4428 Ind. Eng. Chem. Res.

2009, 48, 4428–4439

SEPARATIONS

Modeling and Simulation of Stirred Dead End Ultrafiltration Process Using the
Aspen Engineering Suite
Sabuj Das, Prabirkumar Saha,* and G. Pugazhenthi
Department of Chemical Engineering, Indian Institute of Technology, Guwahati, Assam 781 039, India

Simulation of pressure-driven membrane process has been carried out considering two different types of
solute (silica and dextran) and membrane (partially permeable and totally retentive) in a stirred cell using the
Aspen Engineering Suite. One solute, silica, exerts negligible osmotic pressure but the other, dextran, offers
adequate osmotic pressure. Silica is very susceptible to form a gel layer while dextran has no such tendency.
Two types of membrane are considered for this work. One membrane completely separates solute from the
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solvent (totally retentive membrane) and the other does it partially (partially permeable membrane). The
second type of membrane is regarded as highly compact granulated particle layer which has a different range
of porosity. So the diffusivity within the membrane layer is referred to as hindered back diffusion. Osmotic
pressure model and gel polarization model have been considered for batch and continuous mode operation.
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Silica suspension has been simulated with totally retentive membrane and dextran solution is simulated with
partially retentive membrane in batch and continuous mode, respectively. The effect of applied pressure,
stirring speed, and initial feed concentration on permeate flux, membrane surface concentration, permeate
concentration, and true and observed rejection have been studied.

1. Introduction small noncharged molecules in an aqueous solution using reverse

Pressure-driven membrane processes are being increasingly
incorporated in the process industries for the separation of
valuable chemical and biological compounds from mixtures. Of
these processes, reverse osmosis (RO) and ultrafiltration (UF)
have become increasingly important during the past decades
due to their mild and energetically favorable separation and
concentration technique, which have been commercialized in
pharmaceutical, chemical, and food industries. Among the main
problems hampering its widespread use, concentration polariza-
tion as well as fouling may be mentioned, because both
phenomena give rise to flux decline. The flux decrease could
also be due to an increase in osmotic pressure, formation of gel
layer, solute adsorption on membrane, and pore plugging. In
order to minimize the concentration polarization, much attention
has been paid to rather mechanical aspects, such as cross flow,
back pulsing, and promotion of turbulence, e.g., by gas
purging.1,2 Moreover, any attempt to increase the flux by
increasing pressure causes severe increase in concentration
polarization, thus giving little increase in flux compared to
increase in pressure. Eventually, the flux does not increase
beyond a certain point (called limiting flux) even if the pressure
is increased further. Types of solute and membrane have great
impact for gel formation and concentration polarization.
Flux decline rate also depends on the flow direction and
operating condition. In the dead end filtration, the feed flow is
directed perpendicular to the membrane, whereas in the cross-
flow filtration, feed flow is directed parallel or tangential to the
membrane. The former one is most often used for small volume
laboratory applications and the later one is used for large volume
process applications. Dead end filtration may be carried with
stirred and unstirred cells. Nicolas et al.3 showed a comparison
study of rejection in a stirred and an unstirred batch cell for
* To whom correspondence should be addressed. E-mail: p.saha@
iitg.ac.in. Phone/Fax: +91.361.2582257.
10.1021/ie801293d CCC: $40.75  2009 American Chemical Society
Published on Web 04/09/2009
osmosis and ultrafiltration membranes. The results revealed that
in a stirred cell with high stirring velocity, the concentration
near the membrane was close to the bulk concentration, resulting
in improved rejection compared to the unstirred batch cell
results. Several studies have reported the experimental results
as well as modeling of limiting flux for the separation of macro
solute and colloids by UF that provided strong support to the
gel polarization model.4-6
Karode7 simulated the unsteady-state permeate flux response
for three types of solutes, such as (i) solutes which exert an
osmotic pressure but do not form a gel; (ii) solutes which do
not exert an osmotic pressure but form a gel, and (iii) solutes
which exert an osmotic pressure and also form a gel. He showed
that the concentration at the surface of a membrane was a
function of operating parameters and it was possible to predict
the membrane wall concentration as a function of time. In
addition, a step change in transmembrane pressure showed that
a solute, which exerts osmotic pressure but does not form a gel
layer, exhibited a gradual flux decline over time. Experimental
verification of this work was presented by Zaidi and Kumar.8-10
They experimentally studied unsteady-state flux response to a
step change in transmembrane pressure for dextran8 and
polyethylene glycol (PEG) solution9 and reported that polariza-
tion resistance depended on applied pressures and initial bulk
feed concentrations, whereas the thickness of polarization layer
affected by only feed concentration. They have also investigated
the characteristics of a deposited layer formed in dead end UF
of silica after reaching steady-state flux.10 In addition, the effects
of operating conditions such as applied pressure and bulk
concentration on specific resistance, thickness, porosity, and
silica concentration of gel were reported. Zaidi and Kumar11
have also experimentally investigated the influence of ethanol
concentration on flux in ultrafiltration of PEG and dextran with
a solvent resistance polymeric membrane. They observed that

