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Modeling and Simulation of Fixed bed Adsorption column:

Effect of Velocity Variation


*
B.V. Babu and Suresh Gupta
Department of Chemical Engineering
Birla Institute of Technology & Science
Pilani 333031 (Rajasthan) India

Abstract
The kinetic behavior of a fixed-bed adsorber can be explained and the characteristic breakthrough curve of
the adsorption phenomena can be obtained through mathematical models. In the earlier models, the
kinetics is explained using a mathematical model that takes into account of external and internal masstransfer resistances with a nonideal plug flow behavior. The variation of fluid velocity along the column is
an important aspect, which has not been accounted so far. In the present study, a mathematical model is
proposed for explaining the kinetic behavior of adsorption phenomena incorporating the fluid velocity
variation along the column length also. Internal mass-transfer resistances due to pore diffusion mechanism
are considered in the model. The proposed mathematical model for fixed-bed adsorption is solved
numerically and compared with earlier model reported in literature. The results show that the breakpoint is
obtained earlier which represents the realistic behavior in adsorption phenomena. Initially the sharp front of
the breakthrough curve is seen followed by broadening of tail of the breakthrough curve. Simulations are
carried out using the present model for a systematic parametric study. The effects of various important and
influencing parameters such as flow rate, bed height, inlet adsorbate concentration and particle diameter on
breakthrough curve are studied in detail.
Keywords: adsorption; modeling; pore diffusion control; breakthrough curve; mass transfer

1. Introduction
Use of adsorption contacting systems for industrial and municipal wastewater treatment
has become more prevalent during recent years [1]. The process of adsorption of the
components of a fluid mixture flowing through a packed bed of an adsorbent porous
material is the basis of several important applications in chemical engineering. These
include continuous separation processes for large-scale applications such as bulk
separations [2], and also chromatographic processes for both analytical and preparative
purposes [3]. As a consequence of this applicative interest, a great amount of work has
been devoted to the modeling of these processes [4].
* Corresponding Author: Assistant Dean - ESD & Head of Chemical Engineering Department, B.I.T.S.,
PILANI-333031 (Rajasthan) INDIA.
Email: bvbabu@bits-pilani.ac.in;
Home Page: http://discovery.bits-pilani.ac.in/discipline/chemical/BVb/index.html;
Phone: +91-01596-245073 Ext. 205 / 224;
Fax: +91-01596-244183;

