Pervaporation dehydration of isopropanol with chitosan membranes

Homogeneous and composite chitosan based membranes were prepared by the solution casting technique. The membranes were investigated for the pervaporation dehydration of isopropanol-water systems. The effects of feed concentration and temperature on the separation performance of the membranes were studied. In terms of the pervaporation separation index (PSI), the composite membrane was more productive than the homogeneous membrane for pervaporation of feed with high isopropanol content. It was observed that permeation increased and the separation factor decreased with the temperature. Modification of the homogeneous chitosan membrane by chemical crosslinking with hexamethylene diisocyanate improved the permselectivity but reduced the permeation rate of the membrane.     

Poly(vinyl alcohol)/poly(methyl methacrylate) blend membranes for pervaporation separation of water + isopropanol and water + 1,4-dioxane mixtures

Pervaporation (PV) separation of water + isopropanol and water + 1,4-dioxane mixtures has been attempted using the blend membranes of poly(vinyl alcohol) (PVA) with 5 wt.% of poly(methyl methacrylate) (PMMA). These results have been compared with the plain PVA membrane. Both plain PVA and PVA/PMMA blend membranes have been crosslinked with glutaraldehyde in an acidic medium. The membranes were characterized by differential scanning calorimetry and universal testing machine. Pervaporation separation experiments have been performed at 30 °C for 10, 15, 20, 30 and 40 wt.% of feed water mixtures containing isopropanol as well as 1,4-dioxane. PVA/PMMA blend membrane has shown a selectivity of 400 for 10 wt.% of water in water + isopropanol feed, while for water + 1,4-dioxane feed mixture, membrane selectivity to water was 104 at 30 °C. For both the feed mixtures, selectivity for the blend membrane was higher than that observed for plain PVA membrane, but flux of the blend membrane was lower than that observed for the plain PVA membrane. Membranes of this study are able to remove as much as 98 wt.% of water from the feed mixtures of water + isopropanol, while 92 wt.% of water was removed from water + 1,4-dioxane feed mixtures at 30 °C. Flux of water increased for both the feed mixtures, while the selectivity decreased at higher feed water concentrations. The same trends were observed at 40 and 50 °C for 10, 15 and 20 wt.% of water mixtures containing isopropanol as well as 1,4-dioxane feed mixtures, which also covered their azeotropic composition ranges. Membrane performance was studied by calculating flux (J_p), selectivity (), pervaporation separation index (PSI) and enrichment factor (β). Permeation flux followed the Arrhenius trend over the range of temperatures investigated. It was found that by introducing a hydrophobic PMMA polymer into a hydrophilic PVA, the selectivity increased dramatically, while flux decreased compared to plain PVA, due to a loss in PVA chain relaxation.     

Exploring the characteristics,performance, and modification of Matrimid for development of thin‐film composite and thin‐film nanocomposite reverse osmosis membranes

Reverse osmosis (RO) membrane technology is widely employed to address the demands for freshwater. In this study, fabrication and performance evaluation of customized RO membranes comprised of Matrimid and polyacrylonitrile (PAN) is carried out. While exploring adoption of slip coating procedure, the effects of various modification techniques including incorporation of TiO₂ nanoparticles and polyethylene glycol (PEG) into the skin layer as well as cross‐linking were investigated. The individual and combined effects of parameters on membrane morphology, surface characteristics and performance were also examined. Despite the distinctive characteristics of involved materials, delamination‐free composite membranes were successfully formed with an intimate contact at the interface of two layers. The results also indicated that increasing concentration of Matrimid in dope solution led to increase in membrane thickness and consequently decline in water flux. In the best case, membrane prepared using 1 wt.% Matrimid in dope exhibited water flux of 0.98 LMH and NaCl rejection of 95.7%. Also, incorporation of 3 wt.% TiO₂ nanoparticles offered membranes with improved water flux of 1.37 LMH and salt rejection of 95.8%. On the other hand, water flux and salt rejection in membranes containing 5 wt.% PEG were 1.18 LMH and 96.2%, respectively. The co‐presence of both nanoparticles and PEG provided more insights about the contributing factors in tuned membranes. Modification of skin layer by cross‐linking significantly improved salt rejection at the expense of water flux. The results are scientifically interpreted and compared to the values reported in literature.     

