Influence of compatibility between sol and intermediate layer on the performance of yttria-stabilized zirconia nanofiltration membrane

This paper reports the synergistic effect of the sol and intermediate layer on the performance of yttria-stabilized zirconia (YSZ) nanofiltration (NF) membranes. We have focused on the characterization of the microstructure, pure water permeance, and molecular weight cut-off (MWCO) of the NF membranes derived from zirconia sols of different precursor concentrations on two types of supported ZrO₂ ultrafiltration (UF) membranes. We found that the performance of YSZ membranes strongly depends on the sol concentration and the pore size of the intermediate layer. In addition, YSZ gel membrane formation was found to follow the filtration process. Therefore, it is essential to maintain the compatibility between the sol and intermediate layer to fabricate high-performance NF membranes. A crack-free thin YSZ layer with an MWCO of 816 Da (pore size: 1.4 nm) and a water permeance of 25 L m^-2 h^-1 bar^-1 was fabricated using a precursor concentration of 0.03 mol/L, on ZrO₂ UF membrane with a pore size of 5.5 nm. The YSZ NF membrane exhibited a relatively high retention rate towards MgCl₂ (71%), whereas a lower retention rate was observed for NaCl (35%).     

Interfacially polymerized nanofiltration membranes: Atomic force microscopy and salt rejection studies

Interfacial polymerization is one of the main techniques for producing composite nanofiltration (NF) membranes. In this study, five NF membranes were produced through interfacial polymerization under different conditions of reactions, namely varying reaction time, as well as monomer concentrations. The membranes were then imaged using atomic force microscope (AFM). AFM images provided information of the average pore size, pore size distribution, and surface roughness. For some of the membranes, discrete pore sizes were visible. Increasing the reaction time resulted in decreasing water permeabilities but based on AFM imaging the pore size was of similar value. Increasing the monomer concentration also resulted in decreasing water permeabilities. However, based on AFM imaging the pore size differs considerably. Additional permeation experiments were also carried out using NaCl and Na₂SO₄ solutions with membranes identified as NF. By fitting the rejection data using a model such as the Donnan‐steric‐pore model, the variation in effective charge density of the membranes was also determined. The ability to tailor composite NF membranes with the right properties will significantly improve membrane performance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 605–612, 2005     

Nanofiltration Separation of Aqueous Polyethyleneglycol – Salt Mixtures

To investigate nanofiltration (NF) separation for recycling polyethylenglycol (PEG) from an ion partition process using an aqueous two-phase system, fractionation performance of five different NF membranes (NF270, SR3, SR100, SR2, and BW30) with solutions of NaNO₃, KClO₄, and PEG 4000 in water comprising various mixtures were studied. PEG rejections and salt passage were analyzed and explained based on size exclusion as well as electrostatic interactions. The highest permeate flux at high rejection of PEG as well as the lowest salt rejections were obtained with SR2 and NF270 membranes. Similar salt rejections were observed for mixed solute solutions and complex mixtures, all following this trend: SR3 > NF270 > SR2. The PEG rejections were well above 95%. This study also revealed that high salt passage of above 90% could be achieved with the same NF membrane only by unstirred conditions through concentration polarization mechanism; however, at the expense of low flux, especially with high PEG concentrations.     

Preparation and characterization of polysulfone ultrafiltration membranes for concentrating waste tuna broth

Three sets of ultrafiltration (UF) membranes were prepared containing the following proportions (w/w) of polysulfone and dimethylacetamide: 14.5/85.5, 15.0/85.0 and 15.5/84.5. The membranes were characterized in terms of water flux, molecular weight (MW) cut-off, fouling, average pore size and ratio of pore surface area to membrane area. Membrane water flux was found to decrease as the polysulfone concentration or membrane thickness was increased. Scanning electron microscopy showed an asymmetric pore structure and indicated that the variation in water flux between membrane sets were probably due to differences in the number of pores per unit membrane area and not to differences in pore diameter. The MW cut-off for all the membranes was found to be close to 66 kD. The permeate flux for standard proteins decreased with increasing protein MW. A decrease in water flux was also observed after the UF runs; this could be explained by membrane fouling.

