Simulation of Fixed Bed Processes

Abstract
The numerical simulation of fixed bed processes using the Method of Lines is analyzed from
an efficiency point of view and a discretization scheme is proposed that is easy to implement
and more efficient than conventional schemes. Biasing of the intervals used to discretize the
partial differential equations that describe bulk transport in a fixed bed process is studied.
The amount of biasing that results in the least error is derived. The effect of using unequally
biased intervals is also discussed. The improvement in accuracy that results from using
biased intervals can be used to reduce the number of equations required to get the desired
accuracy . Discretization of the diffusion and adsorption equation using a geometric grid is
studied to determine the improvement in accuracy that can be achieved using a non-linear
grid. The behavior of different adsorption isotherms on the optimal geometric grid is also
discussed.
Two test problems are simulated to validate the discretization scheme developed. The
adsorption of Cadmium on novel organo-silicates developed by Gomez-Salazar et. al.[7] is
used to demonstrate the improvement in efficiency obtained when a non-linear isotherm is
used. Using a geometric grid for discretizing the pellet equations does not result in a significant improvement in accuracy over a linear grid because the non-linear isotherm results
in a concentration front moving through the pellet. Biased intervals in the discretization of
the bed equation are used successfully to improve the accuracy of the breakthrough curve
obtained. The adsorption of Toluene on an activated Carbon packed bed present in a roomair cleaner is simulated assuming a linear isotherm. Discretization of the bed equation using
biased intervals does not result in significant gains in the accuracy of the solution because
the solution profiles in the bed are flat. A geometric grid is used for discretizing the pellet
equation and the solution obtained is more efficient than that obtained with conventional
methods.
An Efficient Numerical Method for the Simulation of Fixed-bed

Processes
by
Manuj Swaroop
BTech, Indian Institute of Technology Kanpur, 2002
Masters thesis
Submitted in partial fulfillment of the requirements for the degree
of Master of Science in Chemical Engineering in the Graduate
School of Syracuse University
December 2004
Approved: _____________________
Prof. John C. Heydweiller
Date: _____________________
Copyright 2004 Manuj Swaroop

All rights reserved.
Contents
List of Figures
vii
Acknowledgements
ix
1 Introduction
1.1
Mathematical model for a fixed bed . . . . . . . . . . . . . . . . . . . . . .
1.2
Numerical methods for simulation of fixed bed . . . . . . . . . . . . . . . .
1.3
Objective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2 The fixed-bed equation
10
2.1
Biased differencing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12
2.2
Integration over biased intervals . . . . . . . . . . . . . . . . . . . . . . . . .
15
2.3
Error analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
2.4
Temporal truncation error . . . . . . . . . . . . . . . . . . . . . . . . . . . .
19
2.4.1
Explicit scheme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
19
2.4.2
Error in trapezoidal integration . . . . . . . . . . . . . . . . . . . . .
20
2.4.3
Unequal biasing
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
21
Convection-Diffusion-Reaction equation . . . . . . . . . . . . . . . . . . . .
23
2.5.1
Error analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
24
2.6
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
26
2.7
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
27
2.8
APPENDIX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
32
2.5
vi
CONTENTS
3 The pellet equation
3.1
35
Geometric grid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
37
3.1.1
Equation at r=0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
38
3.1.2
Equation at r=1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
39
3.2
Simulation procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
39
3.3
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
40
3.3.1
Linear isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
41
3.3.2
Non Linear isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . .
44
4 Simulation of fixed beds
49
4.1
Discretization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
51
4.2
Simulation procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
53
4.3
Cadmium adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
54
4.3.1
Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
54
4.3.2
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
56
Room air cleaner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
58
4.4.1
Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
58
4.4.2
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
60
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
62
4.4
4.5
Bibliography
66
List of Figures
1.1
Model of a fixed bed. The axial coordinate is denoted by x. The bed is

discretized into equal intervals of size x. The concentration profile inside
the pellets in each interval is represented by a single averaged pellet. . . . .
2.1
An upwind-biased interval about a grid point, (c0 < 0) . . . . . . . . . . . .
13
2.2
Advection equation for a smooth function using biased intervals . . . . . . .
29
2.3
Simulation results with different initial conditions using equally biased intervals 30
2.4
Simulation results with different grid sizes using equally biased intervals . .
31
3.1
Two adjacent intervals in a geometric grid . . . . . . . . . . . . . . . . . . .
37
3.2
Simulation of the pellet equation with (c) = 1 . . . . . . . . . . . . . . . .
42
3.3
Geometric factors for a linear isotherm based on amount contained in the

pores and surface concentration . . . . . . . . . . . . . . . . . . . . . . . . .
3.4
Average absolute error for a linear isotherm based on amount contained in

the pores, with a linear grid and a geometric grid . . . . . . . . . . . . . . .
3.5
43
Average absolute error for a linear isotherm based on surface concentration

of pellet, with a linear grid and a geometric grid . . . . . . . . . . . . . . .
3.6
43
44
Solution profiles for non linear isotherm. Number of grid points = 101 and
geometric ratio = 1.01 for (a), (b) and (c). Total simulation time=165 (nondimensional) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.7
46
Geometric factors for a non linear isotherm based on amount contained in

the pores and surface concentration . . . . . . . . . . . . . . . . . . . . . . .
vii
47
LIST OF FIGURES
3.8
Average absolute error for a non linear isotherm based on amount contained
in the pores, with a linear grid and a geometric grid . . . . . . . . . . . . .
3.9
57
Breakthrough curve obtained using partial upwind biasing in the spatial part
compared with the benchmark and optimal biasing curves . . . . . . . . . .
4.4
57
Breakthrough curve obtained using central differencing compared with the

benchmark and optimal biasing curves . . . . . . . . . . . . . . . . . . . . .
4.3
48
Breakthrough curve obtained using simple upwind differencing compared

with the benchmark and optimal biasing curves . . . . . . . . . . . . . . . .
4.2
47
Average absolute error for a non linear isotherm based on surface concentration of pellet, with a linear grid and a geometric grid . . . . . . . . . . . . .
4.1
viii
58
Model of the room air cleaner used for the adsorption of toluene on activated
carbon. For the numerical simulation, the bed is modeled as a thick, short
bed as shown on the right side, obtained by unfolding the cylindrical bed. .
4.5
59
Simulation results for Toluene adsorption on activated carbon in a room air

cleaner, at flow rate Q = 7.44 104 cm3 /s for (a), (b), and (c) and Q =
2.36 104 cm3 /s for (d) using nb = 21 (no. of grid points in the bed), np = 10
(no. of grid points in pellets) and m = 1.4 (geometric factor) . . . . . . . .
4.6
Concentration profiles in the first pellet in the bed at high flow rates for time
<= 5 hrs, dt=0.5 hrs, np = 10, m = 1.4 . . . . . . . . . . . . . . . . . . . .
4.7
63
64
Comparison of concentration in room using geometric and linear grids, nb =

21, time<=5 hrs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
64
Acknowledgements
I would like to express my sincere gratitude and respect to my advisor, Dr. John C.
Heydweiller for his valuable guidance, motivation and patience throughout this research
work. It has been a privilege and a very good learning experience for me to work under his
supervision. I would also like to thank Dr. Tavlarides for allowing me to carry out experiments in his lab and Dr. Jianshun Zhang for introducing me to some practical applications
of this research work and providing me with experimental data.
Dr. Thong Q. Dang gave me valuable insights into various numerical methods that are
applicable to this research work. I am grateful to Dr. Ashok S. Sangani for his support,
encouragement and interest in my research and for the fruitful discussions I had with him.
All the Chemical Engineering staff including Ms. Dawn Long and Mickey Hunter were
very helpful and supportive during my stay at Syracuse University and I would like to take
this opportunity to thank them.
I would also like to thank my friends and colleagues Nitin Agarwal, Bhushan Hole,
Francisco Nam, Shailesh Ozarkar, Wenhao Chen and Gautam Bisht for their encouragement
and assistance with this thesis.
I am very thankful to my friends, parents and brother for their friendship and love.
ix
Chapter 1
Introduction
Adsorption phenomena play an important role in many natural, biological and chemical
systems. Adsorption operations are used extensively in the chemical and petrochemical
industries and are being increasingly used for biotechnology and environmental control
applications. Adsorption maybe used as a separation process or as a step in multiphase
reaction systems. The process of adsorption involves separation of a component of a mixture
from one phase and its accumulation on the surface of another phase, usually solid. The
adsorbing phase is called the adsorbent and the material adsorbed at the surface of that
phase is called the adsorbate.
The most common configuration used for adsorption processes is a fixed bed. In a fixed
bed, adsorbent pellets are held together in place to form a bed, through which the incoming
fluid is made to flow. The fluid flows through interstitial spaces present in the bed and
diffuses into the pores of the adsorbent pellets. Accumulation of the adsorbate takes place
mostly on the surface inside the pores of the pellets, which provide a very large surface
area. This configuration is quite easy to accommodate in a variety of designs for different
applications. The particular application of interest in the present work is indoor room air
cleaners. They consist of a fixed bed usually made of activated carbon cloth or pellets. A
fan is used to blow air from the outside into the bed. The fixed bed is usually small in length
and has a large cross-sectional area. This kind of structure results in faster adsorption of
gases.
Indoor air cleaners are used to remove volatile organic compounds (VOCs) from the air.
1
CHAPTER 1. INTRODUCTION
These gases are typically emitted from adhesives, upholstery, manufactured wood products,
cleaning supplies and some household appliances. The concentration of such gases in indoor
air is usually extremely low (measured in parts per billion). As a result, accurate isotherms
for their adsorption are not available. The low concentration of the gases also means that
the adsorbent will take a very long time to become saturated with the adsorbate. Thus,
indoor room air cleaners are designed to last for several years.
The lifespan and efficiency of an adsorber is characterized by its breakthrough curve.
This curve is a plot of the concentration of the adsorbate at the outlet of the fixed bed
versus time. The breakthrough curve is used to determine the time for which the adsorber
operated within acceptable limits. A breakthrough curve with a sharp slope implies that the
adsorber was working efficiently and has a longer lifetime. On the other hand, if the pellets
are unable to adsorb efficiently, the breakthrough occurs earlier and the slope is less steep,
so that the bed does not saturate optimally. The long life span of these adsorbers poses a
problem in proper testing and design of the fixed beds used in the air cleaner. Experiments
with the same concentrations that are present in indoor air would take too long to complete
to be of any practical use. On the other hand, if higher concentrations of gases are used, the
physics of adsorption is expected to be different and so the results may not be extrapolated
to low concentrations.
Simulation of fixed bed adsorbers for indoor air quality can be used to calculate the
values of the adsorption parameters for VOCs at very low concentrations, and that information can be used to predict the breakthrough curve of an adsorber. However, the nature
of the adsorption isotherm at such low concentrations, combined with the variations in the
kind of flow that takes place in different regions of the bed makes it a difficult task to make
an accurate prediction of the breakthrough curve.
1.1
Mathematical model for a fixed bed
The simplified mathematical model used to simulate a fixed bed can be described as follows.
The flow through the bed is mostly convective. Hence, a one dimensional plug flow approximation in the direction of the flow can be used to represent the flow in the bed. A mass
transfer coefficient coupled with the concentration difference between the concentration in
the bulk fluid and the surface of an average pellet in the same region is used to describe
mass transfer to the pellets. The equation for the bed flow can be written in the following
form[21]:
us
where
3kf
cb
cb
+#
+ b
(cb c|r=R ) = 0
z
t
Rp
0 z0 t0
cb =
cbin z = 0 t > 0
(1.1)
z = axis along the direction of flow

