Concentration of ethanolic extracts from Sideritis ssp. L. by nanofiltration: Comparison of dead-end and cross-flow modes

The present investigation considers the flux decline during concentration of ethanolic extracts from Sideritis ssp. L. by nanofiltration. Membranes Duramem with molecular weight cut-off (MWCO) 300 and 500 Da have been used. Two sets of nanofiltration experiments are performed: dead end filtration in a stirred cell and cross flow filtration in a 4 flat sheet membrane rig. Comparable fluxes and rejections are observed. The membrane behaviour with respect to the operation conditions: transmembrane pressure and feed concentration is studied. The effect of the latter is illustrated by experiments with different feed concentrations and permeate-to-feed ratios. The discussion is supported by rejections and mass balance calculations. In both modes flux decreased with concentration and the observed rejections remained constant. Better conditions for reduced flux decline and tendency to a steady value are obtained by cross-flow nanofiltration. Combined with the greater membrane area and feed volume used in these experiments, these results can be regarded as having potential for larger scale applications.     

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.     

Removal of API's (Active Pharmaceutical Ingredients) from Organic Solvents by Nanofiltration

Abstract

The removal of 5 specific active pharmaceutical ingredients (API's) with molecular weight of 189, 313, 435, 531, and 721, respectively, from toluene, methylene chloride, and methanol was studied by using solvent resistant nanofiltration. Three membranes of the StarMem series (120, 122, and 228), with cut‐off values of 200, 220, and 280 respectively, were used in the experiments. Although the rejections expected from the size difference between solutes and membrane pores are high, the results largely depended on the solvent used. For toluene, rejections were rather small, due to the low molecular weight of the solutes of interest (all API's except for the largest compound). Modelling of the rejection curve showed that the minimum molecular weight of a solute to obtain a rejection of 90% in toluene with the membranes used, is ca. 600. The application in methylene chloride was unsuccessful due to partial dissolution of the membrane top layer; other polymeric membranes such as the Solsep series might be more successful. The rejections in methanol were sufficiently high (>90%) to allow implementation: the rejection can be significantly increased by using a module design with double membrane passage and recirculation of the retentate, as was calculated from mass balances. A comparison of a (single pass) nanofiltration system with a throughput distillation unit, currently in use, showed that the energy consumption is 200 times lower in the nanofiltration system.     

Hexamethylene diisocyanate crosslinking 2‐hydroxypropyltrimethyl ammonium chloride chitosan/poly(acrylonitrile) composite nanofiltration membrane

The effects of membrane preparation conditions on membrane properties were studied in detail. The results suggested that composite nanofiltration (NF) membrane from 2.0 wt % 2‐hydroxypropyltrimethyl ammonium chloride chitosan (HACC) vaporized for 2.5 h at 50°C, and then crosslinked for 9 h at 50°C with hexamethylene diisocyanate (HDI)/ethanol (0.45/50 wt/wt) were found to have optimal performance. The resultant membrane was called HACC/PAN [poly(acrylonitrile)] NF membrane. The characteristics of this membrane such as pure water permeability, molecular weight cut‐off, rejection of salts, and swelling were investigated. And its cut‐off molecular weight (MWCO) was ～520 Da. At 25°C and 1.0 MPa, the permeability of water was 17.24 L/h m² MPa. Swelling in water decreased and rejection of salts increased with increasing HDI concentration, indicating pore contraction and increase in hydrophobicity as well as pore tortuosity due to crosslinking. The order of rejection to different salt solutes followed the decreasing of CaCl₂, MgCl₂, NaCl, KCl, and Na₂SO₄, suggesting that this membrane was positively charged. The rejections to MgCl₂ and CaCl₂ were more than 0.90; therefore, this membrane can be used for hardness removal in water treatment process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

Peptide and Amino Acid Separation with Nanofiltration Membranes

Abstract

Several nanofiltration membranes [UTC-20, 60 (Toray Industries), NF-40 (Film-Tech Corporation), Desal-5, G-20 (Desalination Systems), and NTR-7450 (Nitto Electric Industrial Co.)] were applied to separate amino acids and peptides on the basis of charge interaction with the membranes since most of them contain charged functional groups. Nanofiltration membranes having a molecular weight cutoff (MWCO) below 300 (UTC-20, 60, NF-40 and Desal-5) were not suitable for separation of amino acids. On the other hand, separation of amino acids and peptides with nanofiltration membranes having a MWCO around 2000–3000 (NTR-7450 and G-20) was satisfactory based on a charge effect mechanism; charged amino acids and peptides were rejected while neutral amino acids and peptides permeated through the membranes. Separation of peptides having different isoelectric points with nanofiltration membranes was possible by adjusting the pH.     