Nomenclature
aP

radius of the adsorbent pellets, m

area of cross section, m2

Langmuir isotherm parameter, ml/mg

solute concentration in the liquid phase inside the pores, mg/l

Cb

bulk phase dye concentration, mg/ml

Cs

liquid phase concentration in equilibrium with qs on the surface, mg/ml

Cbo

inlet adsorbate concentration, mg/ml

DL

axial dispersion coefficient, m2/s

DP

pore diffusion coefficient, m2/s

kf

external film mass transfer coefficient, m/s

column length, m

average adsorbed phase dye concentration, mg/g

qm

Langmuir isotherm parameter, mg/g

qs

concentration on the surface of the pellet, mg/g

flow rate, ml/min

radial coordinate, m

time, sec

superficial velocity, m/s

Vo

initial superficial velocity, m/s

Vi

interstitial velocity inside the bed, m/s

axial coordinate, m

Greek letters

bed porosity

porosity of the adsorbent pellet

solution density, kg/m3

particle density, kg/m3

bed density, kg/m3

The key parameters for design of an adsorption system are the process parameters that are
used for modeling the system for predicting the quality of effluent under a wide range of
operating conditions [5]. In most of the large-scale processes, relatively large porous
particles (50-1,000 m in diameter) are used to reduce pressure drop and sorbent cost.
Intraparticle diffusion is usually the rate-limiting step in these systems and it controls the
sharpness of breakthrough curves [6]. One of these models describes diffusion as the
mechanism occurring in the fluid phase with a distributed adsorption along the pore
walls, i.e., the pore diffusion model [7]. For low-affinity solutes in macroporous sorbents,
pore diffusion is usually the dominant intraparticle diffusion mechanism [8].
Pore diffusion model has been used for predicting the kinetics of fixed bed adsorption
process [6,9,10,11]. These models take account of both external and internal masstransfer resistances as well as of nonideal plug flow along the column. The above models
have not incorporated the fluid velocity variation along the bed, which makes a
significant effect on breakthrough curve. In the present work, the effect of operating
variables on the process of fixed-bed adsorption is studied. Furthermore, the kinetics is
studied using a mathematical model that takes account of both external and internal masstransfer resistances, nonideal plug flow along the column and the variation of fluid
velocity along the column.
2. Mathematical Modeling
Before discussing the assumptions needed for model formulation, we first introduce the
physical process considered in this model. Convection along the column axial direction
and axial dispersion are the mass transport mechanisms in the bulk phase. Molecules
from the bulk interstitial phase are transported via axial convection and Fickian diffusion
(film diffusion) onto the particle surface. Inside the particle, molecules can diffuse into
the inner portion of particle via surface diffusion, pore diffusion, or both. This study
focuses on understanding the mechanism in pore diffusion.
Bautista et al. [9] proposed the kinetic mechanism for the adsorption of -amylase from
Aspergillus oryzane in a fixed bed. The model takes account of both external and internal

mass-transfer resistances as well as of nonideal plug flow along the column. They did not
consider the fluid velocity variation along the bed to predict the behavior of breakthrough
curve. In the present study this model is modified by considering the variation of velocity
along the column.
To formulate a generalized model corresponding to the pore diffusion mechanism,
following assumptions are made:
1. The system operates under isothermal conditions.
2. The equilibrium of adsorption is described by Langmuir isotherm, a nonlinear
isotherm.
3. Intra-particle mass transport is due to Fickian diffusion, and it is characterized by the
pore diffusion coefficient, DP.
4. Mass transfer across the boundary layer surrounding the solid particles is
characterized by the external-film mass transfer coefficient, kf.
5. The linear velocity of the liquid phase varies along the column.
6. The macro porous adsorbent particles are spherical and homogeneous in size and
density.
Based on the preceding assumptions, for the control volume, Adz (Figure 1), for limiting
situation z
DL

0, net rate of accumulation or depletion is given as

2C

q
C
C
p
b +V
b + C V + b + 1
=0
b z
p
z
t
t
z 2

(1)

V
C b ( z , t ),

dz
Cb +

C b
z

(C bV )
dz ,
z

Figure 1: Mass balance in element of fixed bed

C b
2C b
+
dz
z
z 2

The following initial condition is considered


C b = C bo

z = 0, t = 0

(2)

Cb = 0

0 < z L, t = 0

(3)

The contour conditions at both ends of the column are given by the following equations
DL

C b
= V0 (C bo C b ), z = 0, t > 0
z

C b
= 0,
z

(4)

z = L, t 0

(5)

The superficial velocity, V in fixed-bed adsorption is not constant because of adsorption.


The following equation was used to estimate (dV/dz), the variation of velocity of bulk
fluid along the axial direction of the bed. For liquid adsorption, assuming the liquid
density to be constant, then the total mass balance gives

q p
V
= (1 ) s
z
t

(6)

Velocity boundary conditions


V = V0 ,

z = 0, t > 0

V
= 0,
t

(7)

z = L, t > 0

(8)

The inter-phase mass transfer rate may be expressed as

q p
t

3k f
(C b C s )
ap

(9)

The intra-pellet mass transfer is due to the diffusion of adsorbate molecules through the
pore. The macroscopic conservation equation is given as

c
q
2 c 2 c
+ (1 p ) p
= Dp
+
t
t
r 2 r r

(10)

Assuming instantaneous equilibrium


q c q
=
t t c

(11)

Then rearranging equation (3)

c
=
t

1
1 P q
1 + p
P c

DP

2 c 2 c
+
r 2 r r

(12)

The following initial condition is considered


c = 0, q = 0,

0 < r < ap , t = 0

(13)

