Desalination 285 (2012) 383–392

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Desalination
journal homepage: www.elsevier.com/locate/desal

Simulation of ammonia removal from industrial wastewater streams by means of a

hollow-fiber membrane contactor
Mashallah Rezakazemi, Saeed Shirazian, Seyed Nezameddin Ashrafizadeh ⁎
Research Lab for Advanced Separation Processes, Department of Chemical Engineering, Iran University of Science and Technology, Narmak, Tehran 16846-13114, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The performance of a hollow-fiber membrane contactor in removing ammonia from aqueous solution was
Received 22 September 2011 simulated. An unsteady state 2D mathematical model was developed to study the ammonia stripping in
Received in revised form 14 October 2011 the hollow-fiber membrane contactor. Two sets of equations were considered for the membrane contactor
Accepted 18 October 2011
and the feed tank. CFD technique was applied to solve the model equations in which concentration distribu-
Available online 17 November 2011
tion was determined using continuity equation. Velocity field is also determined using Navier–Stokes equa-
Keywords:
tions for the contactor. The model was implemented in linked MATLAB–COMSOL Multiphysics. COMSOL
Membrane contactor software was applied to solve the model equations for the contactor while MATLAB software was employed
Mass transfer to consider changes in the concentration of the feed tank. Predictions of the model were then validated
Wastewater treatment against experimental data which were found to be in good agreement. The assumption of Knudsen diffusion
Ammonia removal for the transport of ammonia molecules through the membrane pores increased the accuracy of the model.
CFD The effect of different parameters including feed velocity, feed concentration and pH on the removal of am-
monia was investigated. The results of simulation revealed that the developed model can be used to evaluate
the effective parameters which involve in the ammonia removal by means of membrane contactors.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction The mechanism of separation in this kind of membrane contactors

Ammonia (NH3) has been recognized as a major pollutant in both
municipal and industrial wastewater. Dissolved ammonia exists in in-
dustrial wastewater such as coking, chemical fertilizer, coal gasifica-
tion, petroleum refining, pharmaceutical and catalyst factories [1].
From the environmental point of view, a complete removal of ammo-
nia from wastewater is desirable. This obligation is due to the ex-
tremely toxic nature of ammonia to most fish species and the fact
that it becomes bio-oxidized by nitrifying microorganisms to nitrites
which are undesirable to humans. The concentration of ammonia in
industrial wastewater varies from 5 to 1000 mg/L [2]. The removal
of dissolved ammonia from wastewater is thus mandatory to protect
the environment and human health.
Some conventional separation processes have been applied to re-
move ammonia from water and wastewater including air stripping,
selective ion exchange, break-point chlorination, denitrification, and
biological nitrification [3–8]. Recently, hollow-fiber membrane con-
tactors (HFMCs) have attracted large attentions as a powerful device
for the latter purpose. A major part of the interest towards HFMCs is
due to their capability in setting a dispersion free contact. In addition,
the velocities of both phases can be chosen independently, while nei-
ther flooding nor unloading problems may arise [9–11].
⁎ Corresponding author. Tel.: + 98 21 77240496; fax: + 98 21 77240495.
E-mail address: ashrafi@iust.ac.ir (S.N. Ashrafizadeh).
is based on the mass transfer between the two phases. The ammonia
evaporates from the aqueous solution, diffuses through the mem-
brane pores, and reacts with the stripping solution.
There are few studies on ammonia removal from wastewater.
Hasanŏglu et al. [3] experimentally and theoretically studied the
performance of the hydrophobic hollow-fiber and flat-sheet membrane
contactors under various operational configurations, temperature, and
hydrodynamic conditions for the ammonia removal from wastewater
streams. They developed a model based on a resistance-in-series model.
Tan et al. [12] developed a mass transfer model based on plug flow
behavior for the ammonia removal in polyvinylidene fluoride (PVDF)
hollow fibers. At any cross-section of the lumen, overall mass transfer
coefficient was empirically estimated. Mandowara et al. [13] simulat-
ed the ammonia removal process in HFMCs in an unsteady state
mode. They converted governing equations into a series of stiff
ODEs and solved the equations using MATLAB software. Their model
findings revealed that the plug-flow model over-predicts the removal
of ammonia. Their numerical model which was performed with some
assumptions, although considers the axial and radial diffusions it can
neither investigate the effect of operating parameters nor identify the
concentration variations in the contactor.
Zhu et al. [14] investigated the effect of pH and viscosity of feed
solution on the mass transfer in HFMCs. Based on their results, it is
more accurate to use the equilibrium concentrations instead of the
total concentration of ammonia to simulate the process. Semmens
et al. [15] discussed the effect of pH on the mass transfer coefficients.