Poly(ethylene oxide) induced cross-linking modification of Matrimid membranes for selective separation of CO2

The novel cross-linker, poly(propylene glycol) block poly(ethylene glycol) block poly(propylene glycol) diamine (PPG/PEG/PPGDA), was employed to chemically cross-link Matrimid 5218 at room temperature. The cross-linking reaction process was monitored by FTIR. The XRD was used to indicate the changing of the polymer structure by cross-linking reaction. The effects of the cross-linking reaction on mechanical performance, gel content and H₂, CO₂, N₂ and CH₄ gas transport properties of the cross-linked Matrimid membranes were investigated. The cross-linked Matrimid membranes display excellent CO₂ permeability and CO₂/light gas selectivity compared with the uncross-linked Matrimid membrane. Finally, the potential application of the cross-linked Matrimid membranes for CO₂/light gas separation was explored.     

氧化石墨烯-Ag纳米粒子/聚酰亚胺混合基质膜及其渗透汽化性能

以聚乙二醇(PEG-400)为还原剂,Ag NO3为前驱体,采用浸渍-还原法合成氧化石墨烯-Ag纳米粒子(GO-Ag NP)复合物,再通过共混法制备氧化石墨烯-Ag纳米粒子/聚酰亚胺(GO-Ag NP/PI)混合基质膜,用于苯/环己烷混合物的渗透汽化分离。使用透射电子显微镜、红外吸收光谱、拉曼光谱、热失重以及X射线光电子能谱等分析表征GO-Ag NP复合物、GO-Ag NP/PI混合基质膜的形貌和结构;探讨了Ag掺杂量对GO-Ag NP复合物的结构以及GO-Ag NP/PI混合基质膜的结构和渗透汽化性能的影响。结果发现,Ag+被还原形成Ag NP的同时,GO失去了部分含氧官能团;Ag掺杂破坏了GO的结构,使其无序度增加,但改善了GO-Ag NP复合物在混合基质膜中的分散性,提升了GO-Ag NP/PI混合基质膜的苯/环己烷渗透汽化性能。然而过量的Ag掺杂将使GO片层上产生Ag粒子团聚,从而降低混合基质膜的渗透汽化性能。当Ag掺杂量为15%时,GO-Ag NP/PI混合基质膜渗透汽化性能最佳,渗透通量为1 404 g·m-2·h-1,分离因子可达36.2。     

氧化石墨烯-Ag纳米粒子/聚酰亚胺混合基质膜及其渗透汽化性能

以聚乙二醇（PEG-400）为还原剂,AgNO₃为前驱体,采用浸渍-还原法合成氧化石墨烯-Ag纳米粒子（GO-AgNP）复合物,再通过共混法制备氧化石墨烯-Ag纳米粒子/聚酰亚胺（GO-AgNP/PI）混合基质膜,用于苯/环己烷混合物的渗透汽化分离。使用透射电子显微镜、红外吸收光谱、拉曼光谱、热失重以及X射线光电子能谱等分析表征GO-AgNP复合物、GO-AgNP/PI混合基质膜的形貌和结构;探讨了Ag掺杂量对GO-AgNP复合物的结构以及GO-AgNP/PI混合基质膜的结构和渗透汽化性能的影响。结果发现,Ag⁺被还原形成AgNP的同时,GO失去了部分含氧官能团;Ag掺杂破坏了GO的结构,使其无序度增加,但改善了GO-AgNP复合物在混合基质膜中的分散性,提升了GO-AgNP/PI混合基质膜的苯/环己烷渗透汽化性能。然而过量的Ag掺杂将使GO片层上产生Ag粒子团聚,从而降低混合基质膜的渗透汽化性能。当Ag掺杂量为15%时,GO-AgNP/PI混合基质膜渗透汽化性能最佳,渗透通量为1 404 g·m^-2·h^-1,分离因子可达36.2。     