both steady-state flux and gel formation were significantly
influenced in the UF of both PEG and dextran from blended
solvent (ethanol-water).
The unsteady-state flux behavior for silica and dextran in an
ultrafiltration cell has been studied experimentally by van Oers
et al.12 During the filtration of dextran, only a polarization layer
was built up and the osmotic pressure model provided a good
description of the flux for the experiments with dextran. For
silica suspension also, a gel layer formation occurred and was
well predicted by the gel polarization model. An unsteady-state
model was developed to predict the feed surface and permeate
concentration for ultrafiltration of macromolecules using the
diffusion coefficient of the solution through the membrane.13
This model was proficient in predicting the feed surface
concentration once the operating conditions were fixed and did
not make an implicit assumption of constant feed surface
concentration. It was further shown that, for a certain range of
system parameters, a negative rejection (based on the feed
concentration) was possible at steady state.
Nakao et al.14 reported that no gel layer was found during
the ultrafiltration of dextran even with a very high solute
concentration of 400 kg/m3. The above reason was also further
confirmed by Choe et al.15 They obtained the permeate flux of
dextran for totally retentive membranes in a stirred UF cell as
a function of time for sudden variations of transmembrane
pressures and concluded that only the polarization layer was
formed. The osmotic pressure model was well fitted with the
dextran flux data. They also studied the flux decline of dextran
in UF and concluded that the change in the driving force could
be explained in terms of osmotic pressure at the membrane
surface. Bhattacharjee and Bhattacharya16,17 have developed a
model to predict the flux using a generalized formulation which
takes into account the unsteady-state behavior during the initial
stages of continuous stirred ultrafiltration of PEG. They17
showed the effect of operating variables on limiting flux
phenomena and the membrane parameters, i.e., reflection
coefficient and solute permeability, were determined to char-
acterize the membrane. A correlation was developed to relate
polarized layer resistance with concentration polarization,
osmotic pressure to applied pressure ratio and Reynolds number.
Bhattacharjee and Datta18 used the experimental data reported
in the literature16,17 to integrate the governing partial differential
equation and calculate the back transport coefficient by a least-
squares fit. The model predicted that the flux decline during
ultrafiltration of PEG in a continuous stirred cell using a
cellulose acetate membrane occurred mainly due to the resis-
tance offered by solute molecules during their back transport
to the bulk. The effects of osmotic pressure and cake/gel
formation were assumed to be negligible in this study. A three-
parameter model based on unsteady-state mass transfer was
developed for the prediction of flux and rejection of solute
during ultrafiltration in an unstirred batch cell.19 The main
feature of this model was that it allowed variation of solute
diffusivity with concentration in the boundary layer whose effect
was more pronounced in the case of unstirred batch cell.
Bhattacharjee et al.20 utilized Kedem-Katchalsky (KK) and
Spiegler-Kedem (SK) models for the parameter estimation like
solute permeability and reflection coefficient for ultrafiltration
of black liquor by using an asymmetric membrane in a stirred
batch cell, which was modified to work on a continuous mode.
The variations of parameters with other process variable like
bulk concentration, pressure difference, and stirrer speed were
also established. Shukla and Kumar21-24 have modeled the
separation of aqueous solution of FeCl3, AlCl3, and chromic
Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4429
Figure 1. Schematic representation of a concentration polarization layer
over gel layer and mass balance over the concentration polarization layer.
acid by zeolite-clay composite membrane using a two-
dimensional space charge model. They reported a new scheme
for the solution of space-charge model which reduces the
computational time considerably. An unsteady-state mass
transfer model was developed taking the effect of reversible
pore plugging25 by the diffusing solute molecules into account.
The osmotic pressure model has been used to predict the
membrane surface concentration. The rate of available fractional
area of the membrane that blocked at any time due to pore
plugging phenomenon was assumed to be the function of
dimensionless membrane surface concentration existing at that
time.
In this article, we have modeled the effect of various operating
parameters on the performance of membrane for separation of
dextran and silica suspension using a process engineering
software, viz., Aspen Engineering Suite. The advantage of this
software is manifold. First, this has a dedicated user interface
for both steady-state and dynamic process simulation. Unlike
high-level programming languages such as C++ or Fortran
where the user needs to write rigorous codes, Aspen software
has inbuilt object modules that can handle codes for ODE/PDE
solver, optimization, real-time graphical output, etc. Second, the
software has a rich library of commonly used unit operations
such as distillation column, reactors, heat exchanger, etc., which
are menu-driven and can easily be integrated with various
process operations. And third and most importantly, Aspen has
a huge database of physical as well as thermodynamic properties
of various chemical compounds which could be called in while
simulation progresses as and when required. In other words,
even a minute change of physicochemical property of a target
chemical can be predicted and used in the simulation when
process condition such as temperature, pressure, or concentration
changes. This is contrary to the poor assumption that is usually
considered by other custom-made simulation code that takes
constant density/viscosity etc. while performing real-time
simulation. Two different types of membrane are considered
for batch and continuous mode of operation in a stirred dead
end UF cell. In this analysis, variations of permeate flux,
membrane surface concentration, permeate concentration, ob-
served and true rejection with the transmembrane pressure,
stirrer speed, and initial feed concentration have been studied.
4430 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009

