3rd International Biennial Conference on Oil, Gas, and Petrochemical Engineering.

Persian Gulf University

Bushehr, Iran .28-30 December 2020
◼ 1

Simulation and modeling of nitrate extraction in

membrane contactors using COMSOL and MATLAB

Amin Jasour1*, Milad Salem Ayegh2

1.Sahand University of Technology, Tabriz, Iran

2.Payame Noor University, Tabriz, Iran

ARTICLE INFO ABSTRACT

Article history: Innovative processes for treating industrial

wastewater containing pollutants often include
Received:
methods to reduce toxicity in order to meet the
Received in revised form: required standards. Membrane contactor
technology is one of the methods that has been
Accepted: considered in the last few decades. These
connectors are devices that transfer gas / liquid or
liquid / liquid without mixing one phase into another.
Keywords: Membranes are easily used to separate and transfer
a specific component from one material to another,
Membrane contactors
due to differences in physical or chemical properties
Nitrate between the membrane and the penetrating
components. This study simulates computational
COMSOL fluid dynamics (CFD) for liquid-liquid extraction
MATLAB without nitrate dispersion in the membrane
contactor. Mass and momentum equations (Navier-
Stokes equations) were used to model the transfer
nitrate through the membrane contactor. In this
Corresponding author:
model with using COMSOL, the distribution of
*
Amin Jasour nitrate concentration and the effect of different
*
parameters on the extraction efficiency was studied
E-mail: aminjaasoor@gmail.com and then we performed modeling in MATLAB
software, by presenting a new model, and we
observed that the results obtained from both are
almost same. In addition, the study showed that
CFD can be used as an effective tool for the
development of membrane contactors.
 ◼ 2
1. Introduction
Nowadays, the environmental
importance of water is considered as
basic necessary everywhere in the
world. Water is the primitive
requirement for human livelihood. Every
day the amount of nitrate pollutants in
water is increasing, especially in
agricultural areas, and this increase in
nitrate causes irreparable damage to
humans, especially infants and the
elderly, so one of the current concerns
is the removal of nitrate from water and
higher and higher demands of water are
put onto new separation technologies.
In order to meet these ever-increasing
needs, there is a tendency to combine
processes to a hybrid process[1].
One of the processes that has received
a lot of attention in recent decades is
membrane contactors. Membrane
contactors can be used in several
industrial areas: liquid/liquid extraction,
gas absorption and stripping,
biotechnology applications,
pharmaceutical applications,
wastewater treatment, metal-ion
extraction, the electronics industry, the
automobile industry, the food industry,
air dehumidification, membrane
distillation, membrane crystallizers,
purification of flue gases[2].
Among the most important advantages
of membrane connectors can mention
the high surface/volume ratio, the
hydrophilic or hydrophobic nature of the
membrane determines the position of
the interface between the feed and the
solvent and the velocities of both
phases can be chosen independently,
while neither flooding nor unloading
problems arise, but these connectors
ISSN: ……..
also have disadvantages such as
formation of stable emulsions, thereby
inhibiting the phase separation and
product recovery; avoid using liquids
having similar densities and foaming.
Additional limitations present in packed
towers include loading requirements
and flooding restrictions. However,
Membrane contactors can overcome
the drawbacks of conventional solvent
extraction processes[3].
Membrane contactors are constituted of
two parts, i.e. lumen and shell side.
Both aqueous and organic solutions
flow continuously, the first one in the
lumen of fibers and the second in the
shell side. The two phases are
separated by a microporous membrane
that acts as an interface between two
streams and controls the mass transfer.
The two streams (liquid or gas) flow
tangentially to the membrane: one
stream contains the liquid or gas to be
treated and the other stream contains
an extractant active towards the specific
molecules that must be separated from
the first stream[4].
The driving force for the mass transfer
usually is a (partial) pressure gradient,
a temperature gradient, or a
concentration gradient at the
membrane interface[5].
Figure 1. Schematic of membrane separation process
 ◼ 3 ISSN: ……..