Defatted waste tuna broth, which was obtained from a fish canning plant as steam condensate after autoclaving fresh tuna, was ultrafiltered using the prepared membranes. The rejection coefficient for either protein or carbohydrate solute of the tuna broth was approximately 54.5% while solute recovery was about 90%. The ultrafiltered broth had negligible turbidity and odor.     

Fractionation of β‐Lactoglobulin Tryptic Peptides using Spiral Wound Nanofiltration Membranes

Abstract

Nanofiltration (NF) membranes were previously used to fractionate peptides in β‐lactoglobulin tryptic hydrolysates. It was shown that G‐10 NF polyamide membrane coupons with a molecular weight cut‐off of 2.5 kg · mol^?1 retained all acidic (negatively charged) peptides, making it possible to separate them from basic and neutral peptides. The objective of the work described here was to characterize the ability of G‐10 and G‐50 NF membranes, which differ by their MWCO, mounted in spiral wound modules to fractionate acid, neutral, and basic peptides at pH 9 and at different peptide concentrations (0.1%, 0.5%, and 1.0%). The selectivity of separation of the peptide was influenced by the Donnan and size exclusion effect for both spiral wound NF membranes. The size exclusion effect was more important with the NF G‐50 while Donnan effect was dominant with the NF G‐10 membrane. Acidic peptides were completely retained at pH 9 and the transmission of basic and neutral peptides was optimal on the G‐10 membrane at the lowest peptide concentration (0.1%).     

An advanced treatment of high-strength opium alkaloid processing industry wastewaters with membrane technology: pretreatment, fouling and retention characteristics of membranes

This paper presents the results of the laboratory and pilot-scale membrane experiments of opium alkaloid processing industry effluents. Different types of ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) membranes were evaluated for membrane fouling, permeate flux and their suitability in separating COD, color and conductivity. Experiments demonstrated that membrane treatment is a very promising advanced treatment option for pollution control for opium alkaloid processing industry effluents. Almost complete color removal was achieved with NF and RO membranes. COD and conductivity removals were also greater than 95% and met the current local standards. Nevertheless, pretreatment was an important factor for the NF and RO membrane applications. Membrane fouling occurred with direct NF membrane applications without UF pretreatment. The total estimated cost of the UF and NF treatment system was calculated as $0.96/m³, excluding the concentrate disposal cost.     

Influence of polyethyleneimine layer and zinc nitrate on morphology and structure of PES-based membranes with highly selective properties

In this paper, nanofiltration (NF) polymer membranes based on polyestersulphone (PES) were prepared by the phase inversion method. Polyethyleneimine (PEI) and zinc nitrate (Zn(NO₃)₂) as a surface modifier and glutealdehyde (GA) as cross-linker was used. Fourier transform infrared spectroscopy analysis (FTIR) was used to confirm the chemical composition on the membrane surface. Membranes were also characterized using field emission scanning electron microscopy (FESEM) and 3D surface images. Water contact angle, average pore size and porosity measurements, water flux, salt rejection, and membrane anti-fouling ability were discussed. Modified membranes showed a smoother surface than the original membrane. The amount of pure water flux decreased with increasing the concentration of modifiers at the surface, but the yield of Na₂SO₄ salt increased, 53% in virgin membrane and 83% in M3 membrane. Modified membranes had better anti-fouling and hydrophilicity properties than primary membranes. The lowest contact angle value was 26.2° for M4. Also, the best anti-clogging comparable properties were for the M3 membrane with FRR = 63.37%, R_r = 10.69%, R_ir = 36.6%, and R_t = 47.3%. By increasing the concentration of modifiers, the removal of CuNO₃⁻ and CuSO₄ improved that the M1 membrane (97.59%) had the highest Cu(NO₃)₂ separation and the M4 membrane (87.5%) had the most increased CuSO₄ separation.     

