Soheila Manshad*a,
Mohammad Reza Sazegarb,
Mohd. Ghazali Mohd. Nawawia and
Hashim bin Hassana
aDept. of Chemical Engineering, Fac. of Chemical Engineering, Universiti Technologi Malaysia, Johor, Malaysia. E-mail: smanshad12@yahoo.com
bDept. of Chemistry, Fac. of Science, Islamic Azad University, North Tehran Branch, Tehran, Iran
First published on 25th October 2016
Polyetherimide (PEI) flat-sheet membranes (PM) as a nanohybrid membrane were fabricated through dry-thermal (PMDT) and thermal treatment (PMTT) methods using graphene oxide (GO) as a nanofiller. Characterization of PM membranes was carried out using Fourier transform infrared (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The PMDT membrane cross-section showed a sponge-like structure resulting in higher permeability and lower separation factor. The SEM image (cross-section) of the PMTT membrane showed a dense structure with higher separation factor and lower permeation flux than those of the PMDT membrane. Incorporation of GO into the PEI matrix significantly reduced the contact angle surface hydrophobicity of the membranes. The nanohybrid membrane exhibited an exceptional pervaporation performance at a concentration of 95 wt% n-butanol. The permeation flux of PMDT and PMTT membranes were 1100.26 and 642.69 kg m−2 h−1 and their separation factors were 89.39 and 96.96, respectively. The GO incorporation and novel fabrication techniques resulted in excellent separation performance.
Basically, hydrophilic and hydrophobic polymeric membranes are used to separate water from the organic solvents.4–7 Typically, hydrophilic membranes are considered to dehydrate n-butanol as a biofuel, which is considered as a future energy source to substitute with gasoline.8–14 The heating value of n-butanol (2501 kJ mol−1) is higher than that of ethanol (1329 kJ mol−1); for this reason, this alcohol is used as a biofuel and blended with gasoline and diesel. The combustion of this biofuel resulted in the production of water and carbon dioxide as well.15,16 Since fossil fuels have natural organic sources, the presence of gases with sulfur and nitrogen atoms is expected. Therefore, in addition of CO2 and H2O formation, the gases of SOx, NOx and CO are produced during the fuel combustion process owing to fuel impurities. Production of CO is related to a defect in fuel combustion. NOx emissions were reduced because of its higher heat of evaporation, which resulted in a lower ignition temperature. Combustion of n-butanol increases the temperature to assist the fuel combustion. The results showed that adding n-butanol has more advantages than the widely used ethanol. n-Butanol has a 53% greater heating value than that of ethanol.17,18 n-Butanol (C4H9OH) is an alcohol with a four-carbon chain as a non-polar group and a polar hydroxyl group, which is responsible for its solubility in water and polar solvents. The solubility of this alcohol in water (73 g L−1) is less than the lighter alcohols with lower carbon atoms, such as propanol, ethanol and methanol, owing to its larger non-polar group. These light alcohols are fully miscible in water. Therefore, n-butanol shows limited solubility in comparison with the light alcohols. n-Butanol is produced from the petrochemical industry and fermentation, where it is used as an industrial intermediate and a biofuel for diesel fuel and gasoline. The n-butanol that is obtained from the fermentation process has less than 3.0 wt% concentration of ABE products (acetone, butanol and ethanol).19 The separation process of n-butanol involves two main steps: purification of the dilute solution by distillation to produce a solution of 80 wt% n-butanol and dehydration of the purified solution to concentrate it further to 99.5 wt%. Although the recovery of n-butanol by using membranes shows good separation performance, it is not economically feasible for large-scale industrial applications. Mostly polymeric membranes are not able to separate the water/organic solutions with good results owing to the swelling and cracking of the membranes and the low permeation process. Moreover, though many membranes have been used to dehydrate biofuels with high performance, they are not economical or easily fabricated to use in large-scale in different industries. Some materials, methods and techniques, such as fillers, grafting, cross-linking, support-layer20,21 and coating,22–24 have been used to overcome the current issues with the polymeric materials. Polyetherimide (PEI) with specific properties such as excellent mechanical/chemical properties, less swelling characteristics, solvent resistance, good membrane-forming property, and high separation performance25 is a suitable candidate as a matrix polymer for dehydration of n-butanol. Therefore, this polymer with the attractive features was used for separation of n-butanol from its aqueous solution. Since PEI does not have a significant permeation performance, it should be modified by using graphene oxide (GO) to enhance the permeation process by increasing the hydrophilicity of the membrane.26–33
