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An experimental study on absorption/stripping CO2 using

mono-ethanol amine hollow fiber membrane contactor
Ehsan Kianfar a, Vahid Pirouzfar b,∗, Hossein Sakhaeinia c
a
Young Researchers and Elite Club, Gachsaran Branch, Islamic Azad University, Gachsaran, Iran
b
Young Researchers and Elite Club, Central Tehran Branch, Islamic Azad University, Tehran, Iran
c
Department of Chemical Engineering, Central Tehran Branch, Islamic Azad University, Tehran, Iran

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

Article history: The present article focuses on making asymmetric porous hollow fiber membranes of polysulfone (PSF)
Received 18 April 2017 through alternating phases of process using ethanol (2 wt.%) as a non-soluble additive in polymer so-
Revised 2 August 2017
lution. An aqueous solution of 1-methyl-2-pyrrolidone (NMP) was used as the splitter fluid to prevent
Accepted 6 August 2017
the formation of internal dense crust and water was used as an external coagulant. The surface poros-
Available online xxx
ity, the pore size and the effective porosity of membrane were examined through characteristic tests.
Keywords: The structure of membrane was studied by scanning electron microscopy (SEM). The performance of the
Polysulfone produced membranes was examined to absorb and excrete carbon dioxide in a gas–liquid contactor mem-
Hollow fiber membrane brane through the solution of mono-ethanolamine (MEA). The results of gas absorption and stripping test
Gas–liquid contactor membrane showed that the liquid phase is enhanced by increasing the flow rate. Membranes produced by ethanol
Absorption indicated that the absorption and excretion of carbon dioxide hollow fiber membrane made of PSF were
Stripping
more than other membranes. The highest absorption of carbon dioxide (3.9 × 10−3 mol/m2 /s) and strip-
ping (2.00 × 10−4 mol/m2 /s) could be obtained at the liquid flow rate of 300 and 200 ml/min, respectively.
© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction is the poison of ammonia production catalyst. In case carbon diox-

Gases produced in oil and gas industry have different gross val-
ues. Impurities of industrial gases may damage the equipment or
reduce the quality of the industrial gas. In such cases, it is needed
to remove the impurities from the gas stream. Major impurities
of gas flow are acid gases like carbon dioxide (CO2 ) and hydrogen
sulfide (H2 S) [1–8]. The absorption of acidic gases and impurities
is an important chemical process in many industries including
gas sweetening, coal-to-gas conversion, gas synthesis, ammonia
production and so on. The existence of lots of carbon dioxide and
little amount of hydrogen sulfide in gas make many problems
[9–14]. The presence of hydrogen sulfide in the gas flow creates
corrosion on equipment and pipelines. According to the existing
standards in this area, the amount of hydrogen sulfide should not
exceed 4 ppm in the gas flow and the amount of carbon dioxide is
allowed up to 2 mol.% [15–19]. In some cases, the carbon dioxide
absorption from industrial gases is used to prevent poisoning
the catalyst in industry. For example, ammonia synthesis process,
carbon dioxide is obtained hydrogen flow because carbon dioxide
∗
Corresponding author.
E-mail addresses: v.pirouzfar@iauctb.ac.ir, pirozfar@gmail.com (V. Pirouzfar).
ide is highly concentrated, it can make the equipment corroded.
Consequently, its existence increases both gas volume and the
cost of gas compression and transmission [20]. In addition, carbon
dioxide lowers gas heating value. Carbon dioxide is also one of the
most important greenhouse gases produced by human activities
and industries. Releasing this gas through the air increases global
temperatures. For the sake of improving and economizing equip-
ment of gas refining, there are huge reserves of this vital material
in Iran. Hence, it is necessary to remove carbon dioxide from the
industrial and domestic usages, particularly natural gas (reduced
to 2 mol.%) [21]. There are many carbon dioxide removal (CDR)
methods by absorption in alkanol amines aqueous solutions and
conventional equipment such as tray tower, bubble tower, packed
tower, and spray tower. The use of aqueous alkanolamine makes it
possible to revive liquid solvent by simple heating. Thus, a process
for capturing carbon dioxide includes absorption and excretions in
the units. In this process, operational problems include flooding,
catalyzing, getting stranded and flooring exist. Usually, absorption
tower works at high operating pressure and low temperature
(35 °C), whereas reviving tower works at high temperatures [22].
Membrane processes are the newest separation methods done by
spending less energy. Today, these processes are known as a good
alternative for the industrial processes absorbing gas by the amine

http://dx.doi.org/10.1016/j.jtice.2017.08.017
1876-1070/© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: E. Kianfar et al., An experimental study on absorption/stripping CO2 using mono-ethanol amine hollow fiber
membrane contactor, Journal of the Taiwan Institute of Chemical Engineers (2017), http://dx.doi.org/10.1016/j.jtice.2017.08.017
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processes because they often work at ambient temperature [23].