Thus, the membrane does not act as
selective media, it just acts as an
interface between the two streams. The
selectivity is guaranteed by the
extractant, which is characterized by a
very high affinity for the target molecule.
The extractant must be selected very
carefully in order to accommodate the
process needs. Specifically, it must be
characterized by the following
characteristics: high activity towards the
molecules to be captured; low energy
requirement for regeneration; nontoxic;
noncorrosive; low volatile; low viscosity;
low cost[4].
Trtic-Petrovic et al. used membrane-
based solvent extraction for the
separation of thallium (III) from chloride-
containing acidic solutions with butyl-
acetate. Guo and Ho developed a mass
transfer model for simulation of Cu2+
extraction in a membrane contactor.
Ghadiri et al. used membrane
contactors to measure CO2 absorption
with the mono-ethanol amine extractor
and recently, Pishnamazi et al. used
COMSOL software to simulate
membrane contactors and the amount
of NO2 absorption by the NaOH
extractor.
simulation is to predict the performance
of membrane contactor for extraction of
nitrate.
2. Theory
2.1. Model equations
Figure 2 shows a single flow cell of
hollow fiber module. This flow cell is
divided into three compartments, i.e.,
tube (Lumen side), membrane, and
shell side. One half of the flow cell is
modeled because of symmetrical
geometry. R1, R2, and R3 show the fiber
inside, outside, and shell side radius,
respectively. Aqueous feed that
contains Nitrate is flowing from the
bottom at z = 0, while the Water is fed
at the top at z = L. CNO3-tube, CNO3-mem,
and CNO3-shell denote the concentrations
of Nitrate solute in tube side,
membrane, and shell side of the
module, respectively.

The main purpose of the current study

is to develop and solve a mathematical
model for prediction of nitrate extraction
in membrane contactors. The governing
equations are solved numerically using
CFD techniques.
using CFD techniques. The velocity
field is determined using Navier–Stokes
equations and to ensure the accuracy of
the model by using MATLAB software
Figure 2. A schematic diagram for the membrane
the results of the two simulations will be contactor used for stripping of NO3.
compared to each other. The aim of this
 ◼ 4 ISSN: ……..

The material balance has been carried where 𝐶𝑖 denotes the concentration of
out to model the mass transport across solute (𝑚𝑜𝑙/𝑚3 ), 𝐷𝑖 denotes its
three sections of the module. The diffusion coefficient (𝑚2 ⁄𝑠), 𝑢𝑍 the
model is based on the idea that only velocity vector (𝑚⁄𝑠) and 𝑅𝑖 denotes
portion of fluid surrounding the fiber is the reaction term (𝑚𝑜𝑙/𝑚3 . 𝑠).
considered and may be approximated
𝜕𝐶𝑖 𝜕 2 𝐶𝑖 1 𝜕𝐶𝑖 𝜕 2 𝐶𝑖 (4)
as a circular cross section. Following = 𝐷𝑖 [ 2 + + ]
𝜕𝑡 𝜕𝑟 𝑟 𝜕𝑟 𝜕𝑍 2
assumptions were made in model
development[6, 7], 𝑧 = 𝑡𝑢𝑍 → 𝑑𝑍 = 𝑢𝑍 𝑑𝑡 (5)