Recently, graphene has attracted researchers because of its derivative graphene oxide (GO), which exhibits different characteristics in comparison with graphene. Graphene has been used to prepare a film with highly hydrophobic property containing multilayer graphene platelets, while graphene oxide (GO) is a hydrophilic material with a wide range of active oxygen functional groups, such as hydroxyl, carboxyl and epoxide groups, which are responsible for its polar properties. Therefore, it can be rendered as a good compatible material with PEI to prepare hydrophilic membranes.26–29 These functional groups improved the interfacial interaction between graphene oxide and the polymer matrix, which paved the way for the development of the GO based nano-composites with significant mechanical and thermal properties. Nano-GO is a hydrophilic material with numerous active oxygenated groups that can be used for the dehydration process. The polar groups of nano-GO can easily interact with water molecules and lead to a fast diffusion rate in the permeate side and high selectivity towards water molecules.29 Here, the hydrophilicity of the membranes is increased and promotes the favorable properties of the membranes for the dehydration of organic solvents. Generally, modification with inorganic materials shows low performance in the separation factor, while nano-graphene oxide offers higher performance in the separation process.9,34–39
The application of GO is based on the number of hydroxyl groups of the GO network, which indicates the presence of the large specific surface area, superior mechanical stiffness and flexibility, remarkable optical transmittance, exceptionally high electronic and thermal conductivities, impermeability to gases and water, as well as many other supreme properties. These properties make it a miracle material. Scheme 1 shows the chemical structure of GO.
Most of the conventional membranes are not economical and are not easy to fabricate due to the expensive modifications and preparation processes required.40–43 They are not able to achieve the target of simultaneously improving permeation and separation factor. This study involved the fabrication of hydrophilic PMDT (dry-thermal) and PMTT (thermal treatment) membranes by using two different casting techniques to achieve different micro-structure membranes with different pervaporation performances. The PMDT and PMTT membranes possess significant features, such as an easy and low cost fabrication process without using any modifications, such as grafting and coating. There were no modification techniques in the fabrication processes. The PMDT and PMTT membranes were prepared easily by incorporating nano-graphene oxide to enhance the favorable properties of the permeation process. In addition, the different morphological structures, separation performances and effects of nano-fillers such as nano-graphene oxide in the activity of these membranes were investigated in detail. The nano-filler structure was studied by using XRD patterns and TEM images.
NaNO3 + H2SO4 → HNO3 + NaHSO4 | (1) |
2KMnO4 + H2SO4 → K2SO4 + Mn2O7 + H2O | (2) |
Dihydroxylation in presence of water | (3) |
J = Q/At | (4) |
α = (Ywater/Ybutanol)/(Xwater/Xbutanol) | (5) |
In addition, the well synthesized monolayer graphene oxide was indicated by using transmission electron microscopy (TEM), which is shown in Fig. 1. The surface morphology and cross section of the PMTT and PMDT membranes were evaluated by the representative SEM image, which are shown in Fig. 2.
Fig. 2 The surface morphology SEM of PMTT (A), PMDT (C), cross section SEM of PMTT (B and B-1) and PMDT (D and D-1) membranes (insets are high magnification images and red arrows denote GO sheets). |
Fig. 2A and C show the surface morphology and SEM cross-section B, B-1 and D, D-1 of PMTT and PMDT, respectively. The SEM images show a dense structure for PMTT with a higher separation factor and a lower permeation performance, and exhibited a lower density structure for PMDT with a higher permeation performance for the PV process. These images exhibited the effects of the temperature and drying time on their morphologies. Both of these factors affected the physical (density degree) and chemical (hydrophilicity) properties of the membranes. The SEM results exhibited a physical difference between PMDT with low density and PMTT with high density microstructures, which resulted in the difference in their PV performances. PMDT exhibited a higher permeation due to its lower microstructure density, while PMTT exhibited a lower permeation due to its high microstructure density and its separation factor performance was higher than that of the PMDT membrane as well. The low density PMDT membrane was synthesized by using low temperature and slow solvent evaporation (drying time), which resulted in an improvement in the membrane permeation performance. The high density PMTT membrane was prepared by using high temperature and fast solvent evaporation (thermal treatment), which resulted in a lower permeation and a higher separation factor.