cb = concentration in bed along z
us = superficial bed velocity
# = bed packing fraction
b = density of the bed
p = density of pellets
R = radius of pellets
kf
= bulk mass transfer coefficient
This partial differential equation contains a convection term, along with a source term to
represent mass transfer from the bulk to the surface of a pellet. The source term couples
the bed equation with the pellet equations.
To solve the fixed bed equation, the bed is discretized into equal intervals. The pellets
contained in each interval are represented by a single averaged pellet in that interval (see
Figure 1.1). The total amount transferred to the pellets in a given region can be determined
using a mass balance between the bulk and the pellets. This balance is incorporated in the
source term in the bed equation.
Figure 1.1: Model of a fixed bed. The axial coordinate is denoted by x. The bed is
discretized into equal intervals of size x. The concentration profile inside the pellets in
each interval is represented by a single averaged pellet.
The adsorbate that is transferred to the surface of a pellet diffuses into its pores and
then adsorbs on the surface inside the pores. The pellets are modeled as spherical particles
with identical cylindrical pores. The flow inside the pores is mostly due to diffusion. The
flow and adsorption equation for the pellets can be written as follows[21]:
%
&
q c
#p + p
c t
= De
1
r2 r
'
r2
c
r
c = 0 for t 0;
+ Ds p
1
r2 r
0rR
c
= 0 at r = 0
r
c
Dp
= kf (cb c) at r = R
r
'
r2
q
r
(1.2)
where
c = concentration inside pores of pellet
r = radial axis of pellet
#p = porosity of pellet
p = density of pellet
De = effective pore diffusion coefficient
Ds = surface diffusion coefficient
q = adsorption isotherm (function of c)
The above partial differential equation is a parabolic equation in spherical coordinates and
it represents diffusion inside the pores and on the surface along with the adsorption. It is
linked to the bed equation through the boundary condition at r = R.
The averaged pellets in each interval of the bed are expected to have different concentration profiles because the bulk concentration in the bed is a function of the distance along
the bed axis. The solution of the pellet equation also depends on the rate of change of
the bulk concentration in its section. Hence the pellet equation has to be solved for each
section of the bed. Thus, there is 1 PDE for the bed and nb PDEs for the pellets, where nb
is the number of intervals used in the bed, that have to be solved for a complete fixed-bed
simulation. This approach results in a nested structure of equations.
It should be noted that there are significant differences in the physics and numerical
characteristics of the bed equation and the pellet equation. They can be summarized as
follows:
The bed equation is a convective equation with a linear source term whereas the pellet
equation is a diffusion equation. Typically, the spatial discretization scheme and the
time integration schemes used for these two types of equations are different.
If the isotherm to be used is non-linear, then the pellet equation becomes non-linear
and has to be solved numerically for each section with appropriate approximations.
The two equations are in different spatial domains. As a result, different spatial grid
spacing would be needed for each kind of equation and that would affect the size of
the time step that can be used to solve them simultaneously.
If the two equations are non-dimensionalized, it is noted that the time scale that
emerges for each is quite different. So, the solution would have to proceed at the
smaller of the two time scales and might slow down the solution procedure significantly.
A unified approach to the simulation procedure for such problems, which can solve the
equations resulting from different models simultaneously is desirable and is presented in
this study.
1.2
Numerical methods for simulation of fixed bed
Numerous studies have been published which have dealt with the problem of solving an
advective equation with high accuracy and stability[6]. Similarly, there are many good
techniques for the solution of the diffusion equation. However, not all of them meet the
requirements of an efficient numerical method suitable for simulation of fixed bed problems. High order discretization schemes are usually computationally intensive. Second
order upwind schemes lead to problems in evaluating the boundary condition. The numerical approach must also be capable of solving both the advective equation and the nonlinear
diffusion equation with similar accuracy. Hence specialized methods for either kind of equation may not be suitable and may also be difficult to implement. A suitable numerical
method would have to be able to handle different grid discretizations, be able to solve
non-linear equations, be computationally efficient and easy to implement.
A concise review of the methods that can be used to solve equations arising in fixed
beds is given by Le Lann et. al.[11]. They presented the following classification of numerical
methods used to solve partial differential equations:
Method of Lines (MOL)
Finite difference Methods
Weighted Residuals Methods

Finite Element Methods
Finite Volume Methods
Adaptive Grid Methods
Moving grid Methods
A more specific review of numerical methods suitable for adsorption models was presented
by Costa and Rodrigues[5]. Sun and Meunier[19] developed an improved finite difference
method for fixed bed sorption problems using a higher order implicit scheme. Solution methods based on the method of characteristics were presented by Loureiro and Rodrigues[12].
Weighted residual methods may be used to solve the complete set of equations but they
are generally not suitable for problems that have sharp moving fronts. Sharp fronts or
steep gradients can arise in the bed equation as well as the pellet equations with a non
linear isotherm. Oscillations and negative values of concentrations are often observed in
such cases when weighted residual methods are used[9]. Adaptive grid and moving grid
techniques[16, 17] can be used to reduce the error and enhance stability at the cost of
computational efficiency but they are difficult to implement when both particle and bed
equations have to be solved simultaneously.
The Method of Lines (MOL) converts each Partial Differential Equation (PDE) into a
set of Ordinary Differential Equations (ODEs) in time by discretizing the spatial variable.
The collection of ODEs resulting from each PDE can be combined to form a set of ODEs
that represent the complete problem. The resulting of equations can be solved simultaneously using an ODE solver. The ODE solver integrates the equations in time using a
specified numerical scheme. The advantage with this method is that well established integration routines may be used for solving large sets of ODEs with good accuracy. These
include algorithms that can solve stiff as well as non stiff systems of equation and feature
automatic step size adjustment and integration-order selection to maintain a user-specified
error tolerance and to solve the equations with high efficiency. The main drawback is that
non-stiff ODE solvers may have problems with estimating and controlling the impact of the
space discretization scheme on the overall numerical scheme. Finite element, finite volume
or finite difference methods may also be incorporated in the MOL for the spatial discretization. Only the spatial discretization needs to be done by the user when using the MOL and
as a result the MOL requires less effort on the part of the user as compared to a full finite
element simulation.
The nature of the adsorption problem is such that as the solution proceeds, the time
derivative decreases in magnitude. So a numerical method in which the size of the time
increments can be increased as the solution proceeds is desirable[22]. The MOL can be used
with sophisticated algorithms for controlling the time step, and so it is suitable for such
applications. The method of lines can also be used to simultaneously solve sets of PDEs
which require different kinds of spatial differencing schemes as all of them will result in
ODEs in time, which can be solved together.
The MOL when used with the proper spatial discretization and a reasonably fast and
accurate (depending on the problem) numerical integration scheme turns out to be a very
suitable and convenient method for fixed bed applications. The present work attempts to
formulate a simple and easy to use numerical method based on the MOL, which can be used
to simulate fixed bed adsorbers. The numerical scheme formulation should be more efficient
than conventional methods used in fixed bed simulations. This can be done by reducing
the number of equations required to get the same accuracy as compared to conventional
methods. The numerical scheme should allow solution of advection and diffusion equations
simultaneously. It should also be independent of grid spacing and time step so that it can
be implemented easily in different problems.
1.3
Objective
The goal of the present work is to develop an easy to implement and reasonably fast and
accurate method based on the MOL for the simulation of fixed bed adsorber problems.
This study builds on the ideas presented by Heydweiller and Patel[10] about upwind biased
discretization schemes and attempts to present an in-depth analysis of the problem, leading
to an improved numerical scheme based on biased intervals and the MOL. Other techniques
to make the solution more efficient, like using a non-linear grid for discretization of the
pellet equations have also been investigated. The resulting techniques have been applied to
predict the breakthrough curve of a room air cleaner and also to investigate the adsorption
isotherms of the VOCs adsorbed on it.
The following chapter describes a general scheme for deriving the biasing matrices based
on certain parameters. The non-dimensionalized advection equation is used to demonstrate
the technique throughout the derivation. An error analysis of the resulting set of equations
is done and is used to find the best values for the biasing parameters. This analysis also
shows how different biasing for the temporal and the spatial part can be used to improve
the accuracy further. The amount of biasing would also depend on the particular numerical
scheme used for time integration. The derivation is then generalized to include equations
with diffusion and source terms.
The pellet equations are also solved with the MOL using a non-linear grid in the next
chapter. The effect of different non-linear grids on the accuracy of the solution is investigated
and the grid that results in the least error for the same number of grid points is used. The
optimal geometric grid was determined for various grid sizes for a linear and a non-linear
isotherm[7].
The last chapter deals with applying the numerical schemes developed in this study to
the simulation of two fixed-bed problems. The bed equation and the pellet equations are
solved simultaneously and the solution profiles and the breakthrough curve are presented.
The first problem is the simulation of adsorption of Cadmium on novel organo-ceramic
adsorbents developed by Gomez-Salazar et. al.[7]. The results for this setup were already
available and were used to check the derived numerical scheme for efficiency. Simulation of
adsorption of toluene on activated carbon in a room-air cleaner at very low concentrations
is also performed. The results are then compared with experimental data to examine the
improvements obtained in efficiency.
Chapter 2
The fixed-bed equation

Different spatial discretization schemes can be used with the method of lines for solving
different kinds of PDEs. Second-order centered finite differences yield stable and efficient
solutions for parabolic equations. However, using central differencing for hyperbolic equations results in an unstable solution procedure. Backward differencing can be used with
hyperbolic equations to make the solution procedure stable but the relative inaccuracy of
first order backward differencing results in an inefficient solution as a large number of grid
points are needed to reduce the numerical dissipation that is introduced by this scheme.
Second order backward differencing can also be used but it is more difficult to implement
at boundaries. There are several other schemes available for the solution of hyperbolic
equations[6] including explicit, implicit and several semi implicit schemes. However, only a
few of them are suitable for use with the MOL.
A discretization scheme to be used with the MOL should be based on spatial discretization only, as the time discretization is handled by the ODE solver. If the same numerical
scheme is used discretize the time domain as well as the spatial domain for different kinds
of equations, then the temporal discretization should yield an accurate and stable solution
for all the ODEs being solved simultaneously. This renders many conventional numerical
schemes unusable with the MOL if more than one kind of PDE is being solved.
Discretization schemes that have been proposed for solving the hyperbolic equation using
10
CHAPTER 2. THE FIXED-BED EQUATION
11
the method of lines will be discussed using the advection equation:

ut = c0 ux
(2.1)
Carver and Hinds[3] proposed the following formula, which incorporates biased differencing
of the spatial domain while also using a spatially biased time derivative:
1
6
%'
(
'
(
&
3#
3#
1+
(ut )i1 + 4(ut )i + 1
(ut )i+1
2
2
c0
=
[(1 #)ui+1 + 2#ui (1 + #)ui1 ] (2.2)
2%x
The parameter # was determined empirically using numerical experiments such that the
total error was minimized. Although the solution of the advective equation with c0 = 1
was stable and accurate with the parameter # set to 0.3, the computation time required was
50% greater than the time required using either backward or upstream biased differences.
Using eq. (2.2) necessitates the solving of a matrix problem at each time step even though
a non-stiff integrator is employed.
Heydweiller and Patel[10] formulated an upstream biased differencing scheme for the
solution of hyperbolic PDEs. This scheme does not involve a mass matrix, i.e., the time
derivative at only one grid point is used in any given ODE that results from the spatial
discretization. Hence, it is computationally more efficient than the scheme proposed by
Carver and Hinds. The biased differencing results in a stable solution for hyperbolic equations which have smooth solutions. It also permits sets of coupled hyperbolic and parabolic
equations to be solved simultaneously by the method of lines. This kind of coupling is very
common in mathematical models used by chemical engineers. The parameters used in the
difference formula are functions of the grid spacing and can give accuracy between first and
second order. The biased upwind differencing can be written in the form
(ux )i =
aui+1 + cui bui1

(x)p
(x)2
+C
(uxx )i +
(uxxx )
2x
P
6
(2.3)
12
or
(ux )i =
ui+1 ui1
ui+1 2ui + ui1
+ Dc
2%x
(%x)2
(2.4)
where Dc = C(x)p /P , C = (c0 / |c0 |) and p and P are parameters independent of

the grid spacing x. They also showed that single values of the parameters (p = 1.5 and
P = 1.0) could be used for most problems on a normalized spatial domain.
The idea of discretizing the equations over biased intervals on the spatial grid has been
investigated in detail in the present study. The analysis has been used to formulate an
efficient and easy to use method for solving fixed bed problems, based on the improvements
in accuracy that result from using biased intervals.
An integral formulation for discretizing PDEs in a particular domain has been used in the
present work. This method is essentially a simplified form of the finite volume technique.
The solution domain is divided into intervals, usually of equal size. The equation to be
discretized is integrated over the discretization variable in each interval. The resulting set
of equations are independent of the discretization variable. Numerical integration formulas
can be used to approximate terms that cannot be integrated directly. The accuracy of the
resulting equations depends on the method used for numerical integration. This method
can be used to discretize a variety of equations along with their boundary conditions in a
consistent manner. Several finite difference methods run into problems at a boundary if
one or more imaginary point is needed to incorporate the boundary condition. The integral
method does not have this problem as it can be integrated over a partial interval at the
boundary, within the solution domain.
The integral method can be used very effectively for discretizing equations over a biased
interval. In this chapter, the idea of discretizing PDEs over a biased interval to improve the
accuracy has been explored further using the integral method.
2.1
Biased differencing
The upstream-biased difference scheme presented by Heydweiller and Patel (eq. 2.3) can be
derived by integrating the partial differential equation for each grid point over an interval
x shifted upstream (see Figure 2.1) by an amount defined by biasing parameters, a and b.
13
Figure 2.1: An upwind-biased interval about a grid point, (c0 < 0)

The parameter a represents the part of the interval to the right of the point xi that forms
part of the integration domain while the parameter b represents the part of the interval to
the left of xi that is used. The advection equation (eq. 2.1) has been used to illustrate the
integration method.
The advection equation can be integrated over a biased interval as follows:
)
xi +(ax/2)
xi (bx/2)
u
dx = c0
t
xi +(ax/2)
xi (bx/2)
u
dx
x
(2.5)
The parameters a and b are chosen such that a + b = 2, in order to have non-overlapping
intervals of length x each. Using the trapezoidal rule for the integral on the left hand
side (l.h.s.) of the equation and making suitable approximations, the following difference
equation was obtained:
%
&
dui
aui+1 + (b a)ui bui1
= c0
dt
(a + b)x
(2.6)
The right hand side (r.h.s.) of this equations is the same as eq. (2.3). At the boundaries,
integration is done over a partial interval and the same approximations are used as above
so that the order of accuracy is maintained throughout and the boundaries can be handled
14

conveniently. The integration formula at the left boundary is given by:
)
x0 +(ax/2)
x0
u
dx = c0
t
x0 +(ax/2)
x0
u
dx
x
(2.7)
where x0 denotes the leftmost grid point in the bed. The formula for the right boundary is
given by:
xI
xI (bx/2)
u
dx = c0
t
xI
xI (bx/2)
u
dx
x
(2.8)
where xI denotes the rightmost grid point in the bed.

