Fabrication of highly permeable PDMS@ZIF-8/PVDF hollow fiber composite membrane in module for ethanol-water separation

The construction of high-performance MOF-based hollow fiber composite membrane (HFCM) modules is a significant, yet challenging task for the biofuel production industry. In this study, a novel approach was taken to fabricate PDMS@ZIF-8/PVDF HFCMs in modules through a facile ZIF-8 self-crystallization synthesis followed by pressure-assisted PDMS infusion for pervaporation ethanol-water separation. The as-prepared HFCMs exhibited an ultrathin separation layer (thickness, 370 ± 35 nm), which was achieved through precise regulation of the ZIF-8 membrane and defect repair by PDMS infusion. Moreover, the strategy utilized in this study resolved the defect issues arising from MOF agglomeration in conventional composite membranes. Impressively, at the optimal packing density, the prepared membrane demonstrated a remarkable ethanol flux (1.11 kg m⁻² h⁻¹) with an PSI value (26.59 kg m⁻² h⁻¹) and showed promising long-term stability for the pervaporation of 5 wt% ethanol aqueous solution at 40°C.     

碳纳米管填充PDMS膜的渗透汽化性能

将碳纳米管（CNTs）填充到PDMS中制备出CNTs/PDMS杂化膜,并将其用于乙醇/水体系的分离,发现由多壁碳纳米管制备的膜分离性能优于单壁碳纳米管填充膜,在40℃下,进料乙醇浓度为5%（质量分数）时,膜的分离因子可由8.3提高到10.0,渗透通量为206.2 g·（m²·h）^-1;采用十二烷基三氯硅烷对多壁碳纳米管进行修饰,并对修饰前后碳纳米管的性能进行表征,研究表明修饰后碳纳米管表面形成疏水层,碳纳米管的疏水性增强;将修饰后的碳纳米管填充到PDMS中,可进一步提高杂化膜对乙醇的选择性,膜的分离因子可提高到11.3,渗透通量为130.9 g·（m²·h）^-1。     

High‐performance PDMS membranes for pervaporative removal of VOCs from water: The role of alkyl grafting

To improve the pervaporation performance of PDMS membrane, alkyl groups with different chain length were grafted into PDMS matrix. The prepared membranes were characterized by ATR‐IR, DSC, TGA, PALS, and tensile testing. The effects of alkyl grafting on pervaporation performance of PDMS membrane were investigated in separation of ethyl acetate/water mixture. Experimental results show that the separation factor of PDMS membrane is largely improved by alkyl grafting because of the enhanced preferential sorption of ethyl acetate, and this improvement depends on alkyl grafting ratio and alkyl chain length. The total flux of PDMS membrane reduces after alkyl grafting owing to the decreased free volume. When grafting ratio is above 6.9%, membrane grafted with shorter alkyl groups is preferred for pervaporation. The best pervaporation performance is achieved by 9% octyl grafted PDMS membranes with a separation factor of 592 and a total flux of 188 gm^?2 h^?1 in separation of 1% ethyl acetate/water mixture at 40 °C. Moreover, this octyl grafted PDMS membrane also exhibits excellent separation performance in removal of butyl acetate, methyl‐tert‐butyl ether, and n‐butanol from water. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43700.     

In situ cross‐linked‐PDMS/BPPO membrane for the recovery of butanol by pervaporation

In this study, an in situ crosslinked polydimethylsiloxane/brominated polyphenylene oxide (c‐PDMS/BPPO) membrane on ceramic tube has been prepared for the recovery of butanol by pervaporation. A series of BPPO with different bromide‐substituted ratio were firstly synthesized through Wohl–Ziegler reaction. BPPO and PDMS were sequentially assembled and in situ crosslinked to form the final c‐PDMS/BPPO membrane. The results of solid‐state NMR and Differential Scanning Calorimeter demonstrated that the c‐PDMS/BPPO copolymer has a crosslinking structure and the SEM result proved the coverage of ceramic tube by copolymer layer. The effects of preparation conditions including dipping time and bromide‐substituted ratio of BPPO on the membrane performance were studied. The pervaporation experiments of butanol–water mixture indicated that the c‐PDMS/BPPO membrane exhibited an acceptable flux of 220 g·m^?2·h^?1 and high separation factor of 35 towards butanol, when the bromide‐substituted ratio was 34 wt % and the dipping time was 1.33 h. Moreover, the c‐PDMS/BPPO membrane performed excellent stability in an about 200 h continuous butanol recovery, as compared to the PDMS membrane. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40004.     