Development of polyelectrolyte complexes of chitosan and phosphotungstic acid as pervaporation membranes for dehydration of isopropanol

Using a solution technique, chitosan-based polyelectrolyte complexes (PECs) were developed as pervaporation membranes by incorporating phosphotungstic acid (PTA). The resulting membranes were characterized by Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Membranes were tested for their ability to separate water–isopropanol mixtures by pervaporation in the temperature range of 30–50 °C. The experimental results demonstrated that both flux and selectivity were increased simultaneously with increasing PTA content in the membrane. The permeation flux of pure chitosan membrane was increased dramatically from 4.13 to 11.70 × 10⁻² kg/m² h and correspondingly its separation factor was increased from 4490 to 11,241 and then decreased to 7490 at 30 °C for 10 mass% of water in the feed. The total flux and flux of water were found to be almost overlapping particularly for PECs membranes, suggesting that these could be used effectively to break the azeotropic point of water–isopropanol mixtures. From the temperature dependency of diffusion and permeation values, the Arrhenius activation parameters were estimated and discussed in the context of membranes efficiency. The pure chitosan and a small amount of PTA-incorporated PECs membranes exhibited positive heat of sorption while other PECs membranes exhibited negative heat of sorption, giving exothermic contribution.     

Poly (caprolactone)/poly (ethylene glycol) pervaporation blend membranes: Synthesis,characterization, and performance

Poly (caprolactone) membranes with addition of different poly (ethylene glycol) concentrations were prepared for separation of water/isopropanol azeotropic mixture by pervaporation process. Different characterization tests including Fourier transform infrared, scanning electron microscopy, water contact angle, and thermogravimetric analysis were carried out on the prepared membranes. In addition, the effect of poly (ethylene glycol) PEG content on the swelling degree and the performance of the prepared membranes in pervaporation process were investigated. According to the obtained results, all the membranes were water selective and the blend membrane containing 3 wt% PEG exhibited the best pervaporation performance with a water flux of 0.517 kg/m² hour and separation factor of 1642 at the ambient temperature. Hydrophilicity improvement of the blend membranes was confirmed by constant decrease in water contact angle of the membranes as PEG content increased in the casting solution. Scanning electron microscopy cross‐sectional images indicated that the blend membranes containing PEG had a closed cellular structure. Furthermore, mechanical and thermal properties of the membranes decreased by adding PEG.     

Modified cyclodextrin polymers as selective ion carriers for Pb(II) separation across plasticized membranes

In the present work the hydrophobic β-cyclodextrin (β-CD) polymers have been used as macrocyclic ion carriers for separation of Pb(II), Zn(II), and Cu(II) ions from dilute aqueous solutions by transport across polymer inclusion membranes. The β-CD polymers were prepared by cross-linking of β-CD with 2-(1-docosenyl)-succinic anhydride derivatives in anhydrous N,N-dimethylformamide in the presence of NaH. The metal ions were transported from aqueous solutions containing heavy metal ions through plasticizer triacetate membranes with dimer and polymer β-CD derivatives into distilled water. The selectivity of lead(II) over other metal ions in the transport through polymer inclusion membrane was very high, especially for dimer cyclodextrin carrier. In the case of competitive transport of Pb(II), Cu(II), and Zn(II) ions through plasticized immobilized membranes the selectivity of process is controlled via formation of ion pairs of β-CD hydroxyl groups with metal cations. The polymer and dimer of β-CD linked by 2-(1-docosenyl)-derivative used as ionic carriers for competitive transport of metal ions show preferential selectivity order: Pb(II)  Cu(II) > Zn(II). Application of ion carriers mixtures (β-CD polymers and palmitic acid) causes the increase of Pb(II) maximal removal from dilute aqueous solution. The weight-average molecular weight (M_W) and the chemical structure of the β-CD polymers were determined using high-performance size exclusion chromatography with refractive index detector, and ¹H NMR spectroscopy.     

