Chemical Engineering and Processing 43 (2004) 9
/22

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Breakthrough analysis for adsorption of sulfur-dioxide over zeolites

Arun Gupta, Vivekanand Gaur, Nishith Verma *
Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 2028016, India

Received 31 July 2002; received in revised form 13 December 2002; accepted 15 December 2002

Abstract

The adsorption experiments were carried out under dynamic conditions for the removal of trace sulfur-dioxide (SO2) in nitrogen
by 5A zeolites. The experiments were conducted to characterize the breakthrough characteristics of SO2 in a fixed bed under
different operating conditions including temperature, pellet size, concentration levels, and gas flowrate. At a reaction temperature of
70 8C, the breakthrough time was found to be maximum. The adsorption isotherm was found to be linear over the gas
concentration range from 1000 to 10 000 ppm. The exothermic heat of adsorption assuming Arrehenius type of temperature
dependence of the equilibrium constant was determined to be 9.8 kc/mol. The mathematical model was developed to predict the
breakthrough profiles of SO2 during adsorption over the biporous zeolites (containing both macro and micro-pores). The model
incorporates all resistances to mass transfer, namely: diffusion in the gas film around pellets in the bed, diffusion in the binder-phase
of zeolites and within the crystals, and adsorption/desorption at the interface of binder-phase and crystals. The model was
successfully validated with the observed experimental breakthrough data. The study showed potential application of 5A zeolites in
controlling SO2 emissions at trace levels.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Zeolites; Breakthrough; Adsorption; SO2; Air pollution