Pervaporation separation of levulinic acid aqueous solution by ZSM-5/PDMS composite membrane

This work aims at investigating the special application of ZSM-5/polydimethylsiloxane (PDMS) membrane being used for pervaporation separation of levulinic acid aqueous solutions. The effects of temperature, downstream pressure, feed concentration, and raw material ratio on the separation performance are investigated by self-made flat-sheet films. When the flow rate of feed pump remained at 0.4 ml/min (10 wt% levulinic acid), a levulinic acid permeation flux of 334.13 g/(m²h) and a separation factor of 2.382 at 75°C are observed over the composite membrane doped with 10 wt% ZSM-5. In addition, the acid resistance is enhanced after the PDMS membranes are doped with ZSM-5. Besides, the functionalized process also makes the membranes increase in its hydrophobicity. The results demonstrate that the ZSM-5/PDMS-based membranes show profound prospects for separating levulinic acid aqueous solution.     

Liquid–liquid interface induced PDMS-PTFE composite membrane for ethanol perm-selective pervaporation

Pervaporation has great potential in the separation of many significant mixtures. However, excessive penetration of separation layer into the substrate pores enhances the transport resistance of solvent molecules, which impedes the development of pervaporation membrane. In this study, a facile floating-on-water (FOW) method was used to prepare poly(dimethylsiloxane) (PDMS)/polytetrafluoroethylene (PTFE) composite membranes. The formation of separation layer and preparation of composite membrane were step-by-step completed through this liquid–liquid interface induced method. The PDMS layer thickness could be precisely regulated from 0.5 to 8 μm. Moreover, the pore penetration could be controlled by optimizing pre-crosslinking density, crosslinking time on water and polymer solution volume. The obtained PDMS/PTFE composite membrane exhibited a high flux of 2016 g·m⁻²·h⁻¹ with the separation factor of 12 when separating ethanol from a 5 wt% ethanol/water mixture. The performance of the membrane could be stable for over 200 h, exhibiting great potential in ethanol perm-selective pervaporation.     

聚偏氟乙烯/聚二甲基硅氧烷渗透气化膜在丁醇分离中的应用

通过相转化法制备PVDF多孔支撑膜,在其上涂覆致密的PDMS分离层制备得到PVDF/PDMS复合膜,用于丁醇的分离纯化。以丁醇水溶液为原料液,流速为1.6 L·min^-1,丁醇浓度为15 g·L^-1,温度为37℃时, PVDF/PDMS复合膜的总通量为158.2 g·m^-2·h^-1,分离因子为17.3。向丁醇水溶液中按丁醇：丙酮：乙醇比例为6：3：1添加丙酮和乙醇模拟发酵液,PVDF/PDMS复合膜的总通量升高到189.5 g·m^-2·h^-1,分离因子降低到14.8。进一步考察了以丙酮-丁醇-乙醇（ABE）发酵液为原料液的渗透气化膜分离性能,发酵液中不存在菌体时,PVDF/PDMS复合膜的总通量和分离因子分别为120.2 g·m^-2·h^-1和19.7,而菌体存在时,复合膜的总通量和分离因子分别为122.1 g·m^-2·h^-1和16.7。与PDMS均质膜相比,PVDF/PDMS复合膜在丁醇分离过程中的分离性能有了显著的提升, 具有潜在的应用价值。     