The symmetry condition at the center of the particles and continuity condition on the
external surface of the adsorbent bed are expressed as
c
= 0,
r
k f (C b C s ) = Dp

c
,
r

r = 0, t > 0

(14)

r = ap , t > 0

(15)

The adsorption isotherm was favorable and nonlinear, and it described by Langmuir
isotherm
q=

q m bc
1 + bc

(16)

2.1 Simulation Technique

Since nonlinear adsorption equilibrium is considered, the preceding set of partial


differential equations (1 to 16) is solved numerically by a reduction to set of ordinary
differential equations using the Explicit Finite Difference technique. Finite difference
technique has successfully applied to solve such type of partial differential equations in
other studies by Babu and Chaurasia [12,13,14,15,16,17]. A mathematical algorithm to
solve these coupled equations is developed and implemented into a computer program
using MATLAB (v.6.1) software. The same parameters reported by Bautista et al. [9] are
used for simulation in present study, which are given in Table 1.
3. Results and Discussion

The model used, as described above, determines the outlet adsorbate concentration at
different times based on different operating conditions. In the present model, linear
velocity variation along the bed is considered and the obtained results are compared with
the previous model given by Bautista et al. [9]. Same parameters given by Bautista et al.

Table 1: Model parameters value for simulation [9]


Parameter

Value

,Bed porosity, (-)

0.58

p, Particle porosity, (-)

0.53

p,

Particle density, kg/m3

1970

b,

Bed density, kg/m3 ($)

900

l,

Liquid density, kg/m3 ($)

1000

DL, Axial dispersion coefficient, m2/s ($)

5.9 x 10-10

qm, Maximum adsorption capacity, mg/g

45.4

b, Langmuir isotherm constant, ml/mg

0.84

Dp, Pore diffusivity, m2/sec

2.5 x 10-11

kf, External mass transfer coefficient, m/sec

1.5 x 10-6

d, Bed diameter, m

0.016

($) The values not reported in literature

[9] are used and some parameters (see Table 1) are assumed which are not given in
literature. The present model results show an improvement over the previous model given
by Bautista et al. [9] with respect to better steepness of the breakthrough curve which is
being validated by earlier study [6,18]. The results show that the breakpoint is obtained
earlier (Figure 2). Initially the sharp front of the breakthrough curve is seen followed by
broadening of tail of the breakthrough curve as shown in Figure 2 [18]. These obtained
results are more justifiable with theoretical phenomena occurring in the adsorption
system. The fluid velocity along the bed is a decreasing function of bed length [18]. The
velocity continuously decreases inside the bed with respect to bed length. This
phenomenon is validated by the mass balance (Eq. 6) for velocity variation.

This

establishes the fact that the effect of velocity variation on breakthrough curve is
significant. This fact is also in agreement with the results reported in the literature [18].
Based on the successful implementation of velocity variation in the model, and
supporting evidence in the literature, the simulations are carried out using the present
model to carryout a systematic parametric study. The present model is studied by varying

the different important parameters such as flow rate, bed height, inlet adsorbate
concentration and particle diameter.
1.0

0.8

without velocity variation


with velocity variation

Cb/Cbo

0.6

0.4

0.2

0.0
0

2000

4000

6000

8000

Time (sec)
Figure 2: Breakthrough curve with and without fluid velocity variation
for a velocity of V=0.0020 cm/sec

3.1 Effect of flow rate

The results for different solution flow rates are plotted for a bed height of 0.163 m and an
inlet adsorbate concentration of 1 mg/ml in Figure 3. The flow rates considered are 0.25,
0.5 and 1.0 ml/min. Figure 3 reveals that as the flow rate increases from 0.25 to 1.0
ml/min, the breakthrough curve becomes steeper. The break point time decreases from
1600 to 750 sec without considering the velocity variation along the bed and 1150 to 500
sec with velocity variation. This is because of the residence time of the solute in the
column, which is not long enough for adsorption equilibrium to be reached at high flow
rate. So at high flow rate the adsorbate solution leaves the column before equilibrium
occurs. Furthermore, a fixed saturation capacity of bed based on the same driving force
gives rise to a shorter time for saturation at higher flow rate. As the flow rate is 0.25
ml/min, the break point time is 1600 sec without considering velocity variation and 1150

sec with velocity variation along the bed. The percentage change in break point time is
28%. For the flow rates 0.5 and 1.0 ml/min, the percentage change in breakpoint time
(that is a ratio of difference between breakpoint time without velocity variation and with
velocity variation to the maximum breakpoint time obtained) are 17% and 15%,
respectively. This shows as the flow rate increases the velocity variation effect on
breakthrough curve decreases.
1.0