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.10.030
384 M. Rezakazemi et al. / Desalination 285 (2012) 383–392
There are two approaches for the mass transfer modeling of ammo-
nia removal from wastewater using HFMCs. The first one is based on the
resistance-in-series model. In this model, the resistances in the aqueous
feed phase, boundary layer, and the membrane phase are considered in
series, while the resistance at the shell side is neglected because of in-
stantaneous chemical reaction which occurs between ammonia and
sulfuric acid. The latter approach needs mass transfer coefficients for
the feed and membrane phases to be estimated. The experimental cor-
relations are extensively used to estimate the mass transfer coefficients;
which are dependent on Reynolds and Schmidt numbers. Calculation of
mass transfer coefficients by this method should be thus estimated
using experimental data and may be inaccurate.
The second approach is based on solving conservation equations for
ammonia in the aqueous feed and membrane phases. In this approach,
conservation equations including continuity, energy, and momentum
equations are derived and solved simultaneously by appropriate nu-
merical methods. The applications of computational fluid dynamics
(CFD) are usually carried out in three steps: preprocessing, processing,
and post processing, respectively. To our knowledge, there is no CFD
simulation study on mass and momentum transfers of ammonia in
HFMCs. The difficulty of this process is due to the application of recy-
cling mode of the process which needs an unsteady state simulation.
For the ammonia removal, two sets of equations are required for the
simulation process. The first one is for the feed tank and the second
one is for the membrane contactor. These two sets of equations should
be solved simultaneously to simulate the process.
The main objective of the present study is to develop and solve a
mathematical model for the simulation of ammonia stripping in a
HFMC with recycling mode. The equations of the model are solved by
numerical method based on CFD techniques. An algorithm is developed
for the numerical simulation. Considering the recycling mode makes
the modeling difficult, since it needs a link between the two sets of
equations. Continuity and Navier–Stokes equations are solved simulta-
neously for the membrane contactor to obtain the concentration distri-
bution of ammonia. Concentration of ammonia in the feed tank is
obtained through a mass balance over the feed tank while considering
a complete mixing. The main advantage of the developed model is
that parameters which affect the contactor performance can be modi-
fied and investigated. The model is developed for recycling mode
which is difficult to be built up by CFD techniques.
2. Experimental
2.1. Reagents
All chemicals used were analytical grade reagents from Merck. All
aqueous solutions were prepared using distilled water. Solutions
Fig. 1. Experimental setup used for ammonia stripping.
containing ammonia were prepared through addition of measured
volumes of ammonium hydroxide to distilled water. Aqueous ammo-
nium solutions were buffered with potassium dihydrogen phosphate
and di-potassium hydrogen phosphate. The stripping solution was
prepared through addition of specified volumes of sulfuric acid to dis-
tilled water. The ammonia concentration in the solution was analyzed
by Nesslerization [16]. The concentration of ammonia in the samples
was measured using a UV–visible Scanning Spectrophotometer, Cam-
specM350 model [16].
2.2. Experimental setup
A schematic representation of HFMC used for the removal of dis-
solved ammonia is shown in Fig. 1. The ammonia aqueous solution
was passed through the lumen side whereas the stripping solution con-
taining sulfuric acid was pumped into the shell side of the HFMC. Since
the gas–liquid interface is established on the pore mouth adjacent to the
shell side, passing feed solution through lumen side is more favorable
because it generates higher contact area between two phases.
Both solutions were recycled to their own reservoirs. Since the reac-
tion between ammonium and sulfuric acid is exothermic, a cooling
water system was used to maintain the temperature constant at 20 °C
and prevent increasing the feed temperature. The characteristics of
the HFMC and experimental conditions are presented in Tables 1 and 2.
To calculate Reynolds number, velocity of the feed solution in the
lumen side is required. The velocity of the liquid feed solution can be
obtained from Eq. (1):
Q
V lumen ¼ ð1Þ
nπðr in Þ2
where rin, Q, and n, are inner radius of hollow fiber, volumetric flow
rate, and number of fibers, respectively. Reynolds number for the
feed phase is calculated through Eq. (2):
2  Vlumen  r in
Refeed ¼ ð2Þ
νw
where νw is kinematic viscosity of the feed phase. It is notable that the
kinematic viscosity of ammonia-containing feed solution was as-
sumed equal to that of pure water.
2.3. Analytical procedure
At regular time intervals, 1 mL samples were taken from the feed
solution and were immediately diluted to a certain volume. The con-
centration of ammonia was then determined by Nesslerization tests
 M. Rezakazemi et al. / Desalination 285 (2012) 383–392 385

