Spray-coated PDMS/PVDF composite membrane for enhanced butanol recovery by pervaporation

In this study, spray-coating was used to prepare dihydroxypolydimethylsiloxane (PDMS) composite membranes with high flux and separation factor for biobutanol recovery from aqueous solution. A thin, smooth, and defect-free PDMS layer was prepared by spray-coating on polyvinylidene difluoride ultrafiltration membrane with little PDMS penetration. The effects of process parameters for membrane fabrication and pervaporation on membrane performance were investigated. A membrane with 2 μm active layer was obtained with a high flux of 1306.9 g/m² h. The optimal membrane with the highest pervaporation separation index (PSI) (19.15 kg/m² h) showed a total flux of 530.6 g/m² h and a separation factor of 36.1 at 37°C, and a PSI of 65.61 kg/m² h and a flux of 1927.0 g/m² h at 70°C. Membrane performance was affected by feed composition and temperature. Acetone-butanol-ethanol solution and fermentation broth gave lower butanol fluxes and separation factors compared to butanol model solution.     

仿鱼鳞PDA纳米片复合滤膜的制备及油水分离性能

以聚多巴胺(PDA)为原料、Mg(OH)₂为模板剂，采用液相沉积法原位包覆Mg(OH)₂纳米片制备了PDA纳米片，再以疏水棉布为基底，PDA纳米片为覆盖层制备了PDA纳米片复合滤膜(简称复合滤膜)。通过SEM、TEM、BET、FTIR、XPS、XRD和接触角测量仪对复合滤膜进行了结构表征，同时测定了复合滤膜对油水混合物和乳化油的分离性能、循环使用性能和抗污染性能。结果表明，PDA纳米片的引入显著地增加了复合滤膜的表面粗糙度，在自重作用下复合滤膜对油水混合物和乳化油(均以环己烷为油相)的渗透通量分别为2866.24和1015.13 L/(m²·h)，分离效率达99.5%，且复合滤膜在重复使用10次后，其对乳化油的渗透通量为798.11 L/(m²·h)，分离效率达98.1%。此外，PDA纳米片还具有普适性，能覆盖在不同基底上进行乳化油分离，具有良好的应用前景。     

Investigation on the enhancement of solvent-resistant nanofiltration membrane performance utilizing PDA-UiO-66@CNT as an interlayer

With the growing complexity of separation systems, the application of thin film composite nanofiltration (TFN) membranes in organic solvent separation faces numerous challenges. To augment its solvent stability, an in-situ constructed dopamine hydrogel doped with UiO-66@CNT was developed as an intermediate layer on a polyetherimide (PEI) ultrafiltration membrane. Subsequent interfacial polymerization on this interlayer led to the formation of a solvent-resistant nanofiltration membrane with a vast covalent bond structure, large specific surface area, and enhanced hydrophilicity. Our findings revealed that when the CNT loading in the UiO-66@CNT composite nanoparticles was 2 wt%, the TFN-U₂C₂ membrane exhibited a maximum pure water flux of 126.32 L/(m²·h) and a methanol flux of 45.45 L/(m²·h). The rejection rates for Congo red aqueous and methanol solutions were 96.88% and 92.14%, respectively. The membrane also demonstrated commendable anti-fouling properties. Remarkably, even after 48 h of immersion in various organic solvents, the membrane retained its morphology and separation efficiency. Compared to the TFN-U₂ membrane without CNT addition, the enhancement in separation performance was considerably significant. Hence, this membrane has significant potential for application in treatment of wastewater containing organic solvents and is promising in related fields.     