Blended chitosan and polyvinyl alcohol membranes for the pervaporation dehydration of isopropanol

Homogeneous membranes were prepared by casting the solution of blended chitosan and polyvinyl alcohol (PVA) on a glass plate. The percent weight of chitosan in the membrane was varied from 0 to 100%. The membrane thickness was in the range of 15–30 μm. The membranes were heat treated at 150 °C for an hour. After that the membranes were crosslinked by glutaraldehyde and sulfuric acid in acetone aqueous solution. The membranes were tested at 30–60 °C for dehydration performance of 50–95% isopropanol aqueous solutions. At around 90% of isopropanol in the feed mixture, permeate flux increased whereas the percent of water in permeate tended to decrease when the feed temperature increased for all membranes, except that the water content in permeate from the membrane containing 75 wt.% chitosan remained constant. The swelling degree in water and the total flux increased with increasing chitosan content in membranes. The effect of temperature on permeate flux followed the Arrhenius relationship. The permeate flux decreased when isopropanol in the feed increased for all membranes. However, water content in permeate and isopropanol concentration in the feed formed complex relationship for different chitosan content membranes. Sorption did not appear to have significant effects on separation. The membrane containing chitosan 75% performed the best. For a feed solution containing 90% isopropanol at 60 °C, the permeate flux was 644 g/m² h with water content of nearly 100% in the permeate. At 55% isopropanol in the feed at 60 °C, the permeate flux was 3812 g/m² h. In the range of 55–95% of isopropanol in the feed, the water content in permeate was more than 99.5%. This membrane showed very excellent performance with good mechanical strength. It is promising to develop this membrane for industrial uses.     

Chitosan/poly(tetrafluoroethylene) composite membranes using in pervaporation dehydration processes

Chitosan/PTFE composite membranes were prepared from casting a γ-(glycidyloxypropyl)trimethoxysilane (GPTMS)-containing chitosan solution on poly(styrene sulfuric acid) grafted expended poly(tetrafluoroethylene) film surface. The adhesion between the chitosan skin layer and the PTFE substrate was pretty good to warrant the high performance of chitosan/PTFE composite membranes using in pervaporation dehydration processes on isopropanol. The chitosan/PTFE membrane exhibited a permeation flux of 1730 g/m² h and a separation factor of 775 at 70 °C on pervaporation dehydration of a 70 wt% isopropanol aqueous solution. The membrane also survived after a long-term operation test in 45 days.     

Surface modification of γ-alumina membranes by silane coupling for CO2 separation

Top layers of γ-Al₂O₃ composite membranes have been modified by the silane coupling technique using phenyltriethoxysilane for improving the separation factor of CO₂ to N₂. The separation efficiency of the modified membranes was strongly dependent upon the hydroxylation tendency of the support materials and the amount of the special functional group (i.e. phenyl radical) which was coupled onto a top layer. The separation factor through the TiO₂ supported γ-Al₂O₃ membrane was found to be fairly enhanced by silane coupling, but in case of the -Al₂O₃ supported membrane was not. The CO₂/N₂ separation factor through the modified γ-Al₂O₃/TiO₂ composite membrane is 1.7 at 90°C and ΔP = 2 × 10⁵ Pa for the binary mixture containing 50 vol% CO₂. The separation factor is proportional to the CO₂ concentration in the gas mixture, and the modified membrane is stable up to 100°C. The main mechanism of the CO₂ transport through the modified γ-Al₂O₃ layer is known to be a surface diffusion.     

Preparation and characterization of cross-linked Matrimid membranes for CO2/CH4 separation

For preventing plasticization phenomenon, cross-linked Matrimid membranes were prepared. Matrimid membranes were immersed in a solution of 10% (w/v) ethylenediamine or hexamethylenediamine in methanol for preparation of cross-linked membranes. Using a gas separation membrane unit, permeability properties of pristine and modified membranes for pure gases (CO₂ and CH₄) were investigated. CO₂ plasticization effect on permeability properties of the membranes is discussed. Modified membranes indicated smaller values of tensile strength than pristine membranes. Thermal gravimetric analysis showed that thermal resistance of modified membranes increased in a limited temperature range. In general, modified membranes were thermally stable for separation applications. Formation of amide groups in modified membranes was investigated by Fourier transform infrared spectroscopy analysis.     