多孔陶瓷膜用于碳量子点的分离与纯化

尺寸分布均一的碳量子点由于其良好的光学特性,在光电设备、离子检测、纳米传感器、生物成像和催化剂等领域具有广阔的应用前景。采用陶瓷膜“超滤-纳滤”双膜法,对微波合成的碳量子点进行分离和纯化。研究了pH对碳量子点料液荧光强度和粒径分布的影响。在pH=3时,碳量子点分散较好,荧光强度较高。陶瓷超滤膜可以有效截留碳量子点料液中的大颗粒杂质,渗透侧的碳量子点平均粒径约为2 nm,分散良好,无团聚现象。陶瓷纳滤膜对碳量子点具有良好的截留性能,在浓缩和水洗过程中可以进一步去除料液中的小分子杂质。经双膜法处理后,发射光谱由多峰分布变为单峰分布,且峰宽变窄,碳量子点的发光纯度得到了明显提高。     

Effect of additives concentration on the surface properties and performance of PVDF ultrafiltration membranes for refinery produced wastewater treatment

The aim of this study was to investigate the effect of pore-forming hydrophilic additives on the porous asymmetric polyvinylideneflouride (PVDF) ultrafiltration (UF) membrane morphology and transport properties for refinery produced wastewater treatment. PVDF ultrafiltration membranes were prepared via a phase inversion method by dispersing lithium chloride monohydrate (LiCl·H₂O) and titanium dioxide (TiO₂) nanoparticles in the spinning dope. The morphological and performance tests were conducted on PVDF ultrafiltration membranes prepared from a different additive content. The top surface and cross-sectional area of the membranes were observed using a field emission scanning electron microscope (FESEM) and energy dispersive X-ray (EDX) analysis. The surface wettability of porous membranes was determined by the measurement of a contact angle. The mean pore size and surface porosity were calculated based on the permeate flux. The results indicated that the PVDF/LiCl/TiO₂ membranes with lower TiO₂ nanoparticles loading possessed smaller mean pore size, more apertures inside the membrane with enhanced membrane hydrophilicity. LiCl·H₂O has been employed particularly to reduce the thermodynamic miscibility of dope which resulted in increasing the rate of liquid–liquid demixing process. The maximum flux and rejection of refinery wastewater using PVDF ultrafiltration membrane achieved were 82.50 L/m² h and 98.83% respectively at 1.95 wt.% TiO₂ concentration.     

Ultrafiltration and nanofiltration membranes applied to the removal of the pharmaceuticals amoxicillin,naproxen, metoprolol and phenacetin from water

BACKGROUND: In the removal of pharmaceuticals present in aquatic systems by membrane processes, some important issues must be explored in order to obtain a better knowledge of the global process. Among these issues, a better understanding of the influences of the operating parameters on the membrane flux, an analysis of membrane resistances and fouling, and determination of the removal of specific substances, must be studied. RESULTS: Four selected pharmaceuticals (amoxicillin, naproxen, metoprolol and phenacetin) were subjected to ultrafiltration (UF) and nanofiltration (NF) processes for their removal from several water matrices. The determined permeate fluxes at the steady state were affected by the main operating conditions: molecular weight cut‐off (MWCO) of the membrane, transmembrane pressure TMP, cross‐flow velocity and temperature. The retention coefficients with the UF membranes followed the sequence naproxen > metoprolol > amoxicillin > phenacetin, and with the NF membranes, followed the trend: amoxicillin > naproxen > metoprolol > phenacetin, due to the role of other mechanisms such as size exclusion and electrostatic repulsion. In the case of the selected water matrices, the retention coefficient was referred to some quality parameters (total organic carbon, chemical oxygen demand and absorbance at 254 nm), leading to moderate (UF) or high (NF) removals of the organic matter content. CONCLUSIONS: The NF CK membrane achieved the highest retention of these pharmaceuticals (excepting phenacetin), and provided retentions for quality parameters around 80% in the four water systems tested. Copyright © 2011 Society of Chemical Industry     