1. Introduction sulphate layers remains the major inherent drawback of

There are two types of solid (ad)sorbents commonly
used in controlling SO2 emissions: one is non-regenera-
tive. The common examples are CaO and MgO obtained
from different sources such as hydroxide, carbonate and
acetates. The other is regenerative, such as zeolites, silica
gel, and charcoal. A number of studies pertaining to the
use of non-regenerative type of sorbents have been
reported in open literature [17
/20]. These range from
the theoretical analysis for understanding the mechan-
ism and kinetics of the sorption process to the develop-
ment of novel materials having relatively higher
reactivity for SO2, to the improvement in the solid
/
gas contact patterns. Despite significant progress made
over the last few years in exploiting the non-regenerative
type of materials, the premature termination of the
sorption process due to pore-blocking by the product
* Corresponding author. Tel.: /91-512-597629; fax: /91-512-
590104.
E-mail address: nishith@iitk.ac.in (N. Verma).
0255-2701/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0255-2701(02)00213-1
these materials. The chemical reaction being irreversible,
the commercial value of the spent solids is also often
marginal. It is in this context that zeolites have been in
the recent forefront of many researchers. The major
advantage of using zeolites is their ability for the
successive regeneration. The reaction temperature is
also relatively lower. Successfully commercialized in
early seventies in the area of bulk gas separation due
to their molecular sieving properties, the application of
zeolites in air pollution control has just begun to emerge.
It may, however, be pointed out that zeolites in the latter
application are used due to their adsorption character-
istics rather than molecular sieving actions.
Reviewing recent works reported in open literature, it
is fair to say that a limited number of studies have been
carried out on the adsorption of SO2 over zeolites.
Among some of the pertinent studies, Kopac [1] has
investigated adsorption properties of SO2 on molecular
sieve 13X under equilibrium conditions in a temperature
range of 523
/673 K and reported a significant adsorp-
tion of SO2 below 523 K. The adsorption equilibrium
constants were experimentally determined over the
10 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22
temperature range based on the linear adsorption
isotherm assuming first order adsorption and desorption
rates. In another study, Kopac et al. [2] carried out a
comparative study on different types of zeolites mole-
cular sieves and concluded that the adsorption of SO2
decreased in the order of AW300
/4A
/5A zeolites.
Among some of the studies concerned with the synthesis
aspect, Lin and Deng [3] have reported development of a
wide variety of zeolites from fly ash, having significant
SO2 adsorption characteristics. On the same line,
Srinivasan and Gruyzeck [4] have developed sodalite, a
chemical adsorbent (CuO
/Al2O3) prepared by sol
/gel
process. Among the studies concerning theoretical
analysis, mainly to establish the mechanism of SO2
adsorption over zeolites, [21] developed a simplified
mathematical model for a single and multi-component
adsorbate system assuming the Langmuir
/Freundlich
isotherm. Two diffusional resistances to mass transfer:
film and macropore were assumed to be in series and
incorporated in an overall mass transfer coefficient
using the linear driving force (LDF) approximation.
The micropore resistance was, however, neglected.
Comparing the model results with the experimental
data on breakthrough curves, the authors concluded
that macropore diffusion is the controlling step in the
overall mass transport of SO2 in hydrophobic zeolites.
In contrast, disagreement between the model predictions
and the adsorption data on H2O on zeolites was
attributed due to micropore (crystalline) diffusion, and
probably surface diffusion of moisture, which were not
included in the model. Kopac and Kocabas [5] have
carried out the breakthrough together with adsorption
equilibrium analysis on the adsorption of SO2 on a
monoporous adsorbent like silica gel. In the equilibrium
study, various types of isotherms were used to explain
the adsorption data. The salient finding of the study was
to demonstrate the suitability of the Freundlich and
DRK isotherms in explaining the data. The deactivation
model as proposed by Suyadal et al. [6] for the
adsorption of hydrocarbon on activated carbon (mono-
porous) was adopted to explain the SO2 adsorption on
silica gel. The removal of SO2 by the activated charcoal
adsorbents has also been studied by Gail and Kast [7].
In their study, the sorption was modeled as a combina-
tion of physical adsorption and oxidation (catalytic
conversion) over porous charcoal. In addition, the
authors successfully simulated the breakthrough profiles
of a fixed bed reactor based on the single-pellet
experimental data. Tsibranska and Assenov [8] have
proposed a mathematical model for adsorption in
biporous particles. The primary objective was to deter-
mine the effects of particle size vis-à-vis bed column
diameter on the breakthrough characteristics. The
model assuming the Langmuir isotherm accounted for
macro and micro-pores diffusion within the particle.
Microparticle size distribution and concentration pro-
files within the microparticle were also taken into
account. The comparison between the experimental
breakthrough curves obtained for the adsorption of
SO2 in natural clinoptilolite and model predictions
showed a good agreement for larger size pellets where
macroparticle diffusion control was assumed to be of
importance. The model predictions for the smaller
pellets were, however, found to be less satisfactory.
In the present study, the dynamic adsorption of SO2
by 5A commercial zeolites has been investigated, both
experimentally and theoretically. The primary objective
is to explore the suitability of zeolites materials in
separating trace SO2 (less than 1%) from nitrogen by
adsorption under a wide range of experimental condi-
tions, including adsorption temperature, SO2 inlet gas
concentration, and particle size, and determine the
optimum conditions for the maximum adsorption
(longer breakthrough time). A mathematical model is
developed mainly to predict breakthrough characteris-
tics of the zeolites materials in a fixed bed and ascertain
the key operating parameters that control the adsorp-
tion process so as to scale-up and design a suitable
adsorber for industrial use. The theoretical analysis in
the model takes into account gas film diffusion, intra-
particle diffusion within the bi-pores of zeolites (macro
and micro) and adsorption/desorption within the pores.
The main objectives of the present study can be
summarized as follows: (a) design, fabrication and set-
up of an experimental test bench to carry out the
adsorption study (b) determining the optimal adsorption
temperature for zeolite (c) determining breakthrough
characteristic of the materials under varying operating
conditions such as particle diameter (0.1
/1.2 mm), flue
gas concentration (1000
/10 000 ppm), amount of the
adsorbents (1
/10 g) and flow rate of the gas (0.1
/1
slpm) (d) development of a mathematical model to
characterize the mechanistic steps involved in the entire
removal process, and (e) model parametric study.
2. Theoretical analysis
Zeolite solids are available in the pellets form. These
pellets are made by compressing zeolite crystals to-
gether, usually with a small percentage of binder to join
the crystals together. This results in a porous structure
having macro and micro-pores. A schematic representa-
tion of such a biporous particle is described in Fig. 1.
The crystals are of the order of 0.1
/1 mm, and the zeolite
pellets are of that of 1 mm. The void between the
microparticle contributes to the micro-pores of the
particle. These pores act as conduit to transport
molecules from the surrounding into the interior of the
particle. Once inside the particle, molecules adsorb at
the pore-mouth of the micropores and thence the
adsorbed species diffuse into the interior of the crystal
 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22
Fig. 1. Schematic diagram of the experimental set up to study SO2 breakthrough over zeolite pellets in a packed bed.
through the micro-pores of the crystal. The diffusion
process in the macro and micro-pores follows the
combination of the molecular and Knudsen mechanisms
while that inside the crystal follows an intra crystalline
diffusion mechanism. It may be pointed out that the
overall mechanistic steps involved in the adsorption over
zeolites and the other regenerative adsorbents such as
charcoal and silica gel are identical. The difference lies in
the internal structures of these adsorbents. While
zeolites have biporous structures, charcoal and silica
gel have monoporous structures. Thus, in the case of the
former, adsorption is usually controlled by intra crystal-
line diffusion, while in the case of the latter the
macropore diffusion prevails.
The mathematical model developed to explain the
breakthrough of SO2 in the packed bed consisting of the
zeolite pellets is based on the following assumptions:
1) Temperature is uniform throughout the bed, pellet
and crystals.
2) The adsorbing species (SO2 in this case) is at trace
levels (B/1%) and N2 is a non-adsorbing (inert) gas.
3) Pressure-drop along the bed length is negligible
under the experimental conditions studied. This
(isobaric condition) was found to be true as
described later in the Section 3. The assumption of
constant pressure in the reactor also derives from
the fact that the concentrations in the present study
were at trace levels (less than 1%).
11
Referring to the study by Scholl and Mersmann
[9], the authors have shown that during physical gas
adsorption in single particle adsorbents, the intra-
particle total pressure may change, which should be
incorporated in modeling of adsorption. However,
the authors have also concluded that such pressure
may be assumed to be constant as long as the
concentration levels are low. On the other hand, this
might not be true in cases where the adsorption
concentrations are high or where the total pressure
varies during operation as in the case of a pressure
swing adsorption (PSA) system.
4) Instantaneous equilibrium exists between the gas-
eous SO2 species in the macro-pores of the binder-
phase and the adsorbed phase within the crystal at
the binder
/crystal interface. Such assumption has
also been made in other independent works for most
cases of the physical gas phase adsorption [10
/12].
5) There is a constant fluid velocity through out the
bed. This assumption follows from those made in
(2
/4), i.e. low concentration level and negligible
pressure-drop in the bed. The insignificant change
in the axial flow velocity in comparison with the
time change (unsteady-state) of the concentration of
the adsorbing species at trace levels in the iso-
baric column (a ‘quasi-static’ assumption) has been
mathematically shown by Yang [13]. For the sake of
brevity the detailed mathematical steps are not
reproduced here.
12 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22
2.1. Mass balance in the packed bed reactor
Since the SO2 concentrations were at ppm levels, the
exothermic heat of adsorption was negligible and
isothermal condition was assumed. The assumption of
isothermality in the case of adsorption/desorption of
species at trace levels, unlike in the case of bulk
separation where concentration levels are typically
higher, has also been justified in an independent work
[14]. Thus, considering an isothermal plug flow system
in a packed bed of spherical pellets, a SO2 balance in the
bed of porosity, eb results in the following equation:
@Cb Vz @Cb Dz @ 2 Cb 1 q concentration of the adsorbate inside the crystal
   a
f (z)
@t eb @z eb @z2 eb
The terms in Eq. (1) are transient, convection, axial
dispersion and diffusion flux, respectively. The last term
represents diffusion of the gas from the bulk into the
macropores of the zeolite pellets and is calculated as
f (z) Km (Cb Cp j RR ):
p
Here, a *,external surface area per unit volume of the
3(1  b )
pellet
/ /gas film mass transfer co-efficient; Cp,
Rp
concentration of the reactant gas in the macropores of
the pellet.
The initial and boundary conditions for Eq. (1) are:
t0; Cb  0
t
0; z0; Cb Cb0
@Cb
z1; 0
@z
Here, the theoretical analysis was carried out assum-
ing that only one species (SO2) adsorbs, as the other
species (N2) is non-adsorbing (inert gas). This resulted in
the development of Eq. (1). However, it can be shown
mathematically that in the case of co-sorption of two
components in the binary mixture, the form of the
equation may still remain the same if the concentration
of the strong adsorptive species (SO2) is at trace levels,
and the pressure-drop in the bed is negligible. The
detailed equations to substantiate the above statement
are described in Appendix F.
2.2. Mass balance at any location R within the macro-
pore volume of the binder-phase
Consider that crystals are uniformly distributed in the
binder-phase, as depicted in Fig. 1 and the adsorption of
SO2 by the binder-phase is negligible in comparison with
that at the crystal outer surfaces (interface between the
binder-phase and crystal) [12]. In such case, incorporat-
ing radial diffusion within the macro-pore volume of the
binder-phase, and adsorption at the pore-mouth of the
crystals, the following equation is obtained:
@Cp 1 @(R2 NR ) @ q̄
a  3(1a) 0 (5)
@t R 2 @R @t
The terms in the Eq. (5) are transient, diffusion flux in
the radial direction of the binder-phase (pellet), and the
rate of adsorption at the pore-mouth (or opening) of the
crystals, respectively.
Here, a , void fraction of the macro-pores;
NR molar diffusion flux in the radial direction of the
pellet
(1) /q̄ average concentration of the adsorbate inside the
crystal
2.3. Adsorption isotherm
In the proposed model, a linear isotherm of the form
q /KCp is assumed which correlates the adsorbate
concentration within the crystal with the gaseous phase
concentration within the macro-pore volume of the
binder at the crystal
/binder-phase interface. Here, K
may be considered as the equilibrium or partition
coefficient between the macro and micro-pores volume.
The isotherm can also be seen as an equilibrium
condition obtained by equating first order adsorption
(2) and desorption rates:
(3)
@q
ka Cp kd q where; at equilibrium
(4) @t
K  ka =kd q=Cp : (6)
2.4. Mass balance at any location r within the micro-pore
of the crystal
Mass balance in the crystal is given by the following
solid diffusion equation:
@q Dc @(r2 @q=@r)
 (7)
@t r2 @r
where Dc is the diffusivity of the adsorbate within the
crystal.
The governing Eqs. (1), (5) and (7) form the basis of
the model developed in this study for predicting the
adsorbents performance, especially breakthrough char-
acteristics in the bed. As these equations are coupled
partial differential equations, independent variables
being time (t ), axial (z ) and radial directions (both in
r and R ), an approach is adopted in the present work to
simplify numerical computations and significantly re-
duce the CPU time. Essentially, in this approach radial
(r and R ) concentration profiles within the solid pores
 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22 13