Performance of Nanofiltration Membranes in Ethanol

Abstract

Several nanofiltration membranes were tested for flux and rejection of selected solutes in ethanol. The membranes were initially conditioned with pure solvent containing increasing concentrations of ethanol. Flux decreased with increase in ethanol concentration and increased at higher temperatures and pressures. The type of solute had an influence on membrane rejection profiles. The DK membrane showed increasing rejection of polyethylene glycols (PEG) dissolved in ethanol from 29% at a molecular weight (MW) of 200 to 80% at MW 1000. However, the MW of sugars and lipids had little or no effect on rejection with the DK membrane; their rejection averaged 87%. In contrast, the TFC‐SR1 membrane showed higher rejections with higher MW compounds: lipid rejection increased from 19% to 71%, sugars from 35% to 85%, and lipids from 77% to 89%. The TFC‐SR2 membrane was much more open and showed the lowest rejections of all these compounds. Flux generally showed opposite trends, with the DK showing the lowest flux and the SR2 the highest.     

Treatment of an Oil/Grease Wastewater Using Ultrafiltration: Pilot-Scale Results

Abstract

Wastewater containing about 0.5% oil and grease (O/G) from a metal industry was treated by tubular ultrafiltration using membranes having a molecular weight cutoff (MWCO) of 120,000 and a negative surface charge (P membrane) and of 100,000 and no surface charge (M membrane). Permeate flux decreased dramatically during the first several hours of operation and then leveled-off for the remainder of semibatch operation. The average P membrane flux was significantly higher than the M membrane (38 versus 27 gal/ft ^2.d) because of its higher MWCO and negative surface charge. Increasing the transmembrane pressure and crosstlow velocity increased the permeate flux for both membranes. O/G concentrations less than 50 mg/L and total suspended solids (TSS) levels less than 25 mg/L were common for both membranes. O/G removal efficiencies (rejections) averaged 98% for the M membrane and 97% for the P membrane. TSS rejections were approximately 97% for both membranes. Effluent O/G concentration and turbidity from the P membrane were slightly higher than the M membrane because of the P membrane's higher MWCO and the larger flux. The average volume reduction and residual production were 97% and 32 gal/1000 gal. respectively. Acid cracking of the concentrate with sulfuric acid was marginally successful.     

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.     

Organic solvent nanofiltration with a Poly(dimethylsiloxane) membrane: Parameters affecting its sieving properties

In this study, retention experiments were performed to characterize the variable sieving properties of a poly(dimethylsiloxane) (PDMS) membrane in relation with operating parameters. The swelling, transmembrane pressure, and temperature are all known to impact the physicochemical properties and morphology of PDMS polymer and were therefore varied for the purposes of our retention experiments which assessed them with the homologous series of polyethylene glycols (PEGs; 200–1500 g mol^?1). The objectives were twofold—first, to evaluate the capacity to induce a targeted molecular weight cutoff (MWCO) by selecting appropriate filtration conditions and second to better understand the mechanisms involved during solvent‐resistant nanofiltration with PDMS. The selected solvents or solvent/solvent mixtures used throughout this study were found to induce swelling ratios of 1.16 (ethanol/ethyl acetate: 25/75), 1.26 (ethyl acetate), 1.33 (ethyl acetate/toluene: 50/50), and 1.41 (toluene), respectively. Linear correlations were obtained between the MWCO and the swelling ratio induced by each solvent and between the MWCO and the transmembrane pressure. Pore size calculations using solvent flux and retention data confirmed the variable sieving properties of the PDMS membrane in relation to the solvent‐induced swelling and applied transmembrane pressure. In addition, the study of the solute‐transfer rate through several operating conditions showed that both diffusive and convective transports occurred for the PEG solutes and that their respective contributions appeared dependent on the variable pore size of the PDMS membrane. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41171.     