Table 1 Substitution of Eqs. (4) and (6) into Eq. (7) yields:
Characteristics of Liqui-Cel HFMC and operating conditions of experiments.

Parameter Symbol Value Unit

½OH −  Ka
Fiber inner radius rin 110 μm α NH3 ¼ ¼ : ð9Þ
½OH−  þ K b K a þ ½Hþ 
Fiber outer radius rout 150 μm
Fiber porosity ε 40 %
Fiber tortuosity τ = 1/ε2 6.25 –
Fiber length L 25 cm
Number of fibers N 6000 – Eq. (9) indicates that the relative concentration of the two species
Pore diameter D 0.03 μm depends on the pH of the solution. In the current modeling, concen-
Shell side geometric void fraction – 0.40 – tration of ammonia ([NH3]) was calculated.
Effective area S 1.4 m2
Temperature T 293 K

2.5. Mechanism of ammonia removal in HFMCs

of the dilute solutions. Each reported experimental result is the arith-
metic mean of at least two replicate experiments. Ammonia stripping by means of HFMCs is carried out in recycling
The Taguchi method was used to design the experiments. More mode. Recycling mode increases the removal of ammonia. In this pro-
details on experiments have been mentioned elsewhere [1]. cess, an aqueous solution of ammonia as feed is passed inside the lu-
mens of membrane contactor. The stripping solution, which due to
2.4. Theory the high reaction rate between ammonia and sulfuric acid can be
mostly considered as a dilute sulfuric acid solution, is circulated in
In the dissolved state, ammonia exists in two forms. One is toxic the shell side of the contactor. Some distinct researchers have pre-
ammonia (NH3) and the other is less harmful ammonium ions ferred to circulate the feed solution in the lumen side [3–5]. It has
(NH4+). The composition of these constituents depends on the pH been claimed that using this configuration, the formed interface be-
and temperature of the solution from the following dissociation tween gas and liquid at the outer surface of fibers is higher than
equilibrium: that at the inner surface. Therefore, passage of the feed solution
from the lumen side is presumed to provide higher interfacial mass
Kb þ − transfer area. In spite of this explanation, the experimental data
NH 3 þ H 2 O →
←
NH4 þ OH : ð3Þ
Ka used in the current study have been collected from a configuration
in which the feed solution is passed through inside the lumens. At
Equilibrium constants can be defined from the following equations: the same time, another research is being conducted by the current au-
thors to examine the previously mentioned flow configuration and

 compare the results with the current data.
½NH3  H þ
Ka ¼
þ ð4Þ By contacting two phases in the membrane contactor, ammonia
NH 4
is transferred by convection and diffusion mechanisms from the

þ bulk of the feed towards the feed-membrane interface. At the fiber
NH4 ½OH−  wall (inner radius of hollow fiber), ammonia is volatilized into the
Kb ¼ : ð5Þ
½NH 3  membrane pores which are filled by gas. Ammonia then diffuses
across the gas-filled pores of the HFMC, and is transferred into the
However, Ka and Kb values are equal to 5.6 × 10 − 10 and 1.8 × 10 − 8, stripping solution. At the shell-membrane interface, ammonia imme-
respectively [17]. The total concentration of ammonia in the feed so- diately reacts with stripping solution and forms a nonvolatile com-
lution is the summation of equilibrium concentrations of ammonium pound. Therefore, the ammonia concentration in the stripping
([NH4+]) and ammonia ([NH3]) in the feed solution: solution is assumed to be maintained at zero. On the other hand,
h i water cannot diffuse through the hydrophobic fibers of HFMC. The
þ
C total ¼ NH4 þ ½NH 3  ð6Þ principle of ammonia removal through HFMC is schematically
shown in Fig. 2.