(both macro and micro) are averaged assuming para- @C p

d(C C
b )0
p (13)
bolic concentration profiles and the average gas phase @t
concentration within the pores of the pellet and the
average adsorbate phase concentration within the crys- where, the dimensionless coefficients are defined as:
tals are determined [13,15]. The salient advantage of this
mathematical approximation is the reduction of second 1 eb Vz l
order PDEs to first order PDE with variation only in z g ; Pe  ;
eb Dz
direction. Moreover, the number of the governing
equations to be solved is also reduced to two. The 15(1  eb )Km Dp l
detailed computational steps are described in Appen-
h   ; and
5D
dices B, C, D, E and F. As a consequence of this eb R2p Vz Km  p (14)
Rp
approximation, the simplified governing equations, one  
for the gas phase in the bed and the other for the Km l 27Dc K(1  a) 15Dp
d   
adsorbate in the pellet are obtained as follows: 5D R2c R2p
Vz Km  p a
@Cb Vz @Cb Rp

@t eb @z
Here, Pe is nothing but the Peclet number, which
Dz @ 2 Cb 15(1  eb )Km Dp (Cb  Cp ) compares convective flux to that by dispersion in the
  (8)
eb @z2 eb R2p (Km  5Dp =Rp ) empty packed bed. h can be construed as the resistance
@Cp (Cb  Cp )Km to the overall mass transfer determined by the gas film
 mass transfer coefficient and macro-pore diffusivity
@t (Km  5Dp =Rp )a within the pellet. An inspection of the coefficient d
 