Effect of sol size on nanofiltration performance of a sol-gel derived microporous zirconia membrane

This paper reports the effect of sol size on nanofiltration performances of sol–gel derived microporous zirconia membranes. Microstructure, pure water flux, molecular weight cut-off (MWCO) and salt retention of zirconia membranes derived from zirconia sols with different sizes were characterized. Thermal evolution, phase compo-sition, microstructure and chemical stability of unsupported zirconia membranes (powder) were determined by thermogravimetric and differential thermal analysis, X-ray diffraction, nitrogen adsorption–desorption and static solubility measurements. Results show that nanofiltration performance of zirconia membranes is highly depen-dent on sol size. The sol with an average size of 3.8 nm, which is smaller than the pore size of theγ-Al2O3 support (pore size:5–6 nm), forms a discontinuous zirconia separation layer because of excessive penetration of sol into the support. This zirconia membrane displays a MWCO value towards polyethylene glycol higher than 4000 Da. A smooth and defect-free zirconia membrane with a MWCO value of 1195 Da (pore size:1.75 nm) and relative high retention rates towards MgCl2 (76%) and CaCl2 (64%) was successfully fabricated by dip-coating the sol with an appropriate size of 8.6 nm. Zirconia sol with an average size of 12 nm exhibits colloidal nature and forms a zirconia membrane with a MWCO value of 2332 Da (pore size:2.47 nm). This promising microporous zirconia membrane presents sufficiently high chemical stability in a wide pH range of 1–12.     

Performances of poly(vinylidene fluoride‐co‐hexafluoropropylene) ultrafiltration membranes modified with poly(vinyl pyrrolidone)

The structure and performance of modified poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF‐co‐HFP) ultra‐filtration membranes prepared from casting solutions with different concentrations of poly(vinyl pyrrolidone) (PVP) were investigated in this study. Membrane properties were studied in terms of membrane compaction, pure water flux (PWF), water content (WC), membrane hydraulic resistance ( R _m), protein rejection, molecular weight cut‐off (MWCO), average pore size, and porosity. PWF, WC, and thermal stability of the blend membranes increased whereas the crystalline nature and mechanical strength of the blend membranes decreased when PVP additive concentration was increased. The contact angle (CA) decreased as the PVP concentration increased in the casting solution, which indicates that the hydro‐philicity of the surface increased upon addition of PVP. The average pore size and porosity of the PVdF‐co‐HFP membrane increased to 42.82 Å and 25.12%, respectively, when 7.5 wt% PVP was blended in the casting solution. The MWCO increased from 20 to 45 kDa with an increase in PVP concentration from 0 to 7.5 wt%. The protein separation study revealed that the rejection increased as the protein molecular weight increased. The PVdF‐co‐HFP/PVP blended membrane prepared from a 7.5 wt% PVP solution had a maximum flux recovery ratio of 74.3%, which explains its better antifouling properties as compared to the neat PVdF‐co‐HFP membrane. POLYM. ENG. SCI., 55:2482–2492, 2015. © 2015 Society of Plastics Engineers     