Study on Ce-doped Nonstoichiometric Nano-silica/PSF Composite Membrane for Separation of Chinese Yam Polysaccharide

Abstract

In order to enhance the anti-fouling ability and separation efficiency of polysulfone (PSF) membrane during separating of Chinese yam polysaccharides, a novel composite membrane was prepared through a sol-gel process after adding Ce-doped nonstoichiometric nano-silica with higher activity and hydrophilic property to the porous matrix of PSF. Ce-doped nonstoichiometric nano-silica was synthesized by doping the rare earth Ce element. Novel composite membranes and ordinary membranes without doping Ce-doped nonstoichiometric nanosilica were used to separate Chinese yam polysaccharides while the content of polysaccharide was tested. The results designate that the content of polysaccharide separated by composite membrane which reached 78.3% was higher than that of polysaccharide separated by ordinary membrane which reached 46.7%. The flux of the composite membrane increased with increasing of operation pressure. With the temperature rising, the polysaccharide solution flux of composite membrane ascended from 289 L/(m²h) to 312 L/(m²h). The flux of the composite membrane was kept at a high value for 25 h before reaching a steady state (243 L/(m²h)), which was higher than the stable flux of ordinary membrane (160 L/(m²h)). After the composite membrane was washed for six times, its flux still reached 90% of initial value. The experiment data indicate that the anti-fouling ability and hydrophilic property of composite membrane were significantly enhanced. Therefore, Chinese yam polysaccharides can be efficiently separated by the novel composite membrane.     

Enhanced chlorine-resistant and low biofouling reverse osmosis polyimide-graphene oxide thin film nanocomposite membranes for water desalination

The effect of graphene oxide (GO) loading (0.03, 0.06, 0.09, 0.12, and 0.30 wt%) in the aqueous phase on the performance of reverse osmosis (RO) polyimide (PI) thin film composite (TFC) membrane was investigated. TFC and thin film nanocomposite (TFN) membranes were produced through interfacial polymerization and the imide linkage was confirmed by attenuated total reflection Fourier transform infrared spectroscopy. The spongy-like structure with vertical fingers of RO PI-GO TFN membranes was explored by top-surface and cross-sectional field emission scanning electron microscope (FE-SEM). The roughness of the membranes was determined. All PI-GO TFN membranes exhibited enhanced desalination performance in comparison with PI membranes. Samples with 0.06 wt% GO performed the best with a water flux of 31.80 L/m²/h, salt rejection of 98.8%, and very good antibiofouling properties. This hydrophilic membrane displayed significantly enhanced chlorine-resistance with water flux of 36.3 L/m²/h and salt rejection of 98.5%. This work provides a promising start for designing rapid water permeation PI-GO TFN membranes in water desalination.     

Preparation of graphene oxide/polyamide composite nanofiltration membranes for enhancing stability and separation efficiency

Polyamide (PA) NF membranes are synthesized on a hollow fiber support by the interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC). Then, GO is coated on the PA layer to decorate the NF membrane surface (denoted GO/PA-NF). This strategy aims to improve the hydrophilicity, chlorine resistance and separation stability of the membrane. The optimization, chemical composition, morphology, and hydrophilicity of the synthesized GO/PA-NF membrane are characterized. Results indicate that the optimized GO/PA-NF in terms of rejection rate and flux are with 0.05 wt% GO. The rejection of GO/PA-NF for Na2SO₄ and MgSO₄ is 99.4% and 96.9%, respectively. Even if the GO/PA-NF is immersed in 1000 ppm NaClO solution for 48 h, the NF membrane still maintains stable salt rejection. The developed NF membranes exhibit excellent treatment performance on dying wastewater. The permeate flux and rejection of GO/PA-NF toward Congo red solution are determined to be 44.2 L/m²h and 100%, respectively. Compared with the PA membrane, GO/PA-NF presents a higher rejection for Na₂SO₄ (99.4%) and a lower rejection for NaCl (less than 20%), which shows that the NF membranes have a better divalent/monovalent salt separation performance. This study highlights the superior performance of GO/PA-NF and shows its high potential for application in wastewater treatment.     