27Dc K(1  a) 15Dp reveals that it is a product of two terms. The first term
 0 (9)
R2C R2p includes the effects of film mass transfer and diffusion
within the pellet in the similar manner as in h . The
Eqs. (8) and (9) are the governing equations to predict second term includes the effects of adsorption equili-
the breakthrough characteristics of the bi-porous ad- brium and two time-scales of diffusion: one in the
sorbents like zeolites in a fixed packed bed under macropore and the other within crystal volume.
isothermal condition. The required initial and boundary Furthermore, it may also be noted from Eqs. (13) and
conditions for Eq. (8) remain the same as given by Eqs. (14) that for a zeolite pellet to be ‘sink’ for the adsorbing
(2)
/(4). The corresponding conditions for Eq. (9) are as species, the second term must be negative. Thus, for a
follows: zeoilte
/SO2 system, the above term puts a constraint on,
t0; Cp  0 (10) or in other words, defines a upper limit for the value of
equilibrium constant K as:
@Cp
t
0; R 0; 0 (11)
@R 15Dp R2c
KB (15)
The following dimensionless variables were used to R2p 27Dc (1  a)
make the governing equations dimensionless:
For a given zeolite pellet and the adsorbing gas, the
Gas concentration Cb Cp variables on the right hand side of the above inequality
C 
b ; C 
p
Cb0 Cb0 are known. Assuming typical values for these variables,
t 1 Rp /0.5 mm, Rc /2/107 m, Dp /2.0 /106 m2/s,
Time t  ; tresidence  ;
tresidence Vz Dc /1/1014 m2/s, and a /0.3, the upper limit of the
equilibrium constant K is theoretically calculated to be
Distance in axial direction z z 26.
l Eqs. (12) and (13) are the non-dimensionlized forms
R of the governing equations that were numerically solved
Radius of the pellet R
Rp to predict breakthrough times in a packed fixed bed
consisting of the bi-porous zeolite adsorbents. These
Introducing these dimensionless variables in governing equations containing two dependent variables C b and
Eqs. (8) and (9), the following non-dimensionalized Cp as a function of time and axial location were solved
form of the equations are obtained: simultaneously by the finite difference formulation using
the NAG Fortran library. On a Pentium III machine the
@C b @C b 1 @ 2 C b
g  h(C bC p) (12) CPU time of computation was found to be less than a
@t @z Pe @z2 minute.
14 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22
3. Experimental studies
3.1. Experimental set-up
The experimental set-up used in the study may be
assumed to consist of three sections as schematically
described in Fig. 1: (a) gas-mixing section, (b) test
section, and (c) analytical section. In the gas-mixing
section two electronic mass flow controllers (Model
PSFIC-I, Bronkhorst, Netherlands) were used to control
and measure the flowrates of SO2 and N2. A mixture of
the gases of the desired concentration was prepared by
mixing the two individual streams in a gas-mixing
chamber (135 mm long and 25 mm I.D.) made of
stainless steel tube. The N2 stream was purified using
silica gel purifier to remove moisture in the gas. There
was a provision of bypassing the gaseous mixture
directly to the analytical section for calibration as well
as for the measurement of the inlet concentration of the
gaseous mixture entering the reactor (test section).
The test section consisted of a vertical inconel made
reactor (14 mm I.D. /150 mm L) co-axially mounted in
a 200 mm long tubular furnace. The top end of the
reactor was connected to the gas line using 1/4 in. swage
lock fittings and specially mounted unions made of SS.
The temperature of the furnace was controlled using a
proportional temperature controller (Blue Bell, Mum-
bai). The temperature in the reactor was measured using
a chromel
/alumel thermocouple inserted in a S.S
thermo well (O.D. 3mm). The effluent gas stream from
the reactor was passed to the analytical section. A
manometer was also connected to the two ends of the
reactor to measure the pressure-drop across the adsor-
bent bed. The analytical section consisted of a gas
chromatography (GC) connected to a data station. A
computer was connected to the data station to store the
chromatogram and the peak areas. Thermal conductiv-
ity detector (TCD) was used to detect and measure SO2
concentration in the products stream. Activation of the
zeolite particles was carried out in a vacuum oven. The
vacuum was created with the help of a rotary vacuum
pump (Lawrence & Mayo, New Delhi).
3.2. Experimental procedure
The zeolite materials (type 5A) were obtained in the
form of spherical pellets from Merck Co, Germany,
comprising of three size ranges: 1.16, 0.80, and 0.16 mm.
For these particle sizes, the ratios of the inside diameter
of the reactor to the pellet size were calculated to be
12:1, 35:1, and 280:1, respectively. Tien [16] has recom-
mended a minimum ratio of 10:1 to be able to assume
the radial dispersion insignificant in a tubular reactor. In
a typical test run, the required quantity of fresh zeolites
was first activated in the vacuum oven at 100 8C before
feeding into the reactor. The choice of activation
temperature is predominantly dependent upon the
vacuum used to drive off the moisture and the time
for activation or outgassing. With low vacuum, the
required temperature can be substantially decreased.
Thus, more than one combination of the activation
conditions is possible. In the present work, the fresh
samples were activated at 100 8C for 4 h in a vacuum
oven operated at 100 mm Hg. After a series of trial runs,
this combination of activation conditions was found to
be satisfactory for the maximum adsorption of SO2
(longer breakthrough time). Similar temperature ranges
for activation have also been reported elsewhere [2].
Mesh and quartz wools were put at both ends of the
reactor tube so as to prevent any carry over of the
adsorbents. The thermo well for holding thermocouple
was then placed co-axially in the center of the reactor
tube. First, N2 was allowed to pass through the reactor
at a desired flow rate controlled by MFC. The reactor
was then heated to the desired reaction temperature and
further kept at that temperature for 2 h so that the
system was stabilized and a uniform temperature existed
in the bed. The required flow rate of SO2 was adjusted
using MFC. The concentration of the inlet gaseous
mixture was measured by GC prior to the start of the
reaction through the line bypassing the reactor. The
total pre-reaction time included 2 h to pre-heat the bed
to the desired temperature and 2 h to stabilize. The
reaction time typically varied between 2 and 6 h
depending upon the operating conditions including the
flow rates and the amount of the adsorbents used. The
product gas was analyzed by a GC using Porapak Q-
column (6 in. /2 mm I.D.) and TCD (Model 5700,
Nucon). Table 1 lists the various experimental condi-
tions used in this study on the adsorption of SO2 by 5A
zeolites.
In the adsorption experiments, the gas superficial
velocity in the tubular reactor was chosen between 0.04
and 0.1 m/s, corresponding to the volumetric gas
flowrates range from 0.3 to 1.0 slpm. The pressure-
drops across the reactor measured under these condi-
tions were found insignificant, varying between 4 and 10
mm of the heights of liquid CCl4 used as the manometer
fluid. These values corresponded to the pressures
between 60 and 160 Pa only. The maximum pressure-
drop measured in the case of powder zeolites (0.16 mm