Mixed matrix membranes of polydimethylsiloxane with activated carbon for ABE separation

The demand for the large-scale biofuels production is very high. The use of ethanol and butanol in flex-fuel vehicles have already been achieved, but still need improvement to decrease the gasoline-dependence. In addition to it, the preparation of ethanol and butanol by eco-friendly routes are still a challenge. The use of ABE route, in which acetone, butanol, and ethanol are prepared by fermentation of 5 or 6 carbon sugars, requires higher yields and better separation performance. The goal of this work was to evaluate the use of pervaporation through asymmetric activated carbon (AC) dispersed polymethylsiloxane membranes for the separation of ABE aqueous solution with 1 wt% total organics. The amount of the filler was varied from 0 to 3 wt%. Membranes were characterized by scanning electronic microscopy, Fourier transformed infrared spectroscopy, swelling in solvents, thermogravimetric analysis, and differential scanning calorimetry. Membrane with 1 wt% of AC membrane showed different behaviors both in thermal resistance, which was increased, and also in pervaporation separation index (PSI). In this condition, membrane total flux, separation factor, and PSI for ethanol were 13.2, 2.6, and 19.9 g m⁻² h⁻¹, so that sorption behavior and diffusion rates were changed. Thus, it was possible to modulate membrane properties.     

Tubular composite PVA ceramic supported membrane for bio-ethanol production

Thin polyvinyl alcohol (PVA) layers loaded with fumed silica were coated on porous ceramic supports. Scanning electron microscope (SEM) was used to characterize the ceramic-supported thin PVA active layers and the effects of coating gel PVA concentration on thickness and density of the active layers were investigated. Pervaporation (PV) dehydration of 90 wt.% ethanol was performed at temperatures of 30, 45 and 60 °C. The values of water flux (0.05–2.92 kg/m² h) and selectivity (3–180) exceed typical values obtained for pure PVA membranes. Besides the pervaporation separation index (PSI) varies from 5.84 to 82.81. Compared to pure PVA membrane with maximum PSI of 47.2, the pervaporation performance was significantly improved. The best separation performance was obtained using the membrane prepared from 5 wt.% PVA solution containing 6 wt.% fumed silica and at pervaporation temperature of 45 °C with permeation flux of 1.69 kg/m² h, and selectivity of 50. The highest permeation flux, selectivity and PSI was 2.92 kg/m² h, 180 and 82.81, obtained at 60, 30 and 45 °C, respectively, while using membranes loaded with 8, zero and 6 wt.% of fumed silica in PVA membrane prepared from 5, 10 and 5 wt.% PVA solutions, respectively. The novel ceramic support increased mechanical strength of the membrane and protected the ultrathin polymeric top active layer under aggressive operating conditions, especially high pressure gradient across the membrane. Incorporation of fumed silica also resulted in higher water permeation flux. Due to these results, the synthesized membranes are suitable for ethanol purification in industrial scales.     

Nanometric thin skinned dual‐layer hollow fiber membranes for dehydration of isopropanol

A novel sulfonated polyphenylsulfone (sPPSU)/polyphenylsulfone (PPSU)‐based dual‐layer hollow fiber membrane with a nanometric thin skin layer has been designed for biofuel dehydration via pervaporation. The thickness of skin selective layer is in the range of 15–90 nm under different spinning conditions measured by positron annihilation spectroscopy (PAS) coupled with a mono‐energetic positron beam. The effects of outer‐layer dope properties, coagulation temperature, and dope flow rate during spinning were systematically investigated. By tuning these spinning parameters, a high performance sPPSU/PPSU‐based dual‐layer hollow fiber membrane with desirable morphology was successfully obtained. Particularly owing to its nanometric thin skin layer, a high flux of 3.47 kg/m²h with a separation factor of 156 was achieved for dehydration of an 85 wt % isopropanol aqueous solution at 50°C. After post thermal treatment at 150°C for 2 h, the separation factor was dramatically improved to 687 while flux dropped to 2.30 kg/m²h, which make it comparable to the inorganic membranes. In addition, excellent correlations were found among the results from field emission scanning electron microscopy, PAS spectra, and separation performance. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2943–2956, 2013     

