Advances in Fluid Mechanics and Heat & Mass Transfer

Modeling and simulation for the removal of pollutant gases from

natural gas using membrane contactors

NAYEF GHASEM, MOHAMED AL-MARZOUQI

Department of Chemical & Petroleum Engineering
UAE University, Alain,
UNITED ARAB EMIRATES
nayef@uaeu.ac.ae

Abstract: A comprehensive mathematical model was developed to describe the performance of gas
liquid membrane contactor used for the removal of pollutant gas from natural gas. The model takes
into account the effect of mass, momentum and heat transfer. The model is validated with the
experimental results obtained from the removal of CO2 from CO2/CH4 gas mixture using custom made
polyvinylidene fluoride (PVDF) membrane contactor. Aqueous sodium hydroxide solution was used
as the absorbent liquid. The effect of membrane packing density, inlet gas velocity and absorbent inlet
temperature on the membrane contactor performance was investigated. Increases of gas velocity
decreases percent removal of carbon dioxide, by contrast, increase of absorbent liquid temperature
increases percent removal of CO2. Comparison between experimental results and model predictions
were in good agreement.

Key-Words: absorption, CO2, natural gas, membrane contactor, pollutant gases

1 Introduction disseminated from the gas side across the

Carbon dioxide is believed to be the main
gaseous contaminant in the atmosphere. The
emission of greenhouse gases such as CO2 to
environment causes climatic changes. The
greenhouse gas is believed to increase the
temperature of the earth, accompanying this
temperature increase is extreme weather and a
projected sea level rise which will in turn be
problematic for coastal cities. Therefore, emission
of this gas to atmosphere should be low,
necessitating its removal. The process for removing
carbon dioxide from industrial gases can be
achieved by absorption into aqueous solutions of
alkanolamines and caustic solutions. Conventional
gas processes, such as gas-liquid absorption
column, for the removal of CO2 suffers from weak
points such as flooding, foaming, entraining,
channeling, and high capital and operating costs.
Gas-liquid membrane contactors for absorption of
pollutant gas deemed promising replacement
technology. A comprehensive and excellent review
of the recent developments in membrane-based
technologies for CO2 capture is reviewed by Luis et
al. [1]. In a membrane contactor utilized for CO2
gas absorption, a gas mixture flows on one face of
a hydrophobic microporous membrane while a
liquid absorbent flows on the other side, gas
membrane and approaches the gas-liquid interface,
once the pollutant enters the liquid phase, it can
simply dissolve, or it can react with other
chemicals present in the liquid [2-12]. In hollow
fiber membrane contactor, phase separation after
absorption operation is not necessary because one
phase is not dissolved into other phase in the
module. By contrast, membrane can introduce an
additional resistance to mass transfer, membrane
pores should be small to stop the penetration of
absorbents into the pores, the smaller the pore
radius, the larger the liquid entry pressure. Previous
models developed for membrane contactors
consider only mass transfer through shell,
membrane and tube sections [13,14].
In the present work, and to the best of our
knowledge, it is for the first time, mass, momentum
and energy transport was considered for modeling
of gas-liquid membrane contactor.
2 Model development
A comprehensive mathematical model that takes
into account mass, momentum and heat transfer
was developed for the transport of gas mixture of
carbon dioxide and methane through hollow fiber
membrane (HFM) contactor. The model was based

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 Advances in Fluid Mechanics and Heat & Mass Transfer

on non-wetted mode in which the gas mixture at z = L,

filled the membrane pores for countercurrent gas CCO 2 shell = CCO 2 -initial
liquid contact. Axial and radial diffusion inside the
hollow fiber membrane, through the membrane C CH4 shell = C CH4 -initial (5)
skin, and within the shell side of the contactor were at r = r2, Ci shell = Ci membrane (6)
considered in the model. Furthermore, the model
(i = CO2 and CH4)
was validated for changes in CO2 concentration
Ci shell
with the experimental results obtained for carbon at r = r3, =0 (7)
dioxide removal from CO2/CH4 gas mixture using r
custom made polyvinylidene fluoride (PVDF) (i = CO2 and CH4)
membrane contactor. The effect of inlet gas and
liquid temperature on the membrane performance Membrane: The steady state material balance for
was not validated yet with the experimental data. the transport of CO2 and CH4 inside the membrane
The effect of module packing factor was also for non-wetting condition, which is considered to
investigated. COMSOL software package was used be due to diffusion only, may be written as:
in solving the set of partial, ordinary and algebraic 2CCO Mem 1 CCO Mem 2CCO Mem (8)
D CO 2 Mem + +
2
=0 2 2