2. Theory
Both the models discussed above, viz., gel polarization model
and osmotic pressure model, incorporate the phenomenon of
concentration polarization (see Figure 1).7 Based on the film
theory, the formation of a polarization layer can be described
with the following partial differential equation (PDE), assuming
flux J(t), and diffusivity D, as independent of concentration c
of the macromolecular solutes

∂c ∂c ∂2c
) -J(t) + D 2 (1)
∂t ∂x ∂x
Within the membrane (δpol < x < δpol + δmem), the concentration
is governed by13

∂c ∂2c
) Dm 2 (2)
∂t ∂x
The gel layer and membrane resistance may be considered
as two resistances in series, and the permeate flux is then
described by Darcy’s law:

1 dVP ∆P - ∆π
J) ) (3)
Am dt µ(Rm + Rg)
where
∆π ) π(cm) - π(cp) (4)
The gel-polarization model assumes that the concentration
at the membrane surface cannot exceed the gel concentration
Cg.12 Initially, polarization layer forms when the membrane
surface concentration reaches the gel concentration. The gel
Figure 2. Schematic representation of continuous (a) and batch (b) setup.
layer thickness increases with time and reduces its hydraulic
permeability. Figure 1 shows the schematic representation of
concentration polarization layer over the gel layer. For totally Both the cases, membranes are considered as black box, i.e.,
retentive membrane (where cp ) 0), the rate of growth of the membrane parameters like permeability, reflection coefficient,
gel layer thickness can be calculated by a mass balance as and charge density are not judged. In partially retentive
follows7 membrane, diffusivity within the membrane layer is referred to

( )
∂δg
D ∂c
)J- (5)
∂t Cg ∂x |x)δpol
The hydraulic resistance of the gel layer of particles can be
calculated using the Kozeny-Carmen equation.
(1 - n)2
Rg ) 180 δg (6)
dp2n3
3. Model
In this work, two different types of solute separation are
considered such as (i) solute which has negligible osmotic
pressure in the solution but has a great tendency to form gel
layer (silica suspension) and (ii) solute which has observable
osmotic pressure and no tendency to form gel layer (dextran)
using two different categories of membrane, viz., (i) totally
retentive membrane where solutes cannot pass through the
membrane and (ii) partially retentive membrane where solute
may pass with solvent through the membrane. The following
two cases have been considered here for the performance study
using stirred dead end UF setup and is shown in Figure 2.
Case I: Separation performance of dextran solution using
partially retentive membrane in the continuous mode of opera-
tion (Figure 2a).
as hindered back diffusion. To simplify the modeling, the
membrane layer is represented as granulated layer characterized
by equivalent diffusivity. The same assumption was used by
Agashichev26 and Boudreau27 for calculating effective diffusion
coefficient within the granulated cake layer. The diffusivity of
solute within the membrane can be calculated as
ε
Dm ) D (7)
1 - ln ε2
In this simulation study, we have considered a stirred dead
end UF cell with a membrane area of Am and initial concentra-
tion and volume of the feed are cf0 and Vf0, respectively. If the
mass arrested into the polarization layer is neglected, then for
a totally retentive membrane (no permeation of solute through
membrane), the change of bulk volume (Vf) and concentration
(cf) with time in the UF cell for batch mode operation (Figure
2b) can be written as7
dVf
) -JAm (8)
dt
dcf cf
) JAm (9)
dt Vf
The mass transfer coefficient for a stirred batch cell is
calculated by the following empirical equation:16,18,20