The numerical integration used to obtain the r.h.s. of eq. (2.6) is of order (x)2 as the
value of ui at the two ends of the biased interval was obtained using the lever rule. However,
the integration scheme used for evaluating the l.h.s. results in a larger truncation error. In
general, higher order integration techniques can be used to evaluate both sides of eq. (2.5)
to improve the accuracy of the resulting equations. The number of grid points involved in
the resulting equation for each interval depends on the order of accuracy of the integration
scheme used. If a higher order scheme is to be used for integration, then the integration
domain should encompass more grid points, resulting in a larger interval. However, this
approach can run into problems at the boundary. The number of points available for the
last interval would be less than the number of points available for the adjacent interval.
This would result in a difference between the order of accuracy of the integration used in
the two intervals and can lead to numerical errors.
The resulting set of equations can be expressed with the help of a l.h.s. and a r.h.s.
15

matrix as follows:
Ll1 Ll2
u1 /t
Lc1 Lc2 Lc3

u /t
2
Lc1 Lc2 Lc3
un1 /t
Lr1 Lr2
un /t
Rl1 Rl2
Rc1 Rc2 Rc3
= c0
2.2
u1
u
2
Rc1 Rc2 Rc3

un1
Rr1 Rr2
un
(2.9)
Integration over biased intervals
The advection equation (eq. 2.1) has been used to demonstrate the integration over biased
interval formulation used in this study. The trapezoidal rule is used to integrate terms
that cannot be integrated algebraically. The lever rule is used to calculate the value of any
expression in between grid points. Both these methods are second order accurate. Hence
the order of accuracy of the resulting equation is second order.
Consider a point xi in the space domain. The equation is integrated over an interval of
length x around xi . The interval is upwind -biased as shown in Figure 2.1. The biasing
parameters a and b are used to define the amount of biasing. Since the size of the interval
is kept constant over the entire domain (a + b = 2), only one of them is an independent
parameter (a in the present study). The integration technique used to derive the set of
equations also plays an important role in determining the accuracy of the solution, along
with the amount of biasing.
16

Integration of the spatial derivative results in the following expression:
c0
xi +(ax/2)
xi (bx/2)
0
1
u
dx = c0 u|xi +(ax/2) u|xi (bx/2)
x
%
&
bui1 + (b a)ui + aui+1
= c0
a+b
(2.10)
The discretization of the spatial part obtained with this method is the same as that presented
by Heydweiller and Patel (eq. 2.6).
The integration of the time derivative is evaluated as the area under the two trapezoids
ABEF and BCDE in Figure 2.1 (assuming that ui /t is used instead of ui ).
)
xi +(ax/2)
xi (bx/2)
u
dx =
t
EF
u
dx +
t
DE
u
dx
t
%
&
ui
2 ui1
2 ui+1 x
= b
+ (2ab + 4)
+a
t
t
t
8
(2.11)
The complete discretized equation can be written as:

%
&
ui
2 ui1
2 ui+1 1
b
+ (2ab + 4)
+a
t
t
t
8
= c0
&
(2.12)
(a + b)x
The equations obtained using this method of integration are more accurate than eq.
(2.6) but the solution requires the solution of an additional matrix problem at each time
step. In this respect, the set of equations is similar to eq. (2.2). The difference is that
there is no empirical correlation used to derive the biasing parameters. The equations have
been obtained by simply improving the accuracy of the integration. The only independent
parameter is the amount of biasing and an optimum value for this parameter will be determined using an error analysis. The accuracy of the solution can be improved by using
a more accurate scheme of integration, although it will reduce the efficiency of solution if
more than three adjacent grid points are used per solution point.
This method also makes handling of the boundary condition a simple task. The null
boundary condition can be handled by integrating over the partial interval left at the end:
%
&
uI 1
2 uI1
b
+ (ab + 2b)
t
t 8
= c0
buI1 + (2 a)uI
(a + b)x
&
(2.13)
17

where xI is the last grid point in the spatial domain.
2.3
Error analysis
A complete error analysis was done for the spatially discretized equations. The coefficients
of each term were treated as independent parameters so that the results can be used to find
the truncation error in equations derived using different integration schemes by replacing
the coefficients with their corresponding expressions. The error analysis does not take into
account the truncation error arising from discretization of the time derivative. This is
intentional because the numerical integration in time is done by the ODE solver. Further,
a simple explicit or implicit scheme might not be appropriate for solving all the equations
being solved simultaneously. Hence the time discretization is best left to the ODE solver,
which can use sophisticated algorithms to do the integration in time efficiently. However,
an explicit scheme was analyzed in order to provide a comparison.
After integrating the advection equation over a biased interval for use with the method
of lines as shown in the previous section, it can be expressed in the following manner:
k(ut )i1 + (1 (k + l))(ut )i + l(ut )i+1 =
c0
(pui1 (p + q)ui + qui+1 )
x
(2.14)
The actual value of the biasing parameters is a function of the amount of biasing and the
scheme used for integration. Only schemes using three grid points for a single equation
have been considered in this case. The results from this analysis can therefore be used to
evaluate the truncation error using all the integration schemes used in this study.
Using the Taylor series expansion for u, the r.h.s. can be written as
RHS =
%
&
(x)
(%x)2
(%x)3
c0 (q p)(ux )i + (p + q)
(uxx )i + (q p)
(uxxx )i + (p + q)
(uxxxx )i +
2
6
24
(2.15)
Comparing with eq. (2.1), q p = 1. Substituting in the above expression and replacing ui
18
with u gives
RHS = c0 ux + c0 (p + q)
(x)
(%x)2
(%x)3
uxx + c0
uxxx + c0 (p + q)
uxxxx +
2
6
24
(2.16)
Similarly, using the Taylor series for ut , the l.h.s. can be written as:
(x)2
(%x)3
utxx + (l k)
utxxx + (2.17)
2
6
(x)2
(%x)3
LHS = ut (l k)(x)uxx (l + k)
uxxx (l k)
uxxxx + (2.18)
2
6
LHS = ut + (l k)(x)utx + (l + k)
using relations from eq. (2.59).

The complete equation can now be written as:
ut
%
'
(&
(p + q)
= c0 ux + (x) c0 uxx
(l k)
2
%
'
(&
1 (l + k)
2
+(x) c0 uxxx
6
2
%
'
(&
(p + q) (l k)
+(x)3 c0 uxxxx
+
24
6
(2.19)
Substituting the values of the coefficients of ut and u from eq. (2.12), the error terms can
be written as:
ET {O[(x)]}
ET {O[(x)2 ]}
(p + q)
a1 a1
(l k) =
=0
2
2
2
'
(
1 (l + k)
2
= a2 2a +
6
2
3
(2.20)
The first order error term is identically zero if either both sides of the equation are integrated
over the same interval or if both sides are integrated over a centered interval (l = k and
p + q = 0). The second order term can be reduced to zero by using a root of the quadratic
expression in that term as the value of a. The resulting value of the biasing parameter a is:
1
a = 1 ( 0.423
3
(2.21)
This value of the biasing parameter would yield a third order accurate discretization in
19
space. However, the truncation error derived here does not include the error due to time
discretization. In the actual solution, there would be some error added to the first and
second order error terms depending on the numerical scheme used for time integration. In
principle, if a third order accurate scheme is used for integration in time, the solution would
also be third order accurate.
Caveat: The derivative relations (eq. 2.59) used to obtain this result are applicable only
if the profile of u is continuous and differentiable at all points. If there is any discontinuity
in the first derivative of u, none of the derivatives are defined at that point and hence those
relations are not valid there. The solution is expected to be less accurate at and adjacent
to the points where u is non-differentiable but the accuracy should be unaffected at the
remaining grid points.
2.4
Temporal truncation error
The left hand side can be discretized using a first order time discretization scheme as follows:
LHS = k
n
un+1
i1 ui1
%t
+ [1 (k + l)]
'
un+1
uni
i
%t
+l
n
un+1
i+1 ui+1
%t
(2.22)
where the superscript n denotes the current time step.
2.4.1
Explicit scheme
The r.h.s for an explicit scheme can be written as:

RHS = c0 unx + c0 (p + q)
(x) n
(%x)2 n
(%x)3 n
uxx + c0
uxxx + c0 (p + q)
uxxxx +
2
6
24
(2.23)
Let t = r(x). This substitution enables us to consolidate the truncation error in

the temporal and spatial domains and hence, to obtain the overall truncation error. The
variable r can be considered to be the velocity of the numerical solution. Replacing uni with
20

u and using the Taylor series expansion of the terms on the left hand side gives:
ut
%
&
(p + q)
r
= c0 ux + (x) c0
uxx utt (l k)utx
2
2
%
&
2
1
r
(k + l)
(l k)r
2
+(x) c0 uxxx uttt
utxx
uttx
6
6
2
2
%
&
(p + q)
(l k)
r3
(k + l)r
(l k)r2
3
+(x) c0
uxxxx
utxxx utttt
uttxx
utttx
24
6
24
4
6
+
(2.24)
Substituting the relations given in the appendix for derivatives of u in eq. (2.24), the
following expression is obtained:
ut
%
&
(p + q)
2r
= c0 ux + (x)uxx c0
c0 c0 (l k)
2
2
%
&
2
1
(k + l)
2
3r
2 (l k)r
+(x) uxxx c0 c0 c0
c0
6
6
2
2
%
&
3
2
(p + q)
(l k)
3
4r
2 (k + l)r
3 (l k)r
+(x) uxxxx c0
c0
c0 c0
c0
24
6
24
4
6
+
2.4.2
(2.25)
Error in trapezoidal integration
The expressions for the biasing variables k, l, p and q for integration of equations using the
trapezoidal rule can be obtained by comparing eq. (2.14) to eq. (2.12).
b2
8
a2
l =
8
b
p =
2
a
q =
2
k =
(2.26)
Substituting these expressions in eq. (2.25) and simplifying, we get the total error using
the trapezoidal integration on biased intervals.
21
Explicit scheme:
1
ET {O[(x)]} c20 r
(2.27)
2
1
1
1
1
1
ET {O[(x)2 ]} c0 + c0 a c0 a2 + c20 r c30 r2
(2.28)
12
4
8
4
6
c0
c0 a c20 ra c20 r c20 ra2 c30 r2 a c30 r2 c40 r3
ET {O[(x)3 ]}
(2.29)
24
24
8
8
16
12
12
24
These results clearly show that the spatial discretization is second order accurate. The
time discretization is first order accurate, so the first order error is non-zero and is directly
proportional to the size of the time step relative to the grid size. Hence smaller time steps
will result in better accuracy. However, for a given value of r, a suitable value of the biasing
parameter a can be chosen, such that the second order error is identically zero. This results
in improved accuracy of the overall solution. The accuracy would be better if a higher order
time discretization was used.
2.4.3
Unequal biasing
It should be noted in the preceding error analysis that the first order error term could not
be eliminated because the terms resulting from the l.h.s. and r.h.s. which contained the
biasing parameter, canceled out. If the biasing were different on the two sides, it would
provide an additional degree of freedom that can be used to eliminate the first order error
term. This is the reason for using different biased intervals for the temporal and spatial
parts of the equation.
Using unequal biasing for the l.h.s. and the r.h.s., the biasing variables can be written
as:
b2
8
a2
l =
8
b"
p =
2
a"
q =
2
k =
(2.30)
22
where a is the biasing factor for the l.h.s. of the equation with b = 2 a and a" is the
biasing factor for the r.h.s. of the equation with b" = 2 a" . Substituting these expressions
in eq. (2.25) and simplifying, the following truncation error are obtained:
c0 a + c0 a" c20 r
(2.31)
2
1
1
1
1
1
ET {O[(x)2 ]} c0 + c0 a c0 a2 + c20 r c30 r2
(2.32)
12
4
8
4
6
(c0 a" 2c0 a + c0 ) c20 ra c20 r c20 ra2 c30 r2 a c30 r2 c40 r3
ET {O[(x)3 ]}
+
24
8
8
16
12
12
24
ET {O[(x)]}
(2.33)
The above expressions have three degrees of freedom, including the time step. This
implies that, in principle, the two biasing parameters and a suitable time step can be
chosen to eliminate the error up to the third order. However, if a limit is imposed on the
time step, for example due to stability considerations, the error can be eliminated up to
the first order and the second order error can be minimized. In the case of a fixed bed
simulation, the time step may also be limited by the time scale of the pellet equations.
The results for unequal intervals are applicable only if the time step is fixed. A similar
analysis can be done for an implicit scheme or any other time discretization scheme and
equations can be formulated for minimizing the truncation error. In most problems involving
fixed beds, a fixed time step is not suitable for solving all the equations simultaneously. As
a result, this approach has not been investigated further in this study. The above analysis
has been presented to illustrate how using different biasing for integration of the two sides
of an equation can be used to improve the accuracy. Even when an ODE solver is used,
there may be first or second order error terms resulting from the time discretization used
by the ODE solver, and slightly different biasing for the integration intervals can be used
to reduce that error. The actual difference in biasing needed depends on the problem and
the ODE solver used and may need to be determined by experimentation.
23
2.5
Convection-Diffusion-Reaction equation
The technique used above to calculate the biasing parameters can be applied to a typical
convection-diffusion-reaction equation. In an adsorption problem, the reaction term would
be replaced with a mass transfer term. In general, this term can be called the source term.
The non-dimensional equation can be written as:
u
u
1 2u
= c0
+
+ f (u)
t
x P e x2
(2.34)
The parameters in this equation could have been reduced further by including c0 in the
non-dimensional time but in some practical applications, the time scale used for nondimensionalization may belong to another set of equations (like the ones for particles in
the bed) and in that case, the c0 term will remain as it is. The source term actually
used for computation is usually the linearized form of the actual source term, so that
f " (u) = constant and f "" (u) = 0.
Integrating this equation over a biased spatial interval, we get:
)
xi +(ax/2)
u
dx
t
) xi +(a! x/2)
xi (bx/2)
= c0
xi (b! x/2)
u
1
dx +
x
Pe
xi +(a! x/2)
xi (b! x/2)
2u
dx +
x2
xi +(a! x/2)
f (u)dx (2.35)
xi (b! x/2)
The temporal and spatial parts have been integrated over differently biased intervals. The
biasing parameter for the temporal part is a and for the spatial part it is a" . Using the
trapezoidal rule for integration, we get:
)
c0
xi +(ax/2)
xi (bx/2)
xi +(a! x/2)
xi (b! x/2)
%
&
ui1
ui
ui+1 x
b2
+ (2ab + 4)
+ a2
t
t
t
8
% "
&
u
b ui1 + (b" a" )ui + a" ui+1
dx = c0
x
a" + b"
u
dx =
t