Nomenclature Since 1980, a number of studies have been done to absorb green-
house gases such as carbon dioxide from the gas stream using
MEA mono-ethanolamine gas–liquid membrane system suppliers. To achieve this, a number
NMP 1-methyl-2-pyrrolidone of studies have been done in relation to various factors including
PSF polysulfone liquid solvents, materials, membranes, and membrane modules
SEM scanning electron microscopy to enhance the absorption of carbon dioxide [24]. Within recent
NaOH sodium hydroxide years, several techniques have been developed to absorb carbon
BaCl2 barium chloride solution dioxide. The treatment system of hollow fiber membrane is one of
ε/Lp effective surface porosity the desirable methods considered by scientists [25–30]. In this sys-
εm membrane overall porosity tem, a two-phase fluid system uses a membrane structure which
w1 weight of the wet membrane is appropriate to be collided. For example, the shared level of gas–
w2 weight of the dry membrane liquid is created in the opening of membrane’s pores. Gas–liquid
ρp polymer density hollow fiber membrane contactor can be a promising alternative
ρw water density for the CO2 absorption/stripping processes. In this system, the
QL absorption flow rate (m3 /s) porous membrane acts as a fixed interface between the gas and
MCO2 concentration of carbon dioxide in the absorption liquid phases without dispersing one phase into another [31–33].
solution (mol/L) The mechanism of CO2 absorption/stripping is shown in Fig. 1.
Ai collision surface between air–liquid (m2 ) Among the polymeric materials synthesizing membrane, Poly-
n number of fibers (in this study, 10) sulfone is the most fascinating one due to its outstanding specifica-
di inner diameter of fibers tions such as high thermal and chemical stability, high productivity
L effective fiber length and efficiency of the separation, high mechanical resistant and etc.
Cl,o CO2 concentration in the liquid phase at the outlet [34–38].
of the membrane module (mol/m3 ) Due to the complexities concerned with the preparation of
Cl,i CO2 concentration in the liquid phase of input novel hollow fiber membranes for gas absorption and stripping
membrane module (mol/m3 ) of carbon dioxide from MEA solution in a gas–liquid contactor
JCO2 flux of carbon dioxide excretion (mol/m2 s) membrane. The main objective of this research work is to investi-
Ql rate of liquid’s flow (m3 /s) gate the influence of the material structures on high performance
Ai inner surface of the hollow membrane (m2 ) membrane so as to provide a guideline for investigators fabricat-
R2 correlation coefficient ing high performance hollow fiber membranes. Additionally, the
present study has practiced the blending technique to devise new
method for gas industrial applications.
solution. In comparison to absorption processes, membranes have
major benefits such as lower energy consumption, lower operating 2. Experimental and methodology
costs, lower installation and initial investment. In these systems,
there is no risk of fire and explosion. Since they are able to purify 2.1. Dope solution preparation
gas at well head, high pressure on the well head is very conve-
nient for membrane process and compatible with environmental Sulfone polymer was stored at 70 °C temperature in the furnace
laws. These systems are applied in off-shore operations for the for 24 h to remove moisture. The spinning dopes of 18 wt.% PSF, 0
sake of their lightweight and small size. They are flexible enough and 2 wt.% ethanol and NMP and the solution was stirred at room
to change the flow rate and feed composition as there are not any temperature until a homogeneous solution was prepared. The re-
chemical processes in them. At the same time, they can separate sulting solutions were degassed for 24 h at room temperature be-
hydrogen sulfide, carbon dioxide and water vapor. There is no loss fore spinning. Table 1 indicates an 8% solution of polymer com-
of energy through exchanging heat with the environment in these pounds used in the test.

Fig. 1. Schematic of CO2 absorption/stripping mechanism in gas–liquid membrane contactors: (A) absorption; and (B) stripping [34].

Please cite this article as: E. Kianfar et al., An experimental study on absorption/stripping CO2 using mono-ethanol amine hollow fiber
membrane contactor, Journal of the Taiwan Institute of Chemical Engineers (2017), http://dx.doi.org/10.1016/j.jtice.2017.08.017
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Table 1 The test procedure was based on the volume displacement