Desulfurization performance of polydimethylsiloxane membranes by pervaporation: Effect of crosslinking agents

Polydimethylsiloxane (PDMS), as one of the typical membrane, has been widely applied in gasoline desulfurization via pervaporation. In this work, the PDMS/PVDF composite membranes were prepared by curing PDMS with three different crosslinking agents. They were 3‐Aminopropyltrimethoxylsilane (APTMS), 3‐Glycidyloxypropyltrimethoxylsilane (GPTMS), and 3‐Mercaptopropyltrimethoxylsilane (MPTMS), respectively. These PDMS/PVDF composite membranes were characterized by Fourier transform infrared (FT‐IR), X‐ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), and then evaluated by static tensile test, swelling degree test and surface detach experiment. The results showed that A‐PDMS membrane had highest crosslinking density, best anti‐swelling ability and excellent combination between the separation layer and support layer. Moreover, the effect of operation temperature and the feed sulfur content on separation performance were investigated systematically. Experimental results indicated that PDMS membrane crosslinked with APTMS presented the highest enrichment factor with 3.46°C at 45°C, and PDMS membrane crosslinked with MPTMS presented the highest permeation flux with 21.19 kg/(m²·h) at 45°C. Finally, long‐term stability test showed that these PDMS membranes all have desirable stability. POLYM. ENG. SCI., 57:1127–1135, 2017. © 2017 Society of Plastics Engineers     

Removal of 1,2,4-Trimethylbenzene from Water by Pervaporation Using Styrene–Butadiene–Styrene (SBS) Membrane Incorporated with Carbon Black Nanoparticles

Styrene–butadiene–styrene (SBS) membranes incorporated with carbon black (CB) were prepared and investigated for pervaporation (PV) removal of 1,2,4-trimethylbenzene (TMB) from its aqueous solution. The influence of CB concentration on membrane properties was assessed by applying field emission scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy, and tensile test. Characterization of the prepared membranes implied increased water contact angles at higher CB concentrations. Moreover, membrane swelling was constant zero for all the membranes. Performance of the prepared membranes in PV separation of a volatile organic compound (1,2,4-TMB) from water was studied. The SBS/CB nanocomposite membranes revealed higher separation factor and PV separation index (PSI) compared to pure SBS membrane because of the CB hydrophobic nature. The separation factor and PSI of the nanocomposite membrane loaded with 1 wt. % CB were 3.6 and 1.8 times more than those of the neat SBS membrane, respectively. The membrane obtained at this appropriate CB concentration provided the total flux of 735 g/m²h, separation factor of 950, and PSI of 700,000 g/m²h. POLYM. ENG. SCI., 60: 257–266, 2019. © 2019 Society of Plastics Engineers     

PDMS/陶瓷复合膜用于正丁醇-水体系的渗透汽化分离

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation per-formance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40 C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g•m2•h1 and 26.1, respec-tively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.     

Increasing the performance of asymmetric pervaporation membranes for the separation of methanol/methyl-tert-butyl ether mixtures by the introduction of sulfonated polyimide into the poly(amide-imide) matrix

A series of novel asymmetric membranes from polymer composites of poly(amide-imide) with various content of sulfonated polyimide (1–6 wt%) was obtained through the nonsolvent-induced phase separation process. Selective transport properties of the obtained materials were investigated in terms of pervaporation separation of methanol/methyl-tert-butyl ether mixtures at different temperatures. The introduction of the sulfonated polyimide to the poly(amide-imide) matrix leads to a significant increase in membrane flux and an overall decrease in the process selectivity. Composite membranes having 1 wt% sulfonated polyimide in the matrix showed increased values of membrane flux (0.960 kg m⁻² h⁻¹ in comparison with 0.682 kg m⁻² h⁻¹ for unmodified membranes at 40°C, 10 wt% methanol), while having similar selectivity values (79.2 wt% methanol in permeate in comparison with 82 wt% for unmodified membranes at 40°C, 10 wt% methanol). Modified membrane showed the highest separation factor of 147 while separating methanol from its 3 wt% mixture with methyl-tert butyl ether at 52°C with the overall flux of 1.01 kg m⁻² h⁻¹. A semiempirical mathematical model was developed and applied to test the efficiency of obtained membranes in the hybrid process of methanol/methyl-tert-butyl ether mixtures separation.     