1
Pe
24
6
5
5
u 55
u 55
x 5xi +(a! x/2) x 5xi (b! x/2)

xi (b! x/2)
%
&
1 ui1 2ui + ui+1
=
Pe
x
) xi +(a! x/2)
0 "2
1 x
f (u)dx = b f (ui1 ) + (2a" b" + 4)f (ui ) + a"2 f (ui+1 )
(2.36)
8
xi (b! x/2)
)
xi +(a! x/2)
2u
dx =
x2
1
Pe
It should be noted that integrating over a biased interval results in the same formula for
the parabolic term as a regular finite difference approximation over a centered interval.
The regular approximation for the diffusion term is second order accurate and so trying to
increase the order of accuracy of the integration using biased intervals does not affect its
discretization. Also note that the coefficients of the discretized source term have the same
form as the coefficients of the temporal part. The only difference is that they are based on
different biasing parameters.
2.5.1
Error analysis
In general, the discretized equation can be written as:

k(ut )i1 + (1 (k + l))(ut )i + l(ut )i+1 =
c0
[pui1 (p + q)ui + qui+1 ]
x
1
+
[ui1 2ui + ui+1 ]
P e(x)2
0
1
+ k " f (ui1 ) + [1 (k " + l" )]f (ui ) + l" f (ui+1 )
(2.37)
The error terms resulting from the convective term have already been derived in Section
2.3. The truncation error of the diffusion term is well known. It can be written as:
ET dif f =
1
(x)2 uxxxx + O[(x)4 ]
12P e
(2.38)
The source term can be written using a Taylor series expansion as:
5
5
f (u) 55
(u)2 2 f (u) 55
f (ui1 ) = f (ui ) + (u)
+
+
u 5i
2
u2 5i
where
u = ui1 ui
(2.39)
25
The source term f (u) has been linearized, hence only the first order error term in u is
considered without any loss of accuracy. A Taylor series expansion (2.55) can be used to
write:
%
&
(%x)2
(%x)3
f (ui1 ) = f (ui ) + x(ux )i +
(uxx )i
(uxxx )i + f " (ui )
2
6
%
&
(%x)2
(%x)3
f (ui+1 ) = f (ui ) + x(ux )i +
(uxx )i +
(uxxx )i + f " (ui )
2
6
(2.40)
An error analysis similar to that done in the previous sections can be done to write:
1
uxx + f (u)
Pe
%'
&
(
c0 (p + q)
+(x)
uxx (l k)utx + ux (l" k " )f " (ui )
2
%'
(
&
c0
(k + l)
(k " + l" ) uxxxx
2
"
+(x)
uxxx
utxx + uxx f (ui )
+
6
2
2
12P e
%'
(
&
c0 (p + q)
(l k)
(l" k " )
3
"
+(x)
uxxxx
utxxx + uxxx f (ui )
+ (2.41)
24
6
6
ut = c0 ux +
Using the relations derived from the generalized equation (eq. 2.34) ( given in eq. 2.60),
the above equation can be written as:
1
uxx + f (u)
%P e
'
(
&
0 "
1
(p + q)
uxxx
"
"
+(x) uxx c0
(l k) + ux f (l k ) (l k) (l k)
2
Pe
%
'
(
' "
(
'
(&
"
1
(k
+
l)
k
+
l
k
+
l
u
1
k+l
xxxx
2
"
+(x) uxxx c0
+ f uxx
6
2
2
2
Pe
12
2
ut = c0 ux +
(2.42)
The error terms in the above equation contain different derivatives of u. There is no obvious
way to compare the coefficients of these terms, hence each should be minimized separately.
26

This results in the following equations for improving the accuracy of the solution:
(p + q)
(l k) = 0
2
(2.43)
(l" k " ) (l k) = 0
(2.44)
(l k) = 0
(2.45)
= 0
(2.46)
= 0
(2.47)
= 0
(2.48)
1 (k + l)
6
2
k " + l" k + l
2
2
1
k+l
12
2
Equation (2.43) implies that the biased interval should be the same for the time derivative
term and the convective term. Equation (2.44) implies that the biased interval should
be the same for the time derivative term and the source term. Equation (2.45) means
that the interval of integration should be centered. These three equations are sufficient
to determine the biasing parameters (a = a" = 1) and they yield a second order accurate
spatial discretization.
However, if the diffusion (uxx ) term is not present or is very small relative to the convective term in the original equation, as is the case in many fixed bed problems, a more
accurate discretization can be achieved. Equation (2.46) can be used to determine the value
of the biasing parameter instead of equation (2.45). This equation gives the same value of
a as eq. (2.21) (a = 0.423). Equation (2.47) would be satisfied automatically as equation
(2.44) has already been satisfied if the interval of integration for the source term is the
same as that for the time derivative term. The last equation would be negligible since the
diffusion term is negligible. This formulation would result in a third order accurate spatial
discretization.
2.6
Conclusion
The results obtained in Section 2.4 and Section 2.5 are subject to the same caveat as the
results in Section 2.3. These results are applicable only if the solution is differentiable at
all points. The biasing parameters derived here may still be used for solutions which have
27
a discontinuity in the derivative but the solution may show oscillations in the region of
discontinuity. However, this restriction does not preclude the simulation of fixed bed adsorbers using the above method because the concentration profile along the bed is observed
to be smooth for the most part. The profile has a discontinuity at very short times but it
smoothes out quickly.
The analysis done above resulted in a very straightforward approach to solving a fixed
bed equation using the method of lines. If an ODE solver that controls the time step is to be
used then the values of the biasing parameters are predetermined. They do not depend on
the physical parameters or the spatial or temporal grid. The only factor that they depend
on is the nature of the equation being solved. If the equation is convection dominated
then the appropriate biasing parameter is given by eq. (2.21). If the equation is diffusion
dominated then no biasing is necessary and the interval should be centered about a grid
point. The actual discretized equations can be obtained by integrating over the biased or
non-biased interval. On the other hand, if a fixed time step is to be used, which can be
controlled by the user, then the method for deriving the appropriate biasing factors has
been presented. The biasing factor has been determined for an advective equation to be
solved using an explicit scheme as an example.
2.7
Results and discussion
The formula obtained in the previous section was tested on the following advection equation:
u
t
for
Boundary condition
Initial condition
u
x
0x1
u(0, t) = u0 (0); t 0
u(x, 0) = u0 (x)
(2.49)
The exact solution, given by u(x, t) = u0 (x t) is shown with a dashed line in all the figures
at t = 0.5. A stiff ODE solver was used for the simulation in all cases. The simulation
r [13] using the ode15s ODE solver. The results obtained using the
was done in MATLAB)
28
biased interval formulation were compared to the results using a simple backward difference.
A smooth sinusoidal initial condition was used for the comparison to avoid any errors that
could be introduced by discontinuities in the derivative. The following initial condition was
used:
u0 (x) =
x
1+cos(+ 0.2
2)
2
0 x 0.2
0.2 x 1
(2.50)
It is evident from Figure 2.2 that a drastic improvement in accuracy can be achieved by
using the proper biasing. A biasing parameter different from the one obtained in Section
2.3 results in larger oscillations either leading or trailing the wave depending on the value of
the parameter. This behavior shows that numerical dissipation can be eliminated to a great
extent by using equally biased intervals . However, improper biasing can lead to instability
similar to that observed with using central differencing. The correct biasing can mitigate
both dissipation and dispersion error to a large extent.
The simulation was also carried out for the following initial conditions:
Smooth front:
u0 (x) =
Triangular wave:
u0 (x) =
Step input:
x
1+cos( 0.2
)
2
0.2 x 1
x
0.1
0 x 0.1
1 (x0.1)
0.1
u0 (x) =
0 x 0.2
0.1 x 0.2
(2.51)
(2.52)
0.2 x 1
x=0
0 0<x1
(2.53)
The results of these simulations are shown in Figure 2.3. The smooth front represents
the kind of solution profile that is encountered typically in fixed beds. It is evident from
the figure that there is very little dissipation and dispersion in the solution to the smooth
front. The triangular wave and the step input have at least one discontinuity in their spatial
derivative and as such the solution is not expected to be very accurate. This can be verified
29
in Figure 2.3. There is some numerical dissipation in the overall solution and some dispersion
near the points of discontinuity. However, the solution obtained using biased intervals is
more accurate than that obtained by using a simple backward or central difference with the
same value of x.
deltax=0.01 time=0.5 no mass matrix aRHS=0
deltax=0.01 time=0.5 aLHS=0.423 aRHS=0.423
0.8
0.8
0.6
0.6
u
0.4
0.4
0.2
0.2
0.1
0.2
0.3
0.4
0.5
x
0.6
0.7
0.8
0.9
(a) Simple backward difference
0.1
0.2
0.3
0.4
0.5
x
0.6
0.7
0.8
0.9
(b) Equally biased intervals with a=0.423
0.8
0.8
0.6
0.6
u
0.4
0.4
0.2
0.2
0.1
0.2
0.3
0.4
0.5
x
0.6
0.7
0.8
(c) Equally biased intervals with a=0.2
0.9
0.1
0.2
0.3
0.4
0.5
x
0.6
0.7
0.8
0.9
(d) Equally biased intervals with a=0.8
Figure 2.2: Advection equation for a smooth function using biased intervals
30
0.8
0.8
0.6
0.6
u
0.4
0.4
0.2
0.2
0.1
0.2
0.3
0.4
0.5
x
0.6
0.7
0.8
0.9
0.1
0.2
(a) Sinusoidal wave
0.3
0.4
0.5
x
0.6
0.7
0.8
0.9
0.8
0.9
(b) smooth front
0.8
0.8
0.6
0.6
u
0.4
0.4
0.2
0.2
0.1
0.2
0.3
0.4
0.5
x
0.6
(c) Triangular wave
0.7
0.8
0.9
0.1
0.2
0.3
0.4
0.5
x
0.6
0.7
(d) Step input
Figure 2.3: Simulation results with different initial conditions using equally biased intervals
To show that the above formulation gives reasonable solutions for a range of values of
x, (eq. 2.49) was solved for x = 0.04, 0.02, 0.01 and 0.005 using the initial condition
given in (eq. 2.50). The results are shown in Figure 2.4. It can be seen that there is greater
dissipation and dispersion error with larger values of x, although the solution remains
stable.
The above results show that the biased intervals formulation can be used very effectively
for typical fixed bed equations. It can reduce the error to a great extent in smooth solution
profiles as compared to backward differencing or central differencing. Even for profiles with
31
discontinuous derivatives, the solution obtained is better. It is be appropriate to mention

here that there are other numerical schemes available for solving the advective equation[6].
Some of them can also capture regions with discontinuous derivatives with little or no
oscillations. However, these schemes are specific to the advection equation and most of
them also use a fixed time step.
0.8
0.8
0.6
0.6
u
0.4
0.4
0.2
0.2
0.1
0.2
0.3
0.4
0.5
x
0.6
0.7
0.8
0.9
0.1
0.2
0.3
(a) dx=0.04
0.4
0.5
x
0.6
0.7
0.8
0.9
0.8
0.9
(b) dx=0.02
0.8
0.8
0.6
0.6
u
0.4
0.4
0.2
0.2
0.1
0.2
0.3
0.4
0.5
x
0.6
(c) dx=0.01
0.7
0.8
0.9
0.1
0.2
0.3
0.4
0.5
x
0.6
0.7
(d) dx=0.005
Figure 2.4: Simulation results with different grid sizes using equally biased intervals
The emphasis in the present study was to develop a consistent and easy to implement
numerical scheme that can be used for solving the advection equation along with a source
term and a diffusion term. It should also be independent of the time step used. The biased
32
interval scheme developed above provides a straightforward approach to solving this kind
of problems. This scheme is also easy to implement if the advection equation is coupled
with a parabolic equation. The parabolic equation can be discretized over intervals different
from those used for the advection equation without affecting the solution of the advection
equation. There is no optimum time stepping required to get the desired accuracy for a
given discretization, hence the ODE solver can solve both equations simultaneously without
losing any more accuracy.
2.8
APPENDIX
Evaluating the terms in the integration of eq. (2.5).