set of equations r 2 r r z 2
2CCH 4 Mem 1 CCH 4 Mem 2CCH 4 Mem ( 9)
DCH 4 Mem + + =0
2.1 Material balance equation r 2 r r z 2
Boundary conditions are given as:
Shell Side (gas phase): The steady state continuity
equation for each species during the simultaneous at r = r1, Ci Mem = Ci tube / mi (10)
mass transfer and chemical reaction in a reactive (i = CO2 and CH4)
absorption system can be expressed as:
Ci mi is the solubility of CO2 in aqueous 0)
N i Ri = Vz (1) at r = r2, Ci Mem = Ci shell (11)
z
Where Ci, Ni, Ri, Vz, and z are the concentration, (i = CO2, for non-wetting case)
flux, reaction rate of species i, velocity, and where NaOH.
distance along the length of the membrane,
respectively. Either Ficks law of diffusion or Tube Side: The steady state material balance for
Maxwell-Stefan theory can be used for the the transport of CO2 and aqueous NaOH inside the
determination of fluxes of species i. The overall tube-side, which is considered to be due to
rate of reaction can be determined depending on the diffusion, convection and reaction as well, may be
reaction mechanisms and reaction rates. The left written as:
hand side of the above equation represents the C 1 C
2
C
CO2 tube C
(12)
CO2 tube
2
CO2 tube CO2 tube
DCO2 tube + + + RCO2 = V z tube
diffusion and reaction terms, whereas the right r 2 r r z 2 z

hand side of the equation is the convection term. 2CNaOHtube 1 CNaOHtube 2CNaOHtube CNaOHtube
(13)
+ + + RNaOH = Vz tube
The steady state material balance for the transport DNaOH tube
r 2 r r z 2 z
of CO2 and CH4 in the shell side, where the gas
mixture flows may be written as: Reaction kinetics with NaOH
2 C CO2 shell 1 C CO2 shell 2 C CO2 shell RCO2 = kr CCO2 CNaOH (14)
DCO2 shell + + (2)
r 2 r r z 2 RNaOH = 2kr CCO2 CNaOH (15)
C CO2 shell
= V z shell
z
2CCH shell 1 CCH shell 2CCH shell CCH4 shell
2.2 Equations of motion
DCH4 shell 4
+ 4
+ 4
= Vzshell
(3)
r
2
r r z
2
z
Steady state Navier Stocks equations of motion are
1 used:
r3 = r2 (4)
1 Shell side (gas phase)
and is the volume void fraction of the module. r-direction:
vrs v p 1 2v (16)
g vrs + v zs rs = s + g (rvrs ) + 2rs

Boundary conditions: r z r r r r z

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 Advances in Fluid Mechanics and Heat & Mass Transfer

Thermal insulation boundary at z=0 and z = L.

z-direction: Tube side (Liquid phase)
vzs v p 1 vzs 2vzs (17) Ts Tt 1 Tt 2Tt (22)
g vrs + vzs zs = s + g r + 2 C v
L pL +v rt =k zt r +L
r z z r r r z r z r r r z 2
v zt Boundary conditions:
at z = 0 , the exit of gas flow in tube side, =0 z = 0 , inlet temperature of absorbent liquid in the
z
at z = L , the inlet of gas flow in shell side, tube side, Tt = T0, L
vzs = v0, g and depends on the number of fibers in z = L , exit of absorbent liquid from the tube side,
the membrane contactor module and gas inlet TL
=0
volumetric flow rate. Near the membrane walls, the z
velocity is zero. r = 0 , axial symmetry
r = r1 , The temperature Tt = Tm
Tube side (gas phase)
r-direction:
The numerical values used in the simulation are
vrt v p 1 (18)

(rvrt ) + v2rt
2
L vrt
r
+ v zs rt = t + L
z r
shown in Table 1. The set of the mathematical
r r r z
model equations were solved using the software
z-direction: package COMSOL [15]. The finite element
vzt v p 1 v 2v (19) method were employed by the model solution.
Lvrt +vzt zt = t +L r zt + 2zt
r z z r r r z
Boundary conditions: Table 1 Numerical values of the parameters
at z = L , exit of absorbent liquid flow in the tube used in the modeling.
vzs Parameter Value
side, =0
z mCO2 () 0.85
at z = 0 , inlet of absorbent liquid, vzt = v0, L and
depends on the number of fibers and inlet liquid
(
kr m3 / mol s ) 10^(10.99-
2152/T)/1000
flow rate. Velocities in the shell side and tube side Inner tube radius, r1 ( m ) 0.2 10 3
near membrane walls are zero. Outer tube radius, r2 (m) 0.5 10 3
Module length, L(m ) 0.26
2.3 Energy balance
Inner module diameter d m (m) 0.8 10 2
The steady state equations of energy are presented Inlet gas flow rate, (ml/min) 50
below: Inlet liquid flow rate,
10
(ml/min)
Shell side (gas phase) o
1 Ts 2Ts
Inlet liquid temperature, ( C ) 77
T T (20)
g C pg vrs s + vzs s = k g r + 2 o
r z r r r z Inlet gas temperature, ( C ) 57
Boundary conditions: (T1.75 ) *10-7.2909/P
DCO2 shell (m2 / s)
at z = L , inlet temperature of gas flow in the shell
2.35e - 6 * exp(-2119/ T)
side, Ts = T0 , g DCO2 tube (m2 / s)
Ts DCO2 membrane (m2 / s) ( / ) DCO shell
at z = 0 , exit of gas flow in the shell side, =0 2

z 2
0.5 DCO2 tube
Membrane section
DSolventtube (m / s)
In the membrane section energy is transferred by CCO2 (mol / m3 ) 3.68
conduction
CNaOH (mol / m3 ) 500
1 Tm
0= r (21) Porosity, 0 .3
r r r Tortuosity, (2 ) /