1) Steady state and isothermal

conditions. 𝜕𝐶𝑖 𝜕 2 𝐶𝑖 1 𝜕𝐶𝑖 𝜕 2 𝐶𝑖 (6)
𝑢𝑍 = 𝐷𝑖 [ 2 + + ]
2) Fully developed parabolic 𝜕𝑍 𝜕𝑟 𝑟 𝜕𝑟 𝜕𝑍 2
velocity profile inside both fluids
and have constant density. Eq. 6 is the main equation of mass
3) Laminar flow for two phases in transfer. This equation should be solved
the contactor. numerically to obtain the concentration
4) The membrane is completely distribution of solute in the membrane
extraction-phase filled and contactor. To solve the continuity
equilibrium is achieved at feed- equation Eq. 6 velocity distribution is
membrane interface. needed. Velocity distribution is obtained
5) No mixing of phases occurs. by solving the momentum equation, i.e.
6) No solute transport occurs
Navier–Stokes equations. Therefore,
through the non-porous parts of
the momentum and continuity equation
the membrane.
7) The chemical reaction is very should be coupled and solved
fast and achieves equilibrium. simultaneously to obtain the
concentration distribution of solute. We
The main equation that describes the can conclude that the velocity in z
transfer of solute (NO3) from aqueous direction will be a constant value by
phase to organic phase is continuity using the continuity equation given in
equation. The differential form of Equation 7.
continuity equation for solute may be
𝜕𝜌 1 𝜕 1 𝜕 (7)
written as: + (𝜌𝑟𝑢𝑟 ) + (𝜌𝑢𝜃 )
𝜕𝑡 𝑟 𝜕𝑟 𝑟 𝜕𝜃
𝜕
𝑁𝑖,𝑧 𝐴|𝑧 − 𝑁𝑖,𝑧 𝐴|𝑧+𝑑𝑧 (1) + (𝜌𝑢𝑧 ) = 0
+ 𝑁𝑖,𝑟 𝐴|𝑟 − 𝑁𝑖,𝑟 𝐴|𝑟+𝑑𝑟 + 𝑅𝑖 𝑉 𝜕𝑧
𝜕𝐶𝑖 𝑉 𝜕𝑢𝑧 (8)
= = 0 → 𝑢𝑧 = 𝑐 𝑡𝑒
𝜕𝑡 𝜕𝑧

The flow in tube side is assumed to be

𝜕𝐶𝑖 (2)
𝑁𝑖,𝑧 = −𝐷𝑖 Newtonian and fully developed, so the
𝜕𝑧 following equation is used to calculate
𝜕𝐶𝑖 (3) the velocity:
𝑁𝑖,𝑟 = −𝐷𝑖 𝑟 (9)
𝜕𝑟 𝑢𝑧 = 2𝑢̅ [1 − ( )2 ]
𝑅1
 ◼ 5
Where 𝑢̅ is average velocity in the
lumen side and R1 is inner radius of
tube and the velocity in the shell side is
characterized using Navier–Stokes
equations.
Boundary conditions for momentum
balance Navier-Stokes equations are
as follows:
@ r=R1 → uz-tube=0 (no slip condition)
@ r=R2 → uz-tube=0 (no slip condition)
@ z=0 → uz-tube=u0 (inlet boundary)
@ z=l → P=P0 (inlet boundary)
Boundary conditions for numerical
simulation are listed in Table 1. Where
m is partition coefficient of solute
between aqueous phase and organic
phase. C1, C2, and C3 are concentration
of nitrate in the tube, membrane, and
shell side respectively. 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 is zero due to diffusion across
this boundary. Diffusion mechanism
(V=0) is assumed for mass transfer of
solute within the membrane. The
chemical reaction is assumed to be
zero for all sections (Ri=0).
Table 1. Boundary conditions of mass
transfer equations
Position Tube membrane Shell
z=0 (inlet) Ci=C0 insulated flux
z=l flux insulated Ci=0
(outlet)
r=R2 ------ C2=C3 C2=C3
2.2. CFD simulation
The model equations with the
appropriate boundary conditions were
ISSN: ……..
solved numerically using COMSOL
software. This software employs finite
element method (FEM) for numerical
solutions of model equations. The finite
element analysis is combined with
adaptive meshing and error control
using numerical solver of UMFPACK.
This solver is well suited for solving stiff
and non-stiff non-linear boundary value
problems. An Asus laptop model
R542UN (CPU speed is 2 GHz) was
used to solve the set of equations. The
computational time for solving the set of
equations was about 2 min. Table 2
shows parameters used in the
numerical simulation. Module geometry
was scaled down by a factor of 10 in the
axial direction. Scaling down the
geometry reduces the number of
meshes and thus the time of simulation.
For numerical simulation, it is important
to select a mesh that minimizes the
error in the calculations. It is not easy to
specify mesh sizes manually to
minimize the error. The algorithm must
resolve the solution in great detail only
on small portions of the domain.
Adaptive mesh generation identifies the
regions where high resolution is needed
and it produces an appropriate mesh.
The adaptive solver works on linear or
nonlinear stationary PDE problems
(including parameter-dependent
problems) or eigenvalue PDE problems
using the coefficient or general solution
forms. The adaptive mesh refinement
performs the following iterative
algorithm for numerical simulation of
model's equations:
1. Solve the problem on the existing
mesh using the stationary solver.
2. Evaluate the residual of the PDE on
all mesh elements.
 ◼ 6 ISSN: ……..