Terms occurring in the spatial part:
u|xi (bx/2) =
u|xi +(ax/2) =
u|xi +(ax/2) u|xi (bx/2) =
bui1 + aui
a+b
bui + aui+1
a+b
a+b
Terms occurring in the temporal part:

5
i
b uti1 + a u
u 55
t
=
t 5xi (bx/2)
a+b
5
ui+1
i
b u
u 55
t + a t
=
t 5xi +(ax/2)
a+b
5
4
ui 6
u 5
)
u
bx
t xi (bx/2) + t
dx =
t
2
2
FE
4 u
6
i
b2 ti1 + (2a + b)b u
t
=
x
4(a + b)
4 u 55
ui 6
)
u
ax
t xi +(ax/2) + t
dx =
2
2
ED t
4 u
6
i
a2 ti+1 + (2b + a)a u
t
=
x
4(a + b)
(2.54)
33
Taylor series expansion of variables:

(%x)2
(%x)3
(%x)4
(uxx )i
(uxxx )i +
(uxxxx )i +
2
6
24
(%x)2
(%x)3
(%x)4
= ui + x(ux )i +
(uxx )i +
(uxxx )i +
(uxxxx )i + (2.55)
2
6
24
ui1 = ui x(ux )i +
ui+1
un+1
= uni + (t)(ut )ni +
i
(t)2
(t)3
(t)4
(utt )ni +
(uttt )ni +
(utttt )ni +
2
6
24
(2.56)
(t)2
(t)3
(t)4
(utt )ni1 +
(uttt )ni1 +
(utttt )ni1 +
2
6
24
(x)2
(x)3
(x)4
= uni (x)(ux )ni +
(uxx )ni
(uxxx )ni +
(uxxxx )ni +
2
6
24
%
&
(x)2
(x)3
n
n
n
n
+(t) (ut )i (x)(utx )i +
(utxx )i
(utxxx )i +
2
6
%
&
(t)2
(x)2
n
n
n
+
(utt )i (x)(uttx )i +
(uttxx )i +
2
2
(t)3
(t)4
+
[(uttt )ni (x)(utttx )ni + ] +
[(utttt )ni + ] +
(2.57)
6
24
un+1
= uni1 + (t)(ut )ni1 +
i1
(t)2
(t)3
(t)4
(utt )ni+1 +
(uttt )ni+1 +
(utttt )ni+1 +
2
6
24
(x)2
(x)3
(x)4
= uni + (x)(ux )ni +
(uxx )ni +
(uxxx )ni +
(uxxxx )ni +
2
6
24
%
&
(x)2
(x)3
n
n
n
n
+(t) (ut )i + (x)(utx )i +
(utxx )i +
(utxxx )i +
2
6
%
&
(t)2
(x)2
+
(utt )ni + (x)(uttx )ni +
(uttxx )ni +
2
2
(t)3
(t)4
+
[(uttt )ni + (x)(utttx )ni + ] +
[(utttt )ni + ] +
(2.58)
6
24
un+1
= uni+1 + (t)(ut )ni+1 +
i+1
The following relations can be derived from the hyperbolic equation (eq. 2.1). They are
used to simplify the error expression for the equation:
34
ut = c0 ux
utt = (c0 ux )t = (c0 ut )x = c20 uxx
utx = (c0 ux )x = c0 uxx
uttt = (utt )t = (c20 uxx )t = c20 (utx )x = c30 uxxx
uxxt = (uxx )t = (utx )x = c0 uxxx
uttx = (utt )x = c20 uxxx
utxxx = (ut )xxx = (c0 ux )xxx = c0 uxxxx
utttt = (uttt )t = (c30 uxxx )t = (c30 uxxt )x = c40 uxxxx
uttxx = (uttx )x = c20 uxxxx
utttx = (uttt )x = c30 uxxxx
(2.59)
The following set of relations are used to simplify the terms in the convection diffusion
reaction equation (eq. 2.34):
1
uxx + f (u)
Pe
1
c0 uxx +
uxxx + f " (u)ux
Pe
1
c0 uxxx +
uxxxx + f " (u)uxx
Pe
1
c0 uxt +
uxxt + f " (u)ut
Pe
'
(
2f "
2c0
1
"
"
f f + 2c0 f ux + c0 +
uxx +
uxxx +
uxxxx
Pe
Pe
P e2
ut = c0 ux +
utx =
uxxt =
utt =
=
(2.60)
Chapter 3
The pellet equation

The mass transfer inside pellets in a fixed bed is usually dominated by diffusion. The solute
diffuses from the pellet surface into the pores and gets adsorbed on the surface inside the
pores. The pore structure has been approximated with cylindrical pores arranged radially
in the pellet for the purpose of simulation. The pore diffusion constant was calculated using
the average pore diameter that was determined from experiments. This results in a simple
diffusion equation in spherical coordinates. The pellet is assumed to be symmetric, hence
the equation has spatial dependence only in r. The resulting equation can be written in
non dimensional form as follows:
c
= (c )kp
'
2 c
2 c
+
r2 r r
(3.1)
c = 0 for 0; 0 r 1
5
c 55
=0
r 5r =0
5
c 55
= Bi(cb c |r =1 )
r 5r =1
where (c ) represents the adsorption term, which may be a constant (in the case of a
linear isotherm) or a function of c (in the case of a non linear isotherm). A non-linear
term in c/r resulting from the surface diffusion term was not used in this analysis for the
sake of simplicity. The non-linear term disappears in both the fixed-bed problems that are
simulated in the last chapter and hence, the results are not affected by this omission.
35
CHAPTER 3. THE PELLET EQUATION
36
The non dimensional parameters used in this equations are:

c = c/cb in
r = r/R
= t/
= time scale used for non dimensionalization
Bi =
kp =
Rkf
Dp
Dp
R2
where
cb in = inlet concentration
R = radius of pellet
kf
= bulk mass transfer coefficient
Dp = pore diffusion coefficient

As the adsorbate starts diffusing from the surface of a pellet into an empty pore, the
concentration gradient near the boundary is very steep. In order to capture this part of
the process using the method of lines, a very fine grid is needed near the external boundary. However, towards the center of the pellet, the concentration profile becomes flatter in
accordance with the boundary condition of zero slope at the center. This characteristic of
mass transfer in pellets suggests that a non-linear grid with more points near the external
boundary and fewer towards the center would be able to capture the concentration profile
near the surface with greater accuracy than a linear grid using the same number of grid
points. The non linear grid would be more computationally efficient than a linear grid as the
number of equations required for obtaining the same accuracy as a linear grid is reduced.
Hence, a geometric grid was used for simulating the pellet equations.
37
Figure 3.1: Two adjacent intervals in a geometric grid
3.1
Geometric grid
A geometric grid is made of grid elements whose size is defined by a geometric progression.
For a pellet, the smallest grid element is near the external boundary (r = 1) while the
largest one is near the center (r = 0). The length of any two adjacent intervals has a
predefined ratio m such that the length of an interval is m times the length of its adjacent
outer interval. Two adjacent grid elements are shown in Figure 3.1. The geometric factor
m that gives the most efficient and accurate solution depends on several factors including
the number of grid points used and the adsorption isotherm. The optimal value of m to be
used in a simulation can not be derived but rather has to be determined for each problem
by numerical experimentation. However, using a geometric grid does improve the efficiency
of the simulation by reducing the number of equations required to be solved in order to
obtain the same degree of accuracy as that obtained with a linear grid.
The difference approximations for the first and second derivatives at rj are obtained
from the Taylor series expansions of cj1 and cj+1 about cj :
c"j
c""j =
q 2 cj1 (p2 q 2 )cj + p2 cj+1

p2 q + pq 2
2qcj1 2(p + q)cj + 2pcj+1
p2 q + pq 2
(3.2)
38
where p = mn+1 r and q = mn r (see Figure 3.1) and n = 0 for the outermost interval.
The base interval r is defined as:
1
1 m(np1)
=
r
1m
(3.3)
where np is the number of grid points in the pellet. Substituting the above expressions in
eq. (3.1), the following discretized pellet equation is obtained:
4 7
6
8
7
8
7
p8
2q 1 qr cj1 2(p + q) 1 + pq
c
+
2p
1
+
c
cj
j
j+1
r
r
= (cj )kp
t
p2 q + pq 2
3.1.1
(3.4)
Equation at r=0
The zero-slope boundary condition at the center of the pellet leads to an indeterminate form
for the last term on the r.h.s. of eq. (3.1). This term can be converted to a determinate
form using the LHospital rule as follows:
5
2 c
2 c 55
lim
= 2 25
r0 r r
r r=0
(3.5)
Substituting this expression into eq. (3.1), the following equation is obtained at the center
of the pellet:
' 2 (
c
c
= (c )kp 3 2
(3.6)
This equation can be discretized using eq. (3.2) to get the spatial derivative as:
cj0 1 =
c""j0
(p2 q 2 )cj0 + p2 cj0 +1

q2
6
(cj0 + cj0 +1 )
q2
(3.7)
where j0 denotes the grid point at the center of the pellet. Substituting in eq. (3.6)
%
&
cj0
6
= (cj0 )kp 2 (cj0 + cj0 +1 )
t
q
(3.8)
39
3.1.2
Equation at r=1
The derivative boundary condition at the surface of the pellet is discretized using an imaginary point on the geometric grid outside the pellet. Using eq. (3.2):
cJ+1 =
c""J
'
(
Bi(p2 q + pq 2 )
q 2 Bi(p2 q + pq 2 )
q2
c
+
1
c
+
cJ1
J
p2
p2
p2
p2
'
(
2
2
2Bi
2Bi
c
+
cJ +
c
J1
p2
p2
p
p
(3.9)
where J denotes the grid point at the surface of the pellet. Substituting in eq. (3.1):
%
'
(
'
( &
cJ
2
2
2Bi
1
= (cJ )kp 2 cJ1
+
+ 2Bi cJ + 2Bi 1 +
c
t
p
p2
p
p
(3.10)
where c is the bulk concentration near the surface of the pellet.
3.2
Simulation procedure
The discretized pellet equations do not use biased intervals, hence there is no mass matrix
involved. The spatial discretization is expressed in the form of a tridiagonal matrix. However, the adsorption term (c ) may be non-linear and thus needs to be evaluated at each
time step. A stiff ODE solver is used to integrate the equations in time. The simulation
r [13] using the ode15s ODE solver.
was done in MATLAB)
Initially the pellet is empty, hence the initial condition is:
c(r, 0) = 0;
t=0
(3.11)
The non-dimensional bulk concentration near the surface of the pellet is set to 1. This
leads to a very steep slope of the concentration profile near the boundary. Theoretically, a
very large number of grid points would be needed to capture the slope. A geometric grid
puts more grid points near the boundary and as a result, the accuracy of the solution is
improved. A criterion is needed to decide the number of grid points and the geometric
ratio that is needed to get a reasonably accurate solution. The criterion used here is either
40
the total amount contained in the pores of the pellet or the concentration on the surface
of the pellet. These quantities are plotted against time. The profile obtained with a large
number of equally spaced points is used as the benchmark to compare solutions from other
discretizations against.
The optimal value of the geometric factor m for a range of grid sizes was calculated
by minimizing the error from the benchmark solution. The results depend on the kind of
isotherm used and are given in the next section. The error based on the amount in the
pores is defined as follows:
Enp (pores) =
9time
t=0
|(qp )bench (qp )np |