The uniform and smooth surface areas of the PMDT and PMTT membranes are shown in Fig. 3, which indicated the uniform dispersion of GO as a filler in the PEI polymer. The agglomeration of GO was not observed on the membrane sheet, which confirmed the uniform dispersion of GO into the PEI polymer.
The observation of any agglomerated GO indicated the leaching or cracking on the surface during the separation process .49
Fig. 4 shows the FTIR spectra of the GO and the PMDT and PMTT composite membranes. To verify bonding of the PEI and GO as a nanohybrid membrane, this spectroscopy was used. The characteristic absorption bands of GO and these polymer membranes can be observed at around 3050–3450 cm−1 (O–H bonds of graphene oxide), 2960 and 2850 cm−1 (C–H str), 1716 and 1650 cm−1 (CO str), 1364 cm−1 (C–N str) and 1050 cm−1 (C–O str).44 The results strongly confirmed the synthesis of two types of membranes by observing of two bonds at 1716, and 1364 cm−1, which are evidence of the presence of imide groups (OC–N–CO) in their structures.
The hydrogen bonds due to the interaction between OH groups on the surface of GO with polar groups on the composites shifted the hydrogen broad band from 3290 cm−1 in graphene oxide to 3350 cm−1 in the membranes. This indicates that the surface OH groups of GO have been plugged by the PEI polymer, which results in a decrease in the hydrogen bonding due to the deposition of polymer.
Fig. 5 shows the permeation fluxes and separation factors of PMDT and PMTT at different temperatures of 30, 40 and 50 °C. The results show that the physical and chemical properties of these membranes for dehydration of n-butanol solution are different due to two main factors, namely temperature and drying time. The low density PMDT was synthesized by using low temperature and slow solvent evaporation (drying time), which resulted in an improvement in the membrane permeation performance. The high density PMTT membrane was prepared by using high temperature and fast solvent evaporation (thermal treatment), which resulted in low permeation and a high separation factor.
Fig. 5 Permeation flux (A) and separation factor (B) of PMDT and PMTT membranes at 30, 40 and 50 °C. |
On the contrary, the permeation flux of the PMTT membrane was increased with temperature from 419.36 to 642.69 kg m−2 h−1 at 30 °C and 50 °C, respectively (Fig. 5A). However, the PMTT membrane exhibited a constant separation factor at 40 and 50 °C (Fig. 5B).
The results showed that the PMDT membrane had higher permeation and a lower separation factor owing to the morphological structure, which showed an asymmetric lower density structure, which led to higher diffusion of water molecules. Polyetherimide is relatively hydrophobic with a high contact angle. Table 1 shows that the contact angles of the PMDT and PMTT membranes decreased with adding GO and fabrication techniques, which resulted in an increase in the hydrophilicity property. The presence of graphene oxide, which possesses functional groups, improved the hydrophilicity of the membrane, which resulted in the formation of a greater flux to water molecules.
Membrane | Neat PEI (PMTT) | Neat PEI (PMDT) | Thermal-treatment | Dry-thermal |
---|---|---|---|---|
Contact angle (degree) | 77 | 58 | 66 | 43 |
The GO incorporation into the PEI matrix decreased the contact angle of the membrane. Incorporating nano-GO in the membrane increased the hydrophilicity of the membranes. Hence, hybrid membranes were appropriate for dehydration application. The novel modified techniques were applied for casting of the low (PMDT) and high density (PMTT) membranes for dehydration of n-butanol mixtures.42
Fig. 6 shows the long-term performance of the PMDT and PMTT membranes over 120 h. The long-term stability of the PMDT and PMTT membranes was investigated over 120 h under constant conditions of 0.05 bar and 50 °C for an aqueous solution of 95% n-butanol and 5% water. Although the stability performance of PMTT was constant for about 80 h, the permeation performance of PMDT reduced smoothly after this time. The long-term stability of PMDT was significantly constant for about 60 h. Therefore, the PMTT membrane in comparison with the PMDT sample exhibited more stability owing to its high density microstructure and PMDT with its low density microstructure showed lower stability.
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