3. Estimate the error in the solution on side (z=L) where the concentration of
all mesh elements. The computed error solute is assumed to be zero.
estimate is really just an error indicator
because the estimate involves an
unknown constant.
4. Terminate execution if it has made
the requested number of refinements or
if it has exceeded the maximum number
of elements.
5. Refine a subset of the elements
based on the sizes of the local error
indicators.
6. Repeat from Step 1 Figure 3. Overall dimensionless concentration profile C/C0
(lumen, membrane and shell) C0=1mol/m3, flow lumen=1e-
4 m3/s, flow shell=1e-3 m3/s and pressure=1 atm
Table 2. parameters used in the numerical
simulation
R1 (mm) 10 As the feed flows through the lumen
R2 (mm) 13 side, solute (NO3) is transferred
R3 (mm) 20 towards the membrane due to the
L (cm) 40
concentration difference. At the
D_lumen (m2/s) 1.7e-9
D_shell (m2/s) 2.25e-9 membrane-aqueous phase interface
Porosity (ε) 0.75 chemical reaction occurs and complex
Tortuosity (τ) 1.25 is formed. The formed complex diffuses
Inlet concentration of solute 1 through the membrane pores which is
(mol/m3) filled with the organic phase and
Flow rate of shell side (m3/s) 1e-3 reaches at the shell side. Finally, the
Flow rate of lumen side (m3/s) 1e-4 complex is swept by the moving
extractant and leaves the extractor.
3. Results and discussions Figure 4 confirms that the concentration
decreases along the extractor because
3.1. Profile of concentration in lumen of the extraction of solute.
side

Dimensionless concentration profile

(C/C0) of solute is shown in figure 3. The
concentration profile is obtained in the
lumen side of the membrane contactor
where the aqueous feed flows. It should
be pointed out that the flow pattern in
the contactor (extractor) is parallel and
counter current. The feed phase
Figure 4. Axial concentration of solute along the extractor
including aqueous solution of NO3 flows in lumen side. C0=1mol/m3, flow lumen=1e-4 m3/s and
from one side of the contactor (z=0) pressure=1 atm
where the concentration of solute is the
highest (C0), whereas the organic Figure 5. indicates concentration profile
phase (extractant) flows from the other of solute in the shell side of contactor.
 ◼ 7
According to Figure 5, it can be seen
that the concentration of the solute was
zero at the entry point (z=L) of the
organic phase and the concentration of
the solute increased by moving towards
z=0.
Figure 5. Axial concentration of solute along the extractor
in shell side. C0=0 mol/m3, flow shell=1e-3 m3/s and
pressure=1 atm
3.2.Effect of lumen side flow on
extraction
Fig 6. indicates that increasing feed flow
rate decreases the solute removal in the
contactor. Increasing feed flow rate
decreases residence time of feed phase
in the contactor which in turn results in
lower mass transfer of solute.
Figure 6. Effect of lumen side flow rate on extraction.
C0=1mol/m3
3.3. Effect of tortuosity on extraction in
lumen side
Tortuosity (τ) is important in
characterization of membrane. To study
its effect, simulation was run for
ISSN: ……..
tortuosity ranging from 0.05 and 0.81.
These values correspond to the
porosity of membrane from 0.84 to 13.4.
Figure 7 shows the effect of tortuosity
on solute extraction. Extraction
efficiency was decreased up to 0.28
when the tortuosity was increased to
13.4. In fact, increasing this causes a
decrease in diffusion coefficient
according to following equation.
DNO3−mem = DNO3−shell (ε/τ)
Equation 7 shows that as the tortuosity
increases at constant porosity, the
diffusivity of organic complex decreases
through membrane pores. In other
words, increasing the tortuosity
increases the resistance to solute
transfer in membrane pores which
results in lower extraction efficiency.
Figure 7. Effect of tortuosity on extraction of solute. Flow
lumen=1e-4 m3/s, Flow shell=1e-3 m3/s, C0=1mol/m3 and
P=1atm
4. Model validation with
MATLAB:
Figure 3 shows an overview of mass
transfer in the resistances-in-series
model. The approach is based on
resistances-in-series model. This
model considers three mass transfer
resistances in series for transport of
nitrate from feed to solvent phase.
 ◼ 8 ISSN: ……..