Boundary conditions:
at r = r2 , in the shell side, Tm = Ts
at r = r1 , in the shell side, Tm = Tt

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3 Results and Discussion

The effect of membrane packing density on the
temperature and velocity profile is shown in the
surface diagrams (Figure 1) a, b c, and d are for
membrane modules packed with 10, 20, 30, and 40
fibers, respectively. The figures show that there is
temperature gradient in the shell (gas side), by
contrast, the temperature in the tube side (liquid
phase) is almost negligible thats attributed to the
high specific of absorbent liquid to compare to gas
phase.
Figure 3. Temperature profile in the tube side
The velocity profile across membrane length is
shown in Figure 4. As the number of fibers
increased the liquid velocity inside the tubes
decreased due to increased total cross sectional area
of the tubes, the inlet flow rate is distributed to
more tubes, consequently, the velocity decreased
and the critical distance across the length of
membrane beyond which the velocity is fully
developed is increased. For example with 10 fibers
the velocity profile is fully developed after a
dimensionless length of 0.2, by contrast for 30
fibers the velocity profile is fully developed after a
dimensionless distance of 0.4.

Figure 1: Temperature and velocity surface

diagrams for a module packed with 10, 20, 30 and
40 fibers, a, b, c and d, respectively.

Figure 2 shows the temperature profile in the shell

sides for membrane packing factor of 0.15 (10
fibers). The temperature drop in the gas phase is
around 19 oC, whereas, the temperature drop in
tube side is negligible (Fig. 3). Almost similar
results were observed for modules with 20, 30 and
40 fibers.

Figure 4. Velocity profiles in the tube side for

modules with various numbers of fibers

The effect of packing density on concentration

gradient across the length of membrane is shown in
Figure 5. The figures are for membrane contactor
modules with 10 to 40 fibers per module. With 10
fibers the concentration of CO2 is depleted close to
Figure 2. Temperature profile in the shell side.
the end of the module by contrast with increasing
number of fibers the concentration of CO2 is
depleted much earlier due to increases gas-liquid
contact area and increased residence time.

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Figure 7. Percent CO2 removal at various inlet gas

flow rate (ml/min) at fixed liquid flow rate of 10
ml/min.

Figure 5. Effect of number of fibers on CO2

concentration profile across the membrane in the
shell gas side.

The model was validated for the removal of CO2

from gas mixture consisted of 9%CO2/91%CH4
using aqueous 0.5M NaOH as liquid absorbent at
atmospheric pressure and room temperature for the
experimental set-up shown in Figure 6.
Figure 8. CO2 flux at various inlet gas flow rate
(ml/min) at fixed liquid flow rate of 10 ml/min.
Liquid in the tube side counter current with gas
flow in the shell side.

Figure 6. Schematic diagram of the absorption

membrane contactor module.

Figure 7 and Figure 8 show the model predictions
for the percent CO2 removal and CO2 flux versus
membrane dimensionless length at various gas inlet
flow rates (the values in the legend are in ml/min),
respectively. Comparison between model
predictions and experimental data is shown in
Figure 9; the results were in good agreement with
model predictions. It can also be concluded that the
membrane is not wetted at experimental operating
conditions (1 atm) and the model non-wetting
assumption is valid. The number of fibers used in
the module is 6 fibers (26 cm active length), liquid
flow rate was fixed at 10 ml/min.
Figure 9. Comparison between experimental
results and model validations, dashed line is the
model predictions.
4 Conclusion
A comprehensive mathematical model that
considers mass, momentum and heat transfer was
successfully solved using COMSOL software
package. As far as the comprehensive modeling is
considered, the gas phase temperature drop along
the length of the fiber seems to be large; by
contrast, the temperature gradient in the absorbent
liquid phase is negligible. The CO2 absorption flux

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 Advances in Fluid Mechanics and Heat & Mass Transfer
increased with gas inlet flow rate. Further
investigation in this regard is needed. In addition,
the pressure drop in both the gas and liquid phases
need to be calculated.
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Acknowledgement
We would like to thank the Cooperation
Department, Japan Cooperation Center, Petroleum;
Environment & Product Technology Department,
JX Nippon Research Institute, Ltd.; The Japanese
Government (the Ministry of Economy, Trading
and Industry) for their financial contribution to this
project.
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