Weight percent compounds solution polymer.
technique [40–42]. The gravimetric method was utilized to calcu-
Polymer solutions PSf (wt.%) NMP (wt.%) late the membrane overall porosity(ε m ). It is defined as the pores
Without additives ethanol 18 82 volume divided by the total volume of the hollow fiber membrane
Additives ethanol (2 wt.%) 18 80 determined by the following relation [42]:
(w1 − w2 )/ρW
εm = (5)
Table 2 (W1 − W2 )/ρW + W2 /ρP
Properties of fabricated polysulfone hollow fiber membranes.
where w1 and w2 are the weight of the wet and dry membrane,
Dope extrusion rate (ml/min) 4.5
Bore composition (wt.%) NMP/Water 90/10
respectively; ρ p the polymer density; ρ w water density. In order
Bore flow rate (ml/min) 2 to synthesize the wet membranes, five spun fibers were designed
External coagulant Tap water after 3 days solvent exchange. The hollow fibers were immersed
Air gap distance (cm) 0.0 in distilled water for another day and the remaining water on
Spinneret o.d./i.d. (mm) 1.0/0.50
the inner surface was blown by air stream. Then, the hollow
Coagulantion temperature (°C) 25
fiber membranes were further dried in a vacuum oven for 2 h
at 120 °C, before measuring the dry weight. In order to evaluate
the mechanical stability of the membranes, a collapsing pressure
2.2. Fabrication and characterization of porous hollow fiber check was executed. The shell side upstream pressure was set at
membranes 0.5 × 105 Pa. The final data of this method are presented in Table 3
and detailed in following sections.
PSF was purchased from Merck Company Germany to build hol-
low fiber membranes: 1-methyl, 2-pyrrolidone (NMP > 99.5%) as a
2.4. Experiment of CO2 absorption
gross solvent and ethanol as non-solvent additives. In all cases tap
water was used as the coagulation bath (spinning process). MEA
Collider gas–liquid membrane system was used to measure the
(purity above 98%) was purchased from Sigma-Aldrich Co and used
flux of CO2 . Ten hollow fibers were placed in membrane mod-
as the absorbent liquid.
ule of stainless steel. Pure carbon dioxide used as feed gas in the
Table 2 illustrates the properties of fabricated PSF hollow fiber
tube and MEA (1 M) was applied in the shell antithetic mode as
membranes. Dope was applied as an external coagulant to solidify
the absorption liquid. Control valves and flow gauges monitor gas
polymer solution resulting into the formation of hollow fiber. After
and liquid flow rates in 200 ml/min and 50–300 ml/min. The gas
that, the Spinneret hollow fiber was drowned into the water for 3
side pressure was set to 1 × 105 (Pa). The fluid pressure was kept
days to remove the ethanol and remaining NMP. Then, it was nat-
higher than the gas to prevent the bubbles formation in a liq-
urally hung to be dried in environment temperature for 1–2 days.
uid, as 0.2 × 105 (Pa). Carbon dioxide concentration was measured
The lifetime of developed membrane depends on membrane
by titration in the output liquid in order to determine the flux
thickness, membrane precursors (type of organic or inorganic ma-
of carbon dioxide. In the titration process, 10 ml of output sam-
terial), morphology, filler material, evolution procedure, feed pres-
ple liquid of the module was poured into a beaker and more than
sure and temperature, density, type of module, free volume and
this amount (about 12 ml), the solution of 0.1 M sodium hydroxide
composite or hollow fiber matrix [39].
(NaOH) was added to the solution and completely dissolved with
the ionized carbon dioxide in the solution. Some barium chloride
2.3. Surface area of porous hollow membrane solution (BaCl2 ) was added to the solution. Then, the obtained so-
lution was shaken well until all the carbon dioxide dissolved in
It is essential to consider the characterization of surface poros- the solution (physically or chemically) and deposited as BaCO3 . The
ity and pore size in order to examine mass transfer in the absorp- remaining NaOH solution was titrated in the solution by hydro-
tion of membrane [40]. The total permeation through the asym- gen chloride (HCl) and phenolphthalein was used as an indicator.
metric membrane is considered as the combination of the Knudsen To measure the absorption amount of carbon dioxide, a few drops
and Poiseuille flow [41]. Li et al. [42] presented a modified perme- of methyl orange was added to the solution and the solution was
ation response to obtain the surface porosity and the average pore titrated by HCl. An amount of HCl is used in this stage to calculate
size over the effective pore length of the asymmetric porous mem- the amount of absorption of carbon dioxide by the moles of CO2 to
brane. Through the assuming cylindrical pores in the skin layer of the number of moles of MEA. Before taking samples, all tests were
membrane, the permeance of gas can be given as the following performed for 30 min to achieve a steady state.
equation:  moL 
  (N.V )HCL
2r pε 8RT 0.5 r p2 ε MCO2 = (6)
ji = + p (1) L Vsample
3RT LP π M 8μi RT LP
The total area of the membrane was considered as the sur-
ji = K0 + P0 P (2) face of liquid–gas contact dealt for mass transfer, so the empirical
amount of carbon dioxide flux JCO ( V mol ) is calculated from the
2 sample
According to Eq. (1), the average pore size can be determined following relation:
from the slope (P0 ) and intercept (K0 ) as Eq. (3) by plotting Ji versus
mean pressures: QL .MCO2
JCO2 = ∗ 10 0 0 (7)
 p  8RT 0.5 Vsample
r p = 5.333
0
μi (3) where QL is the absorption flow rate (m3 /s), MCO2 is the concen-
k0 πM
tration of carbon dioxide in the absorption solution (mol/L) and Ai
The effective surface porosity (ε /Lp) over pore length can be is the collision surface between air–liquid (m2 ). The absorption of
also calculated from the slope as below: membrane contactor-module output flow rate was measured by a
ε 8μi RT P0 liquid flow meter. Gas–liquid contact surface is measured based on
= (4) absorption flow on the pipe or the surface contact module. When
LP r p2

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Table 3
Specifications of hollow fiber membranes derived from PSF.