Therefore, concentration of each species can be related to the total

concentration. 3. Mass transfer model

½NH 3  A considerable amount of literature has been published on model-

α NH3 ¼ ð7Þ
C total ing of different membrane processes [18]. In this study, a comprehen-

þ sive 2D mathematical model was proposed to describe the transport
NH4 of ammonia through HFMC. The model was based on the “non-wet-
α NH þ ¼ ð8Þ
4 C total ted” mode in which the gas fills the membrane pores. The stripping
solution flows in the shell side, whereas the aqueous feed solution
is fed to the lumen side of the HFMC. Velocity distribution in the
Table 2 lumen side is determined through Navier–Stokes equations. The am-
Experimental conditions for ammonia removal. monia concentration is determined using continuity equation. Axial
and radial diffusions inside the lumen side and through the mem-
Run Ammonia Ammonia Ammonia Stripping Reynolds
feed initial feed velocity feed velocity number of brane of HFMC are considered in the model equations. Chemical reac-
concentration (m/s) (pH) (m/s) feed (Refeed) tion between ammonia and sulfuric acid, which occurs in the shell
(ppm) side, is assumed to be instantaneous. Recycling mode is considered
1 50 0.053 8 0.02 11.66 in the simulation; which implies that two sets of equations must be
2 200 0.213 10 0.20 46.86 solved to simulate the whole process. The first set of equations is
3 400 0.106 11 0.05 23.32 obtained through a mass balance over the feed tank, and the second
4 800 0.160 9 0.10 35.20
set of equations is for the contactor.
386 M. Rezakazemi et al. / Desalination 285 (2012) 383–392

Fig. 2. Mechanism of ammonia removal in HFMCs.

3.1. Equations of the model 3.2. Equations of lumen side

The ammonia flows with a laminar velocity inside the lumens. As The unsteady state continuity equation for ammonia in the lumen
it is indicated in Table 2, flow regime is laminar and far from turbu- side of the HFMC in cylindrical coordinate is obtained using Fick's law
lent flow. The ammonia aqueous solution is fed to the lumen side of diffusion. From this equation the diffusive flux is estimated:
(at z = 0), while the stripping solution is passed through the shell " #
2 2
side. Ammonia is removed from the aqueous solution by subsequent ∂C NH3 −lumen ∂ C NH3 −lumen 1 ∂C NH3 −lumen ∂ C NH3 −lumen
þ DNH3 −lumen þ þ ð12Þ
diffusion through the bulk of liquid and membrane, and becomes ∂t ∂r 2 r ∂r ∂z2
absorbed into the liquid stripper. The model is built considering the ∂C NH3 −lumen
following assumptions: ¼ V z−lumen :
∂z
• Unsteady state and isothermal conditions.
• Laminar flow for both streams in the HFMC. Velocity distribution in the lumen side is determined by solving the
• Henry's law is applicable for feed-membrane interface (Thermody- momentum equation, i.e. Navier–Stokes equations. Therefore, the
namic equilibrium). momentum and the continuity equations should be coupled and solved
• No pore blockage occurs. simultaneously to obtain concentration distribution of ammonia in the
• Non-wetted mode for the membrane is assumed; in which the feed lumen side. The Navier–Stokes equations describe flow in viscous fluids
aqueous solution do not fills the membrane pores (since the HFMC through momentum balances for each of the components. The latter
is hydrophobic; it prevents passage of feed aqueous solution also assume that density and viscosity of the fluids are constant,
through the pores). which yields to a continuity condition. The Navier–Stokes equations
• There is no reaction zone (the reaction of ammonia with the sulfuric are defined as follows [19]:
acid is fast (instantaneous) and always occurs in excess).  
• Flow rates of both ammonia solution and sulfuric acid are constant. −∇⋅η ∇V z−lumen þ ð∇V z−lumen ÞT þ ρðV z−lumen :∇ÞV z−lumen
ð13Þ
• Feed tank operates at the perfect mixing mode. þ∇p ¼ F∇:V z−lumen ¼ 0

3.1.1. Mass balance over ammonia tank where η ,V, and ρ denote fluid dynamic viscosity (kg/m.s), velocity
The first equation is obtained for the ammonia tank using a mass vector (m/s), and density (kg/m 3), respectively; p is pressure (Pa)
balance. The mass balance equation over ammonia tank considering and F is a body force term (N).
uniform mixing can be written as follows: Boundary conditions for the lumen side are given as:

@ z ¼ 0; C NH3 −lumen ¼ C tank V z−lumen ¼ V 0 ðInlet boundaryÞ: ð14Þ

dC tank 
V ¼ QC Z¼L −Q C tank ð10Þ
dt

@ t ¼ 0; C tank ¼ C 0 ð11Þ

where Q is volumetric flow rate, m 3/s, V is volume of feed, m 3, t is

time, s, and C is ammonia concentration, mol/m 3. C|Z = L is concentra-
tion of ammonia at the outlet of contactor which is inlet of the feed
tank. The characteristic of inlet flow varies with time; therefore un-
steady state equation of continuity for ammonia in the contactor
should be solved to obtain this parameter. Important parameters
and model domain are illustrated in Fig. 3.

3.1.2. Mass transfer equations for HFMC

The second sets of equations are for the membrane contactor.
Membrane contactor is divided in two subdomains, i.e. lumen side
and membrane. Fig. 3. Model domain for numerical simulation.
 M. Rezakazemi et al. / Desalination 285 (2012) 383–392 387

V0 is calculated from the flow rate:
Q error control using numerical solver of UMFPACK version 4.2. This
V0 ¼
nπr2in
where rin, Q, and n are inner radius of hollow fiber, volumetric flow
rate, and number of fibers.
@ z ¼ L; Convective flux; p ¼ patm ðOutlet boundaryÞ
The boundary condition for the convective flux assumes that the
mass passing through this boundary is convection-dominated. In
other words, it assumes that the mass flux due to diffusion across
this boundary is zero.
∂C NH3 −lumen
@ r ¼ 0; ¼ 0 Axial symmetry
∂r
@ r ¼ r in ; C NH3 −lumen ¼ pNH3 −membrane =H No slip condition
where rin, H, and pNH3 − membrane are inner radius of hollow fiber, Hen-
ry's law constant, and partial pressure of ammonia in the gas phase of
membrane pores in equilibrium with the concentration of this com-
pound in the aqueous solution (CNH3 − lumen).
Ammonia at the liquid–membrane interfaces is in thermodynamic
equilibrium with its vapor. Hence, Henry's law is applied and the par-
tial pressures of the ammonia were estimated from the correlation for
Henry's constant. The Henry's constant can be defined as follows [3]:
element method (FEM) for numerical solution of the equations. The
finite element analysis is combined with adaptive meshing and
solver is well suited for solving stiff and non-stiff non-linear boundary
value problems. The applicability, robustness and accuracy of this
method for the membrane contactors have been proved through dis-
tinct researches [11,20–23]. It should be pointed out that the COMSOL
mesh generator creates triangular meshes that are isotropic in size. A
ð15Þ
large number of elements are then created with scaling. A scaling fac-
tor was employed for the contactor in the z direction due to a large
difference between r and z. COMSOL automatically scales back the ge-
ometry after meshing. This generates an anisotropic mesh around
3150 elements. Adaptive mesh refinement in COMSOL, which gener-
ates the best and minimal meshes, was used to mesh the HFMC
geometry.
ð16Þ Since the ammonia concentration in the feed tank varies with
time, COMSOL is linked to MATLAB to solve both equations of the
feed tank and contactor. The algorithm which was developed for the
numerical simulation is shown in Fig. 4. By this method, variations
of both concentration and velocity can be evaluated within the con-
tactor; on the contrary of previous models which fail to investigate
variations inside the contactor. An IBM-PC-Pentium 4 (CPU speed is
2800 MHz) was used to solve the sets of equations.

4200 Start
ln H ¼ − þ 3:133 ð17Þ
T

where H is Henry's constant in atm.m 3 mol − 1, and T is in Kelvin. Input constant

3.3. Equations of membrane

Set t=0
The unsteady-state continuity equation for the transport of am-
monia inside the membrane, which is considered to be due to diffu-
sion alone, may be written as: COMSOL
MATLAB
∂C NH3 −membrane
∂t " 2 # Add subdomain
∂ C NH3 −membrane
2
1 ∂C NH3 −membrane ∂ C NH3 −membrane t = t + Δt equations
þ DNH3 −membrane þ þ ¼ 0:
∂r 2 r ∂r ∂z 2