Composite membranes prepared from glutaraldehyde cross-linked sulfonated cardo polyetherketone and its blends for the dehydration of acetic acid by pervaporation

Cardo polyetherketone (PEK-C) composite membranes were prepared by casting glutaraldehyde (GA) cross-linked sulfonated cardo polyetherketone (SPEK-C) or silicotungstic acid (STA) filled SPEK-C and poly(vinyl alcohol) (PVA) blending onto a PEK-C substrate. The compatibility between the active layer and PEK-C substrate is improved by immersing the PEK-C substrate in a GA cross-linked sodium alginate (NaAlg) solution and using water–dimethyl sulfoxide (DMSO) as a co-solvent for preparing the STA-PVA-SPEK-C/GA active layer. The pervaporation (PV) dehydration of acetic acid shows that permeation flux decreased and separation factor increased with increasing GA content in the homogeneous membranes. The permeation flux achieved a minimum and the separation factor a maximum when the GA content increased to a certain amount. Thereafter the permeation flux increased and the separation factor decreased with further increasing the GA content. The PV performance of the composite membranes is superior to that of the homogeneous membranes when the feed water content is below 25 wt%. The permeation activation energy of the composite membranes is lower than that of the homogeneous membranes in the PV dehydration of 10 wt% water in acetic acid. The STA-PVA-SPEK-C-GA/PEK-C composite membrane using water–DMSO as co-solvent has an excellent separation performance with a flux of 592 g m⁻² h⁻¹ and a separation factor of 91.2 at a feed water content of 10 wt% at 50 °C.     

壳聚糖复合膜及异丙醇／水混合液的渗透汽化分离

用磺化聚乙烯离子膜渗透汽化分离恒沸组成的i-PrOH/H_2O(87.2/12.8W/W),分离系数α高,渗透通量J低(小于300g/m~2·h,40℃),当醇含量高于90％时,膜性能变差;用CA膜、赛璐玢膜[2]、Nation-Na~+膜,J较高,α低(<30)。甲壳素脱乙酰基产物壳聚糖(Chitosan,简称CS),易交联改性,成膜性好。CS膜分离i-PrOH/H_2O,α很高,而J低。经戊二醛交联的CS膜尺寸稳定,增加了醇/水的J值,α虽有所下降,对i-PrOH/H_2O体系仍具有很高的值。为了进一步提高J值,我们研制了以聚丙烯腈(PAN)微孔膜作支撑的CS复合膜,     

Synthesis and Characterization of Poly(ether-block-amide) Membranes

Poly(ether-block-amide) membranes were made via casting a solution on a nonsolvent (water) surface. In this research, effects of different parameters such as ratio of solvent mixture (n-butanol/isopropanol), temperature, composition of coagulation bath (water) and polymer concentration, on quality of the thin film membranes were studied. The mechanism of membrane formation involves solution spreading, solvent–nonsolvent exchange, and partial evaporation of the solvent steps. Solvent- nonsolvent exchange is the main step in membrane formation and determines membrane morphology. However, at higher temperature of polymeric solution greater portion of solvent evaporates. The results showed that type of demixing process (mutual affinity between solvent and nonsolvent) has important role in film formation. Also, addition of solvent to the nonsolvent bath is effective on membrane morphology. The film quality enhances with increasing isopropanol ratio in the solvent mixture. This behavior can be related to increasing of solution surface tension, reduction of interfacial tension between solution and nonsolvent and delayed solvent-nonsolvent demixing. Uniform films were made at a temperature rang of 60–80 °C and a polymer concentration of 4–7 wt%. Morphology of the membranes was investigated with scanning electron micrograph (SEM). Pervaporation of ethyl butyrate/water mixtures was studied using these membranes and high separation performance was achieved. For ethyl butyrate/water mixtures, It was observed that both permeation flux and separation factor increase with increasing ethyl butyrate content in the feed. Increasing temperature in limited range studied resulted in decreasing separation factor and increasing permeation flux.     