0.8

Q = 0.25 ml/min
Q = 0.25 ml/min(*)
Q = 0.5 ml/min
Q = 0.5 ml/min(*)
Q = 1.0 ml/min
Q = 1.0 ml/min(*)

Cb/Cbo

0.6

0.4

0.2

0.0
0

2000

4000

6000

8000

Time (sec)

Figure 3: Effect of flow rate on breakthrough curve


(*) indicates model results with velocity variation

3.2 Effect of bed height

The effect of bed height on the effluent adsorbate concentration is presented for flow rate
of 0.25 ml/min and inlet adsorbate concentration of 1 mg/ml in Figure 4. The bed heights
considered are 0.163 and 0.20 m. It is observed that as the bed height increases from
0.163 to 0.20 m, the break point time increases from 1600 to 3475 sec without
considering the velocity variation and 1150 to 2625 sec with velocity variation along the
bed. This shows that at smaller bed height the effluent adsorbate concentration ratio
increases more rapidly than for a higher bed height. Furthermore, the bed is saturated in
less time for smaller bed heights. Smaller bed height corresponds to less amount of
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adsorbent. Consequently, a smaller capacity for the bed to adsorb adsorbate from solution
and a faster increase in rate of adsorbate adsorption is expected. For the bed height of
0.163 m, the break point time is 1600 sec without considering velocity variation and 1150
sec with velocity variation along the bed. The percentage change in break point time is
13%. The percentage change in breakpoint time is 24% for bed height of 0.20 m. This
shows as the bed height increases the velocity variation effect on breakthrough curve
increases.
1.0

0.8

L = 0.163 m
L = 0.163 m(*)
L = 0.20 m
L = 0.20 m(*)

Cb/Cbo

0.6

0.4

0.2

0.0
0

2000

4000

6000

8000

Time (sec)
Figure 4: Effect of bed height on breakthrough curve
(*) indicates model results with velocity variation

3.3 Effect of Inlet concentration

The effect of inlet adsorbate concentration on effluent concentration is shown in Figure 5.


The two-inlet adsorbate concentrations considered are 0.5 and 1.5 mg/ml. During these
simulations other parameters such as bed height and flow rate are kept constant. It is
observed that as the inlet adsorbate concentration increases from 0.5 to 1.5 mg/ml, the
break point time decreases from 2525 to 2275 sec without considering the velocity
variation and 1875 to 1575 sec with velocity variation along the bed. For larger feed
concentration, steeper breakthrough curves are found, because of the lower mass-transfer

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flux from the bulk solution to the particle surface due to the weaker driving force. In
addition, at high concentration, the isotherm gradient is lower, yielding a higher driving
force along the pores. Thus the equilibrium is attained faster for values of higher
adsorbate concentration. For the inlet adsorbate concentration of 0.5 mg/ml, the break
point time is 2525 sec without considering velocity variation and 1875 sec with velocity
variation along the bed. The percentage change in break point time is 26%. The
percentage change in breakpoint time is 28% for inlet adsorbate concentration of 1.5
mg/ml. This indicates that as the inlet adsorbate concentration increases, there is no
significant effect of the velocity variation on breakthrough curve.
1.0

0.8

Cbo = 0.5 mg/ml


Cbo = 0.5 mg/ml(*)
Cbo = 1.5 mg/ml
Cbo = 1.5 mg/ml(*)

Cb/Cbo

0.6

0.4

0.2

0.0
0

2000

4000

6000

8000

Time (sec)
Figure 5: Effect of inlet adsorbate concentration on breakthrough curve
(*) indicates model results with velocity variation