Improved separation performance of polyamide based reverse osmosis membrane incorporated with poly(dopamine) coated carbon nanotubes

A series of polyamide thin-film nanocomposite (PA TFN) membranes have been fabricated by incorporating hydrophilic poly(dopamine) (PDA) coated carbon nanotubes (CNTs@PDA) into the PA selective layer via interfacial polymerization. The effects of PDA coating thickness on surface characteristics and separation performances of membranes are studied in detail. The PDA coating makes the surface of PA TFN membrane more hydrophilic, smoother and less electronegative. The desalination performance is obviously influenced by the coating thickness of PDA and the loading concentration of PDA@CNTs. The water fluxes of PDA@CNTs incorporated PA TFN membranes have been improved without sacrificing NaCl rejections. When the loading concentration is 0.0010%, the maximum water flux is 48.1 L m⁻² h increasing by 45% compared with that of pristine PA membrane. Meanwhile, the NaCl rejection is up to 99.8%. The CNTs@PDA incorporated PA TFN membranes exhibit better anti-fouling property and separation performance durability. This work proves that CNTs@PDA has great potential application in PA TFN membranes.     

Fabrication,Application and Mathematical Modeling of a new Diamine/Trimesoyl Chloride Reverse Osmosis Composite Membrane for Copper Sulfate Desalination from Wastewaters

Excessive amounts of copper ions in the water sources can be harmful to mammals and especially humans. In this study, a new RO composite membrane is fabricated via the interfacial polymerization (IP) reaction of trimesoyl chloride (TMC), piperazine (PZ) and 3,5-diaminobenzoicacid (DABA). The IP reaction was conducted on a polysulfone (PS) layer which acts as a mounting layer for the separation TMC-DABA-PZ layer. The IP reaction time, TMC concentration and transmembrane pressure were the selected study variables. For IP reaction times around 10 s the rejection and flux were equal to 79% and 21.3 L.m^?2.h^?1, respectively, while increasing the IP reaction time to 40 s elevates the rejection and flux to 92% and 27.7 L.m^?2.h^?1, respectively. TMC concentrations around 0.05% w/w demonstrated rejection and flux equal to 88% and 14.3 L.m^?2.h^?1, respectively, while its elevation to 0.2% w/w, increased the rejection and flux to 90% and 17.5 L.m^?2.h^?1, respectively. As with the transmembrane pressure, the optimum pressure was 20 bars, in which the rejection and flux were 95% and 24.07 L.m^?2.h^?1, respectively. Membrane morphology tests are also supporting evidence for these results. The mathematical modeling has also shown that the relation between the concentration, rejection and flux parameters match the resultant data from the conducted experiments. Since both the rejection and the flux of the fabricated membranes have shown great results, such membranes can be used for wastewater treatment at industrial scales.     

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.     

A TiO2 modified whisker mullite hollow fiber ceramic membrane for high-efficiency oil/water emulsions separation

Design and preparation of membranes with ultrahigh separation performance and antifouling property for oil-in-water (O/W) emulsions remains challenging. In this study, a high flux mullite/TiO₂ ceramic composite membrane was prepared via multi-precipitation of TiO₂ on a whisker mullite hollow fiber support synthesized by combining phase inversion and high-temperature sintering techniques. The results showed that the generated whisker mullite structure improved the permeation flux, and the micro-nano structured TiO₂ functional layer endowed the membrane surface with superhydrophility and stability. The retention of the optimal composite membrane (M20T13) that was soaked in the titanium solution 20 times for 13 min each time for the O/W emulsions like n-hexane, toluene and engine oil maintained over 98 %, and the flux after 6 h filtration was 668.34 L·m⁻²·h⁻¹, 487.25 L·m⁻²·h⁻¹ and 258.66 L·m⁻²·h⁻¹, respectively, much higher than that of the optimal substrate (F3A1, mass ratio of fly ash: Al₂O₃ = 3:1). Moreover, the flux recovery rate of M20T13 was much higher than that of F3A1 after chemical backwashing. This work manifests great potential in O/W treatment fields.     

