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1.
A novel PBI/P84 co-polyimide dual-layer hollow fiber membrane has been specifically fabricated through the dry-jet wet phase inversion process, for the first time, for the dehydration pervaporation of tetrafluoropropanol (TFP). Polybenzimidazole (PBI) was chosen as the outer selective layer because of its superior hydrophilic nature and excellent solvent-resistance together with robust thermal stability, while P84 co-polyimide was employed as the inner supporting layer because of its good solvent-resistance and thermal stability. The PBI/P84 membrane exhibits superior water selectivity and relatively high permeation flux. At 60 °C, the PBI/P84 dual-layer hollow fiber membrane shows a permeation flux of 332 g/(m2 h) and a separation factor of 1990 for a feed solution containing of 85 wt% TFP. The preferential water sorption and the significant diffusivity difference between TFP and water are the main causes of high separation factor. However, an increase in feed temperature will greatly increase the permeation flux but seriously decrease the water selectivity. The activation energy data verify that water can preferentially permeate the PBI membrane due to the strong water affinity of PBI and a much smaller molecular size of water.  相似文献   

2.
In the past studies, electrostatic layer-by-layer (LbL) adsorption of oppositely charged polyelectrolytes has proven to be a promising method for the preparation of polyelectrolyte multilayer membranes (PEMMs). Till now, this method was mainly used to assemble flat sheet and tubular membranes. Since hollow fiber membrane has some advantages such as high-packing density, self-contained mechanical support and hence the consequent economical superiority, this study therefore seeked to assemble inner skin hollow fiber PEMMs by using a dynamic LbL adsorption technique. The assembly process was successfully accomplished by alternatively dynamically filtrating polyacrylic acid (PAA) and polyethyleneimine (PEI) on a hydrolyzed hollow fiber polyacrylonitrile (PAN) membrane under a negative pressure condition. In the case of pervaporation separation of 95 wt.% ethanol–water mixture (50 °C), the membrane obtained with only 4.5 and 6.5 bilayers had separation factor of 245 and 1338 while the permeate fluxes were 290 and 120 g/(m2 h), respectively. The pervaporation separation behavior of various alcohol/water mixtures with the alcohols being t-butanol, 2-propanol and ethanol were also investigated. Finally, scanning electron microscopy and atomic force microscopy clearly confirms a uniform and defect-free layer formed on the inner surface of hollow fiber support. Since different polyelectrolyte pairs could be used to assemble PEMMs for different uses, it was expected that the dynamic negative pressure LbL adsorption technique could also potentially be used to prepare many types of PEMMs in other fields.  相似文献   

3.
Potential fouling reducing coating materials were synthesized via free-radical photopolymerization of aqueous solutions of poly(ethylene glycol) diacrylate (PEGDA). Crosslinked PEGDA (XLPEGDA) exhibited high water permeability and good fouling resistance to oil/water mixtures. Water permeability increased strongly with increasing the water content in the prepolymerization water mixture, going from 10 to 150 L μm/(m2 h bar) as prepolymerization water content increased from 60 to 80 wt.%. However, molecular weight cutoff decreased as water content increased. These materials were applied to polysulfone (PSF) UF membranes to form coatings on the surface of the PSF membranes. Oil/water crossflow filtration experiments showed that the coated PSF membranes had water flux values 400% higher than that of an uncoated PSF membrane after 24 h of operation, and the coated membranes had higher organic rejection than the uncoated membranes.  相似文献   

