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Institute of Chemical Engineers 000 (2017) 1–9 Contents lists available at ScienceDirect Journal of

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Engineers journal homepage: www.elsevier.com/locate/jtice An experimental study on absorption/stripping CO 2

An experimental study on absorption/stripping CO 2 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

Article history:

Received 18 April 2017 Revised 2 August 2017 Accepted 6 August 2017 Available online xxx

Keywords:

Polysulfone Hollow fiber membrane Gas–liquid contactor membrane Absorption Stripping

a b s t r a c t

The present article focuses on making asymmetric porous hollow fiber membranes of polysulfone (PSF) through alternating phases of process using ethanol (2 wt.%) as a non-soluble additive in polymer so- lution. An aqueous solution of 1-methyl-2-pyrrolidone (NMP) was used as the splitter fluid to prevent the formation of internal dense crust and water was used as an external coagulant. The surface poros- ity, the pore size and the effective porosity of membrane were examined through characteristic tests. The structure of membrane was studied by scanning electron microscopy (SEM). The performance of the produced membranes was examined to absorb and excrete carbon dioxide in a gas–liquid contactor mem- brane through the solution of mono-ethanolamine (MEA). The results of gas absorption and stripping test showed that the liquid phase is enhanced by increasing the flow rate. Membranes produced by ethanol indicated that the absorption and excretion of carbon dioxide hollow fiber membrane made of PSF were more than other membranes. The highest absorption of carbon dioxide (3.9 × 10 3 mol/m 2 /s) and strip- ping (2.00 × 10 4 mol/m 2 /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

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 (CO 2 ) and hydrogen sulfide (H 2 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).

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

1876-1070/© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

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Nomenclature MEA mono-ethanolamine NMP 1-methyl-2-pyrrolidone PSF SEM NaOH BaCl 2 ε/ Lp ε m polysulfone
Nomenclature
MEA
mono-ethanolamine
NMP
1-methyl-2-pyrrolidone
PSF
SEM
NaOH
BaCl 2
ε/ Lp
ε m
polysulfone
scanning electron microscopy
sodium hydroxide
barium chloride solution
effective surface porosity
membrane overall porosity
w 1 weight of the wet membrane
w 2 weight of the dry membrane
ρ polymer density
p
M CO2
A
ρ water density
absorption flow rate (m 3 /s)
concentration of carbon dioxide in the absorption
solution (mol/L)
collision surface between air–liquid (m 2 )
w
Q L
i
n
d
number of fibers (in this study, 10)
inner diameter of fibers
i
L
C
effective fiber length
CO 2 concentration in the liquid phase at the outlet
l,o
of the membrane module (mol/m 3 )
C l,i CO 2 concentration in the liquid phase of input
membrane module (mol/m 3 )
J CO2
Q l
A i
R 2
flux of carbon dioxide excretion (mol/m 2 s)
rate of liquid’s flow (m 3 /s)
inner surface of the hollow membrane (m 2 )
correlation coefficient

solution. In comparison to absorption processes, membranes have major benefits such as lower energy consumption, lower operating costs, lower installation and initial investment. In these systems, there is no risk of fire and explosion. Since they are able to purify gas at well head, high pressure on the well head is very conve- nient for membrane process and compatible with environmental laws. These systems are applied in off-shore operations for the sake of their lightweight and small size. They are flexible enough to change the flow rate and feed composition as there are not any chemical processes in them. At the same time, they can separate hydrogen sulfide, carbon dioxide and water vapor. There is no loss of energy through exchanging heat with the environment in these

processes because they often work at ambient temperature [23]. Since 1980, a number of studies have been done to absorb green- house gases such as carbon dioxide from the gas stream using gas–liquid membrane system suppliers. To achieve this, a number of studies have been done in relation to various factors including liquid solvents, materials, membranes, and membrane modules to enhance the absorption of carbon dioxide [24]. Within recent years, several techniques have been developed to absorb carbon dioxide. The treatment system of hollow fiber membrane is one of the desirable methods considered by scientists [25–30]. In this sys- tem, a two-phase fluid system uses a membrane structure which is appropriate to be collided. For example, the shared level of gas– liquid is created in the opening of membrane’s pores. Gas–liquid hollow fiber membrane contactor can be a promising alternative for the CO 2 absorption/stripping processes. In this system, the porous membrane acts as a fixed interface between the gas and liquid phases without dispersing one phase into another [31–33]. The mechanism of CO 2 absorption/stripping is shown in Fig. 1. Among the polymeric materials synthesizing membrane, Poly- sulfone is the most fascinating one due to its outstanding specifica- tions such as high thermal and chemical stability, high productivity and efficiency of the separation, high mechanical resistant and etc.

[34–38].

Due to the complexities concerned with the preparation of novel hollow fiber membranes for gas absorption and stripping of carbon dioxide from MEA solution in a gas–liquid contactor membrane. The main objective of this research work is to investi- gate the influence of the material structures on high performance membrane so as to provide a guideline for investigators fabricat- ing high performance hollow fiber membranes. Additionally, the present study has practiced the blending technique to devise new method for gas industrial applications.

2. Experimental and methodology

2.1. Dope solution preparation

Sulfone polymer was stored at 70 °C temperature in the furnace for 24 h to remove moisture. The spinning dopes of 18 wt.% PSF, 0 and 2 wt.% ethanol and NMP and the solution was stirred at room temperature until a homogeneous solution was prepared. The re- sulting solutions were degassed for 24 h at room temperature be- fore spinning. Table 1 indicates an 8% solution of polymer com- pounds used in the test.

8% solution of polymer com- pounds used in the test. Fig. 1. Schematic of CO 2

Fig. 1. Schematic of CO 2 absorption/stripping mechanism in gas–liquid membrane contactors: (A) absorption; and (B) stripping [34].

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Table 1 Weight percent compounds solution polymer.

Polymer solutions

PSf (wt.%)

NMP (wt.%)

Without additives ethanol Additives ethanol (2 wt.%)

18

82

18

80

Table 2 Properties of fabricated polysulfone hollow fiber membranes.

Dope extrusion rate (ml/min) Bore composition (wt.%) Bore flow rate (ml/min) External coagulant Air gap distance (cm) Spinneret o.d./i.d. (mm) Coagulantion temperature ( °C)

4.5

NMP/Water 90/10

2

Tap water

0.0

1.0/0.50

25

2.2. Fabrication and characterization of porous hollow fiber

membranes

PSF was purchased from Merck Company Germany to build hol- low fiber membranes: 1-methyl, 2-pyrrolidone (NMP > 99.5%) as a gross solvent and ethanol as non-solvent additives. In all cases tap water was used as the coagulation bath (spinning process). MEA (purity above 98%) was purchased from Sigma-Aldrich Co and used as the absorbent liquid. Table 2 illustrates the properties of fabricated PSF hollow fiber membranes. Dope was applied as an external coagulant to solidify polymer solution resulting into the formation of hollow fiber. After that, the Spinneret hollow fiber was drowned into the water for 3 days to remove the ethanol and remaining NMP. Then, it was nat- urally hung to be dried in environment temperature for 1–2 days. The lifetime of developed membrane depends on membrane thickness, membrane precursors (type of organic or inorganic ma- terial), morphology, filler material, evolution procedure, feed pres- sure and temperature, density, type of module, free volume and composite or hollow fiber matrix [39].

2.3. Surface area of porous hollow membrane

It is essential to consider the characterization of surface poros- ity and pore size in order to examine mass transfer in the absorp- tion of membrane [40]. The total permeation through the asym- metric membrane is considered as the combination of the Knudsen and Poiseuille flow [41]. Li et al. [42] presented a modified perme- ation response to obtain the surface porosity and the average pore size over the effective pore length of the asymmetric porous mem- brane. Through the assuming cylindrical pores in the skin layer of membrane, the permeance of gas can be given as the following equation:

j i = 2 rpε

3 RT L

P

8

M 0.5

RT

π

j i = K 0 + P 0 P

+

2 r ε p 8μ i RT L P p
2
r
ε
p
8μ i
RT L P p

(1)

(2)

According to Eq. (1), the average pore size can be determined from the slope ( P 0 ) and intercept ( K 0 ) as Eq. (3) by plotting J i versus mean pressures:

r p = 5.333 p 0

k

0

8

M 0.5

RT

π

μ i

(3)

The effective surface porosity (ε/ Lp) over pore length can be also calculated from the slope as below:

ε 8μ i RT P 0

=

L

P

r p 2

(4)

The test procedure was based on the volume displacement technique [40–42]. The gravimetric method was utilized to calcu- late the membrane overall porosity(ε m ). It is defined as the pores volume divided by the total volume of the hollow fiber membrane determined by the following relation [42]:

ε m =

( w 1 w 2 )/ρ W

(W 1 W 2 )/ρ W + W 2 /ρ P

(5)

where w 1 and w 2 are the weight of the wet and dry membrane, respectively; ρ p the polymer density; ρ w water density. In order to synthesize the wet membranes, five spun fibers were designed after 3 days solvent exchange. The hollow fibers were immersed in distilled water for another day and the remaining water on the inner surface was blown by air stream. Then, the hollow 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 check was executed. The shell side upstream pressure was set at 0.5 × 10 5 Pa. The final data of this method are presented in Table 3 and detailed in following sections.

2.4. Experiment of CO 2 absorption

Collider gas–liquid membrane system was used to measure the flux of CO 2 . Ten hollow fibers were placed in membrane mod- ule of stainless steel. Pure carbon dioxide used as feed gas in the tube and MEA (1 M) was applied in the shell antithetic mode as the absorption liquid. Control valves and flow gauges monitor gas and liquid flow rates in 200 ml/min and 50–300 ml/min. The gas side pressure was set to 1 × 10 5 (Pa). The fluid pressure was kept higher than the gas to prevent the bubbles formation in a liq- uid, as 0.2 × 10 5 (Pa). Carbon dioxide concentration was measured by titration in the output liquid in order to determine the flux of carbon dioxide. In the titration process, 10 ml of output sam- ple liquid of the module was poured into a beaker and more than this amount (about 12 ml), the solution of 0.1 M sodium hydroxide (NaOH) was added to the solution and completely dissolved with the ionized carbon dioxide in the solution. Some barium chloride solution (BaCl 2 ) was added to the solution. Then, the obtained so- lution was shaken well until all the carbon dioxide dissolved in the solution (physically or chemically) and deposited as BaCO 3 . The remaining NaOH solution was titrated in the solution by hydro- gen chloride (HCl) and phenolphthalein was used as an indicator. To measure the absorption amount of carbon dioxide, a few drops of methyl orange was added to the solution and the solution was titrated by HCl. An amount of HCl is used in this stage to calculate the amount of absorption of carbon dioxide by the moles of CO 2 to the number of moles of MEA. Before taking samples, all tests were performed for 30 min to achieve a steady state.

M CO 2 moL

L

= ( N.V ) HCL

V sample

(6)

The total area of the membrane was considered as the sur- face of liquid–gas contact dealt for mass transfer, so the empirical

amount of carbon dioxide flux J CO 2 ( V sample ) is calculated from the

following relation:

mol

J CO 2 = Q L . M CO 2

V sample

10 0 0

(7)

where Q L is the absorption flow rate (m 3 /s), M CO2 is the concen- tration of carbon dioxide in the absorption solution (mol/L) and A i is the collision surface between air–liquid (m 2 ). The absorption of membrane contactor-module output flow rate was measured by a liquid flow meter. Gas–liquid contact surface is measured based on absorption flow on the pipe or the surface contact module. When

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Table 3 Specifications of hollow fiber membranes derived from PSF.

Additive

Without additives

Ethanol (2 wt.%)

Average pore size (nm) Effective surface porosity (ε/Lp (m 1 )) Critical entry pressure water (CEPw) (×10 5 Pa) Overall porosity (%) Collapsing pressure (×10 5 Pa) Contact angle outer surface

24.5

19.3

48.57

76.30

7.50

8.00

70.54

74.90

8.50

7.50

68.30

73.25

8.00 70.54 74.90 8.50 7.50 68.30 73.25 Fig. 2. Flow pilot reactor to absorption carbon

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, mm 2 )

15

250

0.9–1.0

0.45–0.50

180

30

4521

the liquid absorption flows on the shell side, the surface of area is calculated by the following relation:

A 0 = n π d i L

(8)

where n is the number of fibers (in this study, 10), d i 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 CO 2 stripping

The amount of stripping CO 2 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 (N 2 ) flows inside the shell and MEA solution rich in CO 2 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 × 10 5 Pa to avoid forming bubbles on the liquid. Operating pressure and temperature were kept constant in 80 °C and 0.5 × 10 5 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 determine the amount and efficiency. In the titration method, 10 ml of output liquid sample was poured in a beaker from the module and more than this amount (about 12 ml) solution of 0.1 M NaOH was added to the solution to fully ionize carbon dioxide dissolved in the solution. Then, some barium chloride (BaCl 2 ) was added to the solution. Next, the solution was shaken well until all the carbon dioxide dissolved in the solution to be formed deposits of BaCO 3 (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 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:

M CO 2 moL

L

= ( N.V ) HCL

V sample

(9)

Carbon dioxide stripping efficiency was calculated by the fol- lowing module:

η(%) = 1 C l ,o × 100

C l ,i

(10)

where C l,o is carbon dioxide concentration in the liquid phase at the outlet of the membrane module (mol/m 3 ) and C l,i is the con- centration of carbon dioxide in the liquid phase of input membrane module (mol/m 3 ). Laboratory stripping of carbon dioxide flux on

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Institute of Chemical Engineers 0 0 0 (2017) 1–9 5 Fig. 3. Diagram of the laboratory

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

of the laboratory stripping membrane contactor system. Fig. 4. SEM images of the cross section fiber

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:

J CO 2 = C l ,i C l ,o × Q l

A

i

(11)

In relation (11), J CO2 is the flux of carbon dioxide excretion (mol/m 2 /s), Q l is the rate of liquid’s flow (m 3 /s), and A i is the in- ner surface of the hollow membrane (m 2 ). 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- 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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Institute of Chemical Engineers 0 0 0 (2017) 1–9 Fig. 5. SEM images of the structure

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 R 2 = 0.9481 3.00E-07 2.50E-07 2.00E-07 1.50E-07 Y=
3.50E-07
Y = 5E-10x + 9E-08
R 2 = 0.9481
3.00E-07
2.50E-07
2.00E-07
1.50E-07
Y= 7E-10x + 1E-07
R 2 = 0.9543
1.00E-07
5.00E-08
Without additive
PSf+2% Ethanol
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 N 2 as a function of average pressure of the hollow fiber membranes (
without additives,
2 wt.% ethanol).
N 2 Permeance (mol/m 2 s pa)

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 N 2 permeance against the pressure data linked together by a linear equation with a correlation co- efficient ( R 2 ). Thus, this equation contributes to demonstrate that there is a relationship between linear equation and a correlation coefficient ( R 2 ). 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 N 2 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 N 2 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 × 10 5 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 2.50E-07 2.00E-07 y = 7E-10x
3.50E-07
y = 5E-10x + 9E-08
R² = 0.9481
3.00E-07
2.50E-07
2.00E-07
y = 7E-10x + 1E-07
1.50E-07
R² = 0.9543
1.00E-07
Without additive
5.00E-08
PSf+2% Ethanol
0.00E+00
100
150
200
250
300
350
N 2 Permeance (mol/m 2 s pa)

Mean pressure (KPa)

Fig. 7. The amount of permeance of N 2 as a function of average pressure
Fig. 7. The amount of permeance of N 2 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
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
Absorption flux (m0l.m -2 .s -1 )

Liquid flow rate (ml.m -1 )

Fig. 8. The effect of Absorption flow rate (MEA) on the absorption of CO 2 in gas–liquid membrane contactors.

operating pressure test. As shown in this table, breaking down and disintegrating the membrane pressure can be enhanced by increas- ing the diameter of the pores of the membranes. Holistically, nitro- gen gas flow moves easier through the membrane as the diameter of the pores is increased. In fact, higher pressure is needed for the break-up of membrane.

3.2. The effect of additives on the absorption of carbon dioxide

Fig. 7 indicates the effect of the flow of ethanolamine solution made as carbon dioxide flux absorption membranes made. As ob- served, the flow rate increase can make the flux of CO 2 enhance. Liquid phase resistance is a mass transfer process controller for the sake of gas absorption in membrane contactors in liquids [43]. On the other hand, it seems that the rate of CO 2 gas flow has no im- pact on CO 2 flux because applying pure carbon dioxide in the gas has no resistance to transport CO 2 . As reported in other studies, membrane of poly-ethylene tetra-fluoride and poly vinylidene flu-

oride can be applied to absorb CO 2 [44,45]. Fig. 8 illustrates that the CO 2 flux of the membranes prepared without ethanol is signif- icantly lower than the other membranes. Table 4 also shows that the effective porosity of the effective membrane surface is smaller than other membranes. Therefore, the contact area between gas and liquid flux is smaller and absorption is less than other mem- branes. The solution made with 2 wt.% solution of ethanol, as an additive, has the highest amount of absorption and discharge flow.

3.3. Effect of additives on the stripping of carbon dioxide

Fig. 9 displays the amount of carbon dioxide gas to liquid ve- locity of the membranes prepared with 0 and 2 wt.% ethanol. As observed, the amount of carbon dioxide stripping is significantly lower than the other membranes in comparison to the speed of liquid in a membrane produced without ethanol. Effective porosity of this membrane is smaller than the other membranes. Therefore, the contact area between gas and liquid is smaller. Moreover, the

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Institute of Chemical Engineers 0 0 0 (2017) 1–9 Fig. 9. The effect of liquid rate

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 60 50 40 30 20 10 0 0 0.1 0.2 0.3 0.4
90
80
70
60
50
40
30
20
10
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Stripping efficiency (%)

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/m 2 /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

Based on these experiments, the main results are summarized 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.

3. Remarking the critical pressure of water inlet, all mem- branes are used in the additional pressure on the shell side (0.2 × 10 5 Pa) during the process could not resist.

4. The increase of CO 2 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/m 2 /s.

References

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[m5G; August 23, 2017;21:11 ]

E. Kianfar et al. / Journal of the Taiwan Institute of Chemical Engineers 0 0 0 (2017)