Solute transport in non‐aqueous nanofiltration: effect of membrane material

Nanofiltration experiments in methanol and ethanol were carried out for six reference components with different molecular weights (MW 228–880) and polarities (logP 0–12). The contribution of diffusion to solute transport, calculations based on results from cell diffusion experiments, was found to be only 1–7%; solute transport occurs mainly by convection. Furthermore, it was found that solute transport is influenced by solute–solvent–membrane interactions. Solvent–solute interactions (solvation) cause a different effective solute diameter in each solvent: it is smaller in ethanol than in methanol, resulting in lower rejections in ethanol than in methanol. Solute rejection increases with increasing molecular size (for components with similar polarity). Solute–membrane interactions were expressed in polarity terms and charge effects. A decrease of the rejection with decreasing solute polarity (for components with similar MW) was observed. Since non‐polar components (high logP) are exposed to smaller repulsion forces from the polymeric membrane material, the resistance against solute permeation is lower for these components. The solvent–membrane interactions were found to result in solvation of the pore wall; the degree of membrane solvation is different for each solvent. It is determined by the affinity between the solvent and the membrane, and by the molecular size of the solvent. In ethanol, hydrophilic membranes show a larger drop in solute rejection than hydrophobic membranes. The differences in solvent–membrane affinity (measured by contact angle) are much smaller for the first membranes, and therefore pore wall solvation decreases with increasing solvent size. Hydrophobic membranes have a much larger affinity for ethanol than for methanol, leading to stronger interactions, but undergo competitive forces due to the larger solvent size. Therefore, the difference in degree of solvation and effective pore diameter is less pronounced. Based on these three observed or postulated interactions, rejections of all six reference solutes in methanol and ethanol could be explained. Copyright © 2005 Society of Chemical Industry     

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%).     

Rejection of As(III) and As(V) from arsenic contaminated water via electro-cross-flow negatively charged nanofiltration membrane system

A specially designed electro-cross-flow nanofiltration (NF) membrane system was used for this investigation. To enhance the rejection of arsenic ionic species like H₂AsO₄⁻, a NF membrane having a negative surface charge was fabricated via the interfacial polymerization process. The membrane was characterized by SEM, AFM, surface charge density, molecular weight cut-off (MWCO), total and skin thickness and pure water flux. The parameters that affected the rejections of As(III) and As(V) were studied; they included the initial arsenic concentration, the applied potential, pH of the feed, the cross-flow filtration pressure and the presence of different salts in the feed. Among those parameters, the pH of the feed greatly affected As(V) rejection; As(V) ([As(V)]_o = 1000 ppb) rejection was increased from 72.3 to 98.5% when pH of the feed was changed from 3.0 to 10.0. This might be due to the fact that higher pH enhanced the formation of negative divalent anion like HAsO₄²⁻ which should be rejected more effectively by the negative surface charge of the NF membrane. Beside the effect of the negative surface charge of the membrane, applied potential increased the As(V) rejection by 48.2% when the applied potential was increased from 0 to 2.0 V for a feed containing 1000 ppb initially. For the same change of applied potential rejection of As(III) was increased from 52.3 to 70.4%; this might be the result of the formation of anionic species like H₂AsO₃⁻ from the neutral molecule of H₃AsO₃ by the applied potential.     

Preparation and characterization of a novel positively charged nanofiltration membrane based on polysulfone

The goal of this study was to prepare positively charged nanofiltration (NF) membranes to remove cations from aqueous solutions. A composite NF membrane was fabricated by the modification of a polysulfone ultrafiltration support. The active top layer was formed by the interfacial crosslinking polymerization of poly(ethylene imine) (PEI) with p‐xylene dichloride (XDC). Then, it was quaternized by methyl iodide (MI) to form a perpetually positively charged layer. The chemical and morphological changes of the membrane surfaces were studied by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy. To optimize the membrane operation, the PEI solution concentration, PEI coating time, XDC concentration, crosslinking time, and MI concentration were optimized. Consequently, high water flux (5.4 L m^?2 h^?1 bar^?1) and CaCl₂ rejection (94%) values were obtained for the composite membranes at 4 bars and 30°C. The rejections of the NF membrane for different salt solutions, obtained from pH testing, followed the order Na₂SO₄ < MgSO₄ < NaCl < CaCl₂. The molecular weight cutoff was calculated by the retention of poly(ethylene glycol) solutions with different molecular weights, and finally, the stoke radius was calculated as 1.47 nm. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41988.     