@ z=0 → CNO3-in = 1 mol/m3

@ z=l → C* NO3-in = 0 mol/m3

Figure 9. Axial concentration of solute along the extractor

Figure 8. A schematic diagram for the membrane in shell and lumen sides. C0=1 mol/m3, flow shell=1e-3
contactor in the resistances-in-series model. m3/s, Flow lumen=1e-4 m3/s and P=1atm

To validate the modeling findings Figure 9 shows the results obtained

obtained from mass transfer model
developed here, the simulation results
were compared with data obtained from
MATLAB for extraction of nitrate using
a membrane contactor. An additional
equation for feed tank is required for
simulation. The mass balance
equations for feed and permeate sides
containing aqueous solution of nitrate
(solute) can be written as follows:
from modeling with MATLAB. The
model and parameters used to simulate
MATLAB and COMSOL are the same.
As it can be seen from figure 9,
modeling results match the results
obtained from COMSOL quite well. It
confirms that the proposed model is
reliable and accurate.
5. Conclusion

dCNO3−out (10) A 2D mathematical model has been

V1 = F0 CNO3−in used to describe the transport of nitrate
dt
− F0 CNO3−out − Q (NO3) solute in membrane contactor.
The model is based on solving
𝑑𝐶 ∗ 𝑁𝑂3−𝑜𝑢𝑡 (11) conservation equations in the
𝑉2 = −𝐹1 𝐶 ∗ 𝑁𝑂3−𝑜𝑢𝑡 membrane contactor. Computational
𝑑𝑡
+ 𝑄∗ fluid dynamics (CFD) techniques were
applied for numerical solution of the
where F0 is volumetric flow rate (m3/s), equations. Conservation equations of
t is time (s), and C is solute solute including continuity as well as
concentration, (mol/m3) and V1 and V2 Navier–Stokes equations were derived
are volume of feed and permeate (m3), and solved numerically based on finite
respectively. element method (FEM). Flux
distribution was studied in contactor,
Boundary conditions for mass balance and it was found that diffusive flux in
equations are as follows: radial direction increases with
 ◼ 9
decreasing feed flow rate. The
simulation was run to study the effects
of tortuosity on extraction efficiency.
Solute extraction was found to be
increased with increasing tortuosity.
Moreover, the simulation results for the
NO3 using the membrane contactor
were compared with the results
obtained from MATLAB in order to
validate the mass transfer model and
showed good agreement.
References:
1. Klaassen, R., P. Feron, and A. Jansen,
Membrane contactors in industrial
applications. Chemical Engineering
Research and Design, 2005. 83(3): p.
234-246.
2. Drioli, E. and L. Giorno, Membrane
operations: innovative separations and
transformations. 2009: John Wiley &
Sons.
3. Sciubba, L., et al., Membrane-based
solvent extraction of vanillin in hollow
fiber contactors. Desalination, 2009.
241(1-3): p. 357-364.
4. Vajda, M., I. Havalda, and R. Máček,
Membrane-based solvent extraction
and stripping of zinc in a hollow-fibre
contactor operating in a circulating
mode. Desalination, 2004. 163(1-3): p.
19-25.
5. Stanojević, M., B. Lazarević, and D.
Radić, Review of membrane contactors
designs and applications of different
modules in industry. FME
Transactions, 2003. 31(2): p. 91-98.
6. Marjani, A. and S. Shirazian, Simulation
of heavy metal extraction in membrane
contactors using computational fluid
dynamics. Desalination, 2011. 281: p.
422-428.
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7. Ghadiri, M., A. Marjani, and S.
Shirazian, Mathematical modeling and
simulation of CO2 stripping from
monoethanolamine solution using nano
porous membrane contactors.
International Journal of Greenhouse
Gas Control, 2013. 13: p. 1-8.
8. Zhang, Z., et al., Effect of flow and
module configuration on SO2
absorption by using membrane
contactors. Glob Nest J, 2017. 19: p.
716-725.
9. Carolin, C.F., et al., Efficient techniques
for the removal of toxic heavy metals
from aquatic environment: A review.
Journal of environmental chemical
engineering, 2017. 5(3): p. 2782-2799.
10. Klaassen, R., P. Feron, and A. Jansen,
Membrane contactor applications.
Desalination, 2008. 224(1-3): p. 81-87.
11. Klaassen, R. and A. Jansen, The
membrane contactor: environmental
applications and possibilities.
Environmental progress, 2001. 20(1):
p. 37-43.
12. Pishnamazi, M., et al., Computational
fluid dynamics simulation of NO2
molecular sequestration from a
gaseous stream using NaOH liquid
absorbent through porous membrane
contactors. Journal of Molecular
Liquids, 2020. 313: p. 113584.
13. Muhammad, A., M. Younas, and M.
Rezakazemi, CFD simulation of copper
(II) extraction with TFA in non-
dispersive hollow fiber membrane
contactors. Environmental Science and
Pollution Research, 2018. 25(12): p.
12053-12063.
‫‪3rd International Biennial Conference on Oil, Gas, and Petrochemical Engineering. Persian Gulf University‬‬
‫‪Bushehr, Iran .28-30 December 2020‬‬
‫‪◼ 10‬‬