Influence of sodium bromide additive on polyethersulfone ultrafiltration membranes

The effect of sodium bromide (NaBr) on performance and characteristics of ultrafiltration (UF) membranes was studied. Asymmetric UF membranes were prepared by phase inversion technique from a multicomponent dope polymer solution consisting of the polymer; polyethersulfone (PES), solvent; N, N‐dimethylformamide (DMF) and NaBr as micromolecular additive. The dissolution of PES‐DMF‐NaBr was carried out using microwave irradiation technique to induce rapid dissolution through minimal heating time. Various concentrations of NaBr were mixed with PES in the range of 1–5 wt % and its influence on membrane characteristics such as surface hydrophilicity was measured by contact angle and the performance in terms of water flux and rejection rates were evaluated using micromolecular test substances. The morphology and streaming potential of PES UF membranes were analyzed using scanning electron microscopy (SEM) and ζ‐potential measurement, respectively. Overall, the results suggest that the membrane consisting of 1 wt % NaBr exhibits the best performance in terms of rejection and flux rates with molecular weight cutoff (MWCO) of 45 kDa and mean pore size of 6 nm. The membrane with the 1 wt % addition of NaBr demonstrates most negative charge which indicates less fouling characteristics and displays approximately three times higher permeation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Poly(vinyl chloride) hollow‐fiber membranes for ultrafiltration applications: Effects of the internal coagulant composition

Poly(vinyl chloride) (PVC) hollow‐fiber membranes were spun by a dry/wet phase‐inversion technique from dopes containing 15 wt % PVC to achieve membranes with different pore sizes for ultrafiltration (UF) applications. The effects of the N,N‐dimethylacetamide (DMAc) concentration in the internal coagulant on the structural morphology, separation performance, and mechanical properties of the produced PVC hollow fibers were investigated. The PVC membranes were characterized by scanning electron microscopy, average pore size, pore size distribution, void volume fraction measurements, and solubility parameter difference. Moreover, the UF experiments were conducted with pure water and aqueous solutions of poly(vinyl pyrrolidone) as feeds. The mechanical properties of the PVC hollow‐fiber membranes were discussed in terms of the tensile strength and Young's modulus. It was found that the PVC membrane morphology changed from thin, fingerlike macrovoids at the inner edge to fully spongelike structure with DMAc concentration in the internal coagulant. The effective pores showed a wide distribution, between 0.2 and 1.1 μm, for the membranes prepared with H₂O as the internal coagulant and a narrow distribution, between 0.114 and 0.135 μm, with 50 wt % DMAc. The results illustrate that the difference in the membrane performances was dependent on the DMAc concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚丙烯酸接枝型聚偏氟乙烯多孔膜的pH值感应开关特性

A series of pH-responsive gating membranes, with a wide range of grafting yields, were prepared by grafting poly (acrylic acid) (PAAC) onto porous polyvinylidene fluoride (PVDF) membrane substrates with a plasma-induced pore-filling polymerization method. The effect of grafting yields on gating characteristics of pH-responsive gating membranes was investigated systematically. The results showed that the grafting yield heavily affected water flux, pH-responsiveness coefficient and pH-responsive gating factor of membrane pore size. When the grafting yield was smaller than 1.01%, both flux responsiveness coefficient and pH-responsive gating factor of pore size increased with increasing grafting yield. When the grafting yield was in the range from 1.01% to 6.44%, both flux responsiveness coefficient and pH-responsive gating factor of pore size decreased with increasing grafting yield; however, when the grafting yield was higher than 6.44%, both flux responsiveness coefficient and pH-responsive gating factor of membrane pore size approached to 1, i.e. , little gating characteristics existed. In order to obtain a satisfactory pH-responsive gating property of the membrane, the grafting yield must be kept in a proper range.     