diameter, particle Reynolds number /1, i.e. viscous
flowrange) was not more than 6 cm of the liquid (0.937
kPa) at a superficial velocity of 0.1 m/s. This value
compares with 0.69 kPa (/1 atm or /100 kPa) as
predicted by Ergun’s equation. The difference between
the experimental and theoretical values was attributed
due to the pressure-drop across the wool meshes
supporting the zeolites pellets and that across the
reactor fittings. The above pressure-drop measurements
justify the assumption of constant pressure in the bed,
made in the theoretical analysis.
 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22
4. Results and discussion
4.1. Adsorption temperature for zeolites
The tests were carried out on 5A zeolites at various
temperatures. Fig. 2 describes the experimentally ob-
tained breakthrough characteristics of SO2 during
dynamic adsorption by zeolite carried out at six
different reaction temperatures: 35, 50, 60, 80, and
100 8C. The gas flow rate and gas inlet SO2 concentra-
tion were kept constant at 300 cm3/min and 10 000 ppm,
respectively, under each case. The weight of the test
sample was 2.5 gm for the average pellet size of 16 mm.
From Fig. 2, it may be observed that there was
practically no improvement in the breakthrough time
with an increase in the temperature from 35 to 50 8C. In
each case the breakthrough occurred in less than 15 min.
The total adsorption time (time for the exit gas
concentration to approximately reach the inlet concen-
tration, 10 000 ppm) was approximately 30 min. How-
ever, the breakthrough and adsorption times were found
to considerably increase to 25 and 50 min, respectively,
at the bed temperature of 60 8C. Further increase in the
temperature to 80 8C resulted in the marginal increase
in the breakthrough time. As also observed from the
figure, the breakthrough curve shifted to the left as the
reaction temperature was increased to 100 8C, indicat-
ing an early saturation of the bed. In fact, at tempera-
ture as high as 150 8C, the zeolite materials were found
to be unsuitable for adsorption as the breakthrough of
the bed occurred instantaneously ( B/10 min). This type
Fig. 2. Temperature effects on breakthrough of SO2 over 5A zeolites
(w/2.5 g, L/3.5 cm, CSO2 /10 000 ppm, QN2 /300 cm3/min, dp /
1.16 mm).
15
of breakthrough characteristic (optimum adsorption at
an intermediate temperature) for SO2 over zeolite was
observed for all the concentration levels less than 1%.
Thus, the adsorption temperature for all test runs hence
after in this study was chosen as 70 8C.
The model predictions were done under the identical
experimental conditions. As described in the section on
theoretical analysis, the concentration profiles within
the zeolite crystal due to the radial diffusion in the
micro-pores of crystals was averaged and the adsorption
of SO2 at the interface of the crystals and marco-pores
was assumed to be determined by a parameter, called
equilibrium constant. This dimensionless constant has
been used as an adjustable parameter in the model,
wherever necessary, to explain the experimental data.
The remaining variables such as the gas film mass
transfer coefficient around the pellet, dispersion coeffi-
cient in the packed bed and macro-pore diffusivity
incorporating Knudsen effects and intra-particle diffu-
sivity were either calculated or estimated based on the
typical data reported in the literature [12]. The tempera-
ture effects on variation in gas, pore or crystal diffusiv-
ities were incorporated, as necessary.
Fig. 3 compares the model predicted breakthrough
curves with the experimental data. A reasonable good
agreement is observed between two results within the
experimental and computational errors. The values for
equilibrium constant K at 35, 60, and 80 8C were
adjusted at 102, 33, and 13, respectively. The decrease
in the values of K with increase in the temperature is
Fig. 3. Comparison between model predictions and experimental data:
Determination of heat of adsorption for SO2 over 5A zeolites (w/2.5
g, L /3.5 cm, CSO2 /10 000 ppm, QN2 /300 cm3/min, dp /1.16 mm).
16 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22
also found to be consistent with an independent
equilibrium study [2]. Assuming the Arrhenius type
temperature dependence of the equilibrium constant,
the exothermic heat of adsorption was calculated to be
9.8 kc/mol as shown in the inset of Fig. 3, which is
smaller than that (ca. 12 kc/mol) obtained for the
adsorption of lighter hydrocarbons such as propane
and butane on 5A zeolite [12]. Table 2 summarizes the
values of various variables that were either used in the
model, such as crystal radius and crystal diffusivity, or
calculated based on the operating conditions, such as
mass transfer coefficient, and Reynolds number, corre-
sponding to the experimental operating conditions used
in this work. The last column lists the adjusted values of
the model parameter K for these conditions to explain
the observed breakthrough characteristics of SO2 on 5A
zeolites.
4.2. Effect of concentration
To observe the effects of SO2 concentration at trace
levels on the breakthrough characteristic, the experi-
ments were carried out for varying gas inlet concentra-
tions: 2000, 5000, 7500 and 10 000 ppm; the remaining
operating variables (temperature, adsorbent weight and
size, gas flowrate) were kept identical in each case. Fig. 4
describes the breakthrough characteristics at these
concentrations. As observed from the figure, the break-
through time considerably decreases from about 3 h to
less than 1 h as the concentration increases from 2000
ppm to 1%. As also observed, the decrease in the
Fig. 4. Concentration effects on breakthrough of SO2 over 5A zeolites
(w/5.0 g, L/6.5 cm, T /70 8C, QN2 /300 cm3/min, dp /1.16 mm).
breakthrough and adsorption times is relatively larger
at higher concentration levels (7500
/10 000 ppm) than
lower levels (2000
/7500), indicating the suitability of
zeolites in the concentration levels typically less than
1%. The model predictions are observed to be in good
agreement with the data under identical conditions. In
each case, a marginal change (less than 5%) in the model
parameter K (from 30.0 for 10 000 ppm to 31.4 for 2500
ppm) was required to explain the experimentally
obtained breakthrough curves, verifying the assumption
of the linear adsorption isotherm in this study over the
selected concentration range (B/1%).
4.3. Effect of particle size
The experiments were carried out for three different
particle (pellet) sizes: 0.16, 0.80, and 1.16 mm, under
varying gas flow rates and inlet SO2 concentrations. The
test samples having a particle size of 0.16 mm were in
nearly powdered form, while those having higher size
particles were in the spherical pellet forms. The amount
of zeolite materials was taken as 5 g in each case. Fig. 5
describes the representative results of the effects of
particle sizes on the breakthrough characteristics. In
the test run, the inlet SO2 gas concentration and flow
rate were kept constant at 10 000 ppm and 300 cm3/min,
respectively. As observed from the figure, decrease in the
particle size from 1.16 mm (the largest pellet size in this
study) to 0.16 mm (the smallest size) resulted in
significant increase in the breakthrough and adsorption
Fig. 5. Effects of zeolites particle size on SO2 breakthrough (w /5.0 g,
L /6.5 cm, T /70 8C, CSO2 /10 000 ppm, QN2 /300 cm3/min).
 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22 17