3.4 Effect of particle radius

The effect of particle size on effluent concentration is shown in Figure 6. The particle
radii considered are 3.1 x 10-4, 4.1 x 10-4 and 6.1 x 10-4 m. During these simulations other
parameters such as flow rate, bed height, and inlet adsorbate concentration are kept
constant. Figure 6 reveals that as the particle radius increases from 3.1 x 10-4 to 6.1 x 10-4

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m, the steepness of the breakthrough curve decreases. The break point time increases
from 1325 to 2050 sec without considering the velocity variation and 975 to 1450 sec
with velocity variation along the bed. Smaller particle size resins provide quicker kinetic
equilibrium and therefore better breakthrough capacity is obtained at higher linear
velocities. This allows faster cycle times with no reduction in the resin capacity. As the
diameter of the particle increases, the thickness of stagnant film around the particles
increases, and also the total length of the path inside the pores increases. Under these
conditions, the overall kinetics of the process is slow, because the time for a molecule of
adsorbate to reach the adsorption site is more, as the diffusional path along the pores is
large. As the particle radius is 3.1 x 10-4 m, the break point time is 1325 sec without
considering velocity variation and 975 sec with velocity variation along the bed. The
percentage change in break point time is 17%. For the particle radii 4.1 x 10-4 and 6.1 x
10-4 m, the percentage change in breakpoint time is 22% and 29%, respectively. This
shows as the particle radius increases the velocity variation effect on breakthrough curve
increases.
1.0

0.8

aP = 3.1 x 10-4 m
aP = 3.1 x 10-4 m(*)
aP = 4.1 x 10-4 m
aP = 4.1 x 10-4 m(*)
aP = 6.1 x 10-4 m
aP = 6.1 x 10-4 m(*)

Cb/Cbo

0.6

0.4

0.2

0.0
0

2000

4000

6000

Time (sec)
Figure 6: Effect of particle radius on breakthrough curve
(*) indicates model results with velocity variation

12

8000

4. Conclusions

A generalized model that incorporates external film mass transfer resistance and pore
diffusion resistance with velocity variation through column bed has been formulated and
solved numerically. Following conclusions are drawn from the above-discussed results:
1.

There is a significant effect of velocity variation through the bed on breakthrough


curve, wherein the break point is obtained earlier. Initially the sharp front of the
breakthrough curve is seen followed by broadening of tail of the breakthrough
curve.

2.

As the flow rate is increased, the breakthrough curve becomes steeper. The break
point time is obtained earlier and effluent adsorbate concentration ratio increases
more rapidly.

3.

For smaller bed height, the effluent adsorbate concentration ratio increases more
rapidly than for a higher bed height.

4.

For larger feed concentration, steeper breakthrough curves are obtained and break
point time is achieved sooner.

5.

With decrease in particle radius, the breakthrough curve becomes steeper and the
break point time decreases.

These results improve the understanding of adsorption phenomena with reference to pore
diffusion, and are very useful in the design of adsorption columns.
References

[1]

[2]
[3]
[4]
[5]

B.V. Babu, S. Gupta, Modeling and Simulation for Dynamics of Packed Bed
Adsorption, Proceedings of International Symposium & 57th Annual Session of
IIChE in association with AIChE (CHEMCON-2004), Mumbai, December 27-30,
2004.
D.M. Ruthven, and C.B. Ching, Counter-current and simulated counter-current
adsorption separation processes, Chemical Engineering Science, 44 (1989) 10111038.
G. Ganetsos, P.E. Barker, Preparative and Production Scale Chromatography,
Marcel Dekker, New York, 1993.
K. Kaczmarski, M. Mazzotti, G. Storti, M. Morbidelli, Modeling fixed-bed
adsorption columns through orthogonal collocations on moving finite elements,
Computers and Chemical Engineering, 21 (1997) 641-660.
B.V. Babu, V. Ramakrishna, Dominant Design Variables and Modeling
Parameters for Adsorption in Batch Studies, Proceedings of International

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[6]
[7]
[8]
[9]
[10]
[11]
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Symposium & 57th Annual Session of IIChE in association with AIChE