Pervaporation of flavors with hydrophobic membrane

Using a pervaporation process, a surface-modified hydrophobic membrane was used for recovery of esters which are volatile organic flavor compounds; ethyl acetate (EA), propyl acetate (PA), and butyl acetate (BA). A surface-modified tube-type membrane was used to evaluate the effects of the feed concentration (0.15–0.60 wt%) and feed temperature (30–50 °C) on the separation of EA, PA, and BA from dilute aqueous solutions. The permeation flux increased with the increasing feed ester concentration and operating temperature. EA, PA, and BA in the permeate were concentrated up to 9.13–32.26, 11.44–34.95, and 14.96–36.37 wt%, respectively. The enrichment factors for the 0.15–0.60 wt% feed solution of EA and BA were in the range of 48.5-62.8 and 97.7-101.5, respectively. Phase separation occurred in the permeate stream because the ester concentration in the permeate was above the saturation limit. This meant that selectivity of the membrane was high enough for the recovery of esters from dilute aqueous solution, even though the enrichment factor of the membrane was lower than that of non-porous PDMS membrane. The fluxes of EA, PA, and BA at 0.60 wt% (6,000 ppm) feed concentration and 40 °C were 254, 296, and 318 g/m².hr, which are much higher than those obtained with polymer membranes. In the case of non-porous PDMS at feed concentrations of 90-4,800 ppm and at 45 °C, it was reported that the permeate flux of EA was 1.1–5.8 g/m^2.h. Compared to non-porous PDMS, the surface-modified membrane investigated in this study showed a much higher flux and enough selectivity of esters.     

Regulatable pervaporation performance of Zn-MOFs/polydimethylsiloxane mixed matrix pervaporation membranes

Pervaporation (PV) is an emerging separation technique for liquid mixture. Mixed matrix membranes (MMMs) often demonstrate trade-off relationship between separation factor and flux. In this study, by changing the organic linkers (2-methyl imidazolate, imidazole-2-carboxaldehyde, 2-ethyl imidazolate), ZIF-8, ZIF-90 and MAF-6 were prepared and filled in polydimethylsiloxane (PDMS) membranes for dealcoholization of 5% (mass) n-butanol solution, and the membranes properties and pervaporation performances were adjusted. Compared with the pure PDMS membrane, the addition of ZIF-8 resulted in a 9% increase in flux (1136 g·m^-2·h^-1) and a 22.5% increase in separation factor (28.3), displaying anti-trade-off effect. For the MAF-6/PDMS MMMs (2.0% mass loading), the pervaporation separation index (PSI) and separation factor were 32347 g·m^-2·h^-1 and 58.6 respectively (increased by 34% and 154% in contrast with that of the pure PDMS membrane), and the corresponding permeation flux was 552 g·m^-2·h^-1, presenting great potential in the removal butanol from water. It was deduced that the large aperture size combined with moderate hydrophobicity of metal-organic frameworks (MOFs) favor the concurrent increase in permeability and selectivity.     

Pervaporative separation of butanol using a composite PDMS/PEI hollow fiber membrane

In the study, the separation and purification of butanol was carried out using the composite hollow fiber membrane having the active layer of polydimethylsiloxane (PDMS) on the macroporous support of polyetherimide (PEI). The pervaporation results with the initial butanol concentration showed a trade-off between flux and separation factor. However, both the flux and the separation factor increased as the operating temperature increased. The pervaporation results showed the butanol flux and the separation factor were higher than those of the reported results. In this study, butanol was concentrated by the pervaporation as a feasibility study for the biofuel applications.     