Treatment of oily wastewater using low cost ceramic membrane: Comparative assessment of pore blocking and artificial neural network models

This work addresses the performance and modeling of the separation of oil-in-water (o/w) emulsions using low cost ceramic membrane that was prepared from inorganic precursors such as kaolin, quartz, feldspar, sodium carbonate, boric acid and sodium metasilicate. Synthetic o/w emulsions constituting 125 and 250 mg/L oil concentrations were subjected to microfiltration (MF) using this membrane in batch mode of operation with varying trans-membrane pressure differentials (ΔP) ranging from 68.95 to 275.8 kPa. The membrane exhibited 98.8% oil rejection efficiency and 5.36 × 10⁻⁶ m³/m² s permeate flux after 60 min of experimental run at 68.95 kPa trans-membrane pressure and 250 mg/L initial oil concentration. These experimental investigations confirmed the applicability of the prepared membrane in the treatment of o/w emulsions to yield permeate streams that can meet stricter environmental legislations (<10 mg/L). Subsequently, the experimental flux data has been subjected to modeling study using both conventional pore blocking models as well as back propagation-based multi-layer feed forward artificial neural network (ANN) model. Amongst several pore blocking models, the cake filtration model has been evaluated to be the best to represent the fouling phenomena. ANN has been found to perform better than the cake filtration model for the permeate flux prediction with marginally lower error values.     

ETA‐m‐PAN and its Composite Membrane with High Performance Prepared by In Situ Modification/NIPS Principle

Ethanolamine‐modified polyacrylonitrile (ETA‐m‐PAN) membrane is prepared by in situ modification integrated with a nonsolvent‐induced phase separation method for the first time. The results reveal that both the morphology and the separation performance of the modified membrane change greatly with condition parameters. The membrane formation mechanism is carefully investigated, which is related to the change in the molecular structure and hydrophilic property of ETA‐m‐PAN. The cross‐linked structure leads to the formation of ETA‐m‐PAN spongy membrane. The optimized condition parameters are determined by permeability‐selectivity analysis. Furthermore, the composite membrane with ETA‐m‐PAN as the selective layer is prepared by a dual‐casting method. The obtained membrane shows a good property, flux of 650L m^?2 h^?1 bar^?1, 82% BSA rejection, and 84% water flux recovery ratio. This work demonstrates the great potential of this integrated method for new membrane preparation.     

Fabrication of an antifouling GO-TiO2/PES ultrafiltration membrane

PES ultrafiltration membrane is widely used in various fields due to its high-filtration efficiency. However, due to its hydrophobicity, PES ultrafiltration membrane has poor antifouling performance, this reduced service life and increased industrial cost. Blending is a common method in ultrafiltration membrane hydrophilic modification. Adding a small amount of inorganic nanoparticles into the polymer membrane can improve the properties of the polymer membrane. However, nanoparticles are not uniformly dispersed in polymer membrane, which hindering the modification ability of nanoparticles to ultrafiltration membrane. In this paper, GO-TiO₂ materials were prepared by hydrothermal method, and GO-TiO₂/PES blended ultrafiltration membranes were fabricated by nonsolvent induced phase separation (NIPs). The experimental results show that GO-TiO₂ disperse uniformly in GO-TiO₂/PES ultrafiltration membrane, which greatly improved the antifouling performance of the membrane. When the addition amount of GO-TiO₂ is 0.6%, the water flux of membrane reaches 194.5 (L m⁻² h⁻¹), and the rejection rate of BSA reaches 89.4%. After three pollutions-cycles, the flux recovery rate of the membrane is 90.2%.     

PEG/GO/TiO2纳米复合材料改性PVDF膜的制备及其抗污性能

为改善聚偏氟乙烯(PVDF)膜的抗污性能,以聚乙二醇2000接枝的GO/TiO₂(PEG/GO/TiO₂)纳米复合材料为添加剂,通过非溶剂诱导沉淀相分离法制备了一系列PEG/GO/TiO₂/PVDF复合超滤膜。采用FTIR、SEM和接触角测试仪对其结构和形貌进行了表征,采用超滤法评价其纯水通量和抗污性能。结果表明,当PEG/GO/TiO₂纳米复合材料质量分数为0.60%时,制备的PEG/GO/TiO₂/PVDF复合超滤膜(记为0.60%PEG/GO/TiO₂/PVDF)表现出最佳的亲水性和抗污性能,其接触角比PVDF膜下降8.2°,总孔隙率增加13.40%,PEG/GO/TiO₂纳米复合材料在PVDF膜中分散较均匀。在0.08 MPa的工作压力下,0.60%PEG/GO/TiO₂/PVDF的纯水通量高达282.44 L/(m²·h),对腐植酸溶液的过滤通量为131.96 L/(m^2...     