Influences of molecular weight, molecular size, flux, and recovery for aromatic pesticide removal by nanofiltration membranes

Eleven aromatic pesticides were used for a removal study using a 4040 spiral-wound polyamide nanofiltration (NF) membrane. The influences of molecular weight, molecular size (length and width), flux, and recovery were studied. The molecular weights of these pesticides are from 198 Da to 286 Da. Molecular sizes were determined by theoretical calculation for their length and width by “Hyperchem” based on their structures and orientation. Furthermore, the study held constant for two operated recoveries and fluxes to determine their effects. The results showed that the NF membrane can remove pesticides from 46% to 100% based on their molecular weights, lengths, fluxes and recoveries. The rejections were increased as the molecular weight increased, and a sharp increase to complete rejection (100%) was observed around MW 200 Da. Therefore, a molecular weight cut-off (MWC) of 200 Da can be determined for this membrane from this result. In addition, the results showed the molecular length was more significant than molecular width for these pesticides. The rejections were not only dependent on molecular weight and length, but also on operational flux and recovery. For a particular pesticide in the two operational fluxes and recoveries, the highest percent rejections occurred on high flux and low recovery, and lowest percent rejection occurred on low flux and high recovery, which would indicate the basic diffusion control theory.     

Polyamide‐imide nanofiltration hollow fiber membranes with elongation‐induced nano‐pore evolution

The molecular design of nanoporous membranes with desired morphology and selectivity has attracted significant interest over the past few decades. A major problem in their applications is the trade‐off between sieving property and permeability. Here, we report the discovery of elongation‐induced nano‐pore evolution during the external stretching of a novel polyamide‐imide nanofiltration hollow fiber membrane in a dry‐jet wet‐spinning process that simultaneously leads to a decreased pore size but increased pure water permeability. The molecular weight cutoff, pore size, and pore size distribution were finely tuned using this approach. AFM and polarized FTIR verified the nano‐pore morphological evolution and an enhanced molecular orientation in the surface skin layer. The resultant nanofiltration membranes exhibit highly effective fractionation of the monovalent and divalent ions of NaCl/Na₂SO₄ binary salt solutions. More than 99.5% glutathione can be rejected by the nanofiltration membranes at neutral pH, offering the feasibility of recovering this tripeptide. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Study of the characteristics and the performance of self-made nanoporous polyethersulfone membranes

Polyethersulfone (PES) membranes were prepared in this study by using the DIPS technique (diffusion induced phase separation) in view of a better insight into the performance of commercial polyethersulfone membranes and a verification for the limited information given by the manufacturer. During this process, a lot of conditions influence the final membrane structure. Beside the choice of the solvent (dimethylformamide (DMF) or N-methyl-pyrrolidone (NMP)), it was shown that the concentration of the polymer and the relative air humidity are the most crucial ones. Optimizing these factors led to reproducible membranes, which were characterized for hydrophobicity, roughness, surface charge and molecular weight cut-off (MWCO). The performance was studied by doing cross-flow filtration experiments with aqueous solutions of uncharged and charged component. Although the self-made membranes were characterized by a larger MWCO in comparison with commercial polyethersulfone nanofiltration membranes, the retention for the self-made membranes was almost equal to or even higher than the commercial membranes in the case of filtrating negatively, respectively, positively charged component. The high retention of the self-made membranes for positively charged component can be explained by adsorption experiments or by surface charge measurements before and after filtration.     

Polyelectrolyte multilayer modified nanofiltration membranes for the recovery of ionic liquid from dilute aqueous solutions

The feasibility of nanofiltration membranes fabricated by static polyelectrolyte layer‐by‐layer deposition of poly(styrene sulfonate) and poly(allylamine hydrochloride) on poly(ether sulfone) ultrafiltration and alumina microfiltration membranes for the recovery of ionic liquid from low molecular weight sugar was investigated. The surface properties of these modified membranes were correlated with their performances. The selectivity for 1‐butyl‐3‐methylimidazolium chloride over cellobiose and glucose was found to be as high as 50.5/2.3 for modified alumina and 32.3/3.5 for modified poly(ether sulfone) membranes with optimized number of bilayers. The values for membrane permeance were 4.8 and 2.5 L m^?1 h² bar^?1, respectively. For low depositions, the separation mechanism was predominantly governed by size‐exclusion. For higher depositions, the enhanced negative zeta potential of the modified membranes suggested preferred dominating electrostatic interactions, resulting in high selectivity of ionic liquids over low molecular weight sugars. At very high depositions, the molecular weight cut‐off of the membrane becomes constricting for size‐exclusion effect. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45349.     

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.