Additive Without additives Ethanol (2 wt.%)

Average pore size (nm) 24.5 19.3

Effective surface porosity (ε /Lp (m−1 )) 48.57 76.30
Critical entry pressure water (CEPw) (×105 Pa) 7.50 8.00
Overall porosity (%) 70.54 74.90
Collapsing pressure (×105 Pa) 8.50 7.50
Contact angle outer surface 68.30 73.25

Fig. 2. Flow pilot reactor to absorption carbon dioxide.

Table 4
Details of contacting gas–liquid membrane systems.
Module i.d. (mm)
Module length (mm)
Fiber o.d. (mm)
Fiber i.d. (mm)
Effective fiber length(mm)
number of fibers
Contact area (inner, mm2 )
the liquid absorption flows on the shell side, the surface of area is
calculated by the following relation:
A 0 = nπ d i L
where n is the number of fibers (in this study, 10), di is inner di-
ameter of fibers, and L are effective fiber length. The form of the
pilot reactor is presented in Fig. 2.
2.5. Experiment of CO2 stripping
The amount of stripping CO2 and the efficiency contactor of
made membranes were measured by gas–liquid module. Thirty
pieces of hollow fiber membrane were randomly placed in module
in a stainless steel. Details of contact membrane modules are
shown in Table 4. In this method, nitrogen gas (N2 ) flows inside
the shell and MEA solution rich in CO2 in the hollow fiber as
sweep stream flow. Nitrogen gas is inserted to liquid flow module
in order to prevent wetting problem. Pressure and flow rate of
liquid and gas were controlled by a control valve. Fluid pressure
was considered higher than 0.2 × 105 Pa to avoid forming bubbles
on the liquid. Operating pressure and temperature were kept
constant in 80 °C and 0.5 × 105 Pa, respectively. The concentration
of carbon dioxide in the liquid phase in the entry and output
of the stripping module was measured by titration method to
15 determine the amount and efficiency. In the titration method,
250 10 ml of output liquid sample was poured in a beaker from the
0.9–1.0
module and more than this amount (about 12 ml) solution of 0.1 M
0.45–0.50
180 NaOH was added to the solution to fully ionize carbon dioxide
30 dissolved in the solution. Then, some barium chloride (BaCl2 ) was
4521 added to the solution. Next, the solution was shaken well until all
the carbon dioxide dissolved in the solution to be formed deposits
of BaCO3 (physically or chemically). The remaining NaOH solution
was titrated in the solution by HCl and phenolphthalein was used
as an indicator. To measure the amount of the excreted carbon
dioxide, few drops of methyl orange added to the solution and the
(8) solution was titrated with HCl. The amount of HCl used in this
stage is practiced as moles of carbon dioxide to a number of moles
of MEA to calculate the amount of absorbed carbon dioxide. All
experiments were performed within 30 min to achieve steady state
conditions to collect fluid samples. Carbon dioxide concentration
was calculated by the following equation:
 moL 
(N.V )HCL
MCO2 = (9)
L Vsample
Carbon dioxide stripping efficiency was calculated by the fol-
lowing module:
 
C
η (% ) = 1 − l,o × 100 (10)
Cl,i
where Cl,o is carbon dioxide concentration in the liquid phase at
the outlet of the membrane module (mol/m3 ) and Cl,i is the con-
centration of carbon dioxide in the liquid phase of input membrane
module (mol/m3 ). Laboratory stripping of carbon dioxide flux on

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Fig. 3. Diagram of the laboratory stripping membrane contactor system.

Fig. 4. SEM images of the cross section fiber membranes made of hollow sulfone (PSF): (a) without additive, (b) 2 wt% ethanol.

the inner surface of the hollow fiber was calculated as below:
 
Cl,i − Cl,o × Ql
JCO2 =
Ai
In relation (11), JCO2 is the flux of carbon dioxide excretion
(mol/m2 /s), Ql is the rate of liquid’s flow (m3 /s), and Ai is the in-
ner surface of the hollow membrane (m2 ). Fig. 3 features out a
schematic view of the membrane contactor system in the experi-
mental stripping.
3. Results and discussion
PSF hollow fiber membrane was made of wet spinning method
using two different additive concentrations in the spinning solu-
tion. The morphology of membranes was studied by scanning elec-
tron microscopy (SEM) and also studying cross-section and the
inner surface in different magnifications. This made hollow fiber
membrane has an outer diameter from about 0.75 to 0.9 mm, in-
ternal diameter ranges from 0.4 to 0.45 mm and the wall thick-
(11) ness is in the range of 0.175–0.225 mm. The structure of the cross-
section area and the inner surface of the membrane are shown in
Fig. 4(a) and (b) and Fig. 5(a) and (b). Figures reveal that all forms
of hollow fibers have a porous shell and a finger-like substrate with
large holes originated from the outer surface of the hollow fibers
and hollow fiber walls spread. The inner surface of the membrane
is also made of a sponge-like layer. Since the use of mixed sol-
vent solution (NMP) is as a cutting fluid, it delays the solidification
of the membrane. All the membranes of inner surface are shown
without the shell. This event is due to the high content of NMP
in intrinsic coagulation. In fact, this phenomenon in the inner sur-
face is directed into opening micro-porous structure. As water acts
as a strong non-solvent, the work is done by water as the exter-
nal coagulant membranes with a layer outer shell. As observed in
Fig. 5, membrane made from ethanol as an additive to the polymer