4.
To circumvent the common swelling and deteriorated performance of integral asymmetric hollow fiber membranes for pervaporation dehydration, we have developed novel polyamide-imide (PAI)/polyetherimide (PEI) hollow fiber membranes with synergized performance with the aid of dual-layer spinning technology. Dehydration of C1–C4 alcohols has been conducted and the orders of their fluxes and permeances have been analyzed. The hollow fibers spun at 2 cm air gap and annealed at 75 °C exhibit the highest pervaporation performance: separation factors for t-butanol/water and iso-butanol/water binary systems are greater than 50,000 with flux more than 700 g/m2 h. A comparison with literature data shows that the newly developed membranes outperform most other polymeric membranes for the dehydration of IPA and butanols. The dual-layer hollow fiber membranes also exhibit good long-term stability up to 200 h. The superior performance can be attributed to (1) the balanced properties of PAI as the selective layer for dehydration pervaporation; (2) the low water uptake and less swelling characteristic of the PEI supporting layer; and (3) the desirable membrane morphology consisting of a fully porous inner layer, a porous interface, and an ultrathin dense-selective outer skin.  相似文献   

5.
A combined osmotic pressure and cake filtration model for crossflow nanofiltration of natural organic matter (NOM) was developed and successfully used to determine model parameters (i.e. permeability reduction factor (η) and specific cake resistance (αcake)) for salt concentrations, NOM concentrations, and ionic strength of salt species (Na+ and Ca++). In the absence of NOM, with increasing salt concentration from 0.004 to 0.1 M, permeability reduction factor (η)) decreased from 0.99 to 0.72 and 0.94 to 0.44 for monovalent cation (Na+) and divalent cation (Ca++), respectively. This reduced membrane permeability was due to salt concentrations and salt species. In the presence of NOM, specific cake resistance tended to increase with increasing NOM concentration and ionic strength in the range of 0.85 × 1015–3.66 × 1015 m kg−1. Solutions containing divalent cation exhibited higher normalized flux decline (Jv/Jvo = 0.685–0.632) and specific cake resistance (αcake = 2.89 × 1015–6.24 × 1015 m kg−1) than those containing monovalent cation, indicating a highly compacted NOM accumulation, thus increased permeate flow resistance during NF filtration experiments. After membrane cleaning, divalent cation exhibited lower water flux recovery than monovalent cation, suggesting higher non-recoverable (Rnon-rec) resistance than monovalent cation.  相似文献   

6.
Two kinds of polypropylene capillary membranes were used in the membrane distillation (MD). These membranes exhibited a similar morphology, but one of them has an additional low porosity layer on the internal surface of capillaries. The changes of membrane performance during MD process of tap water were investigated. The presence of low porosity layer (thickness below 1 μm) caused that the air permeability was reduced from 1.365 to 0.863 dm3/m2 s kPa, whereas the MD permeate flux was decreased only by 15%. A significantly larger decline of the flux was caused by CaCO3 deposit formed during distillation of tap water. This deposit was removed every 30–70 h by rinsing the modules with a 2–5 wt.% HCl. Unfortunately, a repetition of this operation several times resulted in a gradual decline of the maximum permeate flux (distilled water as a feed). However, the module efficiency with the membranes covered by a surface layer of low porosity was found to decreases twice as slowly. The investigations revealed that a low surface porosity does not limit the possibility of surface wetting of polypropylene membranes, but hindered the scale formation inside the pores.  相似文献   