(CHEMCON-2004), Mumbai, December 27-30, 2004.
Z. Ma, R.D. Whitley, N.H.L. Wang, Pore and Surface Diffusion in
Multicomponent Adsorption and Liquid Chromatography Systems, AIChE
Journal, 42 (1996) 1244-1262.
T.W. Webi, R.K. Chakravort, Pore and Solid Diffusion Models for Fixed-Bed
Adsorbers, AIChE Journal, 20 (1974) 228-238.
E. Furuya, Y. Takeuchi, K.E. Noll, Intraparticle Diffusion of phenols within
Bidispersed Macroreticular Resin Particles, J. Chem. Eng. Japan, 22 (1989) 670L.F. Bautista, M. Martinez, J. Aracil, Adsorption of -Amylase in a Fixed Bed:
Operating Efficiency and Kinetic Modeling, AIChE Journal, 49 (2003) 2631-2641.
S. Ghorai, K.K. Pant, Investigations on the column performance of fluoride
adsorption by activated alumina in a fixed-bed, Chemical Engineering Journal, 98
(2004) 165-173.
J.L. Sotelo, M.A. Uguina, J.A. Delgado, L.I. Celemin, Adsorption of methyl ethyl
ketone and trichloroethane from aqueous solutions onto activated carbon fixed-bed
adsorbers, Separation and Purification Technology, 37 (2004) 149-160.
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Parameters in Pyrolysis of Biomass, Energy Conversion and Management, 44
(2003) 2135-2158.
B.V. Babu, A.S. Chaurasia, Modeling for Pyrolysis of Solid Particle: Kinetics and
Heat Transfer Effects, Energy Conversion and Management, 44 (2003) 2251-2275.
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Profiles of Authors:
Dr B V Babu is Professor & Head of Chemical Engineering Department apart from
being Assistant Dean of Engineering Services Division (ESD) at Birla Institute of
Technology and Science (BITS), Pilani. His biography is included in 2005 & 2006
editions of Marquis Whos Who in the World, and Thirty-Third Edition of the Dictionary
of International Biography in September 2006.

He has 20 years of Teaching, Research, Consultancy, and Administrative experience. He


guided 2 PhD students, 25 ME Dissertation students and 24 Thesis students and around
160 Project students. He is currently guiding 7 PhD candidates, 3 Dissertation students
and 10 Project students. He currently has 3 research projects from UGC & DST.
His research interests include Evolutionary Computation (Population-based search
algorithms for optimization of highly complex and non-linear engineering problems),
Environmental Engineering, Biomass Gasification, Energy Integration, Artificial Neural
Networks, Nano Technology, and Modeling & Simulation.
He is the recipient of many National and International awards, and the Life member of
various professional bodies such as IIChE, ISTE, IE, IEA, SOM, Fellow of ICCE, and
Associate Member of ISSMO.
He has around 102 research publications (International & National Journals &
Conference Proceedings) to his credit. He completed three consultancy projects. He is a
Panel Expert for www.chemicalhouse.com. He has published three books and has written
several chapters in various books and lecture notes of different intensive courses.
He was the Invited Chief Guest and delivered the Keynote addresses at one international
conference and three national seminars. He organized many Seminars & Conferences,
and member of various academic and administrative committees at BITS-Pilani. He also
chaired 10 Technical Sessions at various International & National Conferences. He
delivered 23 invited lectures at various IITs and Univeristies.
He is Editorial Board Member of two International Journals Energy Education Science
& Technology and Research Journal of Chemistry and Environment. He is the referee
& expert reviewer of 15 International Journals, and on the Programme Committees as an
expert reviewer at 12 International Conferences. He reviewed three books of McGraw
Hill, Oxford University Press, and Tata McGraw Hill publishers. He is PhD Examiner
for one candidate and PhD Thesis Reviewer for 3 Candidates.

Mr. Suresh Gupta is a Lecturer in Chemical Engineering Department at BITS-Pilani,


and currently pursuing his PhD under the supervision of Prof B V Babu. He has 3
publications to his credit. He is associate life member of IIChE.

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