M. Rahbari-Sisakhtab,
F. Korminouria,
D. Emadzadehab,
T. Matsuurac and
A. F. Ismail*a
aAdvanced Membrane Technology Research Center (AMTEC), Universiti Teknologi Malaysia (UTM), 81310 Skudai, Johor, Malaysia. E-mail: afauzi@utm.my; fauzi.ismail@gmail.com; Fax: +60 75535925; Tel: +60 75535592
bDepartment of Chemical Engineering, Gachsaran Branch, Islamic Azad University, Gachsaran, Iran
cDepartment of Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur St., Ontario K1N 6N5, Canada
First published on 4th November 2014
Surface Modifying Macromolecule (SMM) blended PSf hollow fibers were spun at different air-gaps to evaluate CO2 stripping from aqueous DEA solution and water. The fabricated membranes were firstly subjected to different characterization methods such as contact angle and liquid entry pressure measurement to evaluate the membrane's hydrophobicity and wetting resistance, respectively. To determine pore size and effective porosity of the membranes, a pure helium permeation test was performed. Morphological study of the membranes was conducted by scanning electron microscopy (SEM) and atomic force microscopy (AFM). A CO2 stripping test was carried out to investigate the effects of operating variables such as liquid and gas velocity, temperature and DEA concentration on the CO2 stripping flux. It was found that the increase of liquid velocity resulted in enhanced CO2 stripping flux. On the other hand, the increase in gas velocity did not exert significant influence on the stripping flux. The increase in temperature and DEA concentration both enhanced the stripping flux. Lastly, it was concluded that the hollow fibers spun in this work at a 15 cm air-gap could achieve the best stripping flux among all the membranes fabricated so far for CO2 stripping.
Polysulfone (PSf) has been used for a long time as a polymeric material for HFM preparation. This polymer, according to Rahbari-Sisakht et al.22 despite not being highly hydrophobic can be a surpassing option for membrane fabrication due to its great thermal and mechanical endurance and high solubility in the solvents. To elevate the hydrophobicity of membrane surface, blending surface modified macromolecules (SMM) in the polymer dope can be a favored method. SMM is an amphipathic macromolecule consisting of hydrophilic and hydrophobic parts. In a polymer blend, thermodynamic incompatibility between polymers usually causes demixing of polymers to occur. If the polymer system is equilibrated in air, the polymer with the lowest surface energy will concentrate at the air interface and reduce the system's interfacial tension as a consequence.23 In our previous work, EDX results showed that during hollow fiber spinning, SMM tends to migrate to membrane – air surface and changes the membrane outer surface properties.24 The SMM surface migration occurs during membrane fabrication process due to the difference in energy levels of the SMM and base polymer, which leads to improve hydrophobicity of the HF surface. The detailed kinetics and mechanism of SMM surface migration is presented in earlier study.25 The air-gap is one of the principal spinning conditions that affects the amount of migrated SMM to the membrane-interface by providing a sufficient amount of time for SMM migration. The study into the effect of air-gap on membrane performance and structure has been conducted over the past few decades for various separation processes.26–36
MC systems have a considerable potential to regenerate or desorb the absorbent solution. In the absorption process, unwanted gas (CO2) is absorbed by the liquid absorbent. In the regeneration procedure, on the other hand, desorption of CO2 takes place. The liquid absorbent is in contact with one end of the HFM pore and CO2 diffuses through the pore, and stripped by the stripping gas at the other end of the pore to regenerate the liquid absorbent.
Many studies have focused on the absorption unit using HFM contactors,37–39 while only a few works have been carried out until now on CO2 stripping through MCs. Recently, a research has been done by Khaisri et al.40 to strip CO2 from monoethanolamine (MEA) solution using polytetrafluoroethylene (PTFE) HFM. They concluded that the stripping efficiency was elevated with the increase of the liquid velocity, operating temperature and absorbent concentration. On the other hand, the gas side mass transfer resistance did not deeply affect the CO2 desorption flux. Kumazawa41 conducted a study on CO2 desorption from 2-amino-2-methyl-1-propanol (AMP) through PTFE membrane. They found that desorption process is ascribed to diffusion and chemical reaction in the liquid side. They concluded that an increase in concentration of AMP and the loaded CO2 in the solution resulted in enhancement of total mass transfer coefficient. Naim et al.42 produced PVDF membrane to strip CO2 from aqueous diethanolamine (DEA) solution. They added LiCl in the polymer solution as an additive to investigate the effect of different LiCl levels on stripping performance of the membrane. A linear increase in stripping flux was observed with increasing LiCl concentration. A study by Mansourizadeh and Ismail43 focused on CO2 stripping from water using PVDF membrane. Their results showed that the increase of inlet liquid concentration led to increase of CO2 stripping performance. Rahbari-Sisakht et al.44 fabricated PVDF fibers modified by SMM to strip CO2 from diethanolamine solution. Their experimental found that the CO2 desorption flux was enhanced with increasing DEA concentration, solution temperature and liquid velocity. In other works,45 wet spun polyetherimide (PEI) membrane blended with polyethylene glycol (PEG) was developed to evaluate the effect of various PEI concentrations (13–16 wt%) on CO2 stripping performance from DEA solution. It was found that the membrane produced with 14 wt% PEI concentration achieved the maximum CO2 flux of 2.7 × 10−2 (mol m−2 s−1).