7.
This paper investigates the microfiltration of skim milk in order to separate caseins micelles from two whey proteins, α-lactalbumin (α-La) and β-lactoglobulin (β-Lg), using a modified dynamic filtration pilot (MSD) consisting in 6 ceramic 9-cm diameter membrane disks of 0.2 μm pores, rotating around a shaft inside cylindrical housing. A comparison was made with another dynamic filtration module consisting in a disk rotating near a fixed PVDF 15.5 cm diameter membrane with 0.15 μm pores. Maximum permeate fluxes were 120 L h−1 m−2 with the MSD module at 1930 rpm and at 40 °C, and 210 L h−1 m−2 at 2500 rpm and 45 °C, with the rotating disk module. Casein rejection was around 99% at high speed for both membranes. α-La transmission decreased with increasing transmembrane pressure (TMP) from 75% to 60% for ceramic membranes and from 25% to 10% for the PVDF one. β-Lg transmissions were lower, ranging from 23% to 15% for ceramic membranes and from 20% to 5% for the PVDF one. In a concentration test with the PVDF membrane at 2000 rpm, the flux decayed from 200 L h−1 m−2 at initial concentration to 80 L h−1 m−2 at VRR = 3.2 and 22.1% of the initial α-La mass was recovered in the permeate, against 8.1% for β-Lg. Permeate fluxes in the mass transfer limited regime (Jlim) of the MSD and rotating disk module operated at various speeds were well correlated by the equation Jlim = 17.13 Vav where Vav denoted the disk azimuthal velocity averaged over the membrane area. Measurements of Jlim, taken from Ref. [G. Samuelsson, P. Dejlmek, G. Tragardh, M. Paulsson, Minimizing whey protein retention in crossflow microfiltration of skim milk. Int. Dairy J. 7 (1997) 237–242] during MF of skim milk using tubular ceramic membranes at velocities from 1.5 to 8 m s−1 with permeate co-current recirculation were found to obey the same correlation.  相似文献   

8.
Novel organic–inorganic hybrid membranes were prepared through sol–gel reaction of poly(vinyl alcohol) (PVA) with γ-aminopropyl-triethoxysilane (APTEOS) for pervaporation (PV) separation of ethanol/water mixtures. The membranes were characterized by FTIR, EDX, WXRD and PALS. The amorphous region of the hybrid membranes increased with increasing APTEOS content, and both the free volume and the hydrophilicity of the hybrid membranes increased when APTEOS content was less than 5 wt%. The swelling degree of the hybrid membranes has been restrained in an aqueous solution owing to the formation of hydrogen and covalent bonds in the membrane matrix. Permeation flux increased remarkably with APTEOS content increasing, and water permselectivity increased at the same time, the trade-off between the permeation flux and water permselectivity of the hybrid membranes was broken. The sorption selectivity increased with increasing temperature, and decreased with increasing water content. In addition, the diffusion selectivity and diffusion coefficient of the permeants through the hybrid membranes were investigated. The hybrid membrane containing 5 wt% APTEOS has highest separation factor of 536.7 at 50 °C and permeation flux of 0.0355 kg m−2 h−1 in PV separation of 5 wt% water in the feed.  相似文献   

9.
PDMS-Ni2+Y zeolite hybrid membranes were fabricated and used for the pervaporation removal of thiophene from model gasoline system. The structural morphology, mechanical stability, crystallinity, and free volume characteristics of the hybrid membranes were systematically investigated. Molecular dynamics simulation was employed to calculate the diffusion coefficients of small penetrants in the polymer matrix and the zeolite. The effect of Ni2+Y zeolite content on pervaporation performance was evaluated experimentally. With the increase of Ni2+Y zeolite content, the permeation flux increased continuously, while the enrichment factor first increased and then decreased possibly due to the occurrence of defective voids within organic–inorganic interface region. The PDMS membrane containing 5.0 wt% Ni2+Y zeolite exhibited the highest enrichment factor (4.84) with a permeation flux of 3.26 kg/(m2 h) for 500 ppm sulfur in feed at 30 °C. The effects of operating conditions on the pervaporation performance were investigated in detail. It has been found that the interfacial morphology strongly influenced the separation performance of the hybrid membrane, and it was of great significance to rationally modify the interfacial region in order to improve the organic–inorganic compatibility.  相似文献   