Multifunctional fly ash-based GO/geopolymer composite membrane for efficient oil-water separation and dye degradation

Membrane fouling and separation materials with low cost and high efficiency are challenges for membrane separation technology in wastewater treatment. Superhydrophilic and underwater superoleophobic membranes show broad application prospects in oily wastewater treatment because of their high permeability, selectivity, and antifouling performance; however, they are generally ineffective for organic pollutant molecules. In this study, a novel graphene oxide (GO)/geopolymer composite membrane with superhydrophilic and underwater superoleophobic characteristics was prepared by dipping a mixed slurry of GO and fly ash-based geopolymer onto a stainless steel mesh via a facile self-assembly process. The results show that GO could adjust the hydrophilicity and water flux of composite membranes. The composite membrane containing 0.4 wt% GO (4GO/GCM) had the best hydrophilic, water flux of 1363 kg/(m²·h), and high separation efficiencies (≥98.2%) for oil-water mixtures and oil-in-water emulsions under gravity-driven. In addition, the 4GO/GCM sample exhibited excellent stability under harsh conditions, including hot water and strong acid, alkali, and salt solutions. Importantly, the sample derived from fly ash exhibited unique photocatalytic degradation performance for organic dye molecules under simulated solar-light irradiation. Thus, it is believed to this strategy has substantial potential for high-value utilization of fly ash and the sustainable treatment of oily and dye wastewater.     

Polyethersulfone composite hollow-fiber membrane prepared by in-situ growth of silica with highly improved oily wastewater separation performance

In order to reduce surface aggregation and enhance the performance of PES membranes, a hydrophilic PES/TEOS HF membrane was developed for the treatment of wastewater containing oil. PES/TEOS was prepared via a sol-gel self assembly and dry–wet spinning method. Silicon dioxide sol was prepared from a mixture of tetraethoxysilane, ethanol, water, and acetic acid (acting as the catalyst). HF hybrid membranes were produced from dope solutions containing polyethersulfone, polyethylene glycol, silicon sol, and NMP. The membranes were characterized by field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDX), porosity, fourier transform infrared spectroscopy (FTIR), and contact angle measurements. The composite membranes were successfully used to treat wastewater containing oil and their separation performance were evaluated. The PES/TEOS-2 membrane displayed the best performance, with a permeate flux of 90.937 L/m² h and an oil retention of 99.98%. In addition, this membrane showed a higher pure water flux of 102.43 L/m² h as compared to PES-0 and PES/SiO₂–1 membranes (87.347 L/m² h and 91.949 L/m² h, respectively). The PES/TEOS-2 membrane also presented enhanced antifouling behavior with a FRR and a RFR of 93.33% and 11.22%, respectively. In addition, this membrane displayed excellent long-term recycling properties, making it a desirable candidate for oily wastewater separation applications.     

Performance evaluation of polyvinylchloride/polyacrylonitrile ultrafiltration blend membrane

Polyvinylchloride (PVC) membranes were modified by blending with polyacrylonitrile (PAN) as a second polymer. The miscibility of PVC/PAN blend was examined using an incompressible regular solution (CRS) model in no need to make a membrane. The results showed that the PVC/PAN blend was immiscible for all compositions at a temperature range of ?25 to 225 °C. Furthermore, the prediction of the phase behavior of a PVC/PAN/DMF ternary system showed that the blend of two polymers was highly incompatible even in their common DMF solvent. However, this incompatibility led to a remarkable increase in the porosity of the blend membrane and pure water flux compared to those for pure PVC membrane. The pure water flux of the PVC membrane (37.9 ± 1.5 L/m² h) increased about 41 and 76% by adding 10 and 20 wt% PAN, respectively. The blend membranes also showed an enhanced flux recovery ratio (FRR) compared to a pure PVC membrane, although the PVC membrane rejection for Bovine serum albumin (BSA) was decreased after blending with PAN. The PVC/PAN (90/10) blend membrane was subjected to hydrolysis with NaOH alkaline solution at three different concentrations and contact times to further enhance its performance. The membrane, which was hydrolyzed with a 0.5 mol/L NaOH solution for 0.5 h, showed a highest pure water flux of 75.6 ± 7.2 L/m² h due to its increased hydrophilicity. This membrane also revealed an improved FRR and better thermal and mechanical properties compared to an unmodified membrane.     