times. In fact, in the latter case, the breakthrough 4.4. Model parametric study
occurred in approximately 2 h. For an intermediate
particle size of 0.80 mm, the breakthrough and satura- There are three resistances to mass transfer as
tion times were observed to be approximately 70 and postulated in the model analysis: (1) in the gas film
120 min, respectively. The noticeable characteristic of surrounding the pellet (2) within the macro-pore volume
the breakthrough responses, especially for the small size (binder-phase), and (3) within the micro-pore volume
particles (nearly powdered form) was the abrupt in- (crystal volume), characterized by mass transfer coeffi-
crease in the concentration levels following the break- cient Km, characteristic times of diffusion tp (R2p /Dp)
through of the bed. These effects have again been and tc (R2c /Dc), respectively. The first two resistances
discussed in the later section of this paper. The BET may considered to be in series as they appear as a sum in
area measurements were made use along with the model both the coefficients h and d of Eq. (14). On the other
predictions to explain the observed superior perfor- hand, the effect of the crystal diffusional resistance on
mance of the relatively smaller size zeolite materials in adsorption may be ascertained only in comparison with
this study. The larger size pellets (1.16 and 0.8 mm) were the macro-pore diffusional resistance, as is evident from
found to have BET area in the range of 170
/200 m2/g, the expression for d. The quasi-steady state adsorption/
while the powdered materials had lower BET area (/70 desorption at the crystal
/macro-pore interface, char-
m2/g). Despite this the increased breakthrough time in acterized by the equilibrium constant K may be
the case of smaller size pellets was attributed due to the considered to be affecting or modifying the character-
significant increase in the gas film mass transfer istic time of crystal diffusion tc. As also seen from the set
coefficient and interfacial surface area. of governing equations, the adsorbent BET area, Sg
As observed from Table 2, the mass transfer coeffi- does not appear explicitly; however, it has the direct
cient for the 0.16 mm zeolite particle was calculated to bearing on the macro-pore radius, rpore through the
be 0.45 m/s in comparison with 0.075 m/s for 1.16 mm intra-particle porosity and bulk density as, rpore /2a /
size particle under the identical gas superficial velocity. Sgrb. The pore radius rpore, in turn, determines the
With the increase in mass transfer co-efficient due to macro-pore diffusivity, Dp and, therefore, tp.
smaller particle radius, the amount of gas or the flux of Fig. 6 describes the comparative effects of gas film
SO2 (mol/m2 s) diffusing into the adsorbents increased. transfer and intra-particle diffusion. The simulated
This, in turn, resulted in higher adsorption rate. As the conditions including the adsorber’s geometrical dimen-
particle radius was decreased for the same amount of sions are shown on the figure. The adsorbent particles
adsorbent the interfacial area per unit volume (a*) also radius was set at 4.16 mm, which gave a ratio of 12:1 for
increased. Hence, there was a combined effect of mass
transfer rate as well as the interfacial area per unit
volume on the total SO2 flux entering the pores of the
pellet, resulting in increased adsorption and break-
through time. Here, it is essential to point out that
relatively longer breakthrough time reflects the com-
paratively superior performance of the adsorbents.
However, the similar inference cannot be made for the
shorter breakthrough time observed during adsorption.
The latter situation may be consequence of either
diffusion controlled adsorption or significantly high
reactivity (favorable adsorption isotherm) of SO2 with
the adsorbents resulting in immediate saturation of the
bed. From Eqs. (12) and (13) it may be seen that a
number of phenomenological effects including diffusion
within the micro and macro-pores of bi-disperse zeolites
materials, and dynamic adsorption/desorption at the
crystal
/binders interface simultaneously take place. The
response of an initial clean bed (i.e. free of adsorbate) to
an influent containing an adsorbate has a complex
dependence on these effects, in addition to the relative
size of crystal to that of a pellet. The following section
Fig. 6. Comparative effects of gas mass film mass transfer and
illustrates the relative importance of these effects in macropore diffusion on SO2 breakthrough (Rp /4.16 mm, Km /
interpreting the breakthrough characteristics obtained 0.0074 m/s, K/133; T/30 8C, CSO2 /10 000 ppm, QN2 /300 cm3/
during adsorption/desorption of SO2 over zeolites. min, w/1 kg, L /1.9 m, I.D./0.05 m).
18 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22