10.
A thermal stable composite membrane was prepared by interfacial polymerization of piperazine (PIP) and trimesoyl chloride (TMC) on poly(phthalazinone ether amide) (PPEA) ultrafiltration membrane. The effect of reaction parameters on the performance of composite membranes was studied and optimized. The surface morphologies of the composite membrane and the substrate were observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The rejection of optimized composite membrane for dyes Congo red (CGR) and Acid chrome blue K (ACBK), the molecular weight (MW) of which is over 400, was over 99.2%, with a flux at about 180 L m−2 h−1. While the rejection for NaCl was only 18.2% with a flux over 270 L m−2 h−1, when tested at 1.0 MPa 60 °C. The composite membrane was applied in the desalination-purification experiment of dye ACBK and NaCl mixed solution. The flux of the membrane increased obviously as the operation pressure and/or temperature increased, while the rejection for dye was constant and kept over 99.3%. The purification experiments were accomplished effectively at 1.0 MPa, 80 °C. Only after five rounds of desalination-concentration experiment, about 160 min, the salt mixed in dye solution was fully removed. The initial flux of the eighth cycle was about 254 L m−2 h−1, which was only 20 L m−2 h−1 lower than that of the first round. The rejection of the membrane was constant and kept over 99.3% through out the eight cycles of purification experiment.  相似文献   

11.
In present work, hollow silica spheres (HSS)/Nafion® composite membranes were prepared by solution casting. The thermal properties, water retention, swelling behavior and proton conductivity of the composite membranes were explored. It was found that HSS dispersed well at micrometer scale in the obtained composite membranes by SEM and TEM observation. Thermal properties of composite membranes were improved than that of recast Nafion® membrane. Compared with the recast Nafion® membrane, the composite membranes showed higher water uptake and lower swelling degree at the temperature range from 40 to 100 °C. At the same HSS loading, the smaller the diameter of HSS in composite membranes, the more the water uptake, however, the swelling degree of composite membranes was increased. The proton conductivity of the composite membrane with 3–5 wt.% HSS (120 and 250 nm) increased distinctively at above 60 °C, reached the optimal value at 100 °C, and decreased slowly when the temperature exceeded 100 °C.  相似文献   

12.
In this paper, a novel method was developed to enhance the assembly of polyelectrolyte composite membranes by inducing an electric field during electrostatic adsorption process. The hydrolyzed polyacrylonitrile (PAN) ultrafiltration (UF) membrane was placed in between a capacitor setup. The polyethyleneimine (PEI) was compulsorily assembled on the PAN support under the action of external electric force. Subsequently, the polyelectrolyte composite membranes were evaluated by pervaporation separation of water and alcohol mixture. The membrane obtained with only one PEI layer had a separation factor of 304 and a permeate flux of 512 g/m2 h (75 °C) for pervaporation of 95 wt% ethanol–water mixture. An atomic force microscopy was also used to observe the microtopographical changes. The regularity of the membranes assembled by the new method was also improved in comparison with the membrane assembled by a dynamic layer-by-layer adsorption.  相似文献   

13.
This investigation was performed to find if the nanometer SiO2 added in the membranes can improve the pervaperation performance of the membranes. Acrylic acid (AA) and acrylonitrile (AN) were synthesized by solution polymerization with and without nanometer SiO2. The copolymer solution was made into main body of the membranes, then composited with the polyvinyl alcohol (PVA) acetal membranes, to make the three-layer sandwich composite pervaporation membranes. The structure and the performance of the membranes were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry (TG), dynamic themomechanical analysis apparatus (DMA) and mechanical property testing. Pervaporation experiments were carried out using these membranes to separate the mixtures of methanol/water over the complete concentration range 70–98%, and results showed that the selectivity of the membranes with nanometer SiO2 had notable improvement. For the 98% mixture at 60 °C, the separate factor is up to 1458, which is improved more than 10 times compared to the membranes without nanometer SiO2, the permeate flux is up to 325 g/(m2 h). For the 70% mixture at 70 °C, the separate factor arrived at 12, the permeate flux is up to 7097 g/(m2 h), which is improved more than 14 times compared to membranes without nanometer SiO2. It was concluded that the pervaperation performance of the membranes can improve greatly by nanometer SiO2.  相似文献   