( Dr )( Dν ) ( ωrν )
Case II: Separation performance of silica suspension using
0.33 2 0.8
totally retentive membrane in the batch mode operation (Figure
k ) 0.0443 (10)
2b).
 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4431
It is also assumed that the time taken for formation of Table 1. Properties of Membrane, Solute, and Operating Conditions
concentration polarization layer is negligible. Polarization layer of the Dead-End UF Cell7
thickness is calculated by film theory. Many researchers have Membrane Parameter
reported that there is no significant influence of molecular weight
membrane radius r ) 0.06 m
of dextran on osmotic pressure.8,9,12 So in this report, osmotic membrane area Am ) πr2 ) 0.0137 m2
pressure of dextran is calculated using the virial expansion membrane porosity ε ) 0-35%
thickness of the ∂mem ) 10-6 m
π ) A1c + A2c2 + A3c3 (11) membrane
hydraulic resistance Rm ) 1013 m-1
The initial and boundary conditions for solving eqs 1 and 2 for
Cell Parameter
both the cases are given below.
transmembrane pressure ∆P ) 1-12 bar
Case I:
operating temperature T ) 298.15 K
t ) 0; 0 e x e δpol ; c ) cf0 stirring speed ω ) 4.8-10000 rpm
Solute and Solvent Parameter
t > 0; x ) 0; c ) cf ; and x ) δpol ; Jc ) D ( ∂x∂c ) - -
x)δpol 1. dextran
water solution
molecular wt 73500 Da (av dia )11.4 nm)
∂c
D ( )
m
initial concentration cf0 ) 28 kg/ m3
∂x +
x)δpol initial volume Vf0 ) 0.02 m3
virial coefficients A1 ) 37.5
Within the membrane, the PDE eq 2 is solved with the A2 ) 0.752
following boundary condition:13 A3 ) 76.4 × 10-4
2. silica viscosity µ ) 0.001 Pa · s
t ) 0; δpol < x < δpol + δmem ; c)0 water solution
∂c ∂c initial concentration cf0 ) 2.5-120 kg/ m3
t > 0; x ) δpol ; Jc ) D ( )
∂x x)δpol
-
- Dm ( )
∂x +
x)δpol
initial volume
particle diameter
Vf0 ) 0.02 m3
dp ) 13 × 10-4 m
∂c particle density from Aspen property file
x ) δpol + δmem ; Jc ) -D ( )
m solution density from Aspen property file
∂x -
x)δpol+mem
diffusivity from Aspen property file
Case II: molecular wt from Aspen property file
gel porosity n ) 0.37 (assuming spherical
t ) 0; 0 e x e δpol ; c ) cf0 particle)
gel concentration Cg ) 230 kg/m3
∂c
t > 0; x ) 0; c ) cf(t); and x ) δpol ; Jc ) D ( )
∂x x)δpol difference method and the nonlinear equations are solved
using mixed Newton method. Implicit Euler method has been
4. Simulation used as integrator.
For modeling, a flat sheet with circular shape membrane is
All the model equations discussed so far are either ordinary considered for both the cases and its properties are given in
differential equations (ODE) or PDE and most of them are Table 1. It is assumed that there is no dead zone in the cell and
nonlinear. Simultaneous solutions of these equations are the stirrer radius (assumed equal to membrane radius) is
computationally extensive and can only be done through sufficient to maintain the uniform mass transfer rate throughout
appropriate numerical techniques. The entire task is gigantic the membrane area. Table 1 gives the summary of all the
and computationally extensive. Aspen Engineering Suite has parameter value and the solution (dextran and silica) properties
been used in this work to overcome the above difficulties. used in this model.12
The suite also provides an extensive database for physical
and thermodynamic property library, viz., DIPPR, that can
5. Results and Discussion
be directly linked in while performing the simulation. It has
readily available GUI, various types PDE, ODE, nonlinear 5.1. Separation Performance of Dextran Solution Using
or linear solvers, or optimization tools. Aspen Engineering Partially Retentive Membrane in the Continuous Mode of
Suite is a chemical process simulation software that provides Operation. It is generally accepted that concentration polar-
a complete library of models for a number of commonly used ization of solute at the membrane surface can lead to solute
unit operations in the chemical processes such as distillation, adsorption, precipitation, and gel layer formation and this
absorption, extraction, heat exchanger, reactor, etc. Process results in flux decline. This increases operating costs due to
industries that use Aspen Engineering Suite include petro- the need for frequent cleaning and possibly reduces mem-
leum, petrochemical, gas processing, polymer, mineral brane lifetime. In this article, we have investigated to
processing, and so on. Unfortunately, the membrane separa- understand this phenomenon so that its effect can be
tion units have not so far been included in the Aspen minimized. Figure 3 shows the steady-state permeate flux of
Engineering Suite as a ready model. In the present work, dextran solution with variation of stirrer speed for three
Aspen Custom Modeler (ACM), version 20.0, is used for different transmembrane pressures (100, 200, and 300 kPa)
the numerical solution of the model equations. All the with feed concentration of 28 kg/m3. It is clear from the figure
membrane model equations have been coded in Aspen that the flux increases with raise of stirrer speed, and after a
Custom Modeler (ACM) and for getting property data (which certain speed, there is no further increase and it becomes
are pressure, temperature, and concentration dependent) are steady. This means that the increasing stirrer speed results
called within the code by using Aspen Property file. For the in the brushing away of solute deposited on the membrane
case I (Figure 2a), both the concentration polarization layer surface and membrane surface acquires in the vicinity to the
and membrane are divided into 100 parts, while in the case bulk concentration. However, higher transmembrane pressure
II (Figure 2b), the concentration polarization layer is divided (300 kPa) requires higher stirrer speed to reach steady-state
into 100 parts. These PDE are solved with backward finite permeate flux compared to the lower pressure (100 kPa). This
4432 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009