Polydopamine Nanocluster Embedded Nanofibrous Membrane via Blow Spinning for Separation of Oil/Water Emulsions

Developing a porous separation membrane that can efficiently separate oil–water emulsions still represents a challenge. In this study, nanofiber membranes with polydopamine clusters polymerized and embedded on the surface were successfully constructed using a solution blow-spinning process. The hierarchical surface structure enhanced the selective wettability, superhydrophilicity in air (≈0°), and underwater oleophobicity (≈160.2°) of the membrane. This membrane can effectively separate oil–water emulsions, achieving an excellent permeation flux (1552 Lm⁻² h⁻¹) and high separation efficiency (~99.86%) while operating only under the force of gravity. When the external driving pressure was increased to 20 kPa, the separation efficiency hardly changed (99.81%). However, the permeation flux significantly increased to 5894 Lm⁻² h⁻¹. These results show that the as-prepared polydopamine nanocluster-embedded nanofiber membrane has an excellent potential for oily wastewater treatment applications.     

Development of thermoplastic polyurethane/polyaniline-doped membranes for the separation of glycine through electrodialysis

Recently, membrane-based separation processes, particularly electrodialysis, have attracted attention for the separation and purification of organic and amino acids from animal feedstock waste. In this study, cation exchange membranes were synthesized by making a composite of thermoplastic polyurethane and polyaniline (PANI) via the doping of various aromatic sulfonic acids, such as β -naphthol sulfonic acid and phenol sulfonic acid. The PANI was prepared using a standard method, which was further used in the composite blending at varying concentrations of 10%–20%. The impact of the concentration of PANI and the nature of the dopant on the membrane characteristics were comparatively studied. The membranes were analyzed by electric conductivity, water swelling, morphological studies (SEM), and thermogravimetric analysis. The membranes were used for the separation of glycine hydrochloride via electrodialysis.     

Preparation of polyphenylsulfone/graphene nanocomposite membrane for the pervaporation separation of cumene from water

Polyphenylsulfone (PPSU) was applied for the first time in the hydrophobic PV process. Nanocomposite membranes of PPSU/graphene (Gr) nanosheets were prepared and used to separate isopropyl benzene (cumene) from water via pervaporation (PV). Analysis of the mechanical properties of the membranes showed that the tensile strength and Young's modulus had an increasing trend with the incorporation of Gr into PPSU. The water contact angle of the membranes had a rising trend with the addition of Gr, confirming the improved hydrophobicity of membranes. In the PV experiments, the membrane containing 3.5 wt% Gr provided the highest separation factor, which was 4.5-fold as much as that of the neat PPSU membrane. Cumene separation from water by the PPSU/3.5 wt% Gr membrane was associated with the total flux of 132.73 gMH, the separation factor of 1566.36, and the PSI of 208,124.8 gMH.     

Pervaporation with chitosan membranes II. Blend membranes of chitosan and polyacrylic acid and comparison of homogeneous and composite membrane based on polyelectrolyte complexes of chitosan and polyacrylic acid for the separation of ethanol-water mixtures

Three different types of blend membranes based on chitosan and polyacrylic acid were prepared from homogeneous polymer solution and their performance on the pervaporation separation of water-ethanol mixtures was investigated. It was found that all membranes are highly water-selective. The temperature dependence of membrane permselectivity for the feed solutions of higher water content (>30 wt%) was unusual in that both permeability and separation factor increased with increase in temperature. This phenomenon might be explained from the aspect of activation energy and suggested that the sorption contribution to activation energy of permeation should not always be ignored when strong interaction occurs in the pervaporation membrane system.A comparison of pervaporation performance between composite and homogeneous membranes was also studied. Typical pervaporation results at 30°C for a 95 wt% ethanol aqueous solution were: for the homogeneous membrane, permeation flux = 33 g/m² h, separation factor = 2216; and for the composite membrane, permeation flux = 132 g/m² h, separation factor = 1008. A transport model consisting of dense layer and porous substrate in series was developed to describe the effect of porous substrate on pervaporation performance.