Highly efficient removal of phenol from aqueous solutions using graphene oxide/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite membrane

To achieve superior separation performance in the phenol aqueous solutions treatment, a novel graphene oxide/Al₂O₃ composite membrane was prepared by a spin coating process. The microstructure measurement shows that the composite membrane has a multilayer structure and graphene oxide has been tightly coated on the surface of the Al₂O₃ membrane interlayer homogeneously. During the treatment of phenol aqueous solutions, the permeation flux and phenol rejection of the composite membrane were investigated. The results show the permeation flux of the membrane is about 1.153 L m^?2 h^?1 bar^?1 and the phenol rejection of the membrane increases to 99.9% when the phenol concentration is 0.01 g L^?1. The high phenol rejection of the composite membrane is mainly attributed to the physical sieving, the solution–diffusion effect and the hydrophobic nature of graphene oxide. All these results indicate the GO/Al₂O₃ composite membrane is a suitable material for the removal of phenol from aqueous solutions in environmental pollution management.     

One-step preparation of asymmetric ceramic membranes based on sea urchin-like mullite whisker skeletons and their oil-water separation properties

In this work, novel sandwich-type asymmetric ceramic microfiltration membranes with a sea urchin-like mullite whisker skeleton were prepared one step. Their structural properties and oil-water separation performance were investigated. The results show that after sintering at 1400 °C, the prepared membrane possesses good hydrophilic, underwater oleophobic, and anti-fouling properties. During the continuous separation of a 300 mg/L oil-in-water emulsion, a maximum stable flux of 267 L·m⁻²·h⁻¹ was achieved without membrane cleaning. After chemical cleaning and simple physical cleaning, the membranes recovered to a steady flux of 397 L·m⁻²·h⁻¹ and 305 L·m⁻²·h⁻¹, respectively, and maintained a 95% oil rejection. The good underwater oleophobicity and selective permeability brought about by the flat-lying whiskers on the top surface, coupled with the efficient water channels between the sea urchin-like structures inside the membrane, are considered to be the main reasons for its improved separation characteristics over conventional low-cost ceramic membranes.     

Preparation and performance of three‐layered structure composite membrane for heavy metal ions and hazardous dyes rejection

A three‐layered structure composite membrane was successfully fabricated by electrospinning cellulose acetate (CA)/poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) fibrous layers and coating the chitosan (CS) solution on the CA/PHBV substrate as a barrier layer. For obtaining the proper mechanical property and high filtration performance, different content of glycerol was investigated to mix in CS coating solution. The ovalbumin tests showed that this triple‐structure type of filtration media exhibited a high flux rate (up to 730 L/m² h at the feed pressure of 0.15 MPa) and an excellent rejection rate (98%). The permeation flux of the membrane was significantly higher than other reported electrospun fiber membranes with similar rejection ratios. The CA/PHBV‐CS composite membrane was also used to remove disperse dye and metal ion for water purification. These prepared membranes exhibited efficient adsorption separation performance toward disperse yellow dye with the maximum adsorption capacity reaching up to 188.52 mg/g. The equilibrium absorption capacities of the three tested ions (Cu(II), Pb(II), and Cr(III)) were 46.26, 88.31, and 190.14 mg/g, respectively. Consequently, these membranes can be promising materials in wastewater treatment. © 2018 Society of Plastics Engineers POLYM. ENG. SCI., 59:E322–E329, 2019. © 2018 Society of Plastics Engineers