Figure 3. Effect of stirring speed on steady-state permeate flux of dextran Figure 4. Effect of stirring speed on steady-state membrane surface
solution for different transmembrane pressure (at feed concentration ) 28 concentration of dextran solution, Cm, for different transmembrane pressures
kg/m3; membrane porosity ) 10%; membrane thickness ) 1 µm). (at feed concentration ) 28 kg/m3; membrane porosity ) 10%; membrane
thickness ) 1 µm).

is due to the increase of concentration at the membrane

surface as the driving pressure increases and consequently
the osmotic pressure also increases. In a stirred cell, the
growth of concentration polarization layer is usually less due
to turbulence and, at higher speed, the layer resistance drops.
The polarization layer is gradually removed by increasing
the stirrer speed and beyond certain extent of turbulence;
the resistance offered by this additional layer is negligible.
It can be seen from eq 3 that the osmotic pressure is only
for the bulk concentration which turns into fixed (as
continuous mode) and the flux becomes unchanging. As
expected, an increase of pressure stands for increase of flux
which is also confirmed by the above reason. van Oers et
al.12 have proved experimentally that the ultrafiltration of
dextran was found to satisfy the case of only osmotic pressure
limited flux, even if flux at higher concentration was found
to be pressure independent. In our case also, there is osmotic
pressure limited flux established due to no gel formation.
Figures 4 and 5 demonstrate the steady-state decrease of
concentration at the surface of membrane (Cm) and permeate
concentration (Cp), respectively, with variation of stirrer
speed. From these figures, it is understandable that with the
augment of stirrer speed, the membrane surface is obtaining Figure 5. Effect of stirring speed on steady-state permeate concentration
toward the bulk concentration. It is expected that an increase of dextran solution, Cp, for different transmembrane pressures (at feed
of applied pressure raises the concentration at the surface of concentration ) 28 kg/m3; membrane porosity ) 10%; membrane thickness
) 1 µm).
membrane. The membrane used in this analysis retained the
solute partially. This high concentration at the membrane Figure 6 explains the observed and true rejection of dextran
surface increases the true rejection (see Figure 6) and the with variation of stirrer speed for different applied trans-
low diffusion coefficient of dextran (4.6 × 10-11 m2 s-1) membrane pressures (100, 200, and 300 kPa). As the
reduces the rate of back transport at higher applied pressure. permeate concentration diminishes with the higher stirrer
It is confirmed from the results that more stirring is required speed, the observed rejection increases for all the pressures
for closely obtaining the bulk concentration at the membrane studied (Figure 6). For a particular stirrer speed, permeate
surface. concentration increases with the applied pressure, resulting
The permeate concentration also depends on the permeate in the reduction of observed rejection (Ro). It can be seen
flux and mass accumulated on the membrane surface and that, for lower stirrer speed, negative observed rejection is
hence increases with applied pressure for a fixed stirrer speed obtained, which is because the adsorbed solute particles
(see Figure 5). This implies that increasing pressure forces within the membrane pores try to come out at higher pressure
the solute to pass more through the membrane pores. and cause the permeate concentration to become more than
Bhattacharjee and Datta18 have also reported that the the feed concentration. Karode13 has also observed the same
membrane surface concentration depends on stirring speed. and explained the possibility of this condition by simulation.