the bed id to the particle radius. The gas film mass

transfer coefficient under the prevailing flow conditions
in the bed was calculated to be 0.0074 m/s. The
simulations were carried out for different BET areas
(15
/215 m2/g) so as to obtain varying values of pore
diffusivity, Dp and hence, those of KmRp/5Dp from a low
value of approximately 1 to a high value of 42. The
numerical values of equilibrium constant K , crystal
radius Rc and crystal diffusivity Dc were chosen such
that both terms in the second product term of Eq. (14)
had the same order of magnitude. In other words, the
effects of both crystal diffusion and macro-pore diffu-
sion were considered in each of the cases simulated. As
observed from the plots on Fig. 6, the breakthrough of
the adsorber bed occurs in a relatively shorter time (less
than 10 min) in all the cases for which the value of
KmRp/5Dp was less than 35, suggesting that the adsorp-
tion was controlled by the gas film mass transfer in these
cases. As a consequence, insignificant amount of the
adsorbate (SO2 flux in this case) reached the adsorbents
surface resulting in immediate breakthrough of the bed
and, therefore, shorter adsorption time. The break- Fig. 7. Comparative effects of gas film mass transfer and macro-pore
through times appreciably improved as the ratio of diffusion on SO2 breakthrough (Rp /0.186 mm, Km /0.102 m/s, K /
KmRp to 5Dp was increased to 40 and greater, suggesting 133; T/30 8C, CSO2 /10 000 ppm, QN2 /300 cm3/min, w /1 kg,
that the resistance to the gas film mass transfer L /1.9 m, I.D./0.05 m).
gradually diminished and the adsorption became inde-
pendent of the film resistance. In such cases the
adsorption was controlled by macro-pore diffusion. In
fact, for KmRp/5Dp /42 a typical ‘S’ type of sigmoidal
curve was obtained with breakthrough and adsorption
times of approximately 50 and 150 min, respectively. It
may be pointed out that the identical simulated adsorp-
tion profiles were obtained if the pellet size was varied
instead and the BET area of the adsorbents (or pore
diffusivity Dp) kept constant so that the numerical
values of the above ratio remained the same as before.
For the sake of brevity, these results are not produced
here. Fig. 7 describes the simulations results for the
similar scenario (comparative effects of two resistances),
however, for the smaller size particle (Rp /0.186 mm).
The mass transfer coefficient in this condition was
calculated to be 0.102 m/s, an increase of almost two
orders of magnitude from the previous case. The values
of pore diffusivity were accordingly adjusted through
the BET areas so as to get the ratios of two effects
approximately in the same range as before. As observed
from the figure, the effects of gas film mass transfer
relative to that of macro-pore diffusion on the break- Fig. 8. Comparative effects of macro-pore and crystal diffusion on
through characteristic are identical as in the previous SO2 breakthrough (Rp /0.186 mm, Km
/30 m/s, K/13; T /30 8C,
case (Fig. 6), except the rise in the concentration levels CSO2 /10 000 ppm, QN2 /300 cm3/min, w/1 kg, L /1.9 m, I.D./
following the breakthrough are relatively sharper. These 0.05 m).
profiles are also characteristically similar to those
observed in the test runs for smaller size particles
(powdered form). carried out for varying ratios of tc and tp. In the
The comparative effects of macro-pore and crystal expression for d , i.e. Eq. (14), by setting the value of K
diffusion are described in Fig. 8. The simulations were at 13 and a at 0.3, it can be shown that for the macro-
 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22
pore diffusion effects to be negligible in comparison with
those of crystal diffusion, tc/16tp /1. This is also
consistent with the imposed constraint that d must be
negative for the adsorption by the zeolite particles. The
different values of tc/16tp were obtained by assuming
various values for the adsorbent BET area, which
determined the pore diffusivity Dp and the correspond-
ing characteristic time of pore diffusion tp. In all these
simulated cases, the ratio KmRp/5Dp was calculated to
be at least 30, implying that the adsorption was not
controlled by the gas film mass transfer. As observed
from the figure, the adsorption remained relatively
insignificant so long the value of tc/16tp was greater
than 2. In each of these cases, the breakthrough
occurred in less than 10 min suggesting that the
adsorption remained crystal or micro-pore diffusion
controlled. The adsorption increased significantly in
the cases for which the above values were adjusted to
approximately 1 or lower. In such cases both macro-
and micro-pores diffusion were relatively important and
as a consequence, the breakthrough times improved
significantly. It may be re-emphasized that due to the
assumption of a quasi (pseudo) steady-state adsorption/
desorption at the interface of crystals and binder-phase,
the effect of K is essentially to modify the characteristic
time of diffusion within the crystals. In other words, Eq.
(14) can also be written as
 
Km l 27 15
d   
5D t? t?p
Vz Km  p a c
Rp
where t? may be considered as an effective time of
crystal diffusion. Therefore, for the maximum adsorp-
tion by the zeolites pellets, the adsorbate’s diffusivity
within the crystals is required to be relatively significant,
i.e. higher value of t c?. Since d assumes a negative value
during adsorption, the effective macro-pore diffusivity is
also required to be higher in the same proportion. The
simulation results on Fig. 8 have illustrated these
remarks.
5. Conclusion
/q̄ volume-averaged concentration over the crystal
A dynamic adsorption/desorption study was carried
out on the removal of trace SO2 (B/1% volume
/q̄
concentration) on zeolites. The breakthrough curves
were experimentally obtained under several operating
conditions, including temperature, gas concentration,
and particle size. The maximum adsorption of SO2 was
observed at a reaction temperature of around 70 8C.
The performance of the zeolites materials in the
powdered form was found to be superior, in terms of
breakthrough times, to that for relatively larger size
pellets, although the breakthrough curves for smaller
19
size particles were observed to be steep. The adsorption
isotherm assuming first order adsorption and desorption
rates with respect to the gas and adsorbate phase
concentrations was found to be linear in the concentra-
tion range (1000
/10 000 ppm) studied in this work. The
equilibrium constant at 70 8C and exothermic heat of
adsorption were determined to be 30 and 10 kcal/mol,
respectively. A mathematical model for the zeolites
particles assuming biporous structures was developed
to predict the breakthrough profiles under varying
operating conditions. With the help of the model, the
dynamic adsorption of SO2 was explained by the
combined effects of gas film mass transfer, diffusion in
the macro-pores and within the crystals of the zeolites
pellet. These effects were mathematically represented by
two dimensionless variables, h and d, in the proposed
model. An upper limit for the adsorption equilibrium
constant was theoretically obtained in terms of the
physical characteristics of the zeolites pellet and crystals
as,
15Dp R2c
KB :
R2p 27Dc (1  a)
The model simulation results were successfully validated
with the experimental data.
Appendix A: Nomenclature
a
external surface area per unit volume of the particle
(m2/m3)
C concentration of reactant gas (mol/m3)
D diffusion co-efficient of reactant gas (m2/s)
k adsorption or desorption rate constant (1/s)
K equilibrium constant/partitioning coffecient (di-
mensionless)
Km average mass transfer co-efficient (m/s)
L length of the packed bed (m)
M molecular weight (kg/kg mol)
N flux, (mol/m2 s)
Q flow rate (slpm)
q concentration of the adsorbate inside the crystal
(mole/m3)
(mol/m3)
¯ volume-averaged concentration over the entire
pellet (mol/m3)
r radial co-ordinate in the crystal (m)
R radial co-ordinate in the particle (m)
Rp pellet radius (m)
Sg BET area (m2/g)
t time (s)
T temperature (8C)
V superficial velocity (m/s)
Z axial position in the packed bed (m)
20 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22