Thin-film nanofibrous composite membranes containing cellulose or chitin barrier layers fabricated by ionic liquids

The barrier layer of high-flux ultrafiltration (UF) thin-film nanofibrous composite (TFNC) membranes for purification of wastewater (e.g., bilge water) have been prepared by using cellulose, chitin, and a cellulose-chitin blend, regenerated from an ionic liquid. The structures and properties of regenerated cellulose, chitin, and a cellulose-chitin blend were analyzed with thermogravimetric analysis (TGA) and wide-angle X-ray diffraction (WAXD). The surface morphology, pore size and pore size distribution of TFNC membranes were determined by SEM images and molecular weight cut-off (MWCO) methods. An oil/water emulsion, a model of bilge water, was used as the feed solution, and the permeation flux and rejection ratio of the membranes were investigated. TFNC membranes based on the cellulose-chitin blend exhibited 10 times higher permeation flux when compared with a commercial UF membrane (PAN10, Sepro) with a similar rejection ratio after filtration over a time period of up to 100 h, implying the practical feasibility of such membranes for UF applications.     

Effect of surface‐modifying macromolecules and membrane morphology on fouling of polyethersulfone ultrafiltration membranes

Polyethersulfone (PES) ultrafiltration (UF) membranes with and without surface‐modifying macromolecules (SMMs) were prepared and characterized in terms of the mean pore size and pore‐size distribution, surface porosity, and pore density. The results demonstrated that both the mean pore size and the molecular weight cutoff (MWCO) of the SMM‐modified membranes are lower than those of the corresponding unmodified ones. Membrane fouling tests with humic acid as the foulant indicated that the permeate flux reduction of the SMM‐modified membranes was much less than that of the unmodified ones. Therefore, fouling was more severe for the unmodified membranes. Moreover, the dry weight of the humic acid deposited on the membrane surface was considerably higher for the unmodified membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3132–3138, 2003     

Pore size of microporous polymer membranes

Pore sizes of microporous polymer membranes were determined by the calculation based on the gas permeability of porous media. The gas permeability coefficient K (given by J = K Δp/l, where J is the steady-state gas flux, Δp is the pressure, difference, and l = the thickness of a membrane) for porous membrane can be given generally by where K₀ is the Knudsen permeability coefficient, η is the viscosity of the permeant gas, B₀ is the geometric factor of a membrane, and Δp? is the mean pressure of the gas on both sides of a membrane. From gas permeability measurements which yield the pressure dependence of gas permeability coefficient (expressed as above equation), the mean pore size of the porous membrane can be estimated as where M is the molecular weight of the permeant gas. The validity of this method was examined with various Millipore filters of which nominal pore sizes are known. It was confirmed that the method provided a simple and reliable means of estimating mean pore size of microporous membranes. The method was applied to investigate the influence of factors involved in preparation of microporous polysulfone membranes by coagulation procedure. It was found that the mean pore size of porous polysulfone membrane increases with (1) increasing with casting thickness, (2) increasing temperature of coagulation bath, and (3) decreasing concentration of polymer in casting solution (DMF as solvent). Water flux and water flux decline due to compaction are also examined as a faction of pore size, porosity, and the thickness of membranes.     

Purification and Concentration of Caustic Mercerization Wastewater by Membrane Processes and Evaporation for Reuse

A membrane-based treatment strategy was developed for purifying the highly alkaline textile mercerization wastewater. 0.2-μm MF and 100 kDa UF membranes were evaluated as pretreatment alternatives before 10 kDa UF and 200 Da NF membranes. Turbidity was almost totally removed by both pretreatment options, while UF (100 kDa) showed higher COD retention than MF. In total recycle mode of filtration, fouling of both UF and MF membranes were 80% reversible by physical and almost totally reversible (≥ 97%) by chemical cleaning. In the second stage filtrations applied to the pretreated wastewater samples, NF could yield high (97-98%) COD retentions and low permeate COD concentrations (≤ 22 mg/L), while 10 kDa UF could only reduce the COD concentration to 150 mg/L. While no NaOH was lost in the MF+UF process, the use of NF as second stage resulted in 12-17% NaOH retention. The permeate flux in all second stage processes were stable, implying that the majority of the feed components that would cause fouling had been removed in the pretreatment stages. Permeate of the MF+NF sequence was concentrated by evaporation with no foaming problems, showing that the hybrid process can be applied to recycle a purified and concentrated caustic stream to the mercerization process.     