14.
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.  相似文献   

15.
NaA zeolite membranes were synthesized on an asymmetric porous alumina support with a lower mass-flow resistance for development of more economically feasible membranes with higher permeation performance. The support influence on permeation fluxes through the membrane using asymmetric support was investigated by vapor permeation at 100–145 °C in a mixture of water (10 wt.%)/ethanol (90 wt.%) in which the higher permeation fluxes up to 37 kg m−2 h−1 or water permeances up to 3.2 × 10−6 mol m−2 s−1 Pa−1at 145 °C were observed. The performance was higher than those in the previously reported NaA membrane on a monolayer porous alumina support of 31 kg m−2 h−1 or water permeances of 2.5 × 10−6 mol m−2 s−1 Pa−1at 145 °C. These results are experimental evidence to show the effect of asymmetric support utilization in membrane preparation on the higher membrane performance. The estimate of the pressure drop over the both types of support indicates that the improvement of higher permeation fluxes in the asymmetric type membrane could be attributed to the suppression of pressure drop in the support layer due to lower mass-flow resistance there.  相似文献   

16.
The severe swelling behavior of most hydrophobic membranes has always been an obstinate problem when separating organic mixtures by pervaporation. In some cases, hydrophilic membranes may be an appropriate alternative. In this study, amphiphilic copolymer Pluronic F127 was employed as a surface modifier to fabricate polyethersulfone (PES) asymmetric pervaporation membranes via surface segregation. The scanning electron microscopy (SEM) photographs showed an asymmetric structure of PES/Pluronic F127 membranes. The Fourier transform-infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and static water contact angle measurements confirmed the hydrophilic modification of the membrane surface. Based on the distinct difference of solubility in water between thiophene and n-octane, the prepared membranes were utilized to remove thiophene from n-octane by pervaporation. The effect of Pluronic F127 content on the pervaporation performance was evaluated experimentally. It has been found that both the permeation flux and enrichment factor exhibited a peak value of approximately 60 wt% of the Pluronic F127 content. The highest enrichment factor was around 3.50 with a permeation flux of 3.10 kg/(m2 h) for 500 mg/L sulfur in the feed at 30 °C. The influence of various operating parameters on the pervaporation performance was extensively investigated.  相似文献   

17.
Separation of an organics/water mixture was carried out by reverse osmosis using an α-alumina-supported MFI-type zeolite membrane. The organic rejection performance is strongly dependent on the ionic species and dynamic size of dissolved organics. The membrane showed high rejection efficiency for electrolytes such as pentanoic acid. An organic rejection of 96.5% with a water flux of 0.33 kg m−2 h−1 was obtained for 100 ppm pentanoic acid solution at an operation pressure of 2.76 MPa. For non-electrolyte organics, separation efficiency is governed by the molecular dynamic size; the organics with larger molecular dynamic size show higher separation efficiency. The zeolite membrane gives an organic rejection of 99.5% and 17% for 100 ppm toluene and 100 ppm ethanol, respectively, with a water flux of 0.03 kg m−2 h−1, 0.31 kg m−2 h−1 at an operation pressure of 2.76 MPa. It was observed that organic rejection and water flux were affected by the organic concentration. As pentanoic acid concentration increased from 100 ppm to 500 ppm, both organic rejection and water flux decreased slightly.  相似文献   

18.
The long-term stability of Pd–23%Ag/stainless steel composite membranes has been examined in H2/N2 mixtures as a function of both temperature and feed pressure. During continuous operation, the membrane shows a good stability at 400 °C while the N2 leakage increases very slowly at a temperature of 450 °C (Pfeed = 10 bar). After 100 days of operation (Pfeed = 5–20 bar, T = 350–450 °C), the N2 permeance equals 7.0 × 10−9 mol m−2 s−1 Pa−1, which indicates that the H2/N2 permselectivity still lies around 500, based on a H2 permeance equal to 3.0 × 10−6 mol m−2 s−1 Pa−1. Despite the generation of small pinholes, a membrane life-time of several (2–3) years (T ≤ 425 °C) is estimated for the experimental conditions employed based on long-term stability tests over 100 days. Post-process characterisation shows a considerable grain growth and micro-strain relaxation in the Pd–23%Ag membrane after the prolonged permeation experiment. Changes in surface area are relatively small. In addition, segregation of Ag to the membrane surfaces is observed. The formation of pinholes is identified as the main source for the increased N2 leakage during testing at higher temperature.  相似文献   