Nt
(3.12)
where
time = total simulation time
np = number of grid points
Nt = number of samples in time
qp = amount in pores
The error based on the surface concentration is defined as follows:
Enp (surf ) =
9time
t=0
|(Cs )bench (Cs )np |

Nt
(3.13)
The number of samples used to calculate the error was based on the time steps resulting
from the integration of the benchmark solution, for consistency across all grid sizes. Linear
interpolation was used to calculate the values of the error at points for which the actual
solution for a given grid size was not available.
3.3
Results and discussion
The simulation was performed with a linear isotherm and a non linear isotherm. The optimum values of the geometric parameter m and the corresponding error have been reported.
41
The solution profile inside the pellet and the amount contained in the pores and the surface
concentration versus time is also shown. The results demonstrate that the improvement in
accuracy obtained by using a geometric grid depends heavily on the form of the isotherm.
3.3.1
Linear isotherm
Linear isotherms are particularly relevant to room air cleaners. Air cleaners operate at very
low concentrations and the adsorption isotherms are typically linear at low concentrations.
The following results have been obtained with a linear isotherm, (c) = 1. The resulting
ODEs are also linear. The solution is then controlled by diffusion. The solution profiles
obtained using the optimal geometric factor for a grid size of 10 nodes are shown in Figure
3.2. The surface concentration rises very rapidly at short times and then rises slowly to the
bulk concentration. The slope of the concentration profile inside the pellet is very steep at
short times but it becomes flatter as time increases.
The optimal geometric factors for a linear isotherm are shown in Figure 3.3. Both the
criteria, surface concentration and amount in the pores lead to the same optimal geometric
factor. The optimal factor m 1 as n as expected. It can be seen in Figure 3.4
and Figure 3.5 that there is more than an order of magnitude improvement in accuracy if a
geometric grid with the optimal geometric factor is used, as compared to a linear grid with
the same number of grid points. The results given in these figures have been fitted with
smooth curves to show the trend.
42
npoints=10
geom ratio =1.4
time=0.0005
npoints=10
0.8
0.8
0.6
0.6
0.4
0.4
0.2
0.2
0.9
0.91
0.92
0.93
0.94
0.95
r
0.96
0.97
0.98
0.99
(a) profile at very short time, t<=5e-4, time

interval dt=5e-5
npoints=10
geom ratio =1.4
0.2
0.3
time=0.4
0.4
npoints=10
4.5
0.9
0.5
r
0.6
0.7
0.8
0.9
geom ratio =1.4
time=0.4
amount in pores (non dimensional)
3.5
0.7
0.6
0.5
0.4
0.3
2.5
1.5
0.2
0.5
0.1
0.1
(b) profiles at longer time t<=0.4, time interval

dt=0.04
0.8
surface concentration (non dimensional)
time=0.4
geom ratio =1.4
0.05
0.1
0.15
0.2
0.25
time (non dimensioanal)
0.3
(c) surface concentration vs time
0.35
0.4
0.05
0.1
0.15
0.2
0.25
time (non dimensional)
0.3
0.35
(d) amount contained in pores vs time
Figure 3.2: Simulation of the pellet equation with (c) = 1
0.4
43

1.45
1.40
geometric factor (m)
1.35
1.30
based on amount in
pellets
1.25
based on surface
concentration
1.20
Poly. (based on
amount in pellets)
1.15
Poly. (based on
surface
concentration)
1.10
1.05
1.00
0
10
15
20
25
30
35
Number of grid points (n)
Figure 3.3: Geometric factors for a linear isotherm based on amount contained in the pores
and surface concentration
Average absolute error
1.0E-01
1.0E-02
using optimal
geometric grid
using a linear grid
Power (using
optimal geometric
grid )
Power (using a
linear grid)
1.0E-03
1.0E-04
0
10
15
20
25
30
35
Figure 3.4: Average absolute error for a linear isotherm based on amount contained in the
pores, with a linear grid and a geometric grid
44
1.0E-01
1.0E-02
using optimal
geometric grid
using a linear grid
Expon. (using a
linear grid)
1.0E-03
Power (using
optimal geometric
grid)
1.0E-04
0
10
15
20
25
30
35
Figure 3.5: Average absolute error for a linear isotherm based on surface concentration of
pellet, with a linear grid and a geometric grid
3.3.2
Non Linear isotherm
The non linear isotherm used has been taken from research done by Gomez-Salazar[8] on
the adsorption of Cadmium on a novel organo-ceramic adsorbent. The isotherm is given in
non-dimensional form by:
q = :
Ac
Bc + h2 + h
The slope of this isotherm is given by:

q
= <
c
A
Bc + h2 + h
=2 <
;2
ABc
=3
Bc + h2 + h
Bc + h2
(3.14)
(3.15)
and
(c ) = <
#p + 1 q
c
(3.16)
where A, B and h are derived from experiments. The values given by Gomez-Salazar
et. al.[7] were used in the above equation. The slope of this isotherm is very large at
45
very low concentrations and falls very rapidly to small values at higher concentrations.
As a result, the resulting equations are highly non-linear. The solution profiles have the
shape of a concentration front moving radially inwards into the pellet. The concentration
profile remains steep as the pellet fills up. The simulation results are shown in Figure
3.6. The profiles shown have been made using a grid of 101 points. The geometric factor
used is m = 1.01. Although m is very close to 1, it results in more even distribution of
irregularities in the solution profile as compared to m = 1. As the number of points is
reduced, the reduction in accuracy can be seen in the form of irregularities in the solution
profile as shown in Figure 3.6(d). These irregularities are a result of the non-linearity of the
isotherm.
The optimal geometric parameters are shown in Figure 3.7. The average error is shown
in Figure 3.8 and Figure 3.9. It can be seen that the geometric grid does not help much
with this isotherm, which is a result of a front moving through the bed. As a result, using a
finer grid near the surface and a coarse grid near the center will not improve the accuracy of
solution for the entire simulation period. However, the moving front is observed to become
less steep towards the center, hence a geometric grid with a small geometric factor will
provide some improvement in accuracy. These irregularities shown in Figure 3.6(d) are
small at short times, when the concentration profile in the pellet is close to the surface and
larger at longer times, when the front in the concentration profile has moved towards the
center. This is a result of using a geometric grid with a larger than optimal geometric factor.
The number of grid points close to the surface as compared to those close to the center is
more than that required to obtain a uniform accuracy throughout the solution. If a smaller
than optimal geometric factor was used, the irregularities would be larger at short times
and smaller at longer times. Hence, a geometric grid with the optimal geometric factor can
be used to obtain more uniform accuracy as compared to a linear grid for this particular
isotherm.
46
npoints=101
geom ratio =1.01
time=165
npoints=101
geom ratio =1.01
time=165
1
0.9
0.8
0.8
0.7
0.6
cs
0.6
0.4
0.5
0.4
0.3
0.2
0.2
0.1
0.1
0.2
0.3
0.4
0.5
r
0.6
0.7
0.8
0.9
40
60
80
100
120
140
160
180
(a) Solution profile in pellet, dt=15
npoints=101
20
geom ratio =1.01
(b) Surface concentration of pellet
time=165
npoints=21
3.5
3.5
2.5
2.5
geom ratio =1.1
time=165
4.5
4.5
1.5
1.5
0.5
0.5
20
40
60
80
t
100
120
140
160
(c) Amount contained in the pores of the pellet
20
40
60
80
t
100
120
140
160
(d) Amount contained in pores with 21 grid

points, m=1.1
Figure 3.6: Solution profiles for non linear isotherm. Number of grid points = 101 and
geometric ratio = 1.01 for (a), (b) and (c). Total simulation time=165 (non-dimensional)
47
1.35
1.30
geometric factor (m)
1.25
based on amount in
pellets
1.20
based on surface
concentration
1.15
Power (based on
surface
concentration)
Power (based on
amount in pellets)
1.10
1.05
1.00
0
10
15
20
25
30
35
Figure 3.7: Geometric factors for a non linear isotherm based on amount contained in the
pores and surface concentration
1.0E-01
using optimal
geometric grid
using a linear
grid
Power (using
optimal
geometric grid)
Power (using a
linear grid)
1.0E-02
0
10
15
20
25
30
35
Figure 3.8: Average absolute error for a non linear isotherm based on amount contained in
the pores, with a linear grid and a geometric grid
48
1.0E-02
using optimal
geometric grid
1.0E-03
using a linear grid

Power (using
optimal geometric
grid)
Power (using a
linear grid)
1.0E-04
0
10
15
20
25
30
35
Figure 3.9: Average absolute error for a non linear isotherm based on surface concentration
of pellet, with a linear grid and a geometric grid
Chapter 4
Simulation of fixed beds

The mathematical model of a fixed bed contains an advective equation with a source term
to describe the bulk flow in the bed, and a diffusion equation to describe the flow inside the
pellets. There is a single equation for the bed and one equation for each averaged pellet
in each interval in the bed. This results in a nested system of ODEs after discretization.
All of them have to solved simultaneously because each pellet equation is linked to the bed
equation at the corresponding grid point via the boundary condition at the surface of the
pellet. It is clear from the analysis in Chapter 2 that using biased intervals for solving the
advective equation would result in a more efficient solution. The diffusion equation, being
parabolic is already second order accurate and does not benefit from biasing. Therefore,
biased intervals are used for discretizing the bed equation and a geometric grid is used for
the pellet equations.
The equations used for simulating a fixed bed were given in Chapter 1 (eq. 1.1 - 1.2).
These equations can be written in non-dimensional form as:
cb
cb
(cb c |r =1 )
z
0 z 0 0
cb =
1 z = 0 > 0
49
(4.1)
50
CHAPTER 4. SIMULATION OF FIXED BEDS

and
c
= (c )kp
'
2 c
2 c
+
r2 r r
(4.2)
c = 0 for 0; 0 r 1
5
c 55
=0
r 5r =0
5
c 55
= Bi(cb c |r =1 )
r 5
r =1
where
=
q
Ds
1+ D
1 c
e
=
(c ) = <
#p + 1 q
c
<
(4.3)
The non dimensional parameters used in the above equations are defined as:
cb = cb /cb in
c = c/cb in
z = z/L
r = r/R
= time scale used for non dimensionalization
= t/
=
=
Bi =
kp =
1 =
us
#L
3kf b
#Rp
Rkf
De
De
R2
p qref
cb in
The non dimensionalization has been done such that different time scales can be chosen
without changing the form of the equations. The simulation can be done either at the time
51
scale of the fixed bed ( = b = #L/us ) or at the time scale of the pellets ( = p = R2 /De ).
The above equations are based on the assumption of spherical pellets packed in a fixed
bed. Variations in the direction perpendicular to the direction of flow have been neglected
and so the discretization has been done in the axial direction. The flow is assumed to be
plug flow, hence the advective equation is used for the bed. The pellets in each discretized
element of the bed are represented by a single average pellet (see Figure 1.1). The source
term in the advective equation is the term accounting for mass transfer to the surface of
the average pellet. This term represents bulk mass transfer to the pellets.
The pellet pores are modeled as straight cylinders through the pellet. The slope of
the solution must be zero at the center of the pellet from symmetry. Mass transfer from
the surface of the pellet inside the pores takes place primarily through diffusion and then
adsorption takes place on the pore surface. Both pore diffusion and surface diffusion have
been accounted for in the equation by the term (c). The importance of surface diffusion
as compared to pore diffusion is given by the term Ds /Dp . This term is usually small for
liquid adsorbates. However, it is not small for gases at low concentrations, and hence it is
included in the pellet equation for the room air cleaner.
The adsorption isotherm is given by q(c). If the isotherm is linear, then q/c is a
constant and hence (c) is a constant. As a result, the pellet equation is reduced to a
linear diffusion equation for a linear isotherm. If the isotherm is non-linear, then (c) is
a function of the concentration and has to be evaluated at each time step. The resulting
pellet equation is non linear for a non-linear isotherm.
4.1
Discretization
The bed equation is essentially a hyperbolic equation with a source term. Therefore, it is
discretized by integrating over biased intervals on a linear grid using the biasing parameter
52
given by eq. (2.21). The discretized equation at the ith grid point can be written as:
%
&
%
&
ci
bci1 + (b a)ci + aci+1
2 ci1
2 ci+1 1
b
+ (2ab + 4)
+a
=
t
t
t
8
(a + b)z
0 2
11
b f (ci1 ) + (2ab + 4)f (ci ) + a2 f (ci+1 )
8
(4.4)
where b = 2 a and f (ci ) = (cb )i (c |r=1 )i .