Figure 6. Effect of stirring speed on steady state observed and true
rejection of dextran solution for different transmembrane pressures (at
feed concentration ) 28 kg/m3; membrane porosity ) 10%; membrane
thickness ) 1 µm).
Figure 7. Effect of stirring speed on steady-state permeate concentration
of dextran solution for different membrane porosities (at feed concentra-
tion ) 28 kg/m3; transmembrane pressure ) 100 kPa; membrane
thickness ) 1 µm).
The same was experimentally proved by Balakrishnan et al.28
The observed rejection is found to be lower than the true
rejection for all the ranges of stirrer speed and transmembrane
pressure studied. This indicates that the concentration
polarization effects are significant and leads to considerable
loss of efficiency. This clearly shows that Ro is strongly
dependent on the operating conditions while Rt represents
the true rejection of the membrane. The porosity of the
membrane has also great impact on permeate concentration.
It can be seen from Figure 7 that the permeate concentration
increases with porosity of membrane which is due to the more
permeation of dextran through the pores. For a particular
porosity, as the stirrer speed increases, membrane surface
concentration decreases and so the permeate concentration
also decreases.
Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4433
Figure 8. Unsteady-state permeate flux of dextran solution with time for
different stirrer speeds (at feed concentration ) 28 kg/m3; transmembrane
pressure ) 200 kPa; membrane porosity ) 10%; membrane thickness ) 1
µm).
Figure 8 depicts the unsteady-state permeate flux variation of
dextran solution with time for different stirrer speed with initial
feed concentration of 28 kg/m3 and transmembrane pressure of
200 kPa. As expected, there is an initial sharp drop in the permeate
flux from the initial value for short filtration time. Zaidi and Kumar8
have experimentally found the similar type of flux decline trend
for the dextran water solution using unstirred batch cell. Chudacek
and Fane29 have also used stirred batch cell with stirrer speed of
1000 rpm for the separation of dextran solution and obtained the
same type of results what we reported in Figure 8. Many researchers
suggested that the permeate flux versus time curve can be divided
into two domains.30-32 Domain 1 is the initial decline of flux that
may be attributed to the membrane fouling. This domain is
characterized by an operationally irreversible deposition of material
in the membrane pores and the sorption on the membrane surface
of the macromolecules initially present in the bulk solution. Domain
2, the remaining flux versus time curve, may be associated with
the concentration polarization and gel layer formation phenomena.
This domain is characterized by the reversible deposition of
macromolecules on the membrane surface. Mehta33 has also
developed a model and reported that the rate of flux decline with
time is a linear function of the difference between the flux at any
time during the time period and the flux at the end of the time
period investigated. The resulting independent solutions were
combined to provide the global solution applicable for the entire
flux vs time curve. However, one can minimize the flux decline
due to adsorption of solute layers at the membrane surface by
changing the membrane material or chemically modifying it. The
adsorption at the membrane surface occurs due to the strong
interaction between the solute and membrane material. The result
of Cherkasov et al.34 study showed that hydrophobic membranes
attracted a thicker irreversible adsorption layer than hydrophilic
membranes.
Figures 9 and 10 demonstrate the unsteady-state effect of
membrane surface concentration and permeate concentration
with time for different stirrer speed with constant transmem-
brane pressure of 200 kPa, respectively. Many studies
4434 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009
Figure 9. Unsteady-state effect of membrane surface concentration (Cm)
of dextran solution with time for different stirrer speeds (at feed concentra-
tion ) 28 kg/m3; transmembrane pressure ) 200 kPa; membrane porosity
) 10%; membrane thickness ) 1 µm).
Figure 10. Unsteady-state effect of permeate concentration (Cp) of dextran
solution with time for different stirrer speeds (at feed concentration ) 28
kg/m3; transmembrane pressure ) 200 kPa; membrane porosity ) 10%;
membrane thickness ) 1 µm).
reported experimentally that, at the start of separation,
membrane surface concentration is equal to bulk concentra-
tion. So, osmotic pressure is contributed only by bulk
concentration of the solution. As the time progress, membrane
surface acquires more mass from the bulk due to the
convection. Some acquired mass on the membrane surface
is returned to the bulk by diffusion due to the higher
concentration than the bulk. After a certain time, membrane
surface reaches the equilibrium concentration (see Figure 9),
which is more than bulk concentration and flux becomes
steady for that transmembrane pressure and stirrer speed. It
is observed from the Figure 9 that flux attains steady state
Figure 11. Unsteady-state effect of permeate flux of dextran solution with
time for different transmembrane pressures (at feed concentration ) 28
kg/m3; stirrer speed ) 57.3 rpm; membrane porosity ) 10%; membrane
thickness ) 1 µm).
quickly with increase of stirrer speed. This is because of the
augmentation of the back diffusion rate resulting in less
concentration at the membrane surface and so flux reaches
steady state quickly. It elucidates that higher stirrer speed
makes the flux variation small for a particular pressure that
is due to less membrane surface concentration and the
permeate concentration decreases with increasing stirrer
speed. It can be clearly seen from the Figures 9 and 10 that
the time required to reach steady-state permeate concentration
(Cp) and membrane surface concentration (Cm) is not same.
In all the cases, membrane surface concentration requires less
time to obtain steady state than the permeate concentration.
Figures 11-13 explain the unsteady-state effects of permeate
flux, membrane surface concentration, and permeate con-
centration of dextran for different transmembrane pressure
(100, 200, and 300 kPa), respectively, at 57.3 rpm stirrer
speed. For a fixed stirrer speed, increasing applied pressure
enhances the flux. Initially, the change of flux with time (dJ/
dt) is different for different pressures and after a certain time,
it becomes the same and the gradient becomes zero after 10 s.
From Figure 11, one can notice that at 1 s, dJ/dt for the
pressures of 100, 200, and 300 kPa are almost equal. This
gradient becomes equal for the pressure of 200 and 300 kPa
at 0.1 s, suggesting that at higher pressure there would be
no gradient difference. The experimental results reported in
ref 8 also support the trend presented in Figure 11, though
the time scales do not match well because experiments were
performed by using unstirred batch cells with low dextran
concentration. The flux decline due to increase of the
concentration of membrane surface is also time dependent.
However, the doubling of applied pressure does not lead to
the doubling of permeate flux, because the increase of applied
pressure partially was compensated by an increase of osmotic
pressure due to increase of membrane surface concentration.
It is observed from Figures 12 and 13 that the membrane
surface and permeate concentration acquire higher concentra-
tion for higher pressure as is common in filtration practice.
Zaidi and Kumar8 experimentally proved that the rejection