‫شبیه سازی و مدل سازی استخراج نیترات در کانتکتورهای غشایی با‬

‫استفاده از نرم افزارهای کامسول و متلب‬

‫عایق‪2‬‬ ‫امین جسور‪ ،*1‬میالد سالم‬

‫‪ .1‬دانشگاه صنعتی سهند‪،‬تبریز‪،‬ایران‬

‫‪ .2‬دانشگاه پیام نور‪،‬تبریز‪،‬ایران‬

‫چکیده‬ ‫مشخصات مقاله‬

‫فرآیندهای تصفیه فاضالب صنعتی حاوی آالینده ها اغلب شامل روش هایی برای کاهش‬ ‫تاریخچه مقاله‪:‬‬
‫سمیت به منظور دستیابی به استانداردهای الزم است‪ .‬فناوری کنتاکتور های غشایی یکی‬ ‫دریافت‬
‫از روشهایی است که در چند دهه گذشته مورد توجه قرار گرفته است‪ .‬این تماس دهنده ها‬ ‫دریافت پس از اصالح‬
‫دستگاههایی هستند که بدون مخلوط کردن یک فاز به فاز دیگر ‪ ،‬گاز ‪ /‬مایع یا مایع ‪ /‬مایع‬
‫پذیرش نهایی‬
‫را منتقل می کنند‪ .‬از غشاها ‪ ،‬به دلیل تفاوت در خصوصیات فیزیکی یا شیمیایی بین غشا‬
‫‪ ،‬به راحتی برای جدا کردن و انتقال یک جز خاص از یک ماده به ماده دیگر استفاده می‬
‫شود‪ .‬برای مدل سازی انتقال نیترات از طریق کنتاکتورهای غشایی از معادالت جرم و‬
‫کلمات کلیدی‪:‬‬
‫مومنتوم (معادالت ناویر‪-‬استوکس) استفاده شده است‪ .‬در این مدل با استفاده از کامسول ‪،‬‬ ‫کانتکتورهای غشایی‬
‫توزیع غلظت نیترات و تأثیر پارامترهای مختلف بر راندمان استخراج بررسی شده و سپس‬ ‫نیترات‬
‫در نرم افزار متلب ‪ ،‬با ارائه مدل جدید ‪ ،‬مدل سازی را انجام دادیم و مشاهده کردیم که‬ ‫کامسول‬
‫نتایج بدست آمده از هر دو تقریباً یکسان است ‪ .‬عالوه بر این ‪ ،‬مطالعه نشان داد که ‪CFD‬‬ ‫متلب‬
‫می تواند به عنوان ابزاری موثر برای توسعه کنتاکتورهای غشایی مورد استفاده قرار گیرد‪.‬‬
‫عهدهدار مکاتبات؛‬
‫*امین جسور‬
‫رایانامه‪aminjaasoor@gmail.com:‬‬