value
c
q
u
u
z
c
c
+
=
c
c) 1 (
1
Velocity of wavefront
Wavefront velocity is constant at
higher conc. but will decrease at
lower conc.
How will the response curve appear?
Pulse Chromatographic Modeling
For Non-linear isotherm
constant
c
q
=
c
c
Unfavorable isotherm

Slope of isotherm increases with
increasing concentration
c
q
u
u
z
c
c
+
=
c
c) 1 (
1
Velocity of wavefront
Wavefront velocity decreases
with increasing concentrations

Tailing front and sharp rear
Pulse Chromatographic Modeling
wrt Bed
length
Tailing
wrt time
Fronting
Diffuse front with sharp rear
Pulse Chromatographic Modeling
What is the nature of isotherm?
Pulse Chromatographic Modeling
Tailing Fronting
For Non-linear isotherm
constant
c
q
=
c
c
Symmetrical for Linear
constant
c
q
=
c
c
Tailing for Favorable

Fronting for unfavorable
Pulse Chromatographic Modeling
0
0.1
0.2
0.3
50 100 150 200 250 300 350 400 450
C
o
n
c

(
k
g
/
m
3
)

Time (sec)
CO2 CH4 N2
The concentration velocity of an adsorbing or desorbing component is less than
that of a component that has no interaction with the solid phase
How to ensure Linear Regime?
c
q
u
t
z
u
z
c
c
+
=
c
c
=
c
c) 1 (
1
Velocity of wavefront
(

c
c
=
c
q
u
L
t
c
c ) 1 (
1
For Linear isotherm
Kc q =
K =
c
c
c
q
(

=
c
c K
u
L
t
) 1 (
1
Mean retention time should not
change with pulse size
0
0.01
0.02
0.03
100 150 200
C
o
n
c

(
k
g
/
m
3
)

Time (sec)
50 ul
100 ul
150 ul
200 ul
Pore Diffusion model with linear adsorption kinetics
the pore diffusion model and the rate of mass exchange between the two phases is much
faster than the diffusion rate. In this section we shall consider the case where such mass
exchange is comparable in rate to the diffusion,
Absorption v/s Adsorption
Absorption - Fluid is dissolved by a liquid or a
solid (absorbent)

Adsorption - Atoms, ions or molecules from a
substance (it could be gas, liquid or dissolved
solid) adhere to a surface of the adsorbent
Adsorption - a film of adsorbate is created on the surface
-surface-based process

Absorption-involves the entire volume of the absorbing
substance
Types of Adsorption
Basis of Separation
Steric separation - the porous solid has pores
having dimension such that it allows small
molecules to enter while excluding large molecules
from entry

Equilibrium separation based on the level of
affinity of the adsorbent towards adsorbate so that
the stronger adsorbing species is preferentially held
by the solid

Kinetic separation - based on the different rates
of diffusion of different species into the pore; the
faster diffusing species is preferentially removed by
the solid