Figure 12. Unsteady-state effect of membrane surface concentration of
dextran solution with time for different transmembrane pressures (at feed
concentration ) 28 kg/m3; stirrer speed ) 57.3 rpm; membrane porosity )
10%; membrane thickness ) 1 µm).
Figure 13. Unsteady-state effect of permeate concentration of dextran
solution with time for different transmembrane pressures (at feed concentra-
tion ) 28 kg/m3; stirrer speed ) 57.3 rpm; membrane porosity ) 10%;
membrane thickness ) 1 µm).
of dextran was more for lower pressure compared to that of
higher applied pressure. This implies that the permeate
concentration is low at low applied pressure while higher
pressure gives high permeate concentration. Our simulation
results reported in Figures 12 and 13 also support this
experimental phenomenon and show the dynamics of mem-
brane surface concentration and permeate concentration.
5.2. Separation Performance of Silica Suspension Using
Totally Retentive Membrane in the Batch Mode Opera-
tion. In this case, we have used a totally retentive membrane
to study the separation performance of silica in the batch
Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4435
Figure 14. Unsteady-state effect of membrane surface concentration of silica
suspension with time for different transmembrane pressures for stirred batch
mode (initial feed concentration cf0 ) 2.5 kg/m3; stirrer speed ) 9.55 rpm).
Figure 15. Unsteady-state effect of permeate flux of silica suspension with
time for different transmembrane pressures for stirred batch mode (initial
feed concentration cf0 ) 2.5 kg/m3; stirrer speed ) 9.55 rpm).
mode of operation using stirred UF cell (see Figure 2b). The
mass of silica in the upstream side is same as the initial mass
for all the process time, as there is no passage of silica
through the membrane and only water is passing through
membrane. It is well-known that the separation of silica
suspension by membrane forms a gel layer on the membrane
surface. The osmotic pressure effect is negligible and hence
flux is governed by a gel polarization model. Figures 14 and
15 demonstrate the plot of unsteady-state membrane surface
concentration (Cm) and permeate flux with time for silica
suspension with different transmembrane pressures (200-900
kPa). The results indicate that there is no reduction of applied
4436 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009

pressure because of negligible osmotic pressure of silica.

There is no flux reduction with the time until the membrane
surface obtains the gel concentration (shown in Figure 15)
and this time is termed as characteristic time.10 Higher
pressures result in less characteristic time than the lower
pressure. For this simulation, we have taken the gel concen-
tration value of silica solute as 230 kg/m3 from the published
literature12 for different operating pressures, though the
thermodynamic relation of gel concentration depends on both
temperature and pressure35,36 and their experimental work
showed almost constant (230 kg/m3)12 for varying pressure
ranges from 100-200 kPa. The gel layer initiates to form
over the membrane surface and increases with the time of
operation. This layer provides an additional resistance that
results in a flux decline. For higher pressures, the membrane
surface acquires the gel concentration much faster than for
the lower pressure for a fixed initial feed concentration, which
can be seen from Figures 14 and 15. For lower pressure, no
gel layer appears within 2000 s. For an example, at 400 kPa
transmembrane pressure, membrane surface reaches gel
concentration at 1135 s while for 500 kPa pressure it takes
170 s. Before gel formation, there is small flux decline that Figure 16. Unsteady-state effect of membrane surface concentration of silica
is due to the increase of viscosity. For all the pressure ranges suspension with time for different initial feed concentrations (transmembrane
studied, the increase of membrane surface concentration has pressure ) 200 kPa; stirrer speed ) 9.55 rpm).
two slopes (see Figure 14). The steepest slope is for initial
unsteady effect due to the formation of concentration
polarization. The second slope is due to the increase of
upstream side concentration. So membrane surface concen-
tration increases until it reaches the gel concentration. This
high concentration at the membrane surface is due to high
rejection of silica which is found to be nearly 100%. The
concentration at the membrane surface increases with the
transmembrane pressure for a fixed initial feed concentration.
This is mainly due to the low rate of back transport of silica
(because of low diffusion coefficient of silica). This implies
that gel formation is rapid and instantaneous at the beginning
of separation, particularly at higher applied pressure. From
Figure 15, it is unambiguous that the permeate flux follows
the same path after a certain time for 700, 800, and 900 kPa
transmembrane pressure; i.e., the flux becomes independent
of pressure which is known as the limiting flux. Figure 16
depicts the unsteady-state effect of initial feed concentration
of silica suspension on the membrane surface concentration
with time. It demonstrates that pressure of 200 kPa is not
sufficient for the initial feed concentration of 120 kg/m3 to Figure 17. Comparison of unsteady-state permeate flux of silica
acquire the gel concentration within 2000 s at the membrane suspension versus time simulated by using Aspen with experimental data
surface. Figure 17 shows the comparison of permeate flux reported by Zaidi and Kumar10 (initial silica feed concentration of 28
kg/m3, pressure of 270 and 405 kPa).
versus time obtained from simulation by using Aspen with
experimental data reported by Zaidi and Kumar10 (initial the stirrer speed of the UF cell from 4.8 to 47.7 rpm by keeping
silica feed concentration of 28 kg/m3, pressure of 270 and the initial feed concentration and transmembrane pressure of
405 kPa). It can be seen that experimental results match well 30 kg/m3 and 1200 kPa, respectively, and the results are shown
with the simulation done in Aspen. So it is strongly advocated in Figures 19-21. As can be seen from Figure 19, at the
that Aspen Engineering Suite is justified as a modeling tool beginning, the permeate flux is a time invariant for all the stirrer
for NF/UF/MF. speed studied. After a few seconds, a sudden drop in the flux is
The effect of gel layer thickness of silica suspension with observed due to the buildup of polarization at the membrane
time for different transmembrane pressures with initial feed surface. This leads to an increase in the concentration at the
concentration of 30 kg/m3 is shown in Figure 18. At higher membrane surface and the same can be seen in Figure 20. As
pressure, gel layer thickness is more which results in more the stirrer speed increases, the time required to reach the gel
resistance. With the initial feed concentration of 30 kg/m3 and layer formation increases which is due to the removal of silica
stirrer speed of 9.55 rpm, the applied pressure of 200 kPa is particle from surface of membrane. Figure 21 represents the
not enough to form gel within 400 s. It is expected that with deposited gel layer thickness as function of time for an initial
increasing pressure the gel layer formation is faster. To study feed concentration of 30 kg/m3 and transmembrane pressure of
the influence of stirrer speed on flux, concentration of the 1200 kPa. At a particular time, the rate of solute deposition is
membrane surface (Cm), and gel layer thickness, we have varied higher for lower stirrer speed that leads to build up of a thick