19.
Hollow fibre liquid-phase microextraction with in situ derivatization using dansyl chloride has been successfully developed for the high-performance liquid chromatography-ultraviolet (HPLC-UV) determination of the biogenic amines (tryptamine, putrescine, cadaverine, histamine, tyramine, spermidine) in food samples. Parameters affecting the performance of the in situ derivatization process such as type of extraction solvent, temperature, extraction time, stirring speed and salt addition were studied and optimized. Under the optimized conditions (extraction solvent, dihexyl ether; acceptor phase, 0.1 M HCl; extraction time, 30 min; extraction temperature, 26 °C; without addition of salt), enrichment factors varying from 47 to 456 were achieved. Good linearity of the analytes was obtained over a concentration range of 0.1–5 μg mL−1 (with correlation coefficients of 0.9901–0.9974). The limits of detection and quantification based on a signal-to-noise ratio of 3–10, ranged from 0.0075 to 0.030 μg mL−1 and 0.03 to 0.10 μg mL−1, respectively. The relative standard deviations based on the peak areas for six replicate analysis of water spiked with 0.5 μg mL−1 of each biogenic amine were lower than 7.5%. The method was successfully applied to shrimp sauce and tomato ketchup samples, offering an interesting alternative to liquid–liquid extraction and solid phase extraction for the analysis of biogenic amines in food samples.  相似文献   

20.
A central composite rotatable design (CCRD) of response surface methodology was used to analyze pervaporation performance of homogeneous poly(vinyl alcohol) (PVA) membranes. A regression model was developed for the pervaporation flux and selectivity as a function of the operating conditions: temperature, concentration and flow-rate. Dehydration experiments were performed on two different alcohol–water systems: isopropanol–water (IPA–water) and ethanol–water (Et–water) mixtures around their azeotropic concentrations. Based on preliminary experiments and CCRD design, the ranges of values of the operating conditions were selected: temperature 33–67 °C, feed flow-rate 46–114 L/h, and concentration 83–92 wt% for IPA and 93–98 wt% for Et in feed mixtures. A total of 20 pervaporation experiments were conducted for each alcohol–water system. Judged by the lack-of-fit criterion, the analysis of variance (ANOVA) showed the regression model to be adequate. From the regression analysis, the flux and selectivity were expressed with quadratic equations of temperature, feed concentration and flow-rate. The predicted flux and selectivity from the regression model were presented in 3D surface plots. For both alcohol–water systems, quadratic terms of temperature and feed alcohol concentration showed significant (p < 0.0001) influence on the flux and selectivity. A strong interaction effect of temperature and concentration was observed on the selectivity for the Et–water system. However, the interaction of flow-rate with temperature or concentration was found to be less significant. In order to optimize the pervaporation flux and selectivity of azeotropic alcohol–water mixtures, the desirability function approach was applied to analyze the regression model equations by commercial software. For the azeotropic IPA–water mixture (87.5 wt% IPA), the optimized dehydration variables were found to be 50.5 °C and 93.7 L/h for temperature and flow-rate, respectively. For the azeotropic Et–water mixture (95.5 wt% Et), the optimized temperature and flow-rate were found to be 57 °C and 89.2 L/h, respectively. Compared with experiments performed at optimized temperature and flow-rate, the predicted flux and selectivity of the azeotropic mixtures showed errors to be within 3–6%.  相似文献   

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