At the null boundary (z = 1) the bed equation can be written as:
%
&
cI 1
2 cI1
b
+ (ab + 2b)
t
t 8
&
bcI1 + (2 a)cI
=
(a + b)z
0 2
11
b f (cI1 ) + (ab + 2b)f (cI )
8
(4.5)
where I denotes the grid point at the outlet of the bed. The first grid point is at the inlet,
hence its value is always equal to the inlet concentration. Hence the bed equation is not
solved at the first grid point.
The pellet equation for each pellet is discretized over a geometric grid as shown in Section
3.1. The geometric factor m used is the optimal geometric factor for the corresponding
number of grid points given in the previous chapter. The resulting equation for a single
averaged pellet at the j th grid point can be written as:
4 7
6
8
7
8
7
8
2q 1 qr cj1 2(p + q) 1 + pq
cj + 2p 1 + pr cj+1
cj
r
= (cj )kp
t
p2 q + pq 2
(4.6)
At the grid point at the center of the pellet (j0 ), the discretized pellet equation can be
written as:
%
&
cj0
6
= (cj0 )kp 2 (cj0 + cj0 +1 )
t
q
(4.7)
At the grid point on the surface of the pellet (J), the discretized pellet equation can be
written as:
%
'
(
'
( &
cJ
2
2
2Bi
1
= (cJ )kp 2 cJ1
+
+ 2Bi cJ + 2Bi 1 +
c
t
p
p2
p
p
where c is the concentration at the corresponding grid point in the bed.
(4.8)
53
4.2
Simulation procedure
The complete set of ODEs resulting from discretization can be represented in matrix form
as:
Mc
Mr
Ml
Ml
Mc
c
/t
b0
c /t
p11
cp12 /t
c /t
p1n
cb1 /t
cp21 /t
c /t
p22
cp2n /t
c /t
b2
A0
Bp1 Cp1
Ap2 Bp2 Cp2
Apn Bpn
Kp
Kc Bb + Kc
Kr Cb + Kr
Ab
=
Bp1 Cp1
Ap2 Bp2 Cp2
Apn Bpn
Kp
Kl Ab + Kl
Kc Bb + Kc
cb0
cp11
cp12
cp1n
cb1
cp21
cp22
cp2n
cb2
(4.9)
54
The mass matrix is implemented using the Thomas algorithm[4], which makes it more
efficient than solving the complete matrix problem at each time step. The ODEs were
r [13]. The resulting matrices are quite
solved using the ode15s ODE solver in MATLAB)
large for a complete fixed bed simulation. As a result they were coded in sparse form in order
to conserve memory. The Jacobian matrix was calculated by the ODE solver numerically
during the simulation. The time scale of the pellets was used for non-dimensionalization in
all the simulation results presented here.
4.3
4.3.1
Cadmium adsorption
Background
The simulation of adsorption of cadmium on organo-ceramic adsorbents with a thiol functionality by Gomez-Salazar[8] was used to test the efficiency of the numerical scheme developed in this study as compared to the scheme used in the referenced work. The equations
used for the simulation are the same as those used by Gomez-Salazar. The isotherm used
in this problem (eq. 3.14) is highly non-linear. As a result, the improvement in accuracy
achieved in the solution of the pellet equations is very little. A geometric grid leads to
uniform accuracy in the solution as discussed in Section 3.3.2. The bed equation used is the
same as that discussed in the present study. A linear grid with biased intervals as discussed
in Chapter 2 is used for the simulation of the bed equation. Hence the most significant
improvement in the efficiency of the complete simulation is expected to be a result of using
biased intervals.
The simulation was performed based on experimental data provided by Gomez-Salazar[8].
The experimental setup consists of a cylindrical fixed bed packed with spherical pellets of
the organo-ceramic adsorbents. An aqueous solution containing Cadmium is made to flow
through the bed at a given flow rate for a given time and the concentration of Cadmium in
the solution at the exit of the bed is measured at regular time intervals. The data collected
in this manner is used to make the breakthrough curve for the bed. The breakthrough curve
obtained from the simulation was compared to the experimentally obtained breakthrough
curve. A numerical simulation of the bed was performed by Gomez-Salazar[8] in order to
55
determine the equilibrium constant in the adsorption isotherm. In the present study, the
same simulation was done using the numerical scheme developed in Chapter 2 and 3. The
breakthrough curve obtained was qualitatively similar to that obtained by Gomez-Salazar.
Due to some uncertainty in the parameters used to do the simulation, an exact match was
not obtained. The parameters used are listed in Table 4.1. The non-dimensional parameters
used in the isotherm are defined as:
A =
%>
8Keq ST cb in +
h2
B = 8Keq ST cb in
Parameter description
+h
&2
(4.10)
Symbol
Value
Units
Weight of adsorbent
4.0
Diameter of bed
dcol
1.0
cm
1.1
cm3 /min
cb in
1.66
mM
Bed density
0.58
g/cm3
Bed void fraction
0.28
Pellet density
0.81
g/cm3
Pellet porosity
#p
0.49
Pellet radius
90
Bulk mass transfer coefficient
kf
0.1093
cm/min
pH of solution
pH
5.2
Adsorption equilibrium constant
Keq
3.32 103
g/l
Pore diffusion coefficient
Dp
1.4 107
cm2 /s
Saturation capacity of adsorbent
ST
2.93
mmol/g
Temperature
25
Flow rate
Inlet concentration
Table 4.1: Experimental conditions and parameters employed in the simulation of Cadmium
adsorption (taken from [7] and [8])
4.3.2
56
Results
The breakthrough curves obtained from the simulation are shown in in Figures 4.1, 4.2 and
4.3. The curve obtained with optimally biased intervals and a large number of grid points
in the bed (nb = 51) is shown as a dash-dot line and serves as the benchmark. This curve
is compared with the results obtained with a grid having a smaller number of grid points
(nb = 21) upwind differencing (Figure 4.1), central differencing (Figure 4.2) and biasing
only in the spatial part (Figure 4.3). The curve obtained with 21 grid points using optimal
biasing is also superimposed on each figure for comparison. The grid used for discretizing
the pellet equations is the same in each case (np = 21, m = 1.134).
In each case, it can be seen that the shape of the curve is maintained most accurately
by using optimally biased intervals when the number of grid points is reduced from 51
to 21. All the curves generated using the coarser grid have irregularities, which are a
result of the isotherm used, and hence they are common in all the curves. The results
obtained using upwind differencing show greater dissipation error in the curve (spreading)
as compared to the results with optimally biased intervals. The results obtained from
central differencing show oscillations at the top (dispersion error), which is characteristic of
the central differencing scheme, and some spreading at the bottom.
A curve was also generated using upwind biasing only for the spatial part as shown in
eq. (2.4). The value of the biasing parameter that gave the least error in the solution of eq.
(2.1) was used. The resulting curve has less spreading than upwind differencing and fewer
oscillations than central differencing. However, the shape of the curve is not preserved
as well as it is by the scheme with optimally biased intervals for the complete equation
because of greater dissipation error. The concentration profiles in the bed resulting from
the central differencing scheme and the upwind biased scheme also show more dispersion
error than those obtained by using optimally biased intervals. It should also be noted that
the curve obtained using optimally biased intervals is slightly shifted in time. Hence, the
biased intervals scheme may be used to get better shape preservation and less dispersion at
the expense of a small shift in time.
57

Breakthrough curve with upwind differencing comparison
outlet concentration (nondimensional)
0.8
0.6
biased intervals; nb=51

upwind differencing; nb=21
0.4
0.2
0
30
35
40
45
50
55
time (hours)
60
65
70
75
Figure 4.1: Breakthrough curve obtained using simple upwind differencing compared with
the benchmark and optimal biasing curves
Breakthrough curve with central differencing comparison
0.8
0.6

upwind differencing; nb=21
0.4
0.2
0
30
35
40
45
50
55
time (hours)
60
65
70
75
Figure 4.2: Breakthrough curve obtained using central differencing compared with the
benchmark and optimal biasing curves
58

Breakthrough curve with only spatial biasing comparison
0.8
0.6
0.4
0.2

partial upwind differencing; nb=21; aRHS=0.85
30
35
40
45
50
55
60
65
70
75
time (hours)
Figure 4.3: Breakthrough curve obtained using partial upwind biasing in the spatial part
compared with the benchmark and optimal biasing curves
4.4
4.4.1
Room air cleaner

Background
The numerical scheme developed in this work was used to simulate the adsorption of a VOC
on activated carbon in a room air cleaner at very low concentrations. The simulation was
used to determine if a linear adsorption isotherm was an appropriate model and if yes, then
the optimal value of the adsorption equilibrium coefficient Kad was found using numerical
experimentation. The experimental setup[23] consists of a closed room of known volume
with the room air cleaner inside it. A known amount of toluene is introduced into the room
and it is allowed to mix uniformly in the room air. A fan is used to ensure proper mixing in
the room. Once the concentration in the room becomes uniform, the air cleaner is switched
on. The room air is sampled at regular intervals and the concentration of toluene in it is
measured. The concentration in the room drops as time increases and the recorded data is
used to predict the values of the adsorption parameters.
59
Figure 4.4: Model of the room air cleaner used for the adsorption of toluene on activated
carbon. For the numerical simulation, the bed is modeled as a thick, short bed as shown
on the right side, obtained by unfolding the cylindrical bed.
TM
The room air cleaner used for collecting the data was an Austin healthmate
[1]. The
air-cleaner consists of a fixed bed in the shape of a hollow cylinder filled with activated
carbon pellets in its walls (Figure 4.4). A fan is used to draw air from outside the wall
of the cylinder through the carbon pellets towards the center of the hollow cylinder and
blow it out along the cylinder axis. As a result of this setup, the fixed bed has a large cross
sectional area and a comparatively small length along the direction of flow. The variation in
cross-sectional area is considered negligible along the length of the bed and the area midway
through the bed is used as the cross-sectional area. Hence the model consists of a linear
packed bed with a rectangular cross-section as shown in Figure 4.4 .
A linear isotherm was used for modeling the adsorption of toluene on activated carbon.
The linear approximation is expected to be sufficiently accurate at very low concentrations because the interaction between adsorbing molecules is expected to be minimal. The
60
adsorption isotherm can be represented as:

q qref p = Kad cb0 c
(4.11)
where qref is the adsorbed amount based on the starting concentration (cb0 ) and Kad is the
adsorption equilibrium coefficient. The term (c ) is then written as (eq. 4.3) where
1 =
qref p
cb0
(4.12)
The isotherm is linear, therefore q /c = 1 for all values of c .

The values of the experimental conditions and parameters used in the simulation are
shown in Table 4.2. The physical parameters of the system like dimensions and flow rates
were measured directly. The pore volume of the activated carbon pellets was determined
experimentally using B.E.T. equipment[20] and was used to calculate the pellet porosity.
Other physical properties of the bed were estimated from existing literature[14]. The simulation was used to calculate the values of Kad and kf by predicting the concentration in
the room as a function of time and fitting it to the experimental data. The value of kf
was also calculated using correlations[15] but the value obtained could not be used to fit
the experimental data, hence kf was estimated by numerical experimentation. The pore
diffusion coefficient was calculated using correlations[2]. The surface diffusion coefficient
was also calculated using correlations[18] but the resulting value could not be used to fit
the experimental data. It was also determined by fitting the simulation to the experimental
results, but a good fit was obtained only if Ds was negligible compared to Dp . Hence surface
diffusion was not used for the simulation.
4.4.2
Results
The values of Kad and kf calculated using simulation are given in Table 4.2. The curves
produced using these values are shown in Figure 4.5. The simulation was performed for
two different flow rates, which was the only experimental data available. The parameters
evaluated were able to fit both the data sets. The fitted curves are shown in Figure 4.5(c)
61
Parameter description
Symbol
Value
Units
Length of bed
2.38
cm
Area of cross section
Ac
1.96 103
cm2
Flow rate
7.55 104
cm3 /s
cb in
16.8
mg/m3
Volume of room
Vr
58.94
m3
Bed density
0.35
g/cm3
Bed void fraction
0.28
Pellet density
0.866
g/cm3
Pellet porosity
#p
0.588
Pellet radius
0.155
cm
Pore tortuosity
Bulk mass transfer coefficient
kf
0.38
cm/s
Adsorption equilibrium constant
Kad
1.3 106
Pore diffusion coefficient
Dp
1.8 103
cm2 /s
Surface diffusion coefficient
Ds
0.0
cm2 /s
Temperature
25
Initial concentration
Table 4.2: Experimental conditions and parameters employed in the simulation of adsorption
of Toluene on activated carbon
and (d) for the high flow rate and the low flow rate data respectively.
Figure 4.5(a) shows the concentration profiles in the bed at times comparable to the time
scale of the bed, b = 1.54105 hrs. The time scale of the bed is very short compared to the
time scale of the pellet, p = 1.53 102 hrs. As a result, the adsorbate moves through the
bed faster than it can diffuse into the pellets. It can be seen that a concentration front exists
in the bed only for times comparable to b . After the initial concentration front has passed
out of the bed, there is no front moving in the bed. The concentration gradient is small
throughout. The concentration in the bed decreases with time as shown in Figure 4.5(b) as
more material diffuses into the pellets and is adsorbed. Simultaneously, the concentration
62
in the room also decreases. Figure 4.6 shows the concentration profiles inside a pellet in the
bed at times <= 5 hrs. It can be seen that very little material has diffused into the pellet.
The above observations suggest that the accuracy of the solution inside the pellets will
dominate the overall accuracy of the simulation. This was indeed found to be the case. The
concentration profile in the bed is very flat for most of the simulation, and so, a coarse grid
can be used to solve the bed equation without significant loss of accuracy. Using a simple
upwind differencing scheme would also not affect the accuracy significantly. It would only
affect the solution during the time when a concentration front moves through the bed, which
lasts for a very short time. The effect of using a geometric grid on the overall simulation
was analyzed. Figure 4.7 shows a comparison of curves generated using a geometric grid
and a linear grid with 10 grid points in each. A geometric grid with 30 grid points is used
as the benchmark. The optimal geometric factor (Figure 3.3) was used in all geometric
grids. It can be seen in Figure 4.7 that there is no noticeable difference in the solution
obtained with a geometric grid with 10 grid points and the benchmark solution. However,
the solution obtained using a linear grid is clearly different from the benchmark solution.
This observation demonstrates that for a linear isotherm, a geometric grid can be used to
get better accuracy than a linear grid with the same number of grid points. As a result,
fewer grid points are needed to get a desired accuracy, resulting in a more efficient solution.
4.5
Conclusion
The numerical scheme developed in Chapter 2 and Chapter 3 was used to solve two different problems to demonstrate the improvements in efficiency achieved over conventional
methods. The drawbacks of using the schemes developed here in certain conditions were
also pointed out.
The Cadmium adsorption problem is used to demonstrate how optimally biased intervals
can be used to achieve the same level of accuracy as an upwind or central differencing scheme
with a significantly smaller number of grid points. The shape of the curve was preserved
better by the biased intervals scheme. However, a small shift in time was noticed in the
resulting breakthrough curve. The shift in time can also be seen in Figure 2.2 in Chapter 2.
63
dx=0.05; time=1.6e5 hrs; aLHS=0.423; aRHS=0.423
dx=0.05; time=5 hrs; aLHS=0.423; aRHS=0.423