Subscript ing the parabolic concentration profiles q (r ), the solid

a adsorption diffusion Eq. (7) leads to the following LDF approxi-
b bed mated equation (Yang et al., 1997):
c crystal
d desorption @ q̄ 15Dc
 (q½rRc  q̄) (21)
k Knudsen @t R2c
m molecular
p pore or pellet Taking the volume
/average of Eq. (21) over the entire
z axial location or dispersion in the packed bed pellet, the following equation is obtained:

@ q̄¯ 15Dc
Superscript  (q½rRc  q̄¯) (22)
* dimensionless variables @t R2c

Greek symbols where, qjrRc is in equilibrium with Cp at location R in

eb bed porosity (dimensionless) the pellet.
a intra-particle porosity (dimensionless) (5) Averaging Eq. (6), the adsorption isotherm is re-
rb bulk density of zeolite (kg/m3) written as:
t tortuosity factor (dimensionless) q̄½rRc KCp (23)

The volume-averaged concentrations q̄ over the

crystal and Cp is obtained by averaging Eq. (20) and
using Eq. (16):
Appendix B
3 3
The detailed computational steps involved in the q̄ A BR2c Cp C  DR2p (24)
5 5
simplification of the governing equations Eqs. (1), (5)
and (7) to obtain Eqs. (8) and (9) are as follows: From Eq. (20) the concentration at R /Rp is eval-
(1) First, the particle volume averaged quantities in uated as:
the pores and within the crystals are calculated:
Cp½RRp C DR2p (25)
3 3
Cp 
R3p g 2
Cp R dR; q̄
R3c g 2
qr dr (16)
Combining Eqs. (23)
/(25) C and D are calculated as:
(2) By integrating Eq. (5) with respect to R and using
5
the volume averaged quantities the following equation is D [Cp½RRp Cp ]
obtained: 2R2p
  (26)
5 3
@Cp 3 @q C Cp  Cp½RRp
a  NR½RR 3(1a) 0 (17) 2 2
@t Rp p
@t
where, q̄¯/ /averaged concentration of the adsorbate over Substituting the values of C and D in Eq. (20), an
the entire pellet and defined as: expression for the average gas phase concentration in
the pore is obtained as:
3
q̄¯ 
R3p g q̄R dR
2
(18) 
5 3
Cp  Cp  Cp½RRp 

5
[Cp½RRp Cp ]R2 (27)
2 2 2R2p
In the integration of Eq. (5), the following boundary
conditions were used: NR /0 at R /0, due to symme- (6) Equating radial diffusion flux (concentration
tricity. At the surface (R /Rp), the diffusion flux into or gradient) at the pellet surface calculated from Eq. (27)
out of the pores: with that from Eq. (19), the gas phase concentration at
NR½RR  Km (Cb Cp½RR ) (19) the surface of the pellet is obtained as:
p p

(3) Parabolic concentration profiles were assumed (Km Cb  5Dp =Rp Cp )

Cp½RRp  (29)
within the pore volume of the pellet and crystals as (Km  5Dp =Rp )
follows:
Similarly, substituting Eq. (20) in Eq. (23), and
Cp C DR2 and qABr2 (20)
identically comparing term by term, A and B are
(4) This has been mathematically shown that assum- evaluated as follows:
 A. Gupta et al. / Chemical Engineering and Processing 43 (2004) 9
/22 21

 
5 3 the zeolites pellet is given by a combination of both
A K Cp  Cp½RRp
2 2 Knudsen (Dk) and molecular (Dm) diffusivities as:

5 (30) 1 1 1
K [Cp½RRp  Cp ]R2  
2R2p D Dk Dm
B
R2c where, Knudesn diffusivity is given as, Dk(m2/s) /
97xRpore (m)[T /M ]1/2.
Once the values of A , B , C , and D are obtained, an
expression for the average adsorbate concentration q̄¯
and that for @q/@t can be expressed in terms of Cb and
Cp as follows:
Appendix F
K
q̄¯  [8Cp 3Cp½RRp ] (31)
5 A general mass balance for A (SO2) in the bed will
@ q̄¯ 9Dc KKm yield the following equation:
 (Cb Cp ) (32)  
@t R2c (Km  5Dp =Rp ) @CA @(uCA ) @q
o  (1o) A 0
@t @z @t
Finally, by expressing the average adsorbate phase
concentration in terms of the bulk gas phase and average An identical equation can be written for B (N2).
gas phase concentration in the macro-pore, the simpli- Assuming that (a) the linear adsorption isotherms for
fied forms of Eqs. (7) and (8) are obtained. both species A and B are non-interfering: qA /KA CA
and qB /KB CB , and (b) the mole-fraction of B is
approximately 1, as A is at ppm levels (less than 1%),
Appendix C the above equation(s) can be recast in terms of total
pressure P as:
The axial dispersion co-efficient in the packed bed, Dz  
@(PY ) @(uPY ) @(PY )
is expressed in terms of Peclet number defined as, Pe / e  (1e)KA 0
@t @z @t
2Rpm /Dz r . The Peclet numbers are correlated with
particles Reynolds and Schmidt numbers through one and,
of the empirical correlations as follows [13]:  
@P @(uP) @P
o  (1o)KB 0
1 0:3 0:5 @t @z @t
 
Pe Re  Sc 1  3:8=(Re  Sc)
. Here, Y is the mole-fraction of SO2. Thus, assuming
for 0:008B ReB 400 and 0:28BSc B2:2 negligible pressure-drop in the bed and also, insignif-
icant variation with time in the total pressure P during
adsorption, it is trivial to show from the last equation
that the flow velocity also remains the same along the
Appendix D bed length, i.e. @u/@z/0. As a consequence, the above
species balance equation for A in the case of co-sorption
The mass transfer co-efficient Km in the packed bed is of A and B is reduced to the identical form as in Eq. (1).
calculated using the following correlation for Sherwood
number defined as, Sh /2KmRp/Dm [13]:
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