ð18Þ Define geometry

Solve mass balance
equation over
Boundary conditions for the membrane are given as: ammonia tank
Result Initialize mesh
@ r ¼ r in ; pNH3 −membrane ¼ C NH3 −lumen  H ðHenry lawÞ ð19Þ

@ r ¼ r out ; C NH3 −lumen ¼ 0 C NH3 −lumen ¼ 0: ð20Þ Adapt mesh

t<=t1 NO

The reaction rate between ammonia and acid sulfuric is assumed to

Set subdomain
YES

be instantaneous; therefore the ammonia concentration in the shell conditions

side of the membrane contactor was not determined and assumed to
be zero.
Set boundary
It is also assumed that there is no mass transfer at both edges of conditions
the fibers, i.e.:

@ z ¼ 0 & L; Insulation Solve coupled

equations

3.4. Numerical solution of the model equations Integrate from outlet

concentration
The main objective of the present study is to model HFMC with
recycling mode using CFD of mass and momentum transfers. The
equations of contactor related to the lumen side and the membrane End
with appropriate boundary conditions were solved using COMSOL
Multiphysics version 3.2 software (Sweden), which uses finite Fig. 4. Algorithm developed for numerical simulation.
388 M. Rezakazemi et al. / Desalination 285 (2012) 383–392

4. Results and discussions Table 3

Comparison between experimental and calculated mass transfer coefficients.

4.1. Model validation Run Reynolds number of feed KExp.(× 105) KCal. .(× 105)
(Refeed) (m/s) (m/s)
The main objective of the present study is to simulate ammonia 1 11.66 0.12 0.13
removal in a HFMC considering recycling mode using CFD techniques. 2 46.86 1.32 1.39
By recycling mode ammonia can be almost completely removed. Var- 3 23.32 1.31 1.42
4 35.20 0.69 0.72
iation of ammonia concentration in the feed tank is a vital parameter
which should be accurately calculated. The experimental results
along with the predictions of the model for the concentrations of am-
monia in the feed tank versus time are presented in Fig. 5.
As it can be seen from Fig. 5, the concentration of ammonia is ex- membrane length was considered in the simulation whereas the
ponentially decreased with time, i.e. ammonia concentration sharply actual length of membrane is lower than simulated length.
drops at the initial durations while slightly decreases at advanced
time intervals. This observation could be attributed to the fact that 4.2. Validation of the model using Knudsen diffusion
at the beginning of the operation, the driving force of ammonia trans-
fer between lumen and shell sides of the contactor is high due to a On the basis of the membrane pore diameter and the mean free
relatively high concentration gradient across the membrane. Appar- path of NH3 molecules, it is possible to consider NH3 diffusion across
ently, as ammonia is transferred to the shell side, its concentration the membrane pores as mainly controlled by a combined bulk-
in the feed decreases and that would result in a lower driving force. Knudsen diffusion mechanism.
The predictions of the model presented in Fig. 5 also confirm the Knudsen mode of ammonia transport through the membrane is
validity of the simulation against experimental data. As it is shown, important when the mean free path of the ammonia molecules is
there is a good agreement among the simulated and experimental much greater than the pore size of the membrane, i.e. (rp/λ ≤ 0.05)
results. [24]. In such situations, the collisions of the molecules with the pore
It is notable that the model overestimates the mass transfer flux. walls are more frequent than the collisions among molecules.
The reason is that the fiber length used in numerical calculations is This mechanism which is often predominant in macroporous and
the nominal length which is reported by the manufacturer. However, mesoporous membranes [25] is described by Knudsen equation
the effective length of fibers is smaller than the nominal one. There- for the diffusive flow of molecules in a capillary tube:
fore, the predicted mass transfer area and consequently the predicted  
mass transfer flux are slightly higher than the experimental values. dC
J k ¼ −Dk ð22Þ
To further validate the mass transfer model developed here, mass dz
transfer coefficients calculated using simulations were compared
with the experimental ones. The mass transfer coefficient is of vital where Dk is the Knudsen diffusion coefficient. This coefficient is
importance for design and optimization of ammonia removal process. dependent on the mean molecular speed, u, and pore radius, rp,
The overall mass transfer coefficient for ammonia transport was de- and is given by:
termined as follows:
2
Dk ¼ ur : ð23Þ
V C0 3 p
K¼ ln ð21Þ
At C t
An expression for the mean molecular speed can be obtained from
the kinetic theory of gases [26]:
where K, V, A, C0 and C are the overall mass transfer coefficient, total
volume of feed solution, membrane surface area, concentration of rffiffiffiffiffiffiffiffiffi
8RT
ammonia at initial and time t in the bulk feed solution, respectively. u¼ ð24Þ
πM
Table 3 shows these comparisons. As can be seen, modeling predic-
tions are in good agreement with the experimental ones. It is notable where M is the molecular weight of permeant (kg/mol). Both of
that the calculated mass transfer coefficients are higher than the ex- the diffusion coefficients were corrected for the effect of membrane
perimental ones. This could be attributed to this fact that whole porosity, ε = 0.4 (Table 1), and tortuosity, τ, using the following
relations:

εDk εDNH3
Dk;ef f ¼ and DNH3 ;ef f ¼ : ð25Þ
τ τ

The effective diffusion coefficient can be obtained using the Bonsaquet

equation [27]:

1 1 1
¼ þ : ð26Þ
Deff Dk;ef f DNH3 ;ef f

Therefore, in the current simulation, diffusion through the mem-

Fig. 5. Experimental and simulated concentrations of ammonia in the feed tank vs.
time.
brane pores is considered to be governed by the combined bulk-
Knudsen mechanism. Comparison among experimental and simulat-
ed results considering Knudsen diffusion is presented in Fig. 6. As it
is seen, considering Knudsen diffusion slightly increases the accuracy
of the model predictions. This implies that although the Knudsen dif-
fusion is not predominant, but has a partial contribution in the overall
diffusion across the membrane pores. Furthermore, Fig. 6 confirms
 M. Rezakazemi et al. / Desalination 285 (2012) 383–392 389

Fig. 6. Concentration of ammonia in the feed tank vs. time: comparison among
experimental results with simulated values considering Knudsen diffusion.

the superiority of the developed model for predicting unsteady state

concentration of ammonia. Therefore, the rest of the reported simula-
tions were investigated with considering Knudsen diffusion.

4.3. Unsteady state concentration distribution of ammonia in the

contactor

The simulation was carried out for run 1 of experiments. Fig. 7 il-
lustrates the concentration distribution of ammonia in the lumen side
of the membrane contactor for different time intervals. The aqueous
feed enters from one side of the contactor (z = 0), whereas the strip-
per solution enters from the opposite side. As the aqueous feed passes
through the lumen side, due to the concentration gradient, ammonia
diffuses from the bulk of the feed towards the membrane surface. At
the surface of the membrane, only ammonia evaporates into the
membrane pores and reaches the shell side. At the shell side of the
membrane surface, an instantaneous chemical reaction occurs be-
tween ammonia and acid sulfuric.
Fig. 7 also illustrates the variations of ammonia concentration dur-
ing the stripping process. As it is seen, at the beginning of the process,
the driving force is higher and thus causes a higher mass transfer rate
of ammonia towards the shell side. This also confirms the trend which Fig. 8. Dimensionless concentration distribution of ammonia (C/Ctank) in the contactor
was observed in at initial periods (Fig. 5). At the end of the process, (t = 1 min).

Fig. 7. Unsteady state concentration distribution of ammonia in the contactor.

390 M. Rezakazemi et al. / Desalination 285 (2012) 383–392

concentration gradient is vanished, which in turn causes a very low

rate of transfer for ammonia.
To investigate the concentration distributions of ammonia in the
lumen side of the membrane contactor in more details, Fig. 8 is
drawn which represents local concentrations. This figure shows di-
mensionless concentration of ammonia at the mesh points used for
numerical simulation. This figure represents the concentrations
1 min after the beginning of the contact. From Fig. 7, it can be seen
that concentration variations in the contactor are significant after
1 min. Therefore, this moment was chosen to further investigate the
contactor performance parameters. As it is seen, the meshes are
more compact in the regions that concentration gradient is large.
Fig. 8 indicates that in the regions near the membrane surface at the
inlet of the lumen side, meshes are very small. In this region, the larg-
est mass transfer flux of ammonia exists. As the feed flows along the
lumen side, concentration gradient decreases, i.e. more uniform dis-
tribution and larger meshes.