Comparison of ceramic and polymeric membranes for natural organic matter (NOM) removal

Ceramic membranes were compared with polymeric membranes with respect to natural organic matter (NOM) removal using two removal mechanisms (i.e., size exclusion and charge repulsion). NOM properties including molecular weight and molecular structure, at different charge densities, were examined, along with membrane characteristics, including molecular weight cut-off (MWCO) and surface charge. Integrated analyses of both NOM and membrane characteristics provided information for membrane evaluation of different membrane materials and configurations (i.e., tubular vs. flat sheet type). A ceramic tight-ultrafiltration (UF) membrane showed the same potential as a similar nanofiltration (NF) polymeric membrane, in terms of the minimization of haloacetic acid (HAA) formation. Moreover, a ceramic OF membrane with a MWCO of 8000 Daltons showed almost the same behavior as an equitable polymeric UF membrane with a MW CO of 8000 Daltons in terms of NOM removal.     

In‐line Flocculation‐Submersed MF/UF Membrane Hybrid System in Tertiary Wastewater Treatment

Abstract

Coagulation/flocculation pre‐treatment of feeds can successfully mitigate the drawbacks of membrane micro‐ and ultra filtration processes: fouling and limited ability to remove organic pollutants. Laboratory experiments conducted with a synthetic wastewater (representing biologically treated secondary effluent) using 0.1 µm pore size hollow fiber membrane showed that simple in‐line flocculation pre‐treatment with inorganic coagulants dramatically reduced membrane fouling rates. The hybrid system also ensured over 70% organic matter removal in terms of dissolved organic carbon (DOC). In the experiments in in‐line flocculation outperformed clarification pre‐treatment at optimum coagulant dosages. Differences in floc characteristics and elevated suspended solids concentrations in the membrane tank may explain this finding, but the exact causes were not investigated in this study. The beneficial effects of in‐line flocculation pre‐treatment to MF/UF separation were also confirmed in the treatment of septic tank effluent in a membrane bioreactor (MBR). The fouling rate of the 0.4 µm pore size (flat‐sheet) membrane was substantially reduced with 10–100 mg L^?1 ferric chloride coagulant doses, and total dissolved chemical oxygen demand (DCOD) removal also increased from 66% up to 93%. These findings are consistent with the results of other experimental studies and show that pre‐treatment controls submersed MF/UF filtration performance.     

Recovery of phenolic compounds from orange press liquor by nanofiltration

This research was undertaken in order to evaluate the potential of a nanofiltration (NF) process for the separation and concentration of phenolic compounds from press liquors obtained by pigmented orange peels. Four different spiral-wound NF membranes, characterised by different molecular weight cut-off (MWCO) (250, 300, 400 and 1000 Da) and polymeric material (polyamide, polypiperazine amide and polyethersulphone), were investigated. The rejection of the investigated membranes towards anthocyanins, flavonoids and sugars was evaluated in order to identify a suitable membrane to separate phenolic compounds from sugars. The performance of the investigated NF membranes was also evaluated in terms of permeate flux and antifouling performance.The obtained results indicated a reduction of the average rejection towards sugars by increasing the MWCO of the selected membranes, while the rejection towards anthocyanins remained higher than 89% for all the NF membranes investigated. The NFPES10 membrane showed the lowest average rejection towards sugar compounds and high rejections towards anthocyanins (89.2%) and flavonoids (70%). Permeate flux values at lower transmembrane pressures were also favourably high compared to the other NF membranes.