1
concentration (nondimensional)
0.8
0.6
0.4
0.2
0.8
0.6
0.4
0.2
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.1
0.2
z (nondimensional)
0.4
0.5
0.6
0.7
0.8
0.9
z (nondimensional)
(a) Concentration profiles in the bed at short

times, t<=1.6e-5 hrs, dt=1.6e-6 hrs
(b) Concentration profiles in bed at longer

times, t<=5 hrs, dt=0.5 hrs
20
Concentration (mg/m^3)
20
Concentration (mg/m^3)
0.3
10
10
0
0
Time (hr)
(c) Concentration in the room at higher flow

rate: comparison with experimental results
Time (hr)
(d) Concentration in the room at lower flow

rate: comparison with experimental results
Figure 4.5: Simulation results for Toluene adsorption on activated carbon in a room air
cleaner, at flow rate Q = 7.44 104 cm3 /s for (a), (b), and (c) and Q = 2.36 104 cm3 /s
for (d) using nb = 21 (no. of grid points in the bed), np = 10 (no. of grid points in pellets)
and m = 1.4 (geometric factor)
64
0.1
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
0.95
0.955
0.96
0.965
0.97 0.975 0.98

r (nondimensional)
0.985
0.99
0.995
Figure 4.6: Concentration profiles in the first pellet in the bed at high flow rates for time
<= 5 hrs, dt=0.5 hrs, np = 10, m = 1.4
20
geometric, n=30, m=1.037
geometric, n=10, m=1.4
linear grid, n=10, m=1.0
18
16
concentration (mg/m3)
14
12
10
8
6
4
2
0
0
0.5
1.5
2.5
3
time (hours)
3.5
4.5
Figure 4.7: Comparison of concentration in room using geometric and linear grids, nb = 21,
time<=5 hrs
65
This can be considered a trade-off in return for less spreading and a smaller dispersion error
in the solution. This problem is also used to show that a geometric grid may not be suitable
for solving the pellet equation if the adsorption isotherms leads to a sharp concentration
front moving through the pellet.
The toluene adsorption problem is used to demonstrate the improvement in efficiency
that can be achieved by using a geometric grid for solving the pellet equation with a linear
isotherm. The number of grid points required with a geometric grid is much smaller than
the number required with a linear grid for achieving the same level of accuracy. As a result,
significant gains can be had in the speed of the solution. A faster numerical scheme would
be useful for predicting the lifetime of room-air cleaners, as the time scales involved are very
large (years). This problem is also used to show how using biased intervals for solving the
bed equation may not result in improvements in efficiency if the solution profile is relatively
flat.
In both the cases, the numerical schemes developed in this study were used to simulate
a fixed bed in a more efficient manner than conventional methods.
Bibliography
[1] Austin Air. The healthmate, http://www.austinair.com/hm.htm.
[2] Hans-Jorg Bart, Rolf Germerdonk, and Ping Ning. Numerical simulation of toluene adsorption on activated carbon in a technical column in low concentration range. Chemical
Engineering Technology, 19:347356, 1996.
[3] M. B. Carver and H. W. Hinds. The method of lines and the advective equation.
Simulation, 31(59):5969, 1978.
[4] Steven C. Chapra and Raymond Canale. Numerical Methods for Engineers. McGrawHill, 4th edition, 2001.
[5] Carlos Costa and Alirio Rodrigues. Numerical methods for the solution of adsorption models.
NATO ASI Series, Series E: Applied Sciences, 158(Adsorpt.: Sci.
Technol.):257265, 1989.
[6] Thor Gjesdal and Rune Teigland. Accuracy and stability of semi-implicit finite difference advection schemes. Commun. Numer. Meth. Engng, 14:647655, 1998.
[7] S. Gomez-Salazar, J. S. Lee, J. C. Heydweiller, and L. L. Tavlarides. Analysis of
cadmium adsorption on novel organo-ceramic adsorbents with a thiol functionality.
AIChE Journal, 2002.
[8] Sergio Gomez-Salazar. Modeling of Cadmium Adsorption on Organo-Ceramic Adsorbents Containing the Thiol group. PhD thesis, Syracuse University, 2002.
66
BIBLIOGRAPHY
67
[9] Sergio Gomez-Salazar, J. C. Heydweiller, and L. L. Tavlarides. Solution of adsorption

problems with steep concentration gradients and nonlinear isotherms. Computers and
Chemical Engg, (28):19131917, 2004.
[10] J. C. Heydweiller and H. S. Patel. An improved biased difference scheme for the
solution of hyperbolic equations by the method of lines. Computers and Chemical
Engg, 6(2):101110, 1982.
[11] Jean-Marc Le Lann, Alain Sargousse, Pierre Sere Peyrigain, and Xavier Joulia. Dynamic simulation of partial differential agebraic systems: Application to some chemical
engineering problems. 3rd ICL joint Conference - Toulouse - 16-18 July, 1998.
[12] Jose M. Loureiro and Alirio E. Rodrigues. Two solution methods for hyperbolic systems
of partial differential equations in chemical engineering. Chemical Engineering Science,
46(12):32593267, 1991.
[13] The Mathworks. Matlab 6 r13, http://www.mathworks.com/products/matlab/.
[14] Young-Ki Ryu, Hyun-Jeong Lee, Han-Kyu Yoo, and Chang-Ha Lee. Adsorption equilibria of toluene and gasoline vapors on activated carbon. Journal of Chemical Engineering
Data, 47:12221225, 2002.
[15] Jung-Yang San, Yuh-Ching Hsu, and Liang-Jen Wu. Adsorption of toluene on activated
carbon in a packed bed. International Journal of Heat and Mass Transfer, (41):3229
3238, 1998.
[16] W. E. Schiesser. The numerical method of lines: integration of partial differential
equations. Academic Press, 1991.
[17] W. E. Schiesser and S. S. Hu. Hybrid approxmations for first-order hyperbolic equations which model separations. East China Pet. Inst., Dongying, Peop. Rep. China.,
Proceedings of the Summer Computer Simulation Conference, pages 203208, 1981.
[18] J. D. Seader and E. J. Henley. Separation Process Principles. Wiley Text Books, 1998.
BIBLIOGRAPHY
68
[19] L. M. Sun and F. Meunier. An improved finite difference method for fixed-bed multicomponent sorption. AIChE Journal, 37(2):244254, 1991.
[20] Larry L. Tavlarides. Hybrid Adsorbents Laboratory. Syracuse University.
[21] C. Tien. Adsorption Calculations and Modeling. Butterworth-Heinemann, Newton,
MA., 1994.
[22] D. U. von Rosenberg, R. P. Chambers, and G. A. Swan. Numerical solution of surface
controlled fixed-bed adsorption. Ind. Eng. Chem. Fundam., 16(1):153156, 1977.
[23] Jianshun Zhang. Building Energy and Environmental Systems Laboratory. Syracuse
University.
Vita
NAME OF AUTHOR: Manuj Swaroop
PLACE OF BIRTH: Lucknow, India
DATE OF BIRTH: July 5, 1980
GRADUATE AND UNDERGRADUATE SCHOOLS ATTENDED:
Syracuse University, Syracuse, New York, USA
Indian Institute of Technology Kanpur, Kanpur, India
DEGREES AWARDED
Master of Science in Chemical Engineering, 2004, Syracuse University
Bachelor of Technology in Chemical Engineering, 2002, Indian Institute of Technology
Kanpur
PROFESSIONAL EXPERIENCE
Teaching Assistant, Syracuse University, 2003-2004
Summer In-plant training, Reliance Industries Ltd., Patalganga, India, summer 2001

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Abstract

An Efficient Numerical Method for the Simulation of Fixed-bed

Copyright 2004 Manuj Swaroop

Mathematical model for a fixed bed . . . . . . . . . . . . . . . . . . . . . .

Numerical methods for simulation of fixed bed . . . . . . . . . . . . . . . .

2 The fixed-bed equation

Integration over biased intervals . . . . . . . . . . . . . . . . . . . . . . . . .

Temporal truncation error . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Error in trapezoidal integration . . . . . . . . . . . . . . . . . . . . .

Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Non Linear isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . .

4 Simulation of fixed beds

Room air cleaner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Model of a fixed bed. The axial coordinate is denoted by x. The bed is

An upwind-biased interval about a grid point, (c0 < 0) . . . . . . . . . . . .

Advection equation for a smooth function using biased intervals . . . . . . .

Two adjacent intervals in a geometric grid . . . . . . . . . . . . . . . . . . .

Simulation of the pellet equation with (c) = 1 . . . . . . . . . . . . . . . .

Geometric factors for a linear isotherm based on amount contained in the

Average absolute error for a linear isotherm based on amount contained in

Average absolute error for a linear isotherm based on surface concentration

Geometric factors for a non linear isotherm based on amount contained in

Breakthrough curve obtained using central differencing compared with the

Breakthrough curve obtained using simple upwind differencing compared

Simulation results for Toluene adsorption on activated carbon in a room air

Comparison of concentration in room using geometric and linear grids, nb =

Mathematical model for a fixed bed

z = axis along the direction of flow

= bulk mass transfer coefficient

Numerical methods for simulation of fixed bed

Weighted Residuals Methods

The fixed-bed equation

CHAPTER 2. THE FIXED-BED EQUATION

the method of lines will be discussed using the advection equation:

aui+1 + cui bui1

CHAPTER 2. THE FIXED-BED EQUATION

where Dc = C(x)p /P , C = (c0 / |c0 |) and p and P are parameters independent of

CHAPTER 2. THE FIXED-BED EQUATION

Figure 2.1: An upwind-biased interval about a grid point, (c0 < 0)

CHAPTER 2. THE FIXED-BED EQUATION

where xI denotes the rightmost grid point in the bed.

CHAPTER 2. THE FIXED-BED EQUATION

Lc1 Lc2 Lc3

Lc1 Lc2 Lc3

Rc1 Rc2 Rc3

Rc1 Rc2 Rc3

Integration over biased intervals

CHAPTER 2. THE FIXED-BED EQUATION

The complete discretized equation can be written as:

CHAPTER 2. THE FIXED-BED EQUATION

CHAPTER 2. THE FIXED-BED EQUATION

using relations from eq. (2.59).

CHAPTER 2. THE FIXED-BED EQUATION

Temporal truncation error

where the superscript n denotes the current time step.

The r.h.s for an explicit scheme can be written as:

Let t = r(x). This substitution enables us to consolidate the truncation error in

CHAPTER 2. THE FIXED-BED EQUATION

Error in trapezoidal integration

CHAPTER 2. THE FIXED-BED EQUATION

CHAPTER 2. THE FIXED-BED EQUATION

CHAPTER 2. THE FIXED-BED EQUATION