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Fig. 5. SEM images of the structure of the inner surface of the hollow fiber membranes made of sulfone (PSF): (a) without additive, (b) 2 wt.% ethanol.

3.50E-07
Y = 5E-10x + 9E-08
R2= 0.9481
3.00E-07
N2 Permeance (mol/m2 s pa)

2.50E-07

2.00E-07

1.50E-07 Y= 7E-10x + 1E-07

R2= 0.9543

1.00E-07
Without additive
PSf+2% Ethanol
5.00E-08 Linear (Without additive)
Linear (PSf+2% Ethanol)
0.00E+00
100 150 200 250 300 350

Mean pressure (KPa)

Fig. 6. The amount of permeance of N2 as a function of average pressure of the hollow fiber membranes ( without additives, 2 wt.% ethanol).

solution has more pores than the membrane without ethanol
which is due to ethanol’s ability to create openings while solidi-
fication.
3.1. Carbon dioxide absorption and stripping in the hollow fiber
membrane
Table 3 briefly illustrates gas permeability test, the measure-
ment of critical pressure of water entering into the membrane
(CEPw), measuring porosity, and coefficient of contact with water
and collapse pressure (collapsing). The porosity ranged from 70.54
to 74.90% is considered to be sufficiently high and assigned to low
concentration of polymer in the polymer solution (dope). Figs. 6
and 7 disclose the average of N2 permeance against the pressure
data linked together by a linear equation with a correlation co-
efficient (R2 ). Thus, this equation contributes to demonstrate that
there is a relationship between linear equation and a correlation
coefficient (R2 ). According to the method mentioned in the experi-
mental section and the results presented in Table 4, the data were
used to calculate the average size of pore. As observed, the cal-
culated permeation of N2 for all membranes has a tendency to in-
crease as pressure gets higher. This phenomenon divulges that both
Poiseuille and Knudsen flows affect the permeation of N2 through
PSF membranes. Remarkably, the slope of the membrane prepared
with 2 wt.% ethanol as an additive is very small and it shows that
Knudsen flows need more gas leakage than Poiseuille flows due to
the size of small holes.
Given the critical water entry pressure, all membranes can re-
sist additional pressure applied on the shell (0.2 × 105 Pa) dur-
ing the absorption of carbon dioxide. Membranes made without
ethanol solution are shown in lower critical entry water pres-
sure than other membranes (Table 4) because of larger size of
this membrane pore. Consequently, this membrane has a fewer
contact ratio than other manufactured membranes. Larger pores
facilitate the entry of water into the membrane and reduce the
membrane contact ratio with water. The broken down and dis-
integrated pressure for all produced membranes is in high levels
for all membranes, this pressure is significantly higher than the

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3.50E-07
y = 5E-10x + 9E-08
R² = 0.9481
3.00E-07

N2 Permeance (mol/m2 s pa)

2.50E-07

2.00E-07

1.50E-07 y = 7E-10x + 1E-07

R² = 0.9543

1.00E-07
Without additive
5.00E-08
PSf+2% Ethanol

0.00E+00
100 150 200 250 300 350
Mean pressure (KPa)
Fig. 7. The amount of permeance of N2 as a function of average pressure of the hollow fiber membranes ( without additives, 2 wt.% ethanol).

4.50E-03

4.00E-03
PSf + 2 wt.% Ethanol
3.50E-03
Without additive
Absorption flux (m0l.m-2.s-1)

3.00E-03

2.50E-03

2.00E-03

1.50E-03

1.00E-03

5.00E-04

0.00E+00
0 50 100 150 200 250 300 350
Liquid flow rate (ml.m-1)
Fig. 8. The effect of Absorption flow rate (MEA) on the absorption of CO2 in gas–liquid membrane contactors.

operating pressure test. As shown in this table, breaking down and oride can be applied to absorb CO2 [44,45]. Fig. 8 illustrates that
disintegrating the membrane pressure can be enhanced by increas- the CO2 flux of the membranes prepared without ethanol is signif-
ing the diameter of the pores of the membranes. Holistically, nitro- icantly lower than the other membranes. Table 4 also shows that
gen gas flow moves easier through the membrane as the diameter the effective porosity of the effective membrane surface is smaller
of the pores is increased. In fact, higher pressure is needed for the than other membranes. Therefore, the contact area between gas
break-up of membrane. and liquid flux is smaller and absorption is less than other mem-
branes. The solution made with 2 wt.% solution of ethanol, as an
3.2. The effect of additives on the absorption of carbon dioxide additive, has the highest amount of absorption and discharge flow.