Figure 18. Unsteady-state effect of gel layer thickness of silica suspension
with time for different transmembrane pressures (initial feed concentration
cf0 ) 30 kg/m3; stirrer speed ) 9.55 rpm).
Figure 19. Unsteady-state permeate flux of silica suspension with time for
different stirrer speeds in batch mode operation (initial feed concentration
cf0 ) 30 kg/m3; transmembrane pressure ) 1200 kPa).
layer and is also confirmed from Figure 19. The reason for this
behavior may be due to the increase in the bulk concentration
at the upstream side of membrane that provides additional
resistance.
6. Conclusion
We have successfully modeled the separation performance
of dextran and silica suspension in a dead-end stirred UF
using Aspen Engineering Suite. For dextran solution, it is
observed that the permeate flux increases with the stirrer
speed up to a certain range beyond which the flux remains
constant. Higher stirrer speed with a constant transmembrane
pressure offers more permeate flux and observed rejection.
Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4437
Figure 20. Unsteady-state effect of membrane surface concentration of silica
suspension with time for different stirrer speeds in batch mode operation
(initial feed concentration cf0 ) 30 kg/m3; transmembrane pressure ) 1200
kPa).
Figure 21. Unsteady-state effect of gel layer thickness of silica suspension
with time for different stirrer speeds in batch mode operation (initial feed
concentration cf0 ) 30 kg/m3; transmembrane pressure ) 1200 kPa).
The flux decline rate is larger for higher applied pressure
with constant stirrer speed. As the membrane porosity
increases, the observed rejection and permeate concentration
decrease. For silica suspension, an increase of stirrer speed
reduces the flux and increases the time required to reach the
gel layer formation at the membrane surface. At the begin-
ning, permeate flux is time invariant for all the stirrer speeds
studied; after a few seconds, a sudden drop in the flux is
observed due to build up of polarization at the membrane
surface. For a fixed transmembrane pressure and stirrer speed,
fouling is more for higher initial feed concentration. It is
also concluded from the above study that higher stirrer speed
and less initial feed concentration are favorable for pressure-
4438 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009

driven membrane filtration process by providing less flux υg thickness of the gel layer
decline. Simulation results of UF of silica suspension using ∂mem thickness of membrane (m)
Aspen Engineering Suite was compared with experimental ∂pol thickness of concentration polarization layer (m)
data reported in the literature and it matches quite well. It
justifies that the Aspen Engineering Suite can also be used
as a modeling tool for NF/UF/MF. Literature Cited
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ReceiVed for reView August 25, 2008
ReVised manuscript receiVed January 14, 2009
Accepted March 16, 2009
IE801293D