4.4. Radial concentration distribution of ammonia in the contactor

Variations of the radial concentration of ammonia in the lumen

side of the membrane contactor were also investigated. In order to
obtain the radial concentration profile in the lumen side, a moment
at which the ammonia removal is significant, was identified. The con-
tact time of 1 min was chosen (see Fig. 6). A plot of the radial concen-
tration profile at t = 1 min and different axial positions along the
lumen side of the membrane contactor is shown in Fig. 9. As it is
seen, in the region near the axis of the fiber (r = 0), the bulk concen-
tration of ammonia only slightly changes. Apparently, the maximum
concentration of ammonia is located in the center of the lumen due
to axial symmetry. Concentration of ammonia reduces gradually in
the region between the center and wall of the lumen side. Eventually,
in the region adjacent the membrane surface, concentration sharply
decreases. This observation could be attributed to the formation of
the concentration boundary layer near the fiber wall. Furthermore,
the ammonia concentration is slightly distributed at Z/L = 1, i.e. at
the lumen exit. On the other hand, at the axial positions near the
lumen entrance, i.e. Z/L = 0.25, concentration changes is more
significant.

4.5. Velocity field in the contactor

The velocity field in the lumen side of membrane contactor was

simulated by solving the Navier–Stokes equations. Fig. 10 shows the
velocity field in the lumen side, within which the aqueous feed
flows. The velocity profile is a parabolic with a mean velocity

Fig. 10. Velocity field in the lumen side of membrane contactor.

increasing along the membrane length. The contours of velocity are

Fig. 9. Radial concentration distribution of ammonia in the contactor at different axial
positions and t = 1 min.
also shown in Fig. 11. At the regions near the membrane surface, ve-
locity reduces because of no-slip condition at the fiber walls. The ef-
fect of viscous forces can be found in this region which causes the
formation of concentration and velocity boundary layers near the
membrane surface. Furthermore, Fig. 11 reveals that the velocity var-
ies in the axial direction. It implies that at the regions close to the
lumen entrance, velocity is not fully developed. This is one of the ad-
vantages of the developed model that considers the entrance effects
which in turn can increase the accuracy of the developed model. In
the middle of the lumen side, the flow tends to be fully developed.
 M. Rezakazemi et al. / Desalination 285 (2012) 383–392 391

4.6. Effect of feed velocity on the concentration distribution of ammonia

in the contactor

Effect of feed velocity on the concentration distribution of ammo-

nia in the contactor is shown in Fig. 12. All provided images are at
t = 1 min for different feed velocities. The values of feed velocities
are in accordance with the experimental data (see Table 2). Obvious-
ly, feed velocity changes the concentration distribution of ammonia in
the lumen side of membrane contactor. Increasing feed velocity re-
sults in a more uniform concentration distribution in both r and z di-
rections. For instance, for the case of Vf = 0.213 m/s, concentration of
ammonia does not reduce significantly along the contactor, i.e. an al-
most uniform distribution is formed except for the regions near the
membrane surface. Increasing feed velocity is not favorable for the
stripping of ammonia; increasing feed velocity reduces the feed resi-
dence time in the contactor which in turn results in a lower mass
transfer rate of ammonia.

5. Conclusions

An unsteady-state, 2D mathematical model was developed to

study the removal of ammonia from aqueous solutions by means of
a hollow-fiber membrane contactor (HFMC). The model predicts the
unsteady state concentration of ammonia in the membrane contactor
as well as the feed tank by solving the conservation equations includ-
ing continuity and momentum. The model was developed consider-
ing a hydrophobic membrane which is not wetted by the aqueous
feed solution. Both axial and radial diffusions within the lumen and
membrane of the contactor were considered. Two sets of equations
were solved simultaneously. The predictions of the mass transfer
model were validated by comparing the results of ammonia stripping
with the experimental data. The simulation results well predict the
unsteady state concentration of ammonia in the feed tank. Further-
more, it was assumed that Knudsen diffusion is responsible for the
ammonia transfer across the membrane pores. The assumption of
combined bulk-Knudsen diffusion increased the accuracy of the
model.

Nomenclature
Fig. 11. Contour of velocity in the lumen side of membrane contactor.
A cross section of tube, m 2
C concentration, mol/m 3
Coutlet outlet concentration of solute in the tube side, mol/m 3
Cintlet inlet concentration of solute in the tube side, mol/m 3
Ci-tube concentration of solute in the tube side, mol/m 3

Fig. 12. Effect of feed velocity on the concentration distribution of ammonia in the contactor (t = 1 min).
392 M. Rezakazemi et al. / Desalination 285 (2012) 383–392

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