Fig. 7 indicates the effect of the flow of ethanolamine solution 3.3. Effect of additives on the stripping of carbon dioxide
made as carbon dioxide flux absorption membranes made. As ob-
served, the flow rate increase can make the flux of CO2 enhance. Fig. 9 displays the amount of carbon dioxide gas to liquid ve-
Liquid phase resistance is a mass transfer process controller for the locity of the membranes prepared with 0 and 2 wt.% ethanol. As
sake of gas absorption in membrane contactors in liquids [43]. On observed, the amount of carbon dioxide stripping is significantly
the other hand, it seems that the rate of CO2 gas flow has no im- lower than the other membranes in comparison to the speed of
pact on CO2 flux because applying pure carbon dioxide in the gas liquid in a membrane produced without ethanol. Effective porosity
has no resistance to transport CO2 . As reported in other studies, of this membrane is smaller than the other membranes. Therefore,
membrane of poly-ethylene tetra-fluoride and poly vinylidene flu- the contact area between gas and liquid is smaller. Moreover, the

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Fig. 9. The effect of liquid rate on the flux rate of stripping of carbon dioxide with 0 and 2 wt.% ethanol concentrations in the membranes made.

90

80

70
Stripping efficiency (%)

60

50

40

30

20

10

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Liquid velocity (m/s)
Fig. 10. The effect of fluid velocity on stripping efficiency (MM 1 = mol/L, T = 80 °C).

absorption flux is smaller than the other membranes. The maxi-
mum speed of the stripping of liquid carbon dioxide was obtained
by the membrane produced by 2 wt.% ethanol as an additive in the
polymer solution. It is inferred from Fig. 10 that the stripping and
desorption efficiency is raised by increasing the fluid velocity. The
highest amount of desorption 2.00 × 10−4 (mol/m2 /s) was achieved
in 200 ml/min (0.7 m/s) liquid flow rate, the efficiency was ob-
tained as 75% at this maximum flow rate. This is due to the de-
crease in boundary layer resistance of liquid and the increase in
carbon dioxide mass transfer coefficient in the higher fluid flow
rate [46–48].
4. Conclusion
3. Remarking the critical pressure of water inlet, all mem-
branes are used in the additional pressure on the shell side
(0.2 × 105 Pa) during the process could not resist.
4. The increase of CO2 absorption is directed into increasing the
flow rate.
5. Uptake and excretion of carbon dioxide absorption is increased
by accelerating the fluid velocity.
6. Increasing the fluid velocity contributes to eke out the amount
of carbon dioxide and maximum process efficiency was 75%.
7. The solution made with 2 wt.% solution of ethanol, as an addi-
tive, has the highest amount of absorption and discharge flow.
8. The liquid flow rate 200 ml/min (0.7 m/s) was obtained at the
highest excretion 2.00 × 10−4 mol/m2 /s.

Based on these experiments, the main results are summarized References

as below:
1. The porosity in the range of 70.54–74.90% is high enough to
be counted and low concentration of polymer in the polymer
solution (dope) is attributed.
2. The collapse pressure and the critical pressure of water inlet for
all manufacturing membranes are significantly higher than the
operating pressure in gas adsorption and desorption tests.
[1] Salimi M, Pirouzfar V, Kianfar E. Novel nanocomposite membranes prepared
with PVA/ABS and silica nanoparticles for C2 H6 /CH4 separation. Polym. Sci. Ser.
A 2017;59(4):566–74.
[2] Salimi M, Pirouzfar V, Kianfar E. Enhanced Gas Transport Properties in Silica
Nanoparticles Filler-Polystyrene Nanocomposite Membranes. Colloid Polym Sci
2017;295(1):215–26.
[3] Pirouzfar V, Hosseini SS, Omidkhah MR. Modeling and optimization of gas
transport characteristics of carbon molecular sieve membranes through sta-
tistical analysis. Polym Eng Sci 2014;54(1):147–57.

Please cite this article as: E. Kianfar et al., An experimental study on absorption/stripping CO2 using mono-ethanol amine hollow fiber
membrane contactor, Journal of the Taiwan Institute of Chemical Engineers (2017), http://dx.doi.org/10.1016/j.jtice.2017.08.017
JID: JTICE
ARTICLE IN PRESS
E. Kianfar et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–9
[4] Ramakul P, Prapasawad T, Pancharoen U, Pattaveekongka W. Separation of ra-
dioactive metal ions by hollow fiber-supported liquid membrane and perme-
ability analysis. J Chin Inst Chem Eng 2007;38(5–6):489–94.
[5] Lin S-H, Chiang P-C, Hsieh C-F, Li M-H, Tung K-L. Absorption of carbon dioxide
by the absorbent composed of piperazine and 2-amino-2-methyl-1-propanol
in PVDF membrane contactor. J Chin Inst Chem Eng 2008;39(1):13–21.
[6] Ahmad NA, Leo CP, Junaidi MUM, Ahmad AL. PVDF/PBI membrane incorpo-
rated with SAPO-34 zeolite for membrane gas absorption. J Taiwan Inst Chem
Eng 2016;63:143–50 June 2016.
[7] Soleymanipour SF, saiedi AH, Pirouzfar V, alihosseini A. Morphology and
gas separation performance of membranes comprising of multi-wall carbon
nanotubes/polysulfone-kapton. J Appl Polym Sci 2016. doi:10.1002/app.43839.
[8] Heydari Sh, Pirouzfar V. The influence of synthesis parameters on the gas se-
lectivity and permeability of carbon membranes: empirical modeling and pro-
cess optimization by response surface. RSC Adv 2016;6:14149–63.
[9] Jamshidi M, Pirouzfar V. influence of nanoparticles on gas transport properties
of mixed matrix membranes: experimental investigation and modeling. Korean
J Chem Eng 2017. doi:10.1007/s11814- 016- 0302- 4.
[10] Nematollahi MH, Saiedi AH, Pirouzfar V, Akhondi E. Mixed matrix mem-
branes comprising PMP polymer with dispersed alumina nanoparticles fillers
for CO2 /N2 separation. Macromol Res 2016;24(9):782–92.
[11] Pirouzfar V, Omidkhah MR. Mathematical modeling and optimization of gas
transport through carbon molecular sieve membrane and determining the
model parameters using genetic algorithm. Iranian Polym J 2016;25(3):203–12.
[12] Pirouzfar V, Omidkhah MR, Moghaddam AZ. Investigating the effect of dianhy-
dride type and pyrolysis condition on the gas separation performance of mem-
branes derived blended polyimides through statistical analysis. J Ind Eng Chem
2014;20(3):1061–70.
[13] Ebrahimi S, Mollaiy-Berneti S, Asadi H, Peydayesh M, Akhlaghian F, Mo-
hammadi T. PVA/PES-amine-functional graphene oxide mixed matrix mem-
branes for CO2 /CH4 separation: experimental and modeling. Chem Eng Res Des
2016;109:647–56.
[14] Dorosti F, Omidkhah M, Abedini R. Fabrication and characterization of
Matrimid/MIL-53 mixed matrix membrane for CO2 /CH4 separation. Chem Eng
Res Des 2014;92(11):2439–48.
[15] Peydayesh M, Asarehpour S, Mohammadi T, Bakhtiari O. Preparation and char-
acterization of SAPO-34 – Matrimid® 5218 mixed matrix membranes for
CO2 /CH4 separation. Chem Eng Res Des 2013;91(7):1335–42.
[16] Feijani EA, Mahdavi H, Tavasoli A. Poly(vinylidene fluoride) based mixed matrix
membranes comprising metal organic frameworks for gas separation applica-
tions. Chem Eng Res Des 2015;96:87–102.
[17] Keshavarz P, Fathikalajahi J, Ayatollahi S. Analysis of CO2 separation and sim-
ulation of a partially wetted hollow fiber membrane contactor. J Hazardous
Mater 2008;152(3):1237–47.
[18] Faiz R, Al-Marzouqi M. Insights on natural gas purification: Simultaneous
absorption of CO2 and H2 S using membrane contactors. Sep Purif Technol
2011;76(3):351–61.
[19] luis p, van Gerven T, van der bruggen B. Recent developments in membrane
based technologies for CO2 capture. Prog Energy Combust 2012;38:419–48.
[20] George G, Bhoria N, AlHallaq S, Abdala A, Mitta V. Polymer membranes for
acid gas removal from natural gas. Sep Purif Technol 2016;158:333–56.
[21] Rahbari-Sisakht M, Ismail A, Rana D, Matsuu T, Emadzadeh D. Effect of SMM
concentration on morphology and performance of surface modified PVDF hol-
low fiber membrane contactor for CO2 absorption. Sep Purif Technol 2013;116
67-22.
[22] Rahbari-Sisakht M, Ismail AF, Rana D, Matsuura T. Carbon dioxide stripping
from diethanolamine solution through porous. J Membr Sci 2013;427:270–5.
[23] Bhide BD, Voskericyan A, Stem SA. Hybrid processes for the removal of acid
gases from natural gas. J Membr Sci 1998;140(1):27–49.
[24] Mansourizadeh A, Ismail A. Effect of additives on the structure and perfor-
mance of polysulfone hollow fiber membranes for CO2 absorption. J Membr
Sci 2009;348:260–7.
[25] Bakeri Gh, Ismail AF, Shariaty-Niassar M, Matsuura T. Effect of polymer con-
centration on the structure and performance of polyetherimide hollow fiber
membranes. J Membr Sci 2010;363(1-2):103–11.
Please cite this article as: E. Kianfar et al., An experimental study on absorption/stripping CO2 using mono-ethanol amine hollow fiber
membrane contactor, Journal of the Taiwan Institute of Chemical Engineers (2017), http://dx.doi.org/10.1016/j.jtice.2017.08.017
[m5G;August 23, 2017;21:11]
9
[26] Naim R, Ismail AF, Mansourizadeh A. Preparation of microporous PVDF hollow
fiber membrane contactors for CO2 stripping from diethanol amine solution. J
Membr Sci 2012;392:29–37.
[27] Rahbari-Sisakht M, Ismail AF, Matsuura T. Development of asymmetric poly-
sulfone hollow fiber membrane contactor for CO2 absorption. Sep Purif Tech-
nol 2012;86:215–20.
[28] Rahbari-Sisakht M, Ismail AF, Rana D, Matsuura T. Effect of different additives
on the physical and chemical CO2 absorption in polyetherimide hollow fiber
membrane contactor system. Sep Purif Technol 2012;98:472–80.
[29] Mansourizadeh A, Ismail A, Abdullah M, Ng B. Preparation of polyvinylidene
fluoride hollow fiber membranes for CO2 absorption using phase-inversion
promoter additives. J Membr Sci 2010;355(1-2):200–7.
[30] A F D I G S a, Ismail SS. Production of super selective polysulfone hollow fiber
membranes for gas Separation. J Membr Sci 1999;40:6499–506.
[31] B V d, Luis BTVGP. Non-dispersive absorption for CO2 capture: from the labo-
ratory to industry. J Chem Technol Biotechnol 2011;86:769–75.
[32] Rahbari-Sisakht M, Ismail AF, Matsuura T. Effect of bore fluid composition on
structure and performance of asymmetric polysulfone hollow fiber membrane
contactor for CO2 absorption. Sep Purif Technol 2012;88:99–106.
[33] Khaisri S, Montigny de D, Tontiwachwuthikul P, Jiraratananon R. CO2 strip-
ping from monoethanolamine using a membrane contactor. J Membr Sci
2011;376:110–18.
[34] Baroña GNB, Choi M, Jung B. High permeate flux of PVA/PSf thin film com-
posite nanofiltration membrane with aluminosilicate single-walled nanotubes.
J Colloid Interf Sci 2012;386(1):189–97.
[35] Kiadehi AD, Rahimpour A, Jahanshahi M, Asghar Ghoreyshi A. Novel carbon
nano-fibers (CNF)/polysulfone (PSf) mixed matrix membranes for gas separa-
tion. J Ind Eng Chem 2015;22:199–207.
[36] Grosso V, Vuono D, Bahattab MA, Di Profio G, Curcio E, Al-Jilil SA,
et al. Polymeric and mixed matrix polyimide membranes. Sep Purif Technol
2014;132:684–96.
[37] Pal G, Kumar S. Modeling of carbon nanotubes and carbon nanotube–polymer
composites. Prog Aerospace Sci 2016;80:33–58.
[38] George G, Bhoria N, AlHallaq S, Abdala A, Mittal V. Polymer membranes for
acid gas removal from natural gas. Sep Purif Technol 2016;158:333–56.
[39] Müller N, Handge UA, Abetz V. Physical ageing and lifetime predic-
tion of polymer membranes for gas separation processes. J Membr Sci
2016;516(2016):33–46.
[40] Luis P, Van der Bruggen B, Van Gerven T. Non-dispersive absorption for
CO2 capture: from the laboratory to industry. J Chem Technol Biotechnol
2011;86:769–75.
[41] Han MJ, Nam ST. Thermodynamic and rheological variation in polysulfone so-
lution by PVP and its effect in the preparation of phase inversion membrane.
J Membr Sci 2002;202:55–61.
[42] Li K, Kong JF, Wang D, Teo W K. Tailor-made asymmetric PVDF hollow fiber
for soluble gas removal. AIChE J 1999;45:1211–19.
[43] Li JaCB. Review of CO2 absorption using chemical solvents in hollow fiber
membrane contactors. Sep Purif Technol 2005;41:109–22.
[44] Rangwala H. Absorption of carbon dioxide into aqueous solutions using hollow
fiber membrane contactors. J Membr Sci 1996;112(2):229–40.
[45] Wang D, Li K, Teo WK. Porous PVDF asymmetric hollow fiber mem-
branes prepared with the use of small molecular additives. J Membr Sci
20 0 0;178(2):13–23.
[46] Naim R, Ismail AF, Mansourizadeh A. Preparation of microporous PVDF hollow
fiber membrane contactors for CO2 stripping from diethanolamine solution. J
Membr Sci 2012;392–393,:29–37.
[47] Naim R, Ismail AF. Effect of polymer concentration on the structure and per-
formance of PEI hollow fiber membrane contactor for CO2 stripping. J Hazard
Mater 2013;250–251:354–61.
[48] Choi S-H, Tasselli F, Jansen JC, Barbieri G, Drioli E. Effect of the preparation
conditions on the formation of asymmetric poly(vinylidene fluoride) hollow
fibre membranes with a dense skin. Eur Polym J 2010;46:1713–25.