Preparation of polymer of intrinsic microporosity composite membranes and their applications for butanol recovery

We fabricated novel composite membranes composed of a polymer of intrinsic microporosity (PIM-1) and carbon black (CB) nanoparticles functionalized with the silane coupling agent aminopropyl triethoxysilane to recover butanol from aqueous solutions by pervaporation (PV). Scanning electron microscopy showed that the composite membranes were dense and defect free and had good adhesion with substrates. Compared with the those of pristine PIM-1 membranes, the water contact angles of the composite membranes increased from around 86° to more than 90°; this confirmed the improvement of the hydrophobicity. The swelling degree of the 6 wt % CB-filled PIM-1 membranes dropped 23%; this indicated an increase in the swelling resistance. Furthermore, the PV results show experimentally that the incorporation of the functionalized CBs into the PIM-1 matrix considerably improved both the permeability and selectivity to butanol. At a 4 wt % CB content, the optimum separation performance, with a separation factor of 19.7 and a permeation flux of 1116 g m⁻² h⁻¹, was achieved in an aqueous solution containing 5 wt % butanol at 30°C. It was noteworthy that the as-fabricated membranes exhibited a good separation stability. This is a step forward in terms of continuous butanol production with hybrid membranes in fermentation processes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46912.     

Polysiloxaneimide membranes for removal of VOCs from water by pervaporation

For the separation of volatile organic compounds (VOCs) from water by pervaporation, three polysiloxaneimide (PSI) membranes were prepared by polycondensation of three aromatic dianhydrides of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA) with a siloxane‐containing diamine. The PSI membranes were characterized using ¹H‐NMR, ATR/IR, DSC, XRD, and a Rame‐Hart goniometer for contact angles. The degrees of sorption and sorption selectivity of the PSI membranes for pure organic compounds and organic aqueous solutions were investigated. The pervaporation properties of the PSI membrane were investigated in connection with the nature of organic aqueous solutions. The effects of feed concentration, feed temperature, permeate pressure, and membrane thickness on pervaporation performance were also investigated. The PSI membranes prepared have high pervaporation selectivity and permeation flux towards hydrophobic organic compounds. The PSI membranes with 150‐μm thickness exhibit a high pervaporation selectivity of 6000–9000 and a high permeation flux of 0.031–0.047 kg/m² h for 0.05 wt % of the toluene/water mixture. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2691–2702, 2000     

Pervaporation properties of a three‐layer structure composite membrane

A novel composite membrane with a three‐layer structure has been prepared. The top layer is a thin dense film of chitosan crosslinked with glutaraldehyde, and the support layer is made of microporous polyacrylonitrile (PAN). Between the dense and the microporous layer, there is an intermolecular crosslinking layer. The performance data show that this is an excellent pervaporation membrane for alcohol dehydration and one‐stage separation is attainable for some alcohol/water mixtures such as ethanol/water and isopropanol/water systems, which has a good separation factor of 1410 and a good flux of 0.33 kg m⁻² h⁻¹ for the EtOH/H₂O mixture, and 5000 and 0.43 kg m⁻² h⁻¹ for the i‐PrOH/H₂O mixture using 90 wt % alcohol concentration at 70°C.Using 90 wt % methanol aqueous solution at 60°C, a flux of 0.17 kg m⁻² h⁻¹ and selectivity of 123 are also obtained. The structure and performance of the novel composite membrane varies with conditions of membrane preparation, such as hydrolysis degree of PAN membrane, content of crosslinking agent, and heat‐curing temperature. The results indicate that the separation factor and the permeation rate of this novel composite membrane increase with the increase of operating temperature. At the same time, the pervaporation properties can be adjusted by changing the structure of the top layer and the middle layer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 740–745, 2000