Despite the above mentioned researches on stripping applications, to our knowledge, no research has been conducted thus far into the effect of SMM migration to the HF membrane surface on CO2 stripping flux from aqueous DEA solution and water. The first attempt is hence made in the present work to manufacture SMM blended PSf HFs with different air-gap distances, to characterize the HFs so manufactured by various methods and to investigate the performance of CO2 stripping flux from DEA and water in a MC application.
Fig. 1 shows the SMM structure, where m represents the repeating units of CF2 and equals to 7.58, y indicates α,ω-aminopropyl poly(dimethyl siloxane) (PDMS) repeating units and is equal to 9.81 and q reveals repeating unit of urea and equals to 10.14. The detailed descriptions of SMM synthesis were given in other literatures.25
Aqueous solution of diethanolamine (DEA > 99%, from Merck) was used as the liquid absorbent in MC application. The sweeping and feed gas were pure N2 and CO2, respectively. After degassing the resulting mixture by the aid of ultrasonic water bath, the PSf HFs (M1–M7) were spun with air-gaps of 0, 5, 10, 15, 20, 30 and 50 cm, respectively, according to the method described earlier.46 Table 1 gives the detailed dry-wet spinning conditions applied in this work. To completely remove the residue of the additive, solvent and any impurities, the spun HFs were soaked in tap water for 3 days, before being dried at room temperature.
Dope extrusion rate (mL min−1) | 4.5 |
Composition of bore fluid | NMP/water (60/40) |
Bore fluid rate (mL min−1) | 2.00 |
Coagulation medium | Tap water |
Spinneret dimension, o.d./i.d (mm) | 1.20/0.55 |
Air-gap (cm) | 0, 5, 10, 15, 20, 30 and 50 |
Temperature of coagulant (°C) | 25 |
Fig. 2 Experimental apparatus of stripping process via MC system.49 |
Module i.d (mm) | 14 |
Length of module (mm) | 270 |
HF o.d (μm) | 0.7–0.9 |
HF i.d (μm) | 0.45–0.5 |
Effective length of HF (mm) | 150 |
Number of HFs | 30 |
Effective contact area (inner, mm2) | 6358.5 |
The flux of stripped CO2 was obtained using the equation below:
(1) |
HF Number | Air-gap distance (cm) | Average pore size (nm) | Effective surface porosity (m−1) | LEPw (×105 pa) | LEPDEA (×105 pa) at 80 °C | CA (outer surface) | Collapsing pressure (×105 pa) | Overall porosity (%) | Roughness (Ra) |
---|---|---|---|---|---|---|---|---|---|
M1 | 0 | 108.95 | 2.00 | 5.00 ± 0.72 | 4.5 ± 0.25 | 85.14 ± 0.87 | 7 | 70 | 4.12 |
M2 | 5 | 141.18 | 1.97 | 5.00 ± 1.32 | 4.5 ± 0.68 | 85.81 ± 1.46 | 7.5 | 70 | 4.85 |
M3 | 10 | 88.61 | 3.84 | 5.00 ± 0.40 | 4.00 ± 1.40 | 87.23 ± 1.23 | 8 | 69 | 5.54 |
M4 | 15 | 21.27 | 33.28 | 5.5 ± 0.64 | 5.00 ± 0.25 | 93.01 ± 0.93 | 8.5 | 68 | 6.41 |
M5 | 20 | 62.96 | 11.40 | 3.5 ± 1.07 | 3.00 ± 0.50 | 88.80 ± 1.37 | 8.5 | 68 | 7.31 |
M6 | 30 | 257.70 | 3.10 | 4 ± 0.82 | 3.50 ± 1.25 | 90.00 ± 1.07 | 9 | 66 | 8.06 |
M7 | 50 | 774.83 | 0.34 | 4.5 ± 0.53 | 3.50 ± 0.50 | 91.78 ± 1.29 | 9 | 58 | 8.58 |
The enhancement of contact angle (CA) from 85.14 ± 0.87° to 93.01 ± 0.93° with increasing air-gap up to 15 cm can be attributed to the presence of a larger amount of SMM at the HF surface. On the other hand, a trend of decline in CA from 15 to 50 cm can be attributed to the increased pore size for larger air-gaps. Notably, the increase of the pore size facilitates penetration of water into the HF membrane pores, resulting the reduction in CA values. According to the AFM analysis the roughness of HF outside surface increased as the air gap increased from 0 to 50 cm, which may also have contributed to the enhancement of CA. Further increase in roughness from the air gap of 15 to 50 cm is most likely associated with the increase in pore size, which, as mentioned above has caused the decrease of CA. In any case, all HF surfaces exhibited CA of higher than that of the plain dry spun PSf HF (63 ± 1.5°) by Rahbari-Sisakht et al.,24 which is another evidence of the surface migration of hydrophobic SMM.
The collapsing pressure of PSf HF membranes has gradually increased as the air-gap changed from 0 to 50 cm, which was mainly caused by interaction of base polymer with surface migrated SMM.
The HFs overall porosities are considered to be high enough for MC due to the low polymer concentration in the spinning solution. Furthermore, surprising decrease of The overall porosity decreased gradually with the increase in the air-gap, which is associated with the reduced HF dimension (i.d, o.d and wall thickness) at the higher air-gaps. In addition, a parallel relationship is found between CA and LEPw, i.e. both CA and LEPw increased up to 15 cm air-gap, decreased a little from 15 to 20 cm and then increased continuously from 20 to 50 cm. Hence, it can be concluded that LEPw was also influenced by both the pore size and the amount of migrated SMM to the surface. M4 membrane showed the highest resistance to the wetting for both water and aqueous DEA solution.
Fig. 6 CO2 stripping flux vs. liquid velocity (DEA solution) (TDEA = 80 °C, MDEA = 1 mol L−1, gas flow rate = 50 mL min−1). |
The membrane that has been fabricated using 15 cm air gap length (M4) is unique in many aspects among all the studied HFs. In particular, M4 has the highest effective surface porosity (see Table 3), enabling the fastest gas transport due either to the large surface porosity or to the small effective membrane thickness. Its LEPw is also the highest due to the smallest pore size and the highest contact angle. Thus, M4 has all the desirable features of MC applications.
In Tables 4 and 5 comparisons were made between the CO2 stripping fluxes from aqueous DEA solution and water, respectively, of the membranes fabricated in this work and those reported in other studies.44,52–55 The velocity of both DEA solution and water flow was maintained at 0.7 m s−1. As the tables show, M4 membrane fabricated in this work at 15 cm air-gap and modified with 1 wt% SMM, shows the best CO2 fluxes.
Membrane | Polymer material | Air-gap (cm) | Additive | CO2 flux (mol m−2 s−1) | Reference | Liquid absorbent |
---|---|---|---|---|---|---|
M1 | PSf | 0 | 1 wt% SMM | 2.70 × 10−2 | This work | DEA |
M2 | PSf | 5 | 1 wt% SMM | 1.20 × 10−2 | This work | DEA |
M3 | PSf | 10 | 1 wt% SMM | 3.30 × 10−2 | This work | DEA |
M4 | PSf | 15 | 1 wt% SMM | 4.60 × 10−2 | This work | DEA |
M5 | PSf | 20 | 1 wt% SMM | 3.90 × 10−2 | This work | DEA |
M6 | PSf | 30 | 1 wt% SMM | 3.10 × 10−2 | This work | DEA |
M7 | PSf | 50 | 1 wt% SMM | 1.00 × 10−2 | This work | DEA |
— | PVDF | 5 | 1 wt% SMM | 1.20 × 10−3 | 44 | DEA |
— | PVDF | 0 | — | 2.20 × 10−2 | 55 | DEA |
— | PVDF | 0 | 5 wt% PEG | 3.70 × 10−2 | 55 | DEA |
— | PVDF | 0 | 5 wt% glycerol | 2.00 × 10−2 | 53 | DEA |
— | PVDF | 0 | 5 wt% LiCl | 3.75 × 10−2 | 53 | DEA |
— | PVDF | 0 | 5 wt% methanol | 2.60 × 10−2 | 53 | DEA |
— | PVDF | 0 | 5 wt% phosphoric acid | 2.70 × 10−2 | 53 | DEA |
— | PVDF | 0 | — | 2.70 × 10−2 | 53 | DEA |
— | PEI | 0 | — | 9.00 × 10−3 | 55 | DEA |
— | PEI | 0 | 5 wt% PEG | 2.35 × 10−2 | 55 | DEA |
Membrane | Polymer material | Air-gap (cm) | Additive | CO2 flux (mol m−2 s−1) | Reference | Liquid absorbent |
---|---|---|---|---|---|---|
M1 | PSf | 0 | 1 wt% SMM | 5.30 × 10−4 | This work | Water |
M2 | PSf | 5 | 1 wt% SMM | 4.70 × 10−4 | This work | Water |
M3 | PSf | 10 | 1 wt% SMM | 8.50 × 10−4 | This work | Water |
M4 | PSf | 15 | 1 wt% SMM | 2.10 × 10−3 | This work | Water |
M5 | PSf | 20 | 1 wt% SMM | 1.10 × 10−3 | This work | Water |
M6 | PSf | 30 | 1 wt% SMM | 6.80 × 10−4 | This work | Water |
M7 | PSf | 50 | 1 wt% SMM | 2.60 × 10−4 | This work | Water |
— | PSf | 0 | 4 wt% glycerol | 1.30 × 10−4 | 54 | Water |
— | PVDF | 0 | 5 wt% glycerol | 1.90 × 10−3 | 52 | Water |
Fig. 8 demonstrates the relationship between gas velocity and stripping flux for both DEA solution and water. The results for M4 membrane (15 cm air-gap) are plotted in the figure, but all other HFs would show a similar trend. As shown in Fig. 8, no noticeable stripping flux was perceived as the gas velocity was varied from 0.005 to 0.002 (m s−1). This finding perfectly validates interpretations by Khaisri et al. that the liquid phase primarily governs mass transfer rate of MC stripping and the mass transfer resistance of gas stream has negligible effect on stripping flux.40
Fig. 8 CO2 stripping flux vs. gas velocity (TDEA&water = 80 °C, MDEA = 1 mol L−1, liquid flow rate = 50 mL min−1). |
The influence of liquid temperature on the stripping performance of M4 membrane was also studied and the results for water and DEA solution in Fig. 9 and 10, respectively. As shown in Fig. 9, a marked increase of stripping flux occurred from 2.50 × 10−4 to 4.60 × 10−2 (mol m−2 s−1) as the temperature of water changed from 25 °C to 80 °C, which can be attributed to the decrease of CO2 solubility as the water temperature increases.44,54 Fig. 10 also shows that the stripping flux of CO2 increased as the DEA temperature was increased from 25 °C to 80 °C. It could be said that diffusion coefficient, equilibrium constant of chemical reaction and equilibrium partial pressure of CO2 are strongly influenced by liquid temperature.40 A decrease in equilibrium constant of the following reaction (eqn (2)) leads to enhancement of CO2 partial pressure in the gas side by the factor of 5 to 8 as the temperature is increased by 10 °C.56 Consequently, an increase in working temperature results in elevated driving force for CO2 stripping from the DEA solution.
CO2 + 2R2NH ↔ R2NH2+ + R2NCOO− | (2) |
Fig. 9 CO2 stripping flux vs. liquid phase temperature (water) (liquid and gas flow rate = 200, 50 mL min−1, respectively). |
Fig. 10 CO2 stripping flux vs. liquid phase temperature (DEA) (liquid and gas flow rate = 200, 50 mL min−1, respectively). |
Fig. 11 reveals the relationship between DEA concentration and stripping flux of M4 HF in the MC system. As illustrated in the figure an increase in DEA concentration from 0.25 to 1 M results in elevation of stripping flux, which can be validated by the reaction represented by eqn (2). As it is interpreted by Rahbari-Sisakht et al., increase of DEA concentration causes enhancement of absorbed CO2 during preloading in the form of R2NCOO− ion.44 During the stripping procedure, release of CO2 causes the elevated CO2 partial pressure at the interface, resulting in increase of driving force.40
Fig. 11 CO2 stripping flux vs. liquid velocity for various DEA concentration (gas flow rate = 50 mL